Ullmann's Chemical Engineering and Plant Design - Vol. 1 Mathematics and Physics in Chem. Eng. - Fundamentals - Vol. 2 Plant and Process Design - Wiley-VCH PDF

ULLMANN’S
Chemical Engineering
and Plant Design
Volume 1
Mathematics and Physics

in Chemical Engineering
Fundamentals of
Chemical Engineering
All books published by Wiley-VCH are carefully Library of Congress Card No.: Applied for.
produced. Nevertheless, authors, editors and publisher
do not warrant the information contained in these books, British Library Cataloguing-in-Publication Data: A
including this book, to be free of errors. Readers are catalogue record for this book is available from the
advised to keep in mind that statements, data, British Library.
illustrations, procedural details or other items may
inadvertently be inaccurate. Bibliographic information published by
The Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists this publication in
the Deutsche Nationalbibliografie; detailed bibliographic
data are available in the Internet at
http://dnb.d-nb.de
ISBN 978-3-527-31111-8
c 2005 WILEY-VCH Verlag GmbH & Co. KGaA,

Weinheim
Printed on acid-free paper.
All rights reserved (including those of translation in other
languages). No part of this book may be reproduced in
any form – by photoprinting, microfilm, or any other
means – nor transmitted or translated into machine
language without written permission from the publishers.
Registered names, trademarks, etc. used in this book,
even when not specifically marked as such, are not to be
considered unprotected by law.
Composition: Steingraeber Satztechnik GmbH,

Dossenheim
Printing: Strauss GmbH, Mörlenbach
Bookbinding: Litges & Dopf Buchbinderei GmbH,
Heppenheim
Cover Design: Gunther Schulz, Fußgönheim
Printed in the Federal Republic of Germany.

V
Preface
Since the unabridged 40-volume Ullmann’s Encyclopedia is inaccessible to many readers – particu-
larly individuals, smaller companies or institutes – all the information on chemical engineering and
plant design has been condensed into this convenient two-volume set.
Based on the very latest print edition of Ullmann’s, this ready reference is the one-stop resource for
the plant design engineering community. Starting with the quantitative treatment and fundamentals
of chemical engineering, it combines all aspects of process development and reactor technology, as
well as detailing their practical applications in sections devoted to plant design, scale-up and plant
safety. Each of the detailed and carefully edited articles is written by relevant experts from industry
or academia. A keyword and an author index complete the contents of this handbook.
Throughout, readers benefit from the rigorous and cross-indexed nature of the parent reference, and
will find both broad introductory information as well as in-depth details of significance to industrial
and academic environments.
The Publisher
Contents VII
Contents
Volume 1 Nondestructive Testing . . . . . . . . . . . . . . . . 785

On-Line Monitoring of Chemical
Symbols and Units . . . . . . . . . . . . . . . . . . . . IX Reactions . . . . . . . . . . . . . . . . . . . . . . . . 821
Conversion Factors . . . . . . . . . . . . . . . . . . . XI
Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . XII
Country Codes . . . . . . . . . . . . . . . . . . . . . . . XVII Volume 2
Periodic Table of Elements . . . . . . . . . . . . XVIII
Plant and Process Design
Mathematics and Physics in Process Development . . . . . . . . . . . . . . . . . 873

Chemical Engineering Separation Processes, Introduction. . . . . . 915
Solid – Liquid Separation, Introduction . . 923
Mathematics in Chemical Engineering . . 3 Solid – Solid Separation, Introduction . . . 931
Mathematical Modeling . . . . . . . . . . . . . . . 165 Mixing, Introduction . . . . . . . . . . . . . . . . . . 939
Transport Phenomena . . . . . . . . . . . . . . . . . 271 Solids Technology, Introduction . . . . . . . . 941
Fluid Mechanics . . . . . . . . . . . . . . . . . . . . . . 371 Reactor Types and Their Industrial
Design of Experiments . . . . . . . . . . . . . . . . 423 Applications. . . . . . . . . . . . . . . . . . . . . . 953
Computational Fluid Dynamics . . . . . . . . 463 Chemical Plant Design and Construction 987
Model Reactors and Their Design Pinch Technology . . . . . . . . . . . . . . . . . . . . . 1075
Equations . . . . . . . . . . . . . . . . . . . . . . . . 487 Pilot Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . 1083
Scale-Up in Chemical Engineering . . . . . 1093
Biochemical Engineering . . . . . . . . . . . . . . 1117
Fundamentals Energy Management in Chemical
of Chemical Engineering Industry . . . . . . . . . . . . . . . . . . . . . . . . . . 1187
Plant and Process Safety . . . . . . . . . . . . . . . 1205
Estimation of Physical Properties . . . . . . . 537 Environmental Management in the
Construction Materials in Chemical Chemical Industry . . . . . . . . . . . . . . . . 1331
Industry . . . . . . . . . . . . . . . . . . . . . . . . . . 605
Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 653
Abrasion and Erosion . . . . . . . . . . . . . . . . . 735 Author Index . . . . . . . . . . . . . . . . . . . . . . . 1359
Mechanical Properties and Testing of
Metallic Materials . . . . . . . . . . . . . . . . 761 Subject Index . . . . . . . . . . . . . . . . . . . . . . . 1363
Mathematics and Physics in Chemical Engineering
Mathematics in Chemical Engineering 3
Mathematics in Chemical Engineering

Bruce A. Finlayson, Department of Chemical Engineering, University of Washington, Seattle, Washington
98195, United States (Chaps. 1 – 9, 11, 12)
Lorenz T. Biegler, Carnegie Mellon University, Pittsburgh, Pennsylvania 15231, United States (Chap. 10)
Ignacio E. Grossmann, Carnegie Mellon University, Pittsburgh, Pennsylvania 15231, United States (Chap. 10)
Arthur W. Westerberg, Carnegie Mellon University, Pittsburgh, Pennsylvania 15231, United States (Chap. 10)
1. Solution of Equations . . . . . . . . 6 7. Ordinary Differential Equations as

1.1. Linear Algebraic Equations . . . . 6 Boundary Value Problems . . . . . 76
1.2. Nonlinear Algebraic Equations . . 12 7.1. Solution by Quadrature . . . . . . . 76
1.3. Linear Difference Equations . . . . 14 7.2. Shooting Methods . . . . . . . . . . . 77
1.4. Eigenvalues . . . . . . . . . . . . . . . 15 7.3. Finite Difference Method . . . . . . 79
2. Approximation and Integration . . 16 7.4. Orthogonal Collocation . . . . . . . 82
2.1. Introduction . . . . . . . . . . . . . . 16 7.5. Orthogonal Collocation on Finite
2.2. Global Polynomial Approximation 16 Elements . . . . . . . . . . . . . . . . . 87
2.3. Piecewise Approximation . . . . . . 18 7.6. Galerkin Finite Element Method . 88
2.4. Quadrature . . . . . . . . . . . . . . . 21 7.7. Cubic B-Splines . . . . . . . . . . . . 90
2.5. Linear Least Squares . . . . . . . . . 24 7.8. Adaptive Mesh Strategies . . . . . . 91
2.6. Nonlinear Least Squares . . . . . . 26 7.9. Comparison . . . . . . . . . . . . . . . 92
2.7. Fourier Transforms 7.10. Singular Problems and Infinite Do-
of Discrete Data . . . . . . . . . . . . 27 mains . . . . . . . . . . . . . . . . . . . 93
2.8. Two-Dimensional Interpolation 8. Partial Differential Equations . . . 94
and Quadrature . . . . . . . . . . . . 29 8.1. Classification of Equations . . . . . 94
3. Complex Variables . . . . . . . . . . 30 8.2. Hyperbolic Equations . . . . . . . . 96
3.1. Introduction to the Complex Plane 30 8.3. Parabolic Equations
3.2. Elementary Functions . . . . . . . . 31 in One Dimension . . . . . . . . . . . 98
3.3. Analytic Functions of a Complex 8.4. Elliptic Equations . . . . . . . . . . . 104
Variable . . . . . . . . . . . . . . . . . 33 8.5. Parabolic Equations in Two
3.4. Integration in the Complex Plane 34 or Three Dimensions . . . . . . . . . 108
3.5. Other Results . . . . . . . . . . . . . . 37 9. Integral Equations . . . . . . . . . . 109
4. Integral Transforms . . . . . . . . . 37 9.1. Classification . . . . . . . . . . . . . . 109
4.1. Fourier Transforms . . . . . . . . . . 37 9.2. Numerical Methods for Volterra
4.2. Laplace Transforms . . . . . . . . . 42 Equations of the Second Kind . . . 111
4.3. Solution of Partial Differential 9.3. Numerical Methods for Fredholm,
Equations by Using Transforms . . 48 Urysohn, and Hammerstein Equa-
5. Vector Analysis . . . . . . . . . . . . 51 tions of the Second Kind . . . . . . 113
6. Ordinary Differential Equations as 9.4. Numerical Methods for Eigenvalue
Initial Value Problems . . . . . . . . 61 Problems . . . . . . . . . . . . . . . . . 115
6.1. Solution by Quadrature . . . . . . . 62 9.5. Green’s Functions . . . . . . . . . . . 115
6.2. Explicit Methods . . . . . . . . . . . 63 9.6. Boundary Integral Equations and
6.3. Implicit Methods . . . . . . . . . . . 67 Boundary Element Method . . . . . 117
6.4. Stiffness . . . . . . . . . . . . . . . . . 68 10. Optimization . . . . . . . . . . . . . . 118
6.5. Differential – Algebraic Systems . 69 10.1. Introduction . . . . . . . . . . . . . . 118
6.6. Computer Software . . . . . . . . . 71 10.2. Conditions for Optimality . . . . . 119
6.7. Stability, Bifurcations, Limit Cy- 10.3. Strategies of Optimization . . . . . 123
cles . . . . . . . . . . . . . . . . . . . . . 72 10.4. Successive Quadratic
6.8. Sensitivity Analysis . . . . . . . . . . 74 Programming (SQP) . . . . . . . . . 127
6.9. Eigenvalues and Roots by Initial 10.5. Linear Programming . . . . . . . . . 130
Value Techniques . . . . . . . . . . . 75 10.5.1. Basic Properties . . . . . . . . . . . . . 131
4 Mathematics in Chemical Engineering
10.5.2. Simplex Algorithm . . . . . . . . . . . 132 11.4. Factorial Design of Experiments

10.6. Mixed-Integer Programming . . . 133 and Analysis of Variance . . . . . . 150
10.7. Solution of Dynamic Optimization 12. Multivariable Calculus Applied to
Problems . . . . . . . . . . . . . . . . . 136 Thermodynamics . . . . . . . . . . . 153
12.1. State Functions . . . . . . . . . . . . . 153
11. Probability and Statistics . . . . . . 142
12.2. Applications to Thermodynamics 154
11.1. Concepts . . . . . . . . . . . . . . . . . 143 12.3. Partial Derivatives of All Thermo-
11.2. Sampling and Statistical Decisions 146 dynamic Functions . . . . . . . . . . 155
11.3. Error Analysis in Experiments . . 150 13. References . . . . . . . . . . . . . . . . 156
Symbols h set of m equality constraints for an opti-

mization problem
Variables
H the inverse of matrix Q. Also the scalar
a scalar constant in quadratic approxima-
Hamiltonian function for a dynamic op-
tion for F, the objective function
timization problem
A m×n matrix of constant coefficients for
I identity matrix
equality constraints in linear program-
k iteration matrix
ming model
L scalar Lagrange function
b vector of constants premultiplying the r
m number of equality constraints for an op-
independent variables u in the quadratic
timization problem
approximation for F, the objective func-
n number of total variables in an optimiza-
tion. Also vector of m right-hand-sides
tion problem
for equality constraints in linear program-
N (n-m)×m matrix corresponding to the
ming problem
non-basis variables in a linear program-
B approximation of the n×n Hessian matrix
ming problem
for the Lagrange function for the succes-
p number of inequality constraints for an
sive quadratic programming algorithm.
optimization problem. Also vector of pa-
Also m×m non-singular matrix corre-
rameters (do not vary with time) for dy-
sponding to the basis variables in a linear
namic optimization problem
programming problem. Also coefficient
Pe Peclet number
matrix for binary variables y in the set of
Q an r×r matrix of constants used in defin-
equality constraints for a mixed integer
ing the quadratic term for a quadratic ap-
programming problem
proximation for F, the objective function
Bi Biot number
r number of independent variables for an
c vector of n constant cost coefficients for
optimization problem (r = n-m)
all variables z in linear programming
Re the space of real numbers
problem
R matrix defined in the quadratic program-
Co Courant number
ming algorithm. Also the vector of resid-
d search direction in the space of all n vari-
ual equations in the finite element ap-
ables z (both dependent and independent
proach to solving dynamic optimization
variables)
problems
D diffusion constant
Ren real number vector space of dimension n
Da Damköhler number
s change in the independent variables u (a
f nonlinear scalar contribution to objective
vector with r elements in it). Also sen-
function which is a function only of the
sitivity of the functions f with respect to
continuous variables, y, for a mixed inte-
the parameter p for a dynamic optimiza-
ger programming problem
tion problem
F scalar objective function for an optimiza-
Sh Sherwood number
tion problem
u vector of r independent variables for an
g set of p inequality constraints for an op-
optimization problem. For a time-varying
timization problem
problem, the independent time-varying optimization problem, the Lagrange mul-

control variables tiplier for the state variable constraints.
W r×r weighting matrix used in computing µ vector of p Kuhn – Tucker multipliers
Frobenius norm ν vector of Lagrange multipliers (vary with
x vector of m dependent variables for an time) for the algebraic equality con-
optimization problem (the state variables straints for a dynamic optimization prob-
for a dynamic optimization problem) lem
y variables used in linear programming τ rescaled time so it lies in range [0,1]
problem. Also binary variables in the for- Y vector of polynomial approximation
mulation of a mixed integer programming function for the control variables for fi-
problem nite element method for dynamic opti-
Y n×m matrix whose columns are vectors mization problem
that span the range space of the linearized
constraints (see section on successive
quadratic programming algorithm) Special symbols
z vector of all n variables – both the m de- | subject to
pendent variables x and the r independent : mapping. For example, h : Rn → Rm ,
variables u – for an optimization problem states that functions h map real numbers
z̄ interior point for linear programming into m real numbers. There are m func-
problem tions h written in terms of n variables
Z n×(n-m) matrix whose columns are vec- ∈ member of
tors that span the null space of the → maps into
linearized constraints (see section on
successive quadratic programming algo-
rithm) Subscripts
A gA are the active constraints (i.e., pre-
Greek symbols cisely equal to zero) among the inequality
constraints
α scalar for setting the step size in a B basis variables in a linear programming
line search algorithm for the successive problem
quadratic programming algorithm. Also f value at the final time for a dynamic op-
a vector of coefficients to form a convex timization problem
combination of extreme points for a linear i i-th element of a vector of variables
programming problem. Also scalar vari- N non-basis variables in a linear program-
able used as the objective for the mixed in- ming problem
teger programming problem in equation NE number of elements in a finite element
76. Also length of an element in the finite model
element approach to solving dynamic op- OA outer approximation
timization problems o value at the initial time for a dynamic op-
γ change in gradient of the objective func- timization problem
tion in moving from point k to point k + 1.
γ is a vector with r elements in it
δ Kronecker delta Superscript
∆ sampling rate k iteration index
ε small scalar L lower bound
φ vector of polynomial approximation T transpose of a vector or matrix
functions for the state variables for finite U upper bound
element method for dynamic optimiza- ˆ base point for a Taylor series expansion
tion problem, also Thiele modulus
κ condition number
λ vector of m Lagrange multipliers for an
optimization problem. Also for a dynamic
1. Solution of Equations 1.1. Linear Algebraic Equations

Mathematical models of chemical engineering Consider the n×n linear system
systems can take many forms: they can be sets
of algebraic equations, differential equations, or a11 x1 + a12 x2 + . . . + a1n xn = f1
integral equations. Mass and energy balances of
chemical processes typically lead to large sets a21 x1 + a22 x2 + . . . + a2n xn = f2
of algebraic equations:
...
a11 x1 + a12 x2 = b1
an1 x1 + an2 x2 + . . . + ann xn = fn
a21 x1 + a22 x2 = b2
In this equation a11 , . . . , ann are known param-
Mass balances of stirred tank reactors may lead eters, f 1 , . . . , fn are known, and the unknowns
to ordinary differential equations: are x 1 , . . . , xn . The values of all unknowns that
dy satisfy every equation must be found. This set of
= f [ y (t)] equations can be represented as follows:
dt
Radiative heat transfer may lead to integral
n
equations: aij xj = fj or A x = f
j=1
1
y (x) = g (x) + λ K (x, s) f (s) ds The most efficient method for solving a set
0 of linear algebraic equations is to perform a
lower – upper (LU) decomposition of the corre-
Even when the model is a differential equation
sponding matrix A. This decomposition is es-
or integral equation, the most basic step in the al-
sentially a Gaussian elimination, arranged for
gorithm is the solution of sets of algebraic equa-
maximum efficiency.
tions. The solution of sets of algebraic equations
The LU decomposition is done by calculating
is the focus of Chapter 1.
in turn
A single linear equation is easy to solve for
either x or y: for i = 1, n do
y = ax + b
for j = 1, n do
If the equation is nonlinear,
(1)
aij = aij
f (x) = 0
it may be more difficult to find the x satisfying enddo

this equation. These problems are compounded
enddo
when there are more unknowns, leading to si-
multaneous equations. If the unknowns appear
for k = 2, n do
in a linear fashion, then an important considera-
tion is the structure of the matrix representing the for i = k + 1, n do
equations; special methods are presented here
for special structures. They are useful because for j = k + 1, n do
they increase the speed of solution. If the un-
knowns appear in a nonlinear fashion, the prob- (k−1)
ai, k−1
(k) (k− 1) (k− 1)
lem is much more difficult. Iterative techniques aij = aij − (k−1)
ak−1,j
ak−1,k−1
must be used (i.e., make a guess of the so-
lution and try to improve the guess). An im-
enddo
portant question then is whether such an iter-
ative scheme converges. Other important types enddo
of equations are linear difference equations and
eigenvalue problems, which are also discussed. enddo
Then two matrices are formed. The upper matrix for i = n − 1, 1 do

U = A(n) is defined as

n
(i) (i)
(n) 0 i >j f i − aij xj
U ij = Aij = (i) j=i+1
a ij i ≤ j, 1 ≤ j ≤ n xi = (i)
aii
The lower matrix L is defined as
 enddo

 0 i<j

1 i = j When f is changed, the last steps can be done
Lij =


(j)
aij without recomputing the LU decomposition.

 (j) i>j
ajj Thus, multiple right-hand sides can be computed
efficiently. The number of multiplications and
The U is upper triangular; it has zero elements divisions necessary to solve for m right-hand
below the main diagonal and possibly nonzero sides is:
values along the main diagonal and above it (see
Fig. 1). The L is lower triangular. It has the value 1 3 1
Operation count = n − n + m n2
1 in each element of the main diagonal, nonzero 3 3
values below the diagonal, and zero values above The actual algorithm used will be different for
the diagonal (see Fig. 1). Thus, parallel computers.
The determinant is given by
A = LU

n
The original problem can be solved in two steps: DetA = aii
(i)
i=1
Ly = f , U x = y solves Ax = LU x = f
This should be calculated as the LU decomposi-
tion is performed. If the value of the determinant
Each of these steps is straightforward because is a very large or very small number, it can be
the matrices are upper triangular or lower trian- divided or multiplied by 10 to retain accuracy in
gular. The solution is performed using the equa- the computer; the scale factor is then accumu-
tions lated separately. The condition number κ can be
defined in terms of the singular value decompo-
for i = 1, n do sition as the ratio of the largest wi to the smallest
(1)
wi (see below). It can also be expressed in terms
fi = fi of the norm of the matrix:
enddo κ (A) = A A−1
for k = 2, n do where the norm is defined as

for i = k + 1, n do A x n
A ≡ supx=0 = maxk |ajk |
x j=1
(k−1)
(k) (k−1)
ai,k−1 (k−1)
f i =f i − f k−1
(k−1)
ak−1,k−1 If this number is infinite, the set of equations
is singular. If the number is too large, the ma-
enddo trix is said to be ill-conditioned. The definition
of “large” refers to the accuracy of the computer
enddo being used; the criterion is the inverse of the
floating point precision. If the machine’s floating
point precision is 10−6 then 106 is large; if dou-
(n) (n)
xn = f n /ann
ble precision is used then the precision is 10−12
(1) and 1012 is large. Calculation of the condition
number can be lengthy so another criterion is
also useful. Compute the ratio of the largest to element can be obtained from only the diagonal
the smallest pivot and make judgments on the entries (partial pivoting) or from all the remain-
ill-conditioning based on that. ing entries. If the matrix is nonsingular, Gaussian
elimination (or LU decomposition) could fail if a
(k)
maxk |akk | zero value were to occur along the diagonal and
Ratio = (k)
mink |akk | were to be a pivot. With full pivoting, however,
the Gaussian elimination (or LU decomposition)
Another empirical test is the quantity V ; when cannot fail because the matrix is nonsingular.
V is small the matrix is ill-conditioned. A matrix is symmetric if
|detA| 1/2
V = , αi = a2i1 + a2i2 +. . . + a2in aij = aji
α1 α2 . . . α n
and it is positive definite if

n
n
xT A x = aij xi xj ≥ 0
i=1 j=1
for all x and the equality holds only if x = 0

(where xT is the transpose of the matrix, see
page 52)
The Cholesky decomposition can be used for
real, symmetric, positive definite matrices. This
algorithm saves on storage (divide by about 2)
and reduces the number of multiplications (di-
vide by 2), but adds n square roots.
The inverse of a matrix can also be used to
solve sets of linear equations. The inverse is a
matrix such that when A is multiplied by its in-
verse the result is the identity matrix, a matrix
with 1.0 along the main diagonal and zero else-
where.
A A−1 = I
Then the linear equations are solved by
x = A−1 f
Generally, the inverse is not used in this way

because it requires three times more operations
than solving with an LU decomposition. How-
ever, if an inverse is desired, it is calculated most
efficiently by using the LU decomposition and
Figure 1. Structure of L and U matrices then solving
When a matrix is ill-conditioned the LU decom- A x(i) =b(i)

position must be performed by using pivoting
(or the singular value decomposition described (i)
bj =
0 j=i
below). With pivoting, the order of the elimi- 1 j=i
nation is rearranged. At each stage, one looks
for the largest element (in magnitude); the next Then set
stages if the elimination are on the row and col-
umn containing that largest element. The largest A−1 = x(1) |x(2) |x(3) |. . .|x(n)
Generally software packages are available to The number of multiplications and divisions for
solve this problem, and the user must submit a problem with n unknowns and m right-hand
the elements of the matrix in proper fashion. sides is
Remembering that the information passed from
calling program to subroutine is a linear array Operation count = 2 (n − 1) + m (3 n − 2)
of numbers, and that actually only the location
of the first number is passed to the computer If
subroutine, is useful for interpretating user in-
|bi | >|ai | +|ci |
structions. If the matrix is an n×n matrix stored
in an m×m array, then what is passed is the lo- no pivoting is necessary. For solving two-point
cation of a11 and the numbers are expected to be boundary value problems and partial differential
in the arrangement > equations this is often the case.
a11 , a21 ,. . . , an1 -, -, -, a12 , a22 ,. . . , an2 -, -, -, . . .
Entry
1, 2, . . . , n, -, -, m, m+1, m+2,. . . , m+n, -, -, 2n, . . .
Solutions of Special Matrices. Special ma-

trices can be handled even more efficiently. A
tridiagonal matrix is one with nonzero entries
along the main diagonal, and one diagonal above
and below the main one (see Fig. 2). The corre-
sponding set of equations can then be written
as
ai xi−1 + bi xi + ci xi+1 = di
The LU decomposition algorithm for solving

Figure 2. Structure of tridiagonal matrices
this set is
A block tridiagonal matrix (see Fig. 3) fre-
b1 = b1
quently arises in solving multiple differen-
tial equations, either two-point boundary value
for k = 2, n do
problems or partial differential equations. When
ak ak solving several simultaneous equations the un-
ak = , bk = bk − ck−1
bk−1 bk− 1 knowns must be arranged in a particular way
to achieve the block tridiagonal form of the
enddo matrix and the resulting efficiencies. Suppose
we are solving for two unknowns, for exam-
d1 = d1 ple, temperature T and concentration c, and a
value for each exists at each node i = 1 to n, the
for k = 2, n do
unknowns are {c1 , c2 , . . . , cn , T 1 , T 2 , . . . , Tn }.
If the unknowns are ordered in this way, how-
dk = dk − ak dk−1
ever, the resulting linear equations to be solved,
enddo
when solving two-point boundary value prob-
lems or partial differential equations, will be
xn = dn /bn dense, that is, the nonzero entries of the ma-
trix A will have no special pattern. However,
for k = n − 1, 1 do if we arrange the unknowns in the pattern
{c1 , T 1 , c2 , T 2 , . . . , cn , Tn }, then special pat-
dk − ck xk+1 terns emerge. If the finite difference method is
xk =
bk used, the block tridiagonal matrix arises. For
enddo
other methods, other special patterns arise. So- and

lution algorithms are most efficient if these pat-
terns are taken into account in the LU decom- Ax = f
position. Clearly, a trade-off occurs between the
programming time (needed to exploit any spe- is solved by using the same LU decomposition
cial structure) and the value received from a of A,
more efficient solution. If the problem is being
Ay = B
solved only a few times or the time is extremely
small, the special structure need not be exploited These problems are sparse and the special meth-
and usual software packages are suitable. If the ods are applied to them. Next, the dense matrix
problem is being solved thousands of times or problem
the computer time is large (when n is large, e.g.,
1000), the special structure must be exploited. (D − C y) v = −C x + g
Suppose the block tridiagonal matrix is com-
posed of blocks that are nb ×nb , with n columns is solved and
of blocks (along the diagonal), then the number
of multiplications and divisions is (for large n u = x − yv
and nb ) [3, p. 61]
is evaluated, the solution is then (uT , v T ).
5
Operation count = n n3b
3
If n = 100 and nb = 3, the block tridiagonal tech-
nique requires only 4500 operations, whereas
the dense matrix technique requires 9×106 op-
erations. Thus, the block tridiagonal technique
is 2000 times faster.
Figure 4. Structure of arrow matrix
Sparse matrices are ones in which the major-

ity of elements are zero. If the zero entries oc-
cur in special patterns, efficient techniques can
be used to exploit the structure, as was done
above for tridiagonal matrices, block tridiagonal
Figure 3. Structure of block tridiagonal matrix matrices, arrow matrices, etc. These structures
typically arise from numerical analysis applied
Another matrix with special structure is the to solve differential equations. Other problems,
arrow matrix (see Fig. 4). This matrix has a such as modeling chemical processes, lead to
large, banded portion, with a much smaller num- sparse matrices but without such a neatly de-
ber of columns at one side and rows at the bot- fined structure – just a lot of zeros in the matrix.
tom. This matrix arises when solving sets of fluid For matrices such as these, special techniques
flow problems with free surfaces, when using must be employed: efficient codes are available
continuation methods or parameter estimation [4]. These codes usually employ a symbolic fac-
methods. The matrix problem is subdivided as torization, which must be repeated only once for

A B u f each structure of the matrix. Then an LU factor-
= ization is performed, followed by a solution step
C D v g
using the triangular matrices. The symbolic fac- Guess x0

torization step has significant overhead, but this
is rendered small and insignificant if matrices Calculate r 0 = f − Ax0
with exactly the same structure are to be used
over and over [5–9]. Solve M t0 = r 0 , and set p0 = t0
The efficiency of a technique for solving sets
of linear equations obviously depends greatly on for k = 1, n (or until convergence)
the arrangement of the equations and unknowns
because an efficient arrangement can reduce the rT
k tk
ak =
bandwidth, for example. Techniques for renum- pT
k A pk
bering the equations and unknowns arising from
elliptic partial differential equations are avail- xk+1 = xk + ak pk
able for finite difference methods [10] and for
r k+1 =r k − ak A pk
finite element methods [11].
Solve M tk+ 1 = r k+1
Solutions with Iterative Methods. Sets of
linear equations can also be solved by using it- rT
k+1 tk+1
erative methods; these methods have a rich his- bk =
rT
k tk
torical background. Some of them are discussed
in Chapter 8 and include Jacobi, Gauss – Seidel, pk+1 = tk+1 + bk pk
and overrelaxation methods. As the speed of
computers increases, direct methods become test for convergence
preferable for the general case, and those are the
methods presented here. One iterative method enddo
deserves special mention, however, because of
its importance in solving partial differential Additional information is available in [14] and
equations. [15].
The conjugate gradient method is an itera- The singular value decomposition is useful
tive method that can solve a set of n linear equa- when the matrix is singular or nearly singular,
tions in n iterations. The method primarily re- or when the system of equations is overdeter-
quires multiplying a matrix by a vector, which mined. An m×n matrix A can be represented by
 
can be done very efficiently on parallel comput- w1
ers: for sparse matrices this is a viable method.  
 w2 
The original method was devised by Hestenes A =U W V T , W =  
 ... 
and Stiefel [12]; however, more recent imple- wn
mentations use a preconditioned conjugate gra-
dient method because it converges faster, pro- where the matrices U and V are orthogonal in
vided a good “preconditioner” can be found. An the following sense:
efficient implementation of such a method is de-
m
scribed by Eisenstat [13]. The system of n lin- Uik Uij = δkj , 1 ≤ k ≤ n
ear equations i=1
A x =f
n
Vik Vij = δkj , 1 ≤ j ≤ n
i=1
where A is symmetric and positive definite, is
to be solved. A preconditioning matrix M is de- In addition
fined in such a way that the problem
V V T =I
M t =r
This decomposition can always be performed,
is easy to solve exactly (M might be diagonal, even for singular matrices. The condition num-
for example). Then the preconditioned conju- ber is the ratio of the largest wj to the smallest
gate gradient method is wj . The inverse of A is
supply various x until f (x) = 0. Another alterna-

A−1 =V W −1 U T tive is to program a microcomputer to make a
The rank r of a matrix is a value such that all table of x, f (x) and look for the root in the table,
r + 1×r + 1 determinants are zero. If an n×n ma- refining the table where needed. These methods
trix A is singular, the rank of the matrix is r < n. can be employed when the problem is not too
The columns of U whose same-numbered ele- hard and it need be solved only once or twice.
ments wj are nonzero are an orthonormal set of Even experienced programmers may do this to
basis vectors that span the range. The columns save time in some problems.
of V whose same-numbered wj are zero pro- Iterative methods are also employed to solve
vide an orthonormal basis for the nullspace. The the equation, and the k-th iteration is denoted as
solution to the problem A x = f is xk . The successive substitution method is writ-
ten as
x =V W −1 U T f
xk+1 = xk + β f xk ≡g xk
In this Equation if wj = 0, 1/wj is replaced with
If the constant β is chosen correctly these itera-
zero [16]. This is also the least-squares solution
tions will converge to a solution. The conditions
to a set of overdetermined equations (i.e., A is
are that [17]
an m×n matrix, x is an n×1 vector, and f is an
dg
m×1 vector).
(x) ≤ µ for |x − α| < h
In dimensional analysis if the dimensions of dx
each physical variable Pj (there are n of them) where µ and h are constants, 0 < µ < 1, and α
are expressed in terms of fundamental measure- is the unknown solution. In other words, if the
ment units mj (such as time, length, mass; there derivative can be bounded by 1.0 for all x then
are m of them): the method converges. The convergence is linear
α α α
and may be slow, requiring many iterations, but
[Pj ] = m1 1j m2 2j . . . mmmj the method is easy to program. This method is
then a matrix can be formed from the αij . If difficult to apply to systems of equations, but it
the rank of this matrix is r, n − r independent is applied in the solution of ordinary differential
dimensionless groups govern that phenomenon. equations. In that case, the constant β is propor-
In chemical reaction engineering the chemical tional to ∆t, and ∆t is reduced until the method
reaction stoichiometry can be written as converges.
The Newton – Raphson method is based on a

n Taylor series of the equation about the k-th iter-
αij Ci = 0, j = 1, 2, . . . , m ate:
i=1
df

where there are n species and m reactions. Then f xk+1 = f xk + k xk+1 − xk
dx x
if a matrix is formed from the coefficients αij ,
which is an n×m matrix, and the rank of the ma- d2 f 1 k+1 2
+ k x − xk + . . .
trix is r, there are r independent chemical reac- dx 2 x 2
tions. The other n − r reactions can be deduced The second and higher-order terms are neglected
from those r reactions. and f (xk+1 ) = 0. Rearrangement gives

f xk
x k+1
= x −
k
1.2. Nonlinear Algebraic Equations df /dx xk
This method converges if the following inequal-

In considering a single nonlinear equation in one ities are satisfied [3, p. 115].
unknown,
df f x0

0 > 0 , |x1 − x0 | = ≤ b,
f (x) = 0 dx x df /dx (x0 ) x0
one quick method for finding a root is to program d2 f

a calculator to evaluate f for a given x and then and 2 ≤ c
dx
where b and c are bounded constants. In prac- If f (x c ) = 0, the root is x c . If f (x 1 ) > 0 and
tice the method may not converge unless the ini- f (x 2 ) > 0, more than one root may exist between
tial guess is good, or it may converge for some x 1 and x 2 (or no roots).
parameters and not others. Unfortunately, when For systems of equations the Newton – Raph-
the method is nonconvergent the results look as son method is widely used, especially for equa-
though a mistake occurred in the computer pro- tions arising from the solution of differential
gramming; distinguishing between these situa- equations.
tions is difficult, so careful programming and
testing are required. If the method converges the fi ({xj }) = 0, 1 ≤i, j ≤n,
difference between successive iterates is some-
thing like 0.1, 0.01, 0.0001, 10−8 . The error where {xj } = (x1 , x2 , . . . , xn ) = x
(when it is known) goes the same way; the
Then, an expansion in several variables occurs:
method is said to be quadratically convergent
when it converges. The method is not robust be- n
∂ fi
cause it can fail for poor initial guesses. If the fi xk+1 = fi xk +
j=1
∂ xj xk
derivative is difficult to calculate a numerical ap-
proximation may be used.
xk+1 − xkj + . . .
d f
j
f xk + ε − f x k
k=
dx x ε The Jacobian matrix is defined as
In the secant method the same formula is used
∂ fi
as for the Newton – Raphson method, except that J kij =
∂xj xk
the derivative is approximated by using the val-
ues from the last two iterates: and the Newton – Raphson method is

d f f xk − f xk−1
n
= J kij xk+1 − xk = − fi xk
dx xk xk − xk−1
j=1
This is equivalent to drawing a straight line
through the last two iterate values on a plot of For convergence, the norm of the inverse of
f (x) versus x. The Newton – Raphson method is the Jacobian must be bounded, the norm of
equivalent to drawing a straight line tangent to the function evaluated at the initial guess must
the curve at the last x. In the method of false po- be bounded, and the second derivative must be
sition (or regula falsi), the secant method is used bounded [3, p. 115], [17, p. 12].
to obtain xk+1 , but the previous value is taken A review of the usefulness of solution
as either xk−1 or xk . The choice is made so that methods for nonlinear equations is avail-
the function evaluated for that choice has the able [18]. This review concludes that the
opposite sign to f (xk+1 ). This method is slower Newton – Raphson method may not be the most
than the secant method, but it is more robust and efficient. Broyden’s method approximates the
keeps the root between two points at all times. inverse to the Jacobian and is a good all-purpose
In all these methods, appropriate strategies are method, but a good initial approximation to the
required for bounds on the function or when Jacobian matrix is required. Furthermore, the
df /dx = 0. Brent’s method combines bracketing, rate of convergence deteriorates for large prob-
bisection, and an inverse quadratic interpolation lems, for which the Newton – Raphson method
to provide a method that is fast and guaranteed is better. Brown’s method [18] is very attractive,
to converge, if the root can be bracketed initially whereas Brent’s is not worth the extra storage
[16, p. 251]. and computation.
In the method of bisection, if a root lies bet- Homotopy methods can be used to ensure
ween x 1 and x 2 because f (x 1 ) < 0 and f (x 2 ) > 0, finding the solution when the problem is espe-
then the function is evaluated at the center, cially complicated. Suppose an attempt is made
x c = 0.5 (x 1 + x 2 ). If f (x c ) > 0, the root lies bet- to solve f (x) = 0, and it fails; however, g (x) = 0
ween x 1 and x c . If f (x c ) < 0, the root lies bet- can be solved easily, where g (x) is some func-
ween x c and x 2 . The process is then repeated. tion, perhaps a simplification of f (x). Then, the
two functions can be embedded in a homotopy curve. Then the homotopy equation is written
by taking along with the arc-length equation.
h (x, t) =t f (x) + (1 −t) g (x) ∂h dx ∂h dt

+ = 0
∂x ds ∂t ds
In this equation, h can be a n×n matrix for 2
problems involving n variables; then x is a vec- dxT dx dt
+ = 1
tor of length n. Then h (x, t) = 0 can be solved ds ds ds
for t = 0 and t gradually changes until at t = 1, The initial conditions are
h (x, 1) = f (x). If the Jacobian of h with respect
to x is nonsingular on the homotopy path (as x (0) =x0
t varies), the method is guaranteed to work.
In classical methods, the interval from t = 0 t (0) = 0
to t = 1 is broken up into N subdivisions. Set
∆t = 1/N and solve for t = 0, which is easy by The advantage of this approach is that it works
the choice of g (x). Then set t = ∆t and use the even when the Jacobian of h becomes singu-
Newton – Raphson method to solve for x. Since lar because the full matrix is rarely singular. Il-
the initial guess is presumably pretty good, this lustrations applied to chemical engineering are
has a high chance of being successful. That so- available [19].
lution is then used as the initial guess for t = 2 ∆t
and the process is repeated by moving stepwise
to t = 1. If the Newton – Raphson method does 1.3. Linear Difference Equations
not converge, then ∆t must be reduced and a
new solution attempted. Difference equations arise in chemical engineer-
Another way of using homotopy is to create ing from staged operations, such as distillation or
an ordinary differential equation by differentiat- extraction, as well as from differential equations
ing the homotopy equation along the path (where modeling adsorption and chemical reactors. The
h = 0). value of a variable in the n-th stage is noted by a
subscript n. For example, if yn,i denotes the mole
dh [x (t) , t] ∂h dx ∂h
= + = 0 fraction of the i-th species in the vapor phase on
dt ∂x dt ∂t
the n-th stage of a distillation column, xn,i is the
This can be expressed as an ordinary differential corresponding liquid mole fraction, R the reflux
equation for x (t): ratio (ratio of liquid returned to the column to
product removed from the condenser), and Kn,i
∂h dx ∂h
= − the equilibrium constant, then the mass balances
∂x dt ∂t about the top of the column give
If Euler’s method is used to solve this equation,
R 1
a value x 0 is used, and dx/dt from the above yn+1,i = xn,i + x0,i
R+1 R+1
equation is solved for. Then
and the equilibrium equation gives
dx
x1,0 = x0 +∆t
dt
yn,i =Kn,i xn,i
is used as the initial guess and the homotopy
equation is solved for x1 . If these are combined,
∂h 1,k+1
Kn+1,i xn+1,i =
R
xn,i +
1
x0,i
x − x1,k = − h x1,k , t R+1 R+1
∂x
Then t is increased by ∆t and the process is re- is obtained, which is a linear difference equa-
peated. tion. This particular problem is quite compli-
In arc-length parameterization, both x and t cated, and the interested reader is referred to [20,
are considered parameterized by a parameter s, Chap. 6]. However, the form of the difference
which is thought of as the arc length along a equation is clear. Several examples are given
here for solving difference equations. More xn+1 −fn xn = 0

complete information is available in [21].
An equation in the form x0 = c
xn+1 −xn = fn the general solution is

n
can be solved by xn = c fi
i=1

n
xn = fi This can then be used in the method of variation
i=1
of parameters to solve the equation
Usually, difference equations are solved analyt-
ically only for linear problems. When the coeffi- xn+1 −fn xn = gn
cients are constant and the equation is linear and
homogeneous, a trial solution of the form
xn = ϕ n
1.4. Eigenvalues
is attempted; ϕ is raised to the power n. For ex-
ample, the difference equation The n×n matrix A has n eigenvalues λi ,
i = 1, . . . , n, which satisfy
c xn−1 + b xn + a xn+1 = 0
det (A −λi I ) = 0
coupled with the trial solution would lead to the
If this equation is expanded, it can be represented
equation
as
a ϕ2 + b ϕ + c = 0
Pn (λ) = (−λ)n + a1 (−λ)n−1 + a2 (−λ)n−2 +
This gives
. . . + an−1 (−λ) + an = 0
√
−b ± b2 − 4 a c
ϕ1,2 = If the matrix A has real entries then ai are real
2a numbers, and the eigenvalues either are real
and the solution to the difference equation is numbers or occur in pairs as complex num-
bers with their complex conjugates (for defi-
xn = A ϕ n n
1 + B ϕ2 nition of complex numbers, see Chap. 3). The
Hamilton – Cayley theorem [20, p. 127] states
where A and B are constants that must be speci- that the matrix A satisfies its own characteris-
fied by boundary conditions of some kind. tic equation.
When the equation is nonhomogeneous, the
solution is represented by the sum of a particular Pn (A) = (−A)n + a1 (−A)n−1 + a2 (−A)n−2
solution and a general solution to the homoge-
neous equation. + . . . + an−1 (−A) + an I = 0
xn = xn,P + xn,H A laborious way to find the eigenvalues of a ma-

trix is to solve the n-th order polynomial for the
The general solution is the one found for the λi – far too time consuming. Instead the matrix
homogeneous equation, and the particular so- is transformed into another form whose eigen-
lution is any solution to the nonhomogeneous values are easier to find. In the Givens method
difference equation. This can be found by meth- and the Housholder method the matrix is trans-
ods analogous to those used to solve differential formed into the tridiagonal form; then, in a fixed
equations: the method of undetermined coeffi- number of calculations the eigenvalues can be
cients and the method of variation of parame- found [16]. The Givens method requires 4 n3 /3
ters. The last method applies to equations with operations to transform a real symmetric matrix
variable coefficients, too. For a problem such as to tridiagonal form, whereas the Householder
method requires half that number [3]. Once the methods for parameter estimation for both linear
tridiagonal form is found, a Sturm sequence and nonlinear models are given in Sections 2.5
is applied to determine the eigenvalues. These and 2.6. Fourier transforms to represent discrete
methods are especially useful when only a few data are described in Section 2.7. The chapter
eigenvalues of the matrix are desired. closes with extensions to two-dimensional re-
If all the eigenvalues are needed, the Q R al- presentations.
gorithm is preferred. In the Q R algorithm [22] a
modified Householder transformation is applied
to A, transforming it to the form 2.2. Global Polynomial Approximation
A = QR A global polynomial Pm (x) is defined over the
entire region of space
where Q is orthogonal and R is upper triangular.
If A is banded, then Q and R are banded.
m
The eigenvalues of a certain tridiagonal ma- Pm (x) = c j xj

j=0
trix can be found analytically. If A is a tridiagonal
matrix with This polynomial is of degree m (highest power
is xm ) and order m + 1 (m + 1 parameters {cj }).
aii = p, ai,i+1 = q, ai+1,i = r, q r > 0 If a set of m + 1 points is given,
then the eigenvalues of A are [23] y1 =f (x1 ) , y2 =f (x2 ) , . . . , ym+1 =f (xm+1 )
iπ
λi = p + 2 (q r)1/2 cos i = 1, 2, . . . , n then Lagrange’s formula yields a polynomial of
n+1
degree m that goes through the m + 1 points:
This result is useful when finite difference meth-
(x − x2 ) (x − x3 ) . . . (x − xm+1 )
ods are applied to the diffusion equation. Pm (x) = y1 +
(x1 − x2 ) (x1 − x3 ) . . . (x1 − xm+1 )
(x − x1 ) (x − x3 ) . . . (x − xm+1 )
2. Approximation and Integration y2 + . . . +
(x2 − x1 ) (x2 − x3 ) . . . (x2 − xm+1 )
2.1. Introduction (x − x1 ) (x − x2 ) . . . (x − xm )
ym+1
(xm+1 − x1 ) (xm+1 − x2 ) .. . (xm+1 − xm )
Two types of problems arise frequently:
Note that each coefficient of yj is a polynomial
1) A function is known exactly at a set of points of degree m that vanishes at the points {xj } (ex-
and an interpolating function is desired. The cept for one value of j ) and takes the value of
interpolant may be exact at the set of points, 1.0 at that point, i.e.,
or it may be a “best fit” in some sense. Al-
ternatively it may be desired to represent a Pm (xj ) =yj j = 1, 2, . . . , m + 1
function in some other way. If the function f (x) is known, the error in the
2) Experimental data must be fit with a math- approximation is [24]
ematical model. The data have experimental
error, so some uncertainty exists. The param- |xm+1 − x1 |m+1
|error (x) | ≤
eters in the model as well as the uncertainty (m + 1)!
in the determination of those parameters is
desired. maxx1 ≤x≤xm+1 | f (m+1) (x) |
These problems are addressed in this chapter. The evaluation of Pm (x) at a point other than the
Section 2.2 gives the properties of polynomi- defining points can be made with Neville’s algo-
als defined over the whole domain and Section rithm [25]. Let P1 be the value at x of the unique
2.3 of polynomials defined on segments of the function passing through the point (x 1 , y1 ); i.e.,
domain. In Section 2.4, quadrature methods are P1 = y1 . Let P12 be the value at x of the unique
given for evaluating an integral. Least-squares polynomial passing through the points x 1 and
x 2 . Likewise, Pijk...r is the unique polynomial b

passing through the points xi , xj , xk , . . . , xr . The I = W (x) [ f (x) − p (x)]2 dx
following scheme is used: a
when
b
W (x) f (x) Pj (x) dx
a
cj = ,
Wj
These entries are defined by using b

Wj = W (x) Pj2 (x) dx
Pi(i+1)...(i+m) = a
(x − xi+m ) Pi(i+1)...(i+m−1) + (xi − x) P(i+1)(i+2)...(i+m)

xi − xi+m
Consider P1234 : the terms on the right-hand Note that each cj is independent of m, the num-
side of the equation involve P123 and P234 . ber of terms retained in the series. The minimum
The “parents,” P123 and P234 , already agree at value of I is
points 2 and 3. Here i = 1, m = 3; thus, the par-
ents agree at xi+1 , . . . , xi+m−1 already. The for- b
m
mula makes Pi(i+1)...(i+m) agree with the func- Imin = W (x) f 2 (x) dx − Wj c2j
tion at the additional points xi+m and xi . Thus, a j=0
Pi(i+1)...(i+m) agrees with the function at all

the points {xi , xi+1 , . . . , xi+m }. Such functions are useful for continuous data,
i.e., when f (x) is known for all x.
Orthogonal Polynomials. Another form of Typical orthogonal polynomials are given in
the polynomials is obtained by defining them so Table 1. Chebyshev polynomials are used in
that they are orthogonal. It is required that Pm (x) spectral methods (see Chap. 6). The last two
be orthogonal to Pk (x) for all k = 0, . . . , m − 1. rows of Table 1 are widely used in the orthogo-
nal collocation method in chemical engineering.
b The last entry (the shifted Legendre polynomial
W (x) Pk (x) Pm (x) dx = 0 as a function of x 2 ) is defined by
a
1

k = 0, 1, 2, . . . , m − 1 W x2 Pk x2 Pm x2 xa−1 dx = 0
0
The orthogonality includes a nonnegative
weight function, W (x) ≥ 0 for all a ≤ x ≤ b. This k = 0, 1, . . . , m − 1
procedure specifies the set of polynomials to
within multiplicative constants, which can be set where a = 1 is for planar, a = 2 for cylindrical,
either by requiring the leading coefficient to be and a = 3 for spherical geometry. These func-
one or by requiring the norm to be one. tions are useful if the solution can be proved to
be an even function of x.
b
2
W (x) Pm (x) dx = 1 Rational Polynomials. Rational polynomi-
a als are ratios of polynomials. A rational poly-
The polynomial Pm (x) has m roots in the closed nomial Ri(i+1)...(i+m) passing through m + 1
interval a to b. points
The polynomial
yi = f (xi ) , i = 1, . . . , m + 1
p (x) = c0 P0 (x) + c1 P1 (x) + . . . cm Pm (x)
is
minimizes
Table 1. Orthogonal polynomials [24]
a b W (x) Name Recursion

relation
−1 1 1 Legendre (i+1) Pi +1 =(2 i+1)xPi − i Pi −1
−1 1 √ 1
Chebyshev Ti +1 =2xTi −Ti −1
1−x2
0 1 x q −1 (1−x)p−q Jacobi ( p, q)
2
−∞ ∞ e−x Hermite Hi +1 =2xHi −2 i Hi −1
0 ∞ x c e−x Laguerre (c) (i+1) L i +1 c =(−x+2 i+c+1) L ci −(i+c) L i −1 c
0 1 1 shifted Legendre
0 1 1 shifted Legendre, function of x 2
Pµ (x) p0 + p1 x+ . . . +pµ xµ 2.3. Piecewise Approximation

Ri(i+1)...(i+m) = = ,
Qν (x) q0 + q1 x + ... + qν xν
Piecewise approximations can be developed
m + 1 = µ+ν + 1 from difference formulas [27]. Consider a case
in which the data points are equally spaced
An alternative condition is to make the rational
polynomial agree with the first m + 1 terms in xn+1 −xn = ∆x
the power series, giving a Padé approximation,
yn = y (xn )
i.e.,
dk Ri(i+1)...(i+m) dk f (x) forward differences are defined by
= k = 0, . . . , m
dxk dxk
∆yn = yn+1 −yn
The Bulirsch – Stoer recursion algorithm can be
used to evaluate the polynomial: ∆2 yn = ∆yn+1 − ∆yn = yn+2 − 2yn+1 + yn
Ri(i+ 1)...(i+m) = R(i+1) ...(i+m)
Then, a new variable is defined
R(i+1)...(i+m) − Ri(i+ 1)...(i+m−1) xα − x 0
+ α =
Den ∆x
and the finite interpolation formula through the

x − xi points y0 , y1 , . . . , yn is written as follows:
Den =
x − xi+m
α (α − 1) 2
yα = y0 + α∆y0 + ∆ y0 + . . . +
R(i+1)...(i+m) Ri(i+ 1)...(i+m−1) 2!
1− −1
R(i+1) ...(i+m) − R(i+ 1)...(i+m−1)
α (α − 1) . . . (α − n + 1) n
∆ y0 (1)
Rational polynomials are useful for approximat- n!
ing functions with poles and singularities, which
occur in Laplace transforms (see Section 4.2). Keeping only the first two terms gives a straight
Fourier series are discussed in Section line through (x 0 , y0 ) − (x 1 , y1 ); keeping the first
4.1. Representation by sums of exponentials is three terms gives a quadratic function of posi-
also possible [26]. tion going through those points plus (x 2 , y2 ). The
In summary, for discrete data, Legendre poly- value α = 0 gives x = x 0 ; α = 1 gives x = x 1 , etc.
nomials and rational polynomials are used. For Backward differences are defined by
continuous data a variety of orthogonal polyno- ∇yn =yn − yn−1
mials and rational polynomials are used. When
the number of conditions (discrete data points) ∇2 yn = ∇yn − ∇yn−1 = yn − 2yn−1 + yn−2
exceeds the number of parameters, then see Sec-
tion 2.5.
The interpolation polynomial of order n through NI=1 = 1 − u , NI=2 = u

the points y0 , y−1 , y−2 , . . . is
α (α + 1) 2 and the expansion as is rewritten as
yα = y0 + α∇y0 + ∇ y0 + . . . +
2!

2
α (α + 1) . . . (α + n − 1) n y (x) = ceI NI (u) (2)
∇ y0
n! I=1
The value α = 0 gives x = x 0 ; α = − 1 gives x in e-th element and ci = ceI within the element
x = x −1 . Alternatively, the interpolation polyno- e. Thus, given a set of points (xi , yi ), a finite ele-
mial of order n through the points y1 , y0 , y−1 , . . . ment approximation can be made to go through
is them.
α (α − 1) 2
yα = y1 + (α − 1) ∇y1 + ∇ y1 + . . . +
2!
(α − 1) α (α + 1) . . . (α + n − 2) n
∇ y1
n!
Now α = 1 gives x = x 1 ; α = 0 gives x = x 0 .
The finite element method can be used for
piecewise approximations [28]. In the finite
element method the domain a ≤ x ≤ b is di-
vided into elements as shown in Figure 5. Each
function Ni (x) is zero at all nodes except xi ;
Ni (xi ) = 1. Thus, the approximation is

NT
NT
y (x) = ci Ni (x) = y (xi ) Ni (x)
i=1 i=1 Figure 5. Galerkin finite element method – linear functions
A) Global numbering system; B) Local numbering system
where ci = y (xi ). For convenience, the trial func-
tions are defined within an element by using new
coordinates: Quadratic approximations can also be used
within the element (see Fig. 6). Now the trial
x − xi functions are
u =
∆xi

1
The ∆xi need not be the same from element NI=1 = 2 (u − 1) u −
2
to element. The trial functions are defined as
Ni (x) (Fig. 5 A) in the global coordinate sys- NI=2 = 4 u (1 − u)
tem and NI (u) (Fig. 5 B) in the local coordinate

system (which also requires specification of the 1
NI=3 = 2 u u− (3)
element). For x i < x < xi+1 2

NT The approximation going through an odd num-
y (x) = ci Ni (x) = ci Ni (x) + ci+1 Ni+1 (x) ber of points (xi , yi ) is then
i=1

3
because all the other trial functions are zero y (x) = ceI NI (u) x in e−th element
there. Thus I=1
y (x) = ci NI=1 (u) + ci+1 NI=2 (u) , with ceI = y (xi ) , i = (e − 1) 2 + I
xi < x < xi+1 , 0 < u < 1 in the e−th element
Then
Splines. Splines are functions that match

given values at the points x 1 , . . . , xN T , shown
in Figure 7, and have continuous derivatives
up to some order at the knots, or the points
x 2 , . . . , xN T −1 . Cubic splines are most common.
In this case the function is represented by a cubic
polynomial within each interval and has contin-
uous first and second derivatives at the knots.
Figure 6. Finite elements approximation – quadratic ele-

ments
A) Global numbering system; B) Local numbering system Figure 7. Finite elements for cubic splines
A) Notation for spline knots. B) Notation for one element
Hermite cubic polynomials H which have
continuous first derivatives can be used for the
NI [28]. Now, write Consider the points shown in Figure 7 A. The
notation for each interval is shown in Figure 7 B.

4
y (x) = ceI HI (u) x in e−th element Within each interval the function is represented
I=1 as a cubic polynomial.
where
Ci (x) = a0i + a1i x + a2i x2 + a3i x3
H1 = (1 −u)2 (1 + 2u)
The interpolating function takes on specified
H2 = u (1 − u)2 ∆xe values at the knots.
H3 = u2 (3 − 2u) Ci−1 (xi ) = Ci (xi ) =f (xi )
H4 = u2 (u − 2) ∆xe Given the set of values {xi , f (xi )}, the objective
Identify the points within the e-th element as is to pass a smooth curve through those points,
xi : u = 0; xi+1 : u = 1. Then and the curve should have continuous first and
second derivatives at the knots.
ce1 = y (xi ) , ce3 = y (xi+1 )

Ci−1 (xi ) = Ci (xi )
dy dy
ce2 = (xi ) ∆xe , ce4 = (xi+1 ) ∆xe

dx dx Ci−1 (xi ) = Ci (xi )
Thus, at the points
The formulas for the cubic spline are derived
x1 , x 2 , . . . , x N T as follows for one region. Since the function is
both the function and first derivative are neces- a cubic function the third derivative is constant
sary: and the second derivative is linear in x. This is
written as
y (x1 ) , y (x2 ) , . . . , y (xN T )
x − xi
dy dy dy Ci (x) = Ci (xi ) + Ci (xi+1 ) − Ci (xi )
(x1 ) , (x2 ) , . . . , (xN T ) ∆xi
dx dx dx
and integrated once to give Orthogonal Collocation on Finite Elements.

In the method of orthogonal collocation on
Ci (x) = Ci (xi ) + Ci (xi ) (x − xi ) +
finite elements the solution is expanded in
a polynomial of order NP = NCOL + 2 within
(x − xi )2
Ci (xi+1 ) − Ci (xi ) each element [28]. The choice NCOL = 1 corre-
2∆xi
sponds to using quadratic polynomials, whereas
and once more to give NCOL = 2 gives cubic polynomials. The nota-
Ci (x) = Ci (xi ) + Ci (xi ) (x − xi ) + Ci (xi )
tion is shown in Figure 8. Set the function to a
known value at the two endpoints
(x − xi )2 (x − xi )3
+ Ci (xi+1 ) − Ci (xi ) y1 =y (x1 )
2∆xi 6∆xi
Now yN T = y (xN T )
yi = Ci (xi ) , yi = Ci (xi ) , yi = Ci (xi ) and then at the NCOL interior points to each el-
is defined so that ement
1
Ci (x) = yi + yi (x − xi ) + y (x − xi )2 yIe = yi = y (xi ) , i = (N COL + 1) e +I
2∆xi i
1 The actual points xi are taken as the roots of the

+ y − yi (x − xi )3 orthogonal polynomial.
6∆xi i+1
A number of algebraic steps make the interpola- PN COL (u) = 0 gives u1 , u2 , . . . , uN COL
tion easy. These formulas are written for the i-th
element as well as the i − 1-th element. Then and then
the continuity conditions are applied for the first
and second derivatives, and the values yi and xi = x(e) + ∆xe uI ≡ xeI
yi −1 are eliminated [29, p. 163]. The result is
The first derivatives must be continuous at the

yi−1 ∆xi−1 + yi 2 (∆xi−1 +∆xi ) + yi+1

∆xi = element boundaries:
dy dy
yi − yi−1 yi+1 − yi =
−6 − dx x=x(2)− dx x=x(2)+
∆xi−1 ∆xi
This is a tridiagonal system for the set of {yi } Within each element the interpolation is a poly-
in terms of the set of {yi }. Since the continu- nomial of degree NCOL + 1. Overall the func-
ity conditions apply only for i = 2, . . . , NT − 1, tion is continuous with continuous first deriva-
only NT − 2 conditions exist for the NT values tives. With the choice NCOL = 2, the same ap-
of yi . Two additional conditions are needed, and proximation is achieved as with Hermite cubic
these are usually taken as the value of the second polynomials.
derivative at each end of the domain, y1 , yN T . If
these values are zero, the natural cubic splines
are obtained; they can also be set to achieve some 2.4. Quadrature
other purpose, such as making the first derivative
match some desired condition at the two ends. To calculate the value of an integral, the func-
With these values taken as zero, in the natural tion can be approximated by using each of the
cubic spline, an NT − 2 system of tridiagonal methods described in Section 2.3. Using the first
equations exists, which is easily solved. Once three terms in Equation (1) gives
the second derivatives are known at each of the
x
0 +h 1
knots, the first derivatives are given by
y (x) dx = yα h dα
yi+1 − yi ∆xi ∆xi
yi = − yi − yi+1 x0 0
∆xi 3 6
The function itself is then known within each h 1 3
= ( y0 + y 1 ) − h y0 (ξ) , x0 ≤ ξ ≤ x0 + h
element. 2 12
Figure 8. Notation for orthogonal collocation on finite elements

• Residual condition; Boundary conditions; | Element boundary, continuity
NE = total no. of elements.
NT = (NCOL + 1) NE + 1
This corresponds to passing a straight line Within each pair of intervals the interpolant is
through the points (x 0 , y0 ), (x 1 , y1 ) and inte- continuous with continuous derivatives, but only
grating under the interpolant. For equally spaced the function is continuous from one pair to an-
points at a = x 0 , a + ∆x = x 1 , a + 2 ∆x = x 2 , . . . , other.
a + N ∆x = xN , a + (N + 1) ∆x = b = xn+1 , the If the finite element representation is used
trapezoid rule is obtained. (Eq. 2), the integral is
Trapezoid Rule. xi+1 1
2
b
h y (x) dx = ceI NI (u) (xi+1 − xi ) du
y (x) dx = ( y0 + 2 y1 + 2 y2 + . . . + 2 yN
2 xi 0 I=1
a
1
+ yN +1 ) + O h3
2
1 1
= ∆xi ceI NI (u) du = ∆xi ce1 + ce2
The first five terms in Equation (1) are retained I=1
2 2
0
and integrated over two intervals.
x0+2h ∆xi
2 = ( yi + yi+1 )
h 2
y (x) dx = yα h dα = ( y0 + 4 y1 + y2 )
3
x0 0 Since ce1 = yi and ce2 = yi+1 , the result is the same
as the trapezoid rule. These formulas can be
h5 (IV) added together to give linear elements:
− y (ξ) , x0 ≤ ξ ≤ x0 + 2 h
90 0
This corresponds to passing a quadratic function b ∆xe
through three points and integrating. For an even y (x) dx = ( y1e + y2e )
e
2
number of intervals and an odd number of points, a
2 N + 1, with a = x 0 , a + ∆x = x 1 , a + 2 ∆x = x 2 , If the quadratic expansion is used (Eq. 3), the

. . . , a + 2 N ∆x = b, Simpson’s rule is obtained. endpoints of the element are xi and xi+2 , and
Simpson’s Rule. xi+1 is the midpoint, here assumed to be equally
b spaced between the ends of the element:
h
y (x) dx = ( y0 + 4 y1 + 2 y2 + 4 y3 + 2 y4
3
a

+ . . . + 2 y2N −1 + 4 y2N + y2N +1 ) + O h5
Next Page
xi+2 1
3
The quadrature is exact when y is a polyno-
y (x) dx = ceI NI (u) (xi+2 − xi ) du mial of degree 2 m − 1 in x. The m weights and
xi 0 I=1
m Gauss points result in 2 m parameters, cho-
sen to exactly represent a polynomial of degree

3 1 2 m − 1, which has 2 m parameters. The Gauss
= ∆xi ceI NI (u) du points and weights are given in Table 2. The
I=1 0 weights can be defined with W (x) in the inte-

grand as well.
1 2 1
= ∆xe ce1 + ce2 + ce3 Table 2. Gaussian quadrature points and weights ∗
6 3 6
For many elements, with different ∆xe , N xi Wi
quadratic elements : 1 0.5000000000 0.6666666667

2 0.2113248654 0.5000000000
b ∆xe
0.7886751346 0.5000000000
3 0.1127016654 0.2777777778
y (x) = ( y1e + 4 y2e + y3e )
6 0.5000000000 0.4444444445
a e
0.8872983346 0.2777777778
4 0.0694318442 0.1739274226
If the element sizes are all the same this gives 0.3300094783 0.3260725774
Simpson’s rule. 0.6699905218 0.3260725774
For Hermite cubic functions the quadrature 0.9305681558 0.1739274226
5 0.0469100771 0.1184634425
rule is 0.2307653450 0.2393143353
0.5000000000 0.2844444444
b 0.7692346551 0.2393143353
1 e e ∆xe e
y (x) dx = ∆xe (c + c ) + (c2 − ce4 ) 0.9530899230 0.1184634425
e
2 1 3 12
a ∗
For a given N the quadrature points x 2 , x 3 , . . . , xN P − 1 are
given above. x 1 = 0, xN P = 1. For N = 1, W 1 = W 3 = 1/6 and for
For cubic splines the quadrature rule within one N ≥ 2, W 1 = WN P = 0.
element is
xi+1 For orthogonal collocation on finite elements
1
Ci (x) dx = ∆xi ( yi + yi+1 )
the quadrature formula is
2
xi
1
NP
y (x) dx = ∆xe Wj y (xeJ )
1
− ∆x3i yi + yi+1

0 e j=1
24
For the entire interval the quadrature formula is Each special polynomial has its own quadrature
formula. For example, Gauss – Legendre poly-
xN T nomials give the quadrature formula
N T −1
1
y (x) dx = ∆ xi ( yi + yi+1 )
2 i=1 ∞
n
x1
e−x y (x) dx = Wi y (xi )
i=1
T− 1
N 0
1
− ∆x3i yi + yi+1

24 i=1
(points and weights are available in mathemati-
cal tables) [24].
with y1 = 0, yN T = 0 for natural cubic splines. For Gauss – Hermite polynomials the quadra-
When orthogonal polynomials are used, as in ture formula is
Equation (1), the m roots to Pm (x) = 0 are cho-
sen as quadrature points and called points {xj }. ∞
n
2
Then the quadrature is Gaussian : e−x y (x) dx = Wi y (xi )
−∞ i=1
1
m
y (x) dx = Wj y (xj ) (points and weights are available in mathemati-
0 j=1 cal tables) [24].
Previous Page
Romberg’s method uses extrapolation tech- squares [25]. If each measurement point yi has
niques to improve the answer [25]. If I 1 is the a measurement error ∆yi that is independently
value of the integral obtained by using interval random and distributed with a normal distribu-
size h = ∆x, I 2 the value of I obtained by using tion about the true model y (x) with standard de-
interval size h/2, and I 0 the true value of I, then viation σi , then the probability of a data set is
the error in a method is approximately hm , or

N 2
1 yi − y (xi )
I1 ≈ I0 +c h m P = exp − ∆y
2 σi
m i=1
h
I2 ≈ I0 + c
2 (For definition of probability, normal distribu-
Replacing the ≈ by an equality (an approximation, and standard deviation, see Chap. 11.) Here
tion) and solving for c and I 0 give yi is the measured value, σi is the standard devi-
ation of the i-th measurement, and ∆y is needed
2m I2 − I1 in order that a measured value ± ∆y has a certain
I0 =
2m − 1 probability. Given a set of parameters (maximiz-
This process can also be used to obtain I 1 , ing this function), the probability that this data
I 2 , . . . , by halving h each time, calculating set ( plus or minus ∆y) could have occurred is P.
new estimates from each pair, and calling them This probability is maximized (giving the maxi-
J 1 , J 2 , . . . (i.e., in the formula above, I 0 is re- mum likelihood) if the negative of the logarithm
placed with J 1 ). The formulas are reapplied for is minimized.
each pair of J ’s to obtain K 1 , K 2 , . . . . The pro-
N
cess continues until the required tolerance is ob- yi − y (xi ) 2
− log P = √ − N log ∆y
tained. i=1
2 σi
I1 I2 I3 I4
J1 J2 J3 Because N, σi , and ∆y are constants, this is the
K1 K2 same as minimizing χ2 :
L1
N
yi − y (xi ; a1 , . . . , aM ) 2
χ2 = (4)
Romberg’s method is most useful for a low- i=1
σi
order method (small m) because significant im-
provement is then possible. with respect to the parameters {aj }. Note that the
When the integrand has singularities, a vari- standard deviations {σi } of the measurements
ety of techniques can be tried. The integral may are expected to be known. The goodness of fit
be divided into one part that can be integrated is related to the number of degrees of freedom,
analytically near the singularity and another ν = N − M. The probability P that χ2 would ex-
part that is integrated numerically. Sometimes ceed a particular value (χ0 )2 is
a change of argument allows analytical inte-
ν 1 2
gration. Series expansion might be helpful, too. P = 1−Q , χ
When the domain is infinite, Gauss – Legendre 2 2 0
or Gauss – Hermite quadrature can be used. Also where Q (a, x) is the incomplete gamma function
a transformation can be made [25]. For example,
let u = 1/x and then x
1
Q (a, x) = e−t ta−1 dt (a > 0)
b
1/a Γ (a)
1 1 0
f (x) dx = f du a, b > 0
u2 u and Γ (a) is the gamma function
a 1/b
∞
Γ (a) = ta−1 e−t dt
2.5. Linear Least Squares 0
The following description of maximum likeli-

hood applies to both linear and nonlinear least
Both functions are tabulated in mathematical Thus, the values of a and b with maximum like-
handbooks. The function P gives the goodness lihood are obtained: the variances of a and b. By
of fit. After Equation (4) is minimized, let χ20 be using the value of χ2 for this a and b, the good-
the value of χ2 at the minimum. Then Q > 0.1 ness of fit P can also be calculated. In addition,
represents a believable fit; Q > 0.001 might be the linear correlation coefficient r is related by
an acceptable fit; smaller values of Q indicate
that the model may be in error (or the σi are re-
N
χ2 = 1 − r2 ( yi − ȳ)2
ally larger). A “typical” value of χ2 for a moder- i=1
ately good fit is χ2 ∼ ν. Asymptotically for large
ν, the statistic χ2 becomes normally distributed Here
√
with a mean ν and a standard deviation 2ν.

N
(xi − x̄)( yi − ȳ)
If values σi are not known in advance, assume σi2
i=1
σi = σ (then its value does not affect the mini- r = ! !
mization of χ2 ). Find the parameters by mini-
N
(xi − x̄)2
N
(yi − ȳ)2
σi2 σi2
mizing χ2 and compute i=1 i=1
N
[ yi − y (xi )]2 Values of r near 1 indicate a positive correlation,
σ2 =
i=1
N r near − 1 means a negative correlation, and r
This gives some information about the errors near zero means no correlation.
(i.e., the variance and standard deviation of each A general linear model is one expressed as
data point), although the goodness of fit P cannot
M
be calculated. y (x) = ak Xk (x)
The minimization of χ2 requires k=1
N
yi − y (xi ) ∂y (xi ; a1 , . . . , aM ) where the parameters are {ak }, and the expres-
= 0,
i=1
σi2 ∂ak sion is linear with respect to them, and Xk (x) can
be any (nonlinear) functions of x, not depending
k = 1, . . . , M (5) on the parameters {ak }. Equation (5) is then
When the model is a straight line  
N
1  M
N yi − aj Xj (xi ) Xk (xi ) = 0 ,
yi − a − b xi 2 σ2
χ2 (a , b) = i=1 i j=1
i=1
σi
Define k = 1, . . . , M

N
1
N
xi
N
yi which is rewritten as
S = , Sx = , Sy =
σi2 σ 2 σi2
i=1 i=1 i i=1 N
M 1 N
yi
Xj (xi ) Xk (xi ) aj = Xk (xi )
N
x2i N
xi y i σ
j=1 i=1 i
2 σ
i=1 i
2
Sxx = , S xy = ,
σ2
i=1 i
σi2
i=1 or as

N
1 Sx
M
ti = xi − , Stt = t2i αkj aj = βk (6)
σi S i=1 j=1
Then
Solving this set of equations gives the parame-
1 ti yi
N
Sy − Sx b ters {aj }, which maximize the likelihood. The
b = , a = ,
Stt i=1 σi S variance of aj is

1 Sx2 1 σ 2 (aj ) = Cjj
σa2 = 1+ , σb2 =
S S Stt Stt
Sx Cov (a, b)
Cov (a, b) = − , rab =
S Stt σ a σb
−1
where Cjk = αjk , i.e., C is the inverse of α. The be added to the criterion and the equation mini-
covariance of aj and ak is given by Cjk . If round- mized:
off errors affect the result, try to make the func-
b 2
tions orthogonal. For example, using dy
I = α1 χ2 + α2 dx =
dx
k−1 a
Xk (x) = x
will cause round-off errors for a smaller M than

N
N b
dNi dNj
α1 χ2 + α2 aj ai dx
j=1 i=1
dx dx
Xk (x) = Pk−1 (x) (7) a
where Pk−1 are orthogonal polynomials. If nec- Generally, small values of α2 are used. The for-
essary, a singular value decomposition can be mat for the last term, in terms of finite elements
used rather than solving Equation (6) directly. (see Section 7.6), is
Various global and piecewise polynomials b 1
dNi dNj 1 dNI dNJ
can be used to fit the data. Some of the approxi- dx = du
mations only make sense for N = M, leading to a dx dx e
∆xe du du
a 0
perfect fit of the data but perhaps a highly oscilla-
tory model. These include the Lagrangian poly- The effect of this smoothing on the statistics for
nomial, and the forward and backward differ- {ak } is unknown.
ences. However, the other approximations can
be used with M < N. Consider orthogonal poly-
nomials as expressed in Equation (7). Simply 2.6. Nonlinear Least Squares
evaluate the polynomials at the points {xi }, and
solve Equation (6) for the coefficients. When The Levenberg – Marquardt method is used
piecewise polynomials are used, write when the parameters of the model appear non-
linearly. Define

M
NP
N
y (x) = ak Nk (x) = aej NJ (u) yi − y (xi ; a) 2
k=1 e J=1 χ2 (a) =
i=1
σi
and then minimize
and, near the optimum, represent χ2 by
 2
N
P
1 T
N  yi − aeJ NJ (uI )  χ2 (a) = χ20 − dT ·a + a ·D · a
 e J=1 
2
χ =   2
 σi2 
i=1 where d is an M×1 vector and D is an M×M
matrix. Then calculate iteratively
Equation (6) is still solved, but with Xj (xi ) given
by Nj (xi ), as shown in Figure 9 for NP = 2. D · ak+1 −ak = − ∇χ2 ak (8)
The notation akl means the l-th component of a

evaluated on the k-th iteration. If ak is a poor
approximation to the optimum, steepest descent
might be used instead

ak+1 −ak = −constant × ∇χ2 ak (9)
and the constant chosen somehow to decrease

Figure 9. Fitting discrete data using linear elements χ2 as much as possible. The gradient of χ2 is
Sometimes, particularly in two-dimensional ∂χ2 yi − y (xi ; a) ∂y (xi ; a)

N
= −2
problems, elements may have no, or too few, ∂ak i=1
σi2 ∂ak
data points in them. Then the matrix αkj would
be singular. In that case a smoothing term can k = 1, 2, . . . , M
The second derivative (in D) is For normally distributed errors the parameter
region in which χ2 = constant can give bound-
N (
∂ 2 χ2 1 ∂y (xi ; a) ∂y (xi ; a) aries of the confidence limits. The value of a
= 2
∂ak ∂al σ
i=1 i
2 ∂ak ∂al obtained in the Marquardt method gives the min-
imum χ2min . Setting χ2 = χ2min + ∆χ2 for some
)
∂ 2 y (xi ; a) ∆χ21 and looking at contours in parameter space
− [ yi − y (xi ; a)]
∂ak ∂al where χ21 = constant give confidence boundaries
at the probability associated with χ21 . For ex-
Equations (8) and (9) are included in ample, in a chemical reactor with radial disper-
sion, the heat-transfer coefficient and radial ef-

M
αkl ak+1
l − akl = βk (10) fective heat conductivity are closely connected:
l=1 decreasing one and increasing the other can still
give a good fit. Thus, the confidence bound-
where
aries may look something like Figure 10. The
N ellipse defined by ∆χ2 = 2.3 contains 68.3 % of
1 ∂y (xi ; a) ∂y (xi ; a)
akl = 2
k= l the normally distributed data. The curve defined
σ ∂ak ∂al
i=1 i by ∆χ2 = 6.17 contains 95.4 % of the data.
N
1 ∂y (xi ; a) 2
akk = (1 + λ)
σ2
i=1 i
∂ak
N
yi − y (xi ; a) ∂y (xi ; a)
βk =
i=1
σi2 ∂ak
The second term in the second derivative is

dropped because it is usually small [remem-
ber that yi will be close to y (xi , a)]. The
Levenberg – Marquardt method then iterates as
follows: Figure 10. Parameter estimation for heat transfer
2
1) Choose a and calculate χ (a).
2) Choose λ, say λ = 0.001.
3) Solve Equation (10) for ak +1 and evaluate 2.7. Fourier Transforms of Discrete
χ2 (ak +1 ).
4) If χ2 (ak +1 ) ≥ χ2 (ak ), increase λ by a fac-
Data [25]
tor of 10, for example, and go back to step
Suppose a signal y (t) is sampled at equal inter-
3. This makes the step more like a steepest
vals
descent.
5) If χ2 (ak +1 ) < χ2 (ak ), then update a (i.e., yn = y (n∆) , n = . . . , − 2, − 1, 0, 1, 2, . . .
use a = ak +1 ), decrease λ by a factor of 10,
and go back to step 3. ∆ = sampling rate
6) Stop the iteration when the decrease in χ2
from one step to another is not statistically (e.g., number of samples per second)
meaningful (i.e., less than 0.1 or 0.01 or
0.001). The Fourier transform and inverse transform are
7) Set λ = 0 and compute the estimated covari- ∞
ance matrix. Y (ω) = y (t) eiωt dt
−∞
C =α−1
∞
1
This gives the standard errors in the fitted pa- y (t) = Y (ω) e−iωt dω
2π
rameters a. −∞
(For definition of i, see Chap. 3.) The Nyquist the Fourier transform of the even components
critical frequency or critical angular frequency of {yj } and is of length N/2; similarly Y ok is the
is k-th component of the Fourier transform of the
odd components of {yj } and is of length N/2;
1 π
fc = , ωc = and W is a constant, taken to the k-th power.
2∆ ∆
If a function y (t) is bandwidth limited to fre- W = e2πi/N
quencies smaller than f c , i.e.,
Because Yk has N components, whereas Y ek and
Y (ω) = 0 for ω > ωc Y ok have N/2 components, Y ek and Y ok are re-
peated once to give N components in the cal-
then the function is completely determined by culation of Yk . This decomposition can be used
its samples yn . Thus, the entire information con- recursively. Thus, Y ek is split into even and odd
tent of a signal can be recorded by sampling at a terms of length N/4.
rate ∆−1 = 2 f c . If the function is not bandwidth
limited, then aliasing occurs. Once a sample rate Yke =Ykee +W k Ykeo
∆ is chosen, information corresponding to fre-
quencies greater than f c is simply aliased into Yko =Ykoe +W k Ykoo
that range. The way to detect this in a Fourier
transform is to see if the transform approaches This process is continued until only one com-
zero at ± f c ; if not, aliasing has occurred and a ponent remains. For this reason the number N is
higher sampling rate is needed. taken as a power of 2. The vector {yj } is filled
Next, for N samples, where N is even with zeroes, if need be, to make N = 2p for some
p. For the computer program, see [25, p. 381].
yk = y (tk ) , tk = k∆, k = 0, 1, 2, . . . , N − 1 The standard Fourier transform takes N 2 op-
erations to calculate, whereas the fast Fourier
and the sampling rate is ∆; with only N values
transform takes only N log2 N. For large N the
{yk } the complete Fourier transform Y (ω) can-
difference is significant; at N = 100 it is a factor
not be determined. Calculate the value Y (ωn ) at
of 15, but for N = 1000 it is a factor of 100.
the discrete points
The discrete Fourier transform can also be
2πn N N used for differentiating a function; this is used
ωn = , n = − , . . . , 0, . . . ,
N∆ 2 2 in the spectral method for solving differential
equations. Consider a grid of equidistant points:

N −1
Yn = yk e2πikn/N L
k=0 xn = n∆x , n = 0, 1, 2, . . . , 2 N − 1 , ∆x =
2N
Y (ωn ) = ∆Yn the solution is known at each of these grid points
{Y (xn )}. First, the Fourier transform is taken:
The discrete inverse Fourier transform is
2N −1
N −1 1
1 yk = Y (xn ) e−2ikπxn /L
yk = Yn e−2πikn/N 2 N n=0
N k=0
The fast Fourier transform (FFT ) is used to The inverse transformation is

calculate the Fourier transform as well as the
N
1
inverse Fourier transform. A discrete Fourier Y (x) = yk e2ikπx/L
L
transform of length N can be written as the k=−N
sum of two discrete Fourier transforms, each of
which is differentiated to obtain
length N/2.
dY 1
N
2 πi k 2ikπx/L
Yk = Yke +W k Y o
k = yk e
dx L k=−N
L
Here Yk is the k-th component of the Fourier
transform of y, and Y ek is the k-th component of Thus, at the grid points
gest computing NY different cubic splines of size

dY
N
1 2 πi k 2ikπxn /L NX along lines of constant y, for example, and
= yk e
dx n L k=−N
L storing the derivative information. To obtain the
value of f at some point x, y, evaluate each of
The process works as follows. From the solu- these splines for that x. Then do one spline of
tion at all grid points the Fourier transform is size NY in the y direction, doing both the deter-
obtained by using FFT {yk }. This is multiplied mination and the evaluation.
by 2 π i k/L to obtain the Fourier transform of the If the points are distributed randomly within
derivative: the domain, the finite element method can be
2 πi k used, which is especially useful if the domain is
yk = yk irregular. The expansion is
L
The inverse Fourier transform is then taken by
M
z (x, y) = z̃l Nl (x, y)
using FFT, to give the value of the derivative at
l=1
each of the grid points:
Let the data points be zi = z (xi , yi ), i = 1, . . . , N.
dY
N
1 The maximum likelihood of the parameter fit is
= yk e2ikπxn /L
dx n L  2
k=−N
M
N  zi − z̃l Nl (xi ; yi ) 
 l=1 
χ2 =  
 σi2 
i=1
2.8. Two-Dimensional Interpolation and

Quadrature and this is minimized with respect to zk .

N
1
M
If the domain is square, a ≤ x ≤ b, c ≤ y ≤ d, 2
zi − z̃l Nl (xi yi ) Nk (xi ; yi ) = 0
σ
then the approximation can be made by using i=1 i l=1
tensor products of orthogonal polynomials.

k = 1, . . . , M

m1
m2
z (x, y) = cij Pi (x) Pj ( y) With two-dimensional domains, ensuring
i=0 j=0 enough data points with each element is dif-
ficult. Thus, minimize
The coefficients are chosen to minimize I.
I = αl χ2 + α2 ∇z ·∇z dx dy
b d
Ω
I = W (x) W ( y)
a c The minimum is achieved for
 2

M N
1 1

m1
m2
α1 Nl (xi , yi ) Nk (xi , yi )
z (x, y) − cij Pi (x) Pj ( y) dxdy σ 2 σ2
l=1 i=1 i k
i=0 j=0


b d + α2 ∇Nl ·∇Nk dx dy z̃l
ckl = W (x) W ( y) z (x, y) Pk (x) Pl (x) dxdy / 
Ω
a c
N
z̃i Nk (xi , yi )
b d = α1
W (x) Pk2 (x) dx W ( y) Pl2 ( y) dy σ2
i=1 i
σk2
a c
The finite element integrals are calculated by
Bicubic splines can be used to interpolate a set [28]
of values on a regular array, f (xi , yj ). Suppose
NX points occur in the x direction and NY points ∇Nl ·∇Nk dx dy = ∇NL ·∇NK dx dy
occur in the y direction. Press et al. [25] sug- e
Ω Ωe
If linear elements on triangles are used and the 3. Complex Variables

nodes are (xJ , yJ ), (xK , yK ), and (xL , yL ), the
integral is 3.1. Introduction to the Complex Plane

1
∇NL ·∇NK dx dy = (bL bK + cL cK ) A complex number is an ordered pair of real
4∆
Ωe numbers, x and y, that is written as
where z = x +i y
 
1 xJ yJ The variable i is the imaginary unit which has
 
∆ = 2 det 1 xK yK  , the property
1 xL yL
i2 = −1
bK = yL − yJ , and cK = xJ − xL
The real and imaginary parts of a complex num-
plus permutations on J, K, L that are arranged in ber are often referred to:
a counterclockwise orientation.
Quadrature follows directly from the approx- Re (z) =x, Im (z) = y
imation. If orthogonal polynomials are used,
then A complex number can also be represented
graphically in the complex plane, where the real
b d m2−1
m1−1 part of the complex number is the abscissa and
z (x, y) dxdy = Wxj Wjk z (xj , yk ) the imaginary part of the complex number is the
j=1 k=1
a c ordinate (see Fig. 11).
and the limits of integration must be transformed
to coincide with those of the defining polyno-
mial. If finite elements are used, then

M
z (x, y) dxdy = z̃l Nl (x, y) dxdy
Ω l=1 Ω

NP
e
= z̃L NL (x, y) dxdy
e L=1
Ωe
For the same linear elements on triangles

∆
NL (x, y) dxdy =
3
Ωe
Multidimensional integrals can also be broken

down into one-dimensional integrals. For exam- Figure 11. The complex plane
ple,
Another representation of a complex number
b f2 (x) b
is the polar form, where r is the magnitude and
z (x, y) dxdy = G (x) dx;
θ is the argument.
a f1 (x) a -
r = |x +i y| = x2 + y 2 , θ = arg (x +i y)
f
2 (x)
Write
G (x) = z (x, y) dx
f1 (x) z = x +i y = r (cos θ + i sin θ)
so that The complex conjugate is z∗ = x − i y when

x = rcos θ, y = r sin θ z = x + i y and | z∗ | = | z |, arg z∗ = − arg z
and For complex conjugates then
y
θ = arctan z ∗ z = |z|2
x
Since the arctangent repeats itself in multiples of The reciprocal is
π rather than 2 π, the argument must be defined
carefully. For example, the θ given above could 1 z∗ 1 1
= = (cos θ − i sin θ) , arg = −argz
also be the argument of − (x + i y). The function z |z|2 r z
z = cos θ + i sin θ obeys | z | = | cos θ + i sin θ | = 1. Then
The rules of equality, addition, and multipli-
cation are z1 x1 +i y1 x2 − i y2
= = (x1 +i y1 ) 2
z2 x2 +i y2 x2 + y22
z1 =x1 + i y1 , z2 =x2 + i y2
x1 x2 + y1 y2 x2 y1 − x1 y2
Equality : = +i
x22 + y22 x22 + y22
z1 = z2 if and only if x1 = x2 and y1 = y2 and

z1 r1
Addition : = [cos (θ1 − θ2 ) +i sin (θ1 − θ2 )]
z2 r2
z1 + z2 = (x1 + x2 ) + i (y1 + y2 )
Multiplication :
3.2. Elementary Functions
z1 z2 = (x1 x2 − y1 y2 ) + i (x1 y2 + x2 y1 )
The last rule can be remembered by using the Properties of elementary functions of complex
standard rules for multiplication, keeping the variables are discussed here [31]. When the po-
imaginary parts separate, and using i2 = − 1. In lar form is used, the argument must be spec-
the complex plane, addition is illustrated in Fig- ified because the same physical angle can be
ure 12. In polar form, multiplication is achieved with arguments differing by 2 π. A
complex number taken to a real power obeys
z1 z2 =r1 r2 [cos (θ1 +θ2 ) + i sin (θ1 +θ2 )]
u = z n , |z n | =|z|n , arg (z n ) =n argz (mod 2π)
The magnitude of z1 + z2 is bounded by
|z1 ±z2 | ≤ |z1 | + |z2 | and |z1 | − |z2 | ≤ |z1 ± z2 | u = z n = r n (cos nθ + i sin nθ)
as can be seen in Figure 12. The magnitude and Roots of a complex number are complicated by
arguments in multiplication obey careful accounting of the argument
|z1 z2 | =|z1 | |z2 |, arg (z1 z2 ) = argz1 + argz2 z = w1/n with w = R (cosΘ+ i sinΘ) , 0 ≤Θ ≤ 2π
then
(
Θ 2π
zk = R1/n cos + (k − 1)
n n
)
Θ 2π
+i sin + (k − 1)
n n
such that
Figure 12. Addition in the complex plane

(zk )n = w for every k eiz + e−iz eiz − e−iz

cos z = , sin z = ,
2 2
z = r (cos θ + i sin θ)
sin z
tan z =
n cos z
r = R, nθ = Θ (mod 2 π)
and satisfy
The exponential function is
sin (−z) = − sin z, cos (−z) = cos z
ez = ex (cos y +i sin y)
sin (iz) = i sinh z, cos (iz) = −cosh z
Thus,
All trigonometric identities for real, circular
z = r (cos θ +i sin θ) functions with real arguments can be extended
without change to complex functions of complex
can be written arguments. For example,
z = reiθ sin2 z + cos2 z = 1,
and
sin (z1 +z2 ) = sin z1 cos z2 + cos z1 sin z2
x
|e | = e , arg e = y (mod 2π)
z z
The same is true of hyperbolic functions. The
absolute boundaries of sin z and cos z are not
The exponential obeys
bounded for all z.
ez =0 for every finite z
Trigonometric identities can be defined by us-
ing
and is periodic with period 2 π:
eiθ = cos θ + i sin θ
z+2πi z
e =e
For example,
Trigonometric functions can be defined by using
ei(α+β) = cos (α + β) + i sin (α + β)
eiy = cos y + i sin y, and e−iy = cos y − i sin y
= eiα eiβ = (cos α + i sin α)
Thus,
(cos β + i sin β)
eiy + e−iy
cos y = = cosh i y
2 = cos α cos β − sin α sin β
eiy − e−iy + i (cos α sin β + cos β sin α)

sin y = = − i sinh i y
2i
Equating real and imaginary parts gives
The second equation follows from the defini-
tions cos (α + β) = cos α cos β − sin α sin β
ez + e−z ez − e−z sin (α + β) = cos α sin β + cos β sin α

cosh z ≡ , sinh z ≡
2 2
The logarithm is defined as
The remaining hyperbolic functions are
ln z = ln |z| + i arg z
sinh z 1
tanh z ≡ , coth z ≡
cosh z tanh z and the various determinations differ by multi-
ples of 2 π i. Then,
1 1
sech z ≡ , csch z ≡
cosh z sinh z eln z =z
The circular functions with complex arguments
are defined ln (ez ) − z ≡ 0 (mod 2 πi)
Also, Theorem [32]. The function f (z) is ana-

lytic in a domain D if and only if u and v
ln (z1 z2 ) − lnz1 − lnz2 ≡ 0 (mod 2πi) are continuously differentiable and satisfy the
Cauchy – Riemann conditions there.
is always true, but If f 1 (z) and f 2 (z) are analytic in domain D,
then α1 f 1 (z) + α2 f 2 (z) is analytic in D for any
ln (z1 z2 ) = ln z1 + ln z2
(complex) constants α1 , α2 .
holds only for some determinations of the loga- f1 (z) + f2 (z) is analytic in D
rithms. The principal determination of the argu-
ment can be defined as − π < arg ≤ π. f1 (z) /f2 (z) is analytic in D except where f2 (z) = 0
An analytic function of an analytic function
is analytic. If f (z) is analytic, f (z) = 0 in D,
3.3. Analytic Functions of a Complex f (z1 ) = f (z2 ) for z1 = z2 , then the inverse func-
Variable tion g (w) is also analytic and
1
Let f (z) be a single-valued continuous function g (w) = where w = f (z) ,
f (z)
of z in a domain D. The function f (z) is differ-
entiable at the point g (w) = g [ f (z)] = z
z0 in D if
Analyticity implies continuity but the converse
lim
f (z0 + h) − f (z0 ) is not true: z∗ = x − i y is continuous but, because
h→0 h the Cauchy – Riemann conditions are not sat-
exists as a finite (complex) number and is in- isfied, it is not analytic. An entire function is
dependent of the direction in which h tends to one that is analytic for all finite values of z. Ev-
zero. The limit is called the derivative, f (z0 ). ery polynomial is an entire function. Because
The derivative now can be calculated with h ap- the polynomials are analytic, a ratio of polyno-
proaching zero in the complex plane, i.e., any- mials is analytic except when the denominator
where in a circular region about z0 . The function vanishes. The function f (z) = | z2 | is continu-
f (z) is differentiable in D if it is differentiable ous for all z but satisfies the Cauchy – Riemann
at all points of D; then f (z) is said to be an an- conditions only at z = 0. Hence, f (z) exists
alytic function of z in D. Also, f (z) is analytic only at the origin, and | z |2 is nowhere an-
at z0 if it is analytic in some ε neighborhood of alytic. The function f (z) = 1/z is analytic ex-
z0 . The word analytic is sometimes replaced by cept at z = 0. Its derivative is − 1/z2 , where
holomorphic or regular [31]. z = 0. If ln z = ln | z | + i arg z in the cut domain
The Cauchy – Riemann equations can be used − π < arg z ≤ π, then f (z) = 1/ln z is analytic in
to decide if a function is analytic. Set the same cut domain, except at z = 1, where
log z = 0. Because ez is analytic and ± i z are an-
f (z) =f (x +i y) =u (x, y) + i v (x, y) alytic, e±iz is analytic and linear combinations
are analytic. Thus, the sine and cosine and hy-
perbolic sine and cosine are analytic. The other
Theorem [31]. Suppose that f (z) is defined functions are analytic except when the denomi-
and continuous in some neighborhood of z = z0 . nator vanishes.
A necessary condition for the existence of f (z0 ) The derivatives of the elementary functions
is that u (x, y) and v (x, y) have first-order partials are
and that the Cauchy – Riemann conditions (see d z d n
below) hold. e = ez , z = n z n−1
dz dz
∂u ∂v ∂u ∂v d 1 d
= and =− at z0 (ln z) = , sin z = cos z ,
∂x ∂y ∂y ∂x dz z dz
d
cos z = − sin z
dz
In addition, and only if, it is the real part of an analytic func-

tion. The imaginary part is also harmonic. Given
d dg df
( f g) = f +g any harmonic function u, a conjugate harmonic
dz dz dz
function v can be constructed such that f = u + i v
d d f dg is locally analytic [31, p. 85].
f [g (z)] =
dz dg dz
Maximum Principle. If f (z) is analytic in a
d dw d dw domain D and continuous in the set consisting of
sin w = cos w , cos w = − sin w
dz dz dz dz D and its boundary C, and if | f (z) | ≤ M on C,
Define z a = ea ln z for complex constant a. If the then | f (z) | < M in D unless f (z) is a constant
determination is −π < arg z ≤ π, then z a is ana- [32].
lytic on the complex plane with a cut on the neg-
ative real axis. If a is an integer n, then e2πin = 1
and zn has the same limits approaching the cut 3.4. Integration in the Complex Plane
from either side. The function can be made con-
tinuous across the cut and the function is analytic Let C be a rectifiable curve in the complex plane
there, too. If a = 1/n where n is an integer, then
C:z = z (t) , 0 ≤t ≤ 1
z 1/n = e(lnz)/n =|z|l/n ei(argz)/n
where z (t) is a continuous function of bounded
So w = z1/n has n values, depending on the variation; C is oriented such that z1 = z (t 1 ) pre-
choice of argument. cedes the point z2 = z (t 2 ) on C if and only if
t 1 < t 2 . Define
Laplace Equation. If f (z) is analytic, where
1
f (z) =u (x, y) + i v (x, y) f (z) dz = f [z (t)] dz (t)
C 0
the Cauchy – Riemann equations are satisfied.
Differentiating the Cauchy – Riemann equations The integral is linear with respect to the inte-
gives the Laplace equation: grand:

∂2u ∂2v ∂2v ∂2u
2
= = = − or [α1 f1 (z) + α2 f2 (z)] dz
∂x ∂x ∂y ∂y ∂x ∂y 2
C
∂2u ∂2u
+ = 0
∂x2 ∂y 2 = α1 f1 (z) dz + α2 f2 (z) dz
C C
Similarly,
The integral is additive with respect to the path.
∂2v ∂2v
2
+ = 0 Let curve C 2 begin where curve C 1 ends and
∂x ∂y 2
C 1 + C 2 be the path of C 1 followed by C 2 . Then,
Thus, general solutions to the Laplace equation
can be obtained from analytic functions [31, f (z) dz = f (z) dz + f (z) dz
p. 83], [32, p. 223]. For example, C1 +C2 C1 C2
1
ln Reversing the orientation of the path replaces the
|z −z0 | integral by its negative:
is analytic so that a solution to the Laplace equa-
tion is f (z) dz = − f (z) dz
. /−1/2 −C C
ln (x − a)2 + (y − b)2
If the path of integration consists of a finite num-
A solution to the Laplace equation is called a ber of arcs along which z (t) has a continuous
harmonic function. A function is harmonic if, derivative, then
1 Power Series. If f (z) is analytic interior to a

f (z) dz = f [z (t)] z (t) dt circle | z − z0 | < r 0 , then at each point inside the
C 0 circle the series
∞
Also if s (t) is the arc length on C and l (C ) is f (n) (z0 )
f (z) = f (z0 ) + (z − z0 )n
the length of C n!
n=1

converges to f (z). This result follows from
f (z) dz ≤ max | f (z) | l (C)
C
z∈C
Cauchy’s integral. As an example, ez is an en-
tire function (analytic everywhere) so that the
and MacLaurin series
∞
1 zn
ez = 1 +
f (z) dz ≤ | f (z) | |dz| = | f [z (t)] |ds (t) n!
n=1
C C 0
represents the function for all z.
Another result of Cauchy’s integral formula
Cauchy’s Theorem [31]. Suppose f (z) is an is that if f (z) is analytic in an annulus R,
analytic function in a domain D and C is a sim- r 1 < | z − z0 | < r 2 , it is represented in R by the
ple, closed, rectifiable curve in D such that f (z) Laurent series
is analytic inside and on C. Then ∞

0 f (z) = An (z − z0 )n , r1 < |z − z0 | ≤ r2
f (z) dz = 0 (11) n=−∞
C
where
If D is simply connected, then Equation (11)
1 f (z)
holds for every simple, closed, rectifiable curve An = dz ,
2 πi (z − z0 )n+1
C in D. If D is simply connected and if a and b C
are any two points in D, then
n = 0, ± 1, ± 2, . . . ,
b
f (z) dz
and C is a closed curve counterclockwise in R.
a
Singular Points and Residues [33, p. 159].
is independent of the rectifiable path joining a If a function in analytic in every neighborhood of
and b in D. z0 , but not at z0 itself, then z0 is called an isolated
singular point of the function. About an isolated
Cauchy’s Integral. If C is a closed contour singular point, the function can be represented
such that f (z) is analytic inside and on C, z0 is by a Laurent series.
a point inside C, and z traverses C in the coun-
A−2 A−1
terclockwise direction, f (z) = . . . + + + A0
(z − z0 )2 z − z0
0
1 f (z)
f (z0 ) = dz +A1 (z − z0 ) + . . . 0 < |z − z0 | ≤ r0 (12)
2 πi z − z0
C
In particular,
0
1 f (z) 0
f (z0 ) = dz 1
2 πi (z − z0 )2 A−1 = f (z) dz
C 2 πi
C
Under further restriction on the domain [31,
where the curve C is a closed, counterclockwise
p. 178],
curve containing z0 and is within the neighbor-
0 hood where f (z) is analytic. The complex num-
m! f (z)
f (m) (z0 ) = dz ber A−1 is the residue of f (z) at the isolated
2 πi (z − z0 )m+1
C singular point z0 ; 2 π i A−1 is the value of the
integral in the positive direction around a path p (z0 )

containing no other singular points. A−1 =
q (z0 )
If f (z) is defined and analytic in the exterior
| z − z0 | > R of a circle, and if If q(i−1) (z0 ) = 0, i = 1, . . . , m, then z0 is a pole of
f (z) of order m.
1 1
v (ζ) = f z0 + obtained by ζ =
ζ z − z0
Branch [33, p. 163] A branch of a multiple-
has a removable singularity at ζ = 0, f (z) is an- valued function f (z) is a single-valued function
alytic at infinity. It can then be represented by a that is analytic in some region and whose value
Laurent series with nonpositive powers of z − z0 . at each point there coincides with the value of
If C is a closed curve within which and on f (z) at the point. A branch cut is a boundary that
which f (z) is analytic except for a finite number is needed to define the branch in the greatest pos-
of singular points z1 , z2 , . . . , zn interior to the sible region. The function f (z) is singular along
region bounded by C, then the residue theorem a branch cut, and the singularity is not isolated.
states For example,
0
√ θ θ
f (z) dz = 2 πi (1 + 2 + . . . n ) z 1/2 = f1 (z) = r cos + i sin
2 2
C
where n denotes the residue of f (z) at zn . − π < θ < π, r > 0

The series of negative powers in Equation
is double valued along√the negative real axis.
(12) is called the principal part of f (z). If the
principal part has an infinite number of nonvan- √ function tends to ri when θ → π and to
The
− ri when θ → − π; the function has no limit
ishing terms, the point z0 is an essential singu-
as z → − r (r > 0). The ray θ = π is a branch cut.
larity. If A−m = 0, A−n = 0 for all m < n, then z0
is called a pole of order m. It is a simple pole if
m = 1. In such a case, Analytic Continuation [33, p. 165]. If f 1 (z)
is analytic in a domain D1 and domain D con-
∞
tains D1 , then an analytic function f (z) may ex-
A−1
f (z) = + An (z − z0 )n ist that equals f 1 (z) in D1 . This function is the
z − z0 n=0
analytic continuation of f 1 (z) onto D, and it is
If a function is not analytic at z0 but can be made unique. For example,
so by assigning a suitable value, then z0 is a re- ∞
movable singular point.
f1 (z) = z n , |z| < 1
When f (z) has a pole of order m at z0 , n=0
ϕ (z) = (z − z0 )m f (z) , 0 <|z − z0 | <r0 is analytic in the domain D1 : | z | < 1. The se-
ries diverges for other z. Yet the function is the
has a removable singularity at z0 . If MacLaurin series in the domain
ϕ (z0 ) = A−m , then ϕ (z) is analytic at z0 . For
a simple pole, 1
f1 (z) = , |z| < 1
1−z
A−1 = ϕ (z0 ) = lim (z − z0 ) f (z) Thus,
z→z0
Also | f (z) | → ∞ as z → z0 when z0 is a pole. f1 (z) =

1
Let the function p (z) and q (z) be analytic at z0 , 1−z
where p (z0 ) = 0. Then is the analytic continuation onto the entire z
p (z) plane except for z = 1.
f (z) = An extension of the Cauchy integral formula
q (z)
is useful with Laplace transforms. Let the curve
has a simple pole at z0 if, and only if, q (z0 ) = 0 C be a straight line parallel to the imaginary
and q (z0 ) = 0. The residue of f (z) at the simple axis and z0 be any point to the right of that
pole is
(see Fig. 13). A function f (z) is of order zk as Conformal Mapping. Let u (x, y) be a har-
| z | → ∞ if positive numbers M and r 0 exist such monic function. Introduce the coordinate trans-
that formation
|z −k f (z) | < M when |z| > r0 , i.e., x = x̂ (ξ, η) , y = ŷ (ξ, η)
|f (z) | < M |z|k for |z| sufficiently large It is desired that
U (ξ, η) =u [x̂ (ξ, η) , ŷ (ξ, η)]
be a harmonic function of ξ and η.

Theorem [32, p. 237]. The transformation
z = f (ζ) (13)
takes all harmonic functions of x and y into har-

monic functions of ξ and η if and only if ei-
ther f (ζ) or f ∗ (ζ) is an analytic function of
ζ = ξ + i η.
Equation (13) is a restriction on the transfor-
mation which ensures that
∂2u ∂ 2u ∂2 U ∂2U
if 2
+ 2 = 0 then + 2 = 0
∂x ∂y ∂ζ 2 ∂η
Such a mapping with f (ζ) analytic and

f (ζ) = 0 is a conformal mapping.
If Laplace’s equation is to be solved in the
Figure 13. Integration in the complex plane
region exterior to a closed curve, then the point
Theorem [33, p. 167]. Let f (z) be analytic at infinity is in the domain D. For flow in a long
when R (z) ≥ γ and O (z−k ) as | z | → ∞ in that channel (governed by the Laplace equation) the
half-plane, where γ and k are real constants and inlet and outlet are at infinity. In both cases the
k > 0. Then for any z0 such that R (z0 ) > γ transformation

γ+iβ az + b
1 f (z) ζ =
f (z0 ) = − lim dz , z − z0
2 πi β→∞ z − z0
γ−iβ takes z0 into infinity and hence maps D into a
i.e., integration takes place along the line x = γ. bounded domain D∗ .
3.5. Other Results 4. Integral Transforms

Theorem [31, p. 84]. Let P (z) be a polyno- 4.1. Fourier Transforms
mial of degree n having the zeroes z1 , z2 , . . . , zn
and let π be the least convex polygon containing Fourier Series [34]. Let f (x) be a function
the zeroes. Then P (z) cannot vanish anywhere that is periodic on − π < x < π. It can be ex-
in the exterior of π. panded in a Fourier series
If a polynomial has real coefficients, the roots
∞
are either real or form pairs of complex conju- a0
f (x) = + (an cos n x + bn sin n x)
gate numbers. 2 n=1
The radius of convergence R of the Taylor se-
ries of f (z) about z0 is equal to the distance from where
z0 to the nearest singularity of f (z).
π π
1 1 ∂T ∂2T
a0 = f (x) dx , an = f (x) cos n x dx , =
π π ∂t ∂x2
−π −π
π T (x, 0) = f (x)
1
bn = f (x) sin n x dx
π T (−π, t) = T (π, t)
−π
Let
The values {an } and {bn } are called the finite
∞

cosine and sine transform of f , respectively. Be-
T = cn (t) e−inx
cause −∞
1 inx Then,
cos n x = e + e−inx
2 ∞ ∞
dcn −inx
cn (t) −n2 e−inx
1 inx e =
and sin n x = e − e−inx −∞
dt −∞
2i
Thus, cn (t) satisfies
the Fourier series can be written as
dcn 2
∞ = − n2 cn , or cn = cn (0) e−n t
dt
f (x) = cn e−inx
n=−∞
Let cn (0) be the Fourier coefficients of the initial
conditions:
where ∞

f (x) = cn (0) e−inx
1
2
(an + i bn ) for n ≥ 0 −∞
cn = 1
2
(a−n − i b−n ) for n < 0
The formal solution to the problem is
and ∞
2
T = cn (0) e−n t e−inx
π −∞
1
cn = f (x) einx dx
2π
−π
Fourier Transform [34]. When the function
If f is real f (x) is defined on the entire real line, the Fourier
transform is defined as
c−n = c∗n .
∞
If f is continuous and piecewise continuously F [ f ] ≡ fˆ (ω) = f (x) eiωx dx
differentiable −∞
∞
This integral converges if

f (x) = (−i n) cn e−inx ∞
−∞
| f (x) |dx
If f is twice continuously differentiable −∞
∞
does. The inverse transformation is

−inx
f (x) = −n 2
cn e ∞
1
−∞ f (x) = fˆ (ω) e−iωx dω
2π
−∞
Inversion. The Fourier series can be used to If f (x) is continuous and piecewise continuously
solve linear partial differential equations with differentiable,
constant coefficients. For example, in the prob- ∞
lem f (x) eiωx dx
−∞
converges for each ω, and ∞

lim | f (x) − fn (x) |2 dx = 0
lim f (x) = 0 n→∞
x→±∞ −∞
then The sequence also satisfies the Cauchy criterion

∞
df
F = − i ωF [ f ] lim | fn − fm |2 dx = 0
dx n→∞
m→∞
−∞
If f is real F [ f (− ω)] = F [ f (ω)∗ ]. The real part
is an even function of ω and the imaginary part Theorem [34, p. 307]. If a sequence of square
is an odd function of ω. integrable functions fn (x) converges to a func-
A function f (x) is absolutely integrable if the tion f (x) uniformly on every finite interval
improper integral a ≤ x ≤ b, and if it satisfies Cauchy’s criterion,
then f (x) is square integrable and fn (x) con-
∞
verges to f (x) in the mean.
| f (x) |dx
Theorem (Riesz – Fischer) [34, p. 308]. To
−∞
every sequence of square integrable functions
has a finite value. Then the improper integral fn (x) that satisfy Cauchy’s criterion, there cor-
responds a square integrable function f (x) such
∞ that fn (x) converges to f (x) in the mean. Thus,
f (x) dx the limit in the mean of a sequence of functions
−∞ is defined to within a null function.
converges. The function is square integrable if Square integrable functions satisfy the Parse-
val equation.
∞
∞ ∞
| f (x) |2 dx
| fˆ (ω) |2 dω = 2 π | f (x) |2 dx
−∞
−∞ −∞
has a finite value. If f (x) and g (x) are square This is also the total power in a signal, which can
integrable, the product f (x) g (x) is absolutely be computed in either the time or the frequency
integrable and satisfies the Schwarz inequality: domain. Also
∞ 2 ∞ ∞

f (x) g (x) dx fˆ (ω) ĝ∗ (ω) dω = 2 π f (x) g ∗ (x) dx
−∞
−∞ −∞
∞ ∞ Fourier transforms can be used to solve dif-

≤ | f (x) |2 dx |g (x) |2 dx ferential equations too. Then it is necessary to
−∞ −∞ find the inverse transformation. If f (x) is square
integrable, the Fourier transform of its Fourier
The triangle inequality is also satisfied:
transform is 2 π f (− x), or
 ∞ 1/2
  . / ∞
| f + g|2 dx 1
  f (x) = F fˆ (ω) = fˆ (ω) e−iωx dω
−∞
2π
−∞
 ∞ 1/2  ∞ 1/2
    ∞ ∞
1
≤ | f |2 dx |g|2 dx = f (x) eiωx dxe−iωx dω
    2π
−∞ −∞ −∞ −∞
A sequence of square integrable functions fn (x)

1 1
converges in the mean to a square integrable f (x) = F [F f (−x)] or f (−x) = F [F [ f ]]
2π 2π
function f (x) if
Properties of Fourier Transforms [34,

∂T ∂2T
p. 324], [35]. =
∂t ∂x2

df
F = − i ωF [ f ] = i ω fˆ T (x, 0) = f (x) , − ∞ < x <∞
dx
d d ˆ T bounded
F [i x f (x)] = F [f ]= f
dω dω
take the Fourier transform
1 iωb/a ˆ ω
F [ f (a x − b)] = e f dT̂
|a| a + ω 2 T̂ = 0
dt
. /
F eicx f (x) = fˆ (ω + c)
T̂ (ω, 0) = fˆ (ω)
1 .ˆ /
The solution is
F [cos ω0 xf (x)] = f (ω + ω0 ) + fˆ (ω − ω0 )
2
2
T̂ (ω, t) = fˆ (ω) e−ω t
1 .ˆ /
F [sin ω0 xf (x)] = f (ω + ω0 ) − fˆ (ω − ω0 )
2i The inverse transformation is
. /
F e−iω0 x f (x) = fˆ (ω − ω0 ) ∞
1 2
T (x, t) = e−iωx fˆ (ω) e−ω t dω
2π
If f (x) is real, then f (− ω) = f̂ ∗ (ω). −∞
If f (x) is imaginary, then f̂ (− ω) = − f̂ ∗ (ω).
Because
If f (x) is even, then f̂ (ω) is even.
If f (x) is odd, then f̂ (ω) is odd.
2 1 2
If f (x) is real and even, then f̂ (ω) is real and e−ω t
=F √ e−x /4t
4πt
even.
If f (x) is real and odd, then f̂ (ω) is imaginary the convolution integral can be used to write the
and odd. solution as
If f (x) is imaginary and even, then f̂ (ω) is imag- ∞
inary and even. 1 2
T (x, t) = √ f ( y) e−(x−y) /4t
dy
If f (x) is imaginary and odd, then f̂ (ω) is real 4πt
−∞
and odd.
Convolution [34, p. 326].
Finite Fourier Sine and Cosine Transform
∞
[36]. In analogy with finite Fourier transforms
f ∗ h (x0 ) ≡ f (x0 − x) h (x) dx
(on − π to π) and Fourier transforms (on − ∞
−∞
to + ∞), finite Fourier sine and cosine transforms
∞ (0 to π) and Fourier sine and cosine transforms
=
1
eiωx0 fˆ (−ω) ĥ (ω) dω (on 0 to + ∞) can be defined.
2π The finite Fourier sine and cosine transforms
−∞
are
Theorem. The product π
2
fs (n) = F n
s [f ]= f (x) sin n x dx ,
fˆ (ω) ĥ (ω) π
0
is the Fourier transform of the convolution prod- n = 1, 2, . . . ,

uct f ∗ h. The convolution permits finding inverse
transformations when solving differential equa-
tions. To solve
π
2 df
fc (n) = F n Fn = − nF n
c [f ]
c [f ]= f (x) cos n x dx s
π dx
0

df 2 2
n = 0, 1, 2, . . . Fn
c s [f ] −
=nF n f (0) + (−1)n f (π)
dx π π
∞
When two functions F (x) and G (x) are defined
f (x) = fs (n) sin n x,
n=1
on the interval − 2 π < x < 2 π, the function
∞ π
1
f (x) = fc (0) + fc (n) cos n x F (x) ∗ G (x) = f (x − y) g ( y) dy
2 n=1 −π
They obey the operational properties is the convolution on − π < x < π. If F and G are
both even or both odd, the convolution is even; it
d2 f
Fn
s = − n2 F n
s [f ] is odd if one function is even and the other odd. If
dx2
F and G are piecewise continuous on 0 ≤ x ≤ π,
2n then
+ [ f (0) − (−1)n f (π)]
π
1 ∗

f, f are continuous, f is piecewise continuous fs (n) gs (n) = F n
c − F 1 (x) G1 (x)
2
on 0 ≤ x ≤ π.

1
fs (n) gc (n) = F n
s F1 (x) ∗ G2 (x)
2

1 ∗
fc (n) gc (n) = F n
c F2 (x) G2 (x)
2
and f1 is the extension of f, k is a constant where F 1 and G 1 are odd extensions of F and G,
respectively, and F 2 and G2 are even extensions
of F and G, respectively. Finite sine and cosine
transforms are listed in Tables 3 and 4.
On the semi-infinite domain, 0 < x < ∞, the
Fourier sine and cosine transforms are
Also, ∞
s [f ] ≡
Fω f (x) sin ω x dx,
d2 f 2 df
Fn
c = − n2 F n
c [f ] − (0) 0
dx2 π dx
∞
2 df
+ (−1)n (π) c [f ] ≡
Fω f (x) cos ω x dx and
π dx
0

1 1
fc (n) cos n k = F n
c f2 (x − k) + f2 (x + k) 2 ω 2 ω
2 2 f (x) = F [F ω ω
s [f ]] , f (x) = F c [F c [ f ]]
π s π
fc (n) (−1)n = F n
c [ f (π − x)] The sine transform is an odd function of ω,
and f 2 is the extension of f. whereas the cosine function is an even function
of ω. Also,

d2 f
Fω
s = f (0) ω − ω 2 F ω
s [ f]
dx2

d2 f df
Fω
c = − (0) − ω 2 F ω
s [f ]
Also, dx2 dx
Table 3. Finite sine transforms [36]
π
fs (n) = F (x) sin n x dx (n = 1, 2, . . .) F (x) (0<x<π)
0
(−1)n+1 f s (n) F (π−x)
1 π−x
n π
(−1)n+1 x
n π
1−(−1)n
n 1

π (π − c) x (x ≤ c)
sin n c (0<c<π)
n2 c (π − x) (x≥c)

−x (x<c)
π
n cos n c (0 ≤c ≤ π)
π−x (x > c)
π 2 (−1)n−1 2 [1−(−1)n ]
n − n3
x2

π2
π (−1)n 6
n3
− n x3
n
n2 +c2
[1 − (−1)n ecπ ] ecx
n sinh c (π−x)
n2 +c2 sinh cπ
n sin k (π−x)
n2 −k2
(|k|=0, 1, 2, . . .) sin k π
π
0 (n=m) ; fs (m) = 2 sin m x (m = 1,2, . . . )
n
n2 −k2
[1 − (−1)n cos k x] cos k x (| k | = 1,2, . . . )

n
n2 −m2
1 − (−1)n+m , (n=m) cos m x (m = 1,2, . . . )
The material is reproduced with permission of McGrawHill, Inc.
provided f (x) and f (x) → 0 as x → ∞. Thus,

the sine transform is useful when f (0) is known L [F + G] = L [F ] + L [G]
and the cosine transform is useful when f (0) is
known. Thus, the techniques described herein can be ap-
Hsu and Dranoff [37] solved a chemical plied only to linear problems. Generally, the as-
engineering problem by applying finite Fourier sumptions made below are that F (t) is at least
transforms and then using the fast Fourier trans- piecewise continuous, that it is continuous in
form (see Chap. 2). each finite interval within 0 < t < ∞, and that
it may take a jump between intervals. It is also
of exponential order, meaning e−αt | F (t) | is
4.2. Laplace Transforms bounded for all t > T , for some finite T .
The unit step function is

Consider a function F (t) defined for t > 0. The 0 0 ≤ t<k
Laplace transform of F (t) is [36] Sk (t) =
1 t>k
∞ and its Laplace transform is
L [F ] = f (s) = e−st F (t) dt
0
e−ks
L [Sk (t)] =
s
The Laplace transformation is linear, that is, In particular, if k = 0 then
Table 4. Finite cosine transforms [36]
π
fc (n) = F (x) cos n x dx (n = 0, 1, . . .) F (x) (0<x<π)
0
(−1)n fc (n) F (π−x)
0 when n=1,2, . . . ; fc (0)=π 1

1 (0<x<c)
2
n sin n c; fc (0) =2 c − π
−1 (c<x<π)
1−(−1)n π2
− n2
; fc (0) = 2 x
(−1)n π2 x2
n2
; fc (0) = 6 2π
(π−x)2
1
n2
; fc (0) = 0 2π − π
6
(−1)n ecx −1
n2 +c2
1
c ecx
1 cosh c (π−x)
n2 +c2 c sinh c π
(−1)n cos k π−1 1

n2 −k2
(|k|=0, 1, . . .) k sin k x
(−1)n+m −1 1
n2 −m2
; fc (m) = 0 (m = 1, . . .) m sin m x
cos k (π−x)
1
n2 −k2
(|k|=0, 1, . . .) − k sin k x
π
o (n=m) ; fc (m) = 2 (m = 1, 2, . . .) cos m x
The material is reproduced with permission of McGrawHill, Inc.
1 isolated points have the same Laplace transform.

L [1] = They are unique to within a null function. Thus,
s
if
The Laplace transforms of the first and second
derivatives of F (t) are L [F1 ] =f (s) and L [F2 ] =f (s)

dF
L = s f (s) − F (0) it must be that
dt
F2 = F1 + N (t)
d2 F dF
L = s2 f (s) − s F (0) − (0)
dt2 dt
T
More generally, where (N (t)) dt = 0 for every T
0
dn F
L = sn f (s) − sn−1 F (0)
dtn Laplace transforms can be inverted by using Ta-
ble 5, but knowledge of several rules is helpful.
dF dn−1 F
− sn−2 (0) − . . . − (0) Substitution.
dt dtn−1

The inverse Laplace transformation is f (s − a) =L eat F (t)
F (t) = L−1 [f (s)] where f (s) = L [F ]

This can be used with polynomials. Suppose
1 1 2s + 3
The inverse Laplace transformation is not unique f (s) = + =
s s+3 s (s + 3)
because functions that are identical except for
Because The step function


1 
0 0 ≤ t< h
1
L [1] =
s S (t) = 1 1
≤ t< h
2

2
h
2
≤ t< h
3
Then h
has the Laplace transform

F (t) = 1 + e−3t , t ≥ 0
1 1
L [S (t)] =
More generally, translation gives the following. s 1 − e−hs
Table 5. Laplace transforms (see [38] for a more complete list)

The Dirac delta function δ (t − t 0 ) (see Equa-
tion 116 in → Mathematical Modeling) has the
L [F] F (t) property
1
s 1 ∞
1
δ (t − t0 ) F (t) dt = F (t0 )
s2
t
0
tn−1
1
sn (n−1)! Its Laplace transform is
1
√
s
√1
πt
L [δ (t − t0 )] = e−st0 , t0 ≥ 0, s > 0

s−3/2 2 t/π The square wave function illustrated in Figure 14
has Laplace transform
Γ (k)
(k > 0) tk−1
sk 1 cs
L [Fc (t)] = tanh
1
s−a e at s 2
The triangular wave function illustrated in Fig-
1
(s−a)n
(n = 1, 2, . . .) 1
tn−1 eat
(n−1)! ure 15 has Laplace transform
tk −1 eat
Γ (k)
(s−a)k
(k > 0) 1 cs
L [Tc (t)] = tanh
s2 2
1 1
eat − ebt
(s−a) (s−b) a−b Other Laplace transforms are listed in Table 5.

s
(s−a) (s−b)
1
a−b aeat − bebt
1 1
s2 +a2 a sin a t
s
s2 +a2
cos a t
1 1
s2 −a2 a sinh a t
s
s2 −a2
cosh a t
s t
sin a t
(s2 +a2 )2 2a
Figure 14. Square wave function

s2 −a2
t cos a t
(s2 +a2 )2
1
(s−a)2 +b2
1
b eat sin b t
s−a
(s−a)2 +b2
eat cos b t
Translation.

b 1 bt/a t
f (a s − b) = f a s − =L e F ,
a a a
Figure 15. Triangular wave function
a>0
Convolution properties are also satisfied: p (s) Am Am−1

f (s) = = + +
t q (s) (s − a)m (s − a)m−1
F (t) ∗ G (t) = F (τ ) G (t − τ ) dτ
A1
0 ... + + h (s)
s−a
and where
f (s) g (s) =L [F (t) ∗ G (t)] (s − a)m p (s)
ϕ (s) ≡
q (s)
1 dm−k ϕ (s)
Am = ϕ (a) , Ak = ,
Derivatives of Laplace Transforms. The (m − k)! dsm−k a
Laplace integrals L [F (t)], L [t F (t)],
L [t 2 F (t)], . . . are uniformly convergent for k = 1, . . . , m − 1
s1 ≥ α> α and
The term h (s) denotes the sum of partial frac-
n tions not under consideration. The inverse trans-
lim f (s) = 0, lim L [t F (t)] = 0, n = 1, 2, . . .
s→∞ s→∞ formation is then
and
tm−1 tm−2
F (t) = eat Am + Am−1 + ...
(m − 1)! (m − 2)!
dn f
= L [(−t)n F (t)]
dsn
t
+ A2 + A1 + H (t)
1!
Integration of Laplace Transforms. The term in F (t) corresponding to
∞
f (ξ) dξ = L
F (t) s − a in q (s) is ϕ (a) eat
t
s
(s − a)2 in q (s) is ϕ (a) + ϕ (a) t eat
If F (t) is a periodic function, F (t) = F (t + a),
then 1
(s − a)3 in q (s) is ϕ (a) + 2ϕ (a) t
2
a
1
f (s) = e−st F (t) dt , + ϕ (a) t2 eat
1 − e−as
0
For example, let
where F (t) = F (t + a) 1
f (s) =
(s − 2) (s − 1)2
For the factor s − 2,

Partial Fractions [39, p. 229]. Suppose q (s)
1
has m factors ϕ (s) = , ϕ (2) = 1
(s − 1)2
q (s) = (s − a1 ) (s − a2 ) . . . (s − am ) For the factor (s − 1)2 ,
All the factors are linear, none are repeated, and 1 1
ϕ (s) = , ϕ (s) = −
the an are all distinct. If p (s) has a smaller de- s−2 (s − 2)2
gree than q (s), the Heaviside expansion can be
used to evaluate the inverse transformation: ϕ (1) = − 1, ϕ (1) = − 1
m The inverse Laplace transform is then
p (s) p (ai ) ai t
L−1 = (a )
e
q (s) q i
i=1 F (t) = e2t + [− 1 −t] et
If the factor (s − a) is repeated n + 1 times, then
Quadratic Factors. Let p (s) and q (s) have To solve an integral equation:
real coefficients, and q (s) have the factor
t
2 Y (t) = a + 2 Y (τ ) cos (t − τ ) dτ
(s − a) + b , b > 0
2
0
where a and b are real numbers. Then define it is written as
ϕ (s) and h (s) and real constants A and B such
that Y (t) = a + Y (t) ∗ cos t
p (s) ϕ (s) Then the Laplace transform is used to obtain

f (s) = =
q (s) (s − a)2 + b2 a s
y (s) = + 2 y (s) 2
s s +1
As+B
= + h (s)
(s − a)2 + b2 a s2 + 1
or y (s) =
Let ϕ1 and ϕ2 be the real and imaginary parts of s (s − 1)2
the complex number ϕ (a + i b). Taking the inverse transformation gives

ϕ (a + i b) ≡ϕ1 + i ϕ2 Y (t) = s 1 + 2tet
Then Next, let the variable s in the Laplace transform

be complex. F (t) is still a real-valued function of
1 (s − a) ϕ2 + b ϕ1 the positive real variable t. The properties given
f (s) = + h (s)
b (s − a)2 + b2 above are still valid for s complex, but additional
techniques are available for evaluating the inte-
1
F (t) = eat (ϕ2 cos b t + ϕ1 sin b t) + H (t) grals. The real-valued function is O [exp (x 0 t)]:
b
To solve ordinary differential equations by us- |F (t) | < M ex0 t , z0 = x0 +i y0
ing these results: The Laplace transform
Y (t) − 2Y (t) +Y (t) = e2t ∞
f (s) = e−st F (t) dt

Y (0) = 0, Y (0) = 0 0
Taking Laplace transforms is an analytic function of s in the half-plane

x > x 0 and is absolutely convergent there; it is
1 uniformly convergent on x ≥ x 1 > x 0 .
L Y (t) − 2L Y (t) + L [Y (t)] =
s−2
dn f
using the rules = L [(−t)n F (t)] n = 1, 2, . . . , x > x0
dsn
s2 y (s) − s Y (0) − Y (0) − 2 [s y (s) − Y (0)] and f ∗ (s) = f (s∗ )
1 The functions | f (s) | and | x f (s) | are bounded

+ y (s) =
s−2 in the half-plane x ≥ x 1 > x 0 and f (s) → 0 as
| y | → ∞ for each fixed x. Thus,
and combining terms
| f (x + i y) | < M , |x f (x + i y) | < M ,
1
s2 − 2 s + 1 y (s) =
s−2 x ≥ x 1 > x0
1
y (s) = lim f (x + i y) = 0, x > x0
(s − 2) (s − 1)2 y→±∞
lead to If F (t) is continuous, F (t) is piecewise contin-

uous, and both functions are O [exp (x 0 t)], then
Y (t) = e2t − (1 + t) et | f (s) | is O (1/s) in each half-plane x ≥ x 1 > x 0 .
Next Page
Series of Residues [36]. Let f (s) be an ana-

lytic function except for a set of isolated singu-
|s f (s) | <M
lar points. An isolated singular point is one for
If F (t) and F (t) are continuous, F (t) is piece- which f (z) is analytic for 0 < | z − z0 | < but
wise continuous, and all three functions are z0 is a singularity of f (z). An isolated singular
O [exp (x 0 t)], then point is either a pole, a removable singularity,
or an essential singularity. If f (z) is not defined
|s2 f (s) −s F (0) | <M, x ≥ x1 >x0 in the neighborhood of z0 but can be made an-
The additional constraint F (0) = 0 is necessary alytic at z0 simply by defining it at some addi-
and sufficient for | f (s) | to be O (1/s2 ). tional points, then z0 is a removable singularity.
The function f (z) has a pole of order k ≥ 1 at z0
Inversion Integral [36]. Cauchy’s integral if (z − z0 )k f (z) has a removable singularity at
formula for f (s) analytic and O (s−k ) in a half- z0 whereas (z − z0 )k−1 f (z) has an unremovable
plane x ≥ y, k > 0, is isolated singularity at z0 . Any isolated singular-
ity that is not a pole or a removable singularity

γ+iβ is an essential singularity.
1 f (z)
f (s) = lim dz , Re (s) > γ Let the function f (z) be analytic except for
2 πi β→∞ s−z
γ−iβ the isolated singular point s1 , s2 , . . . , sn . Let
n (t) be the residue of ezt f (z) at z = sn (for def-
Applying the inverse Laplace transformation on inition of residue, see Section 3.4). Then
either side of this equation gives
∞

γ+iβ
F (t) = n (t)
1
F (t) = lim ezt f (z) dz n=1
2 πi β→∞
γ−iβ
When sn is a simple pole
If F (t) is of order O [exp (x 0 t)] and F (t) and
F (t) are piecewise continuous, the inversion n (t) = lim (z − sn ) ezt f (z)
z→sn
integral exists. At any point t 0 , where F (t) is
discontinuous, the inversion integral represents = esn t lim (z − sn ) f (z)
z→ sn
the mean value
1 When
F (t0 ) = lim [F (t0 + ε) + F (t0 − ε)]
ε→∞ 2
p (z)
f (z) =
When t = 0 the inversion integral represents q (z)
0.5 F (O +) and when t < 0, it has the value zero.
If f (s) is a function of the complex variable where p (z) and q (z) are analytic at z = sn ,
s that is analytic and of order O (s−k−m ) on p (sn ) = 0, then
R (s) ≥ x 0 , where k > 1 and m is a positive in- p (sn ) sn t
teger, then the inversion integral converges to n (t) = e
q (sn )
F (t) and
If sn is a removable pole of f (s), of order m, then

γ+iβ
dn F 1 zt n
= lim e z f (z) dz ,
dtn 2 πi β→∞ ϕn (z) = (z − sn )m f (z)
γ−iβ
is analytic at sn and the residue is
n = 1, 2, . . . , m
Φn (sn )
Also F (t) and its n derivatives are continuous n (t) =
(m − 1)!
functions of t of order O [exp (x 0 t)] and they
vanish at t = 0. ∂ m−1
where Φn (z) = ϕn (z) ezt
∂z m−1
F (0) =F (0) = . . . F (m) (0) = 0
An important inversion integral is when
Previous Page
1 Applied to the differential equation

f (s) = exp −s1/2
s ∂2T
F = − ω 2 αF [T ]
The inverse transform is ∂x2

1 1 ∂ T̂
F (t) = 1 − erf √ = erfc √ + ω 2 α T̂ = 0, T̂ (ω, 0) = fˆ (ω)
2 t 2 t ∂t
where erf is the error function and erfc the com- By solving
plementary error function. 2
T̂ (ω, t) = fˆ (ω) e−ω αt
the inverse transformation gives [34, p. 328],

4.3. Solution of Partial Differential
[40, p. 58]
Equations by Using Transforms
L
1 2
A common problem facing chemical engineers T (x, t) = lim e−iωx fˆ (ω) e−ω αt
dω
2 π L→∞
is to solve the heat conduction equation or dif- −L
fusion equation
Another solution is via Laplace transforms; take
∂T ∂2T ∂c ∂2c the Laplace transform of the original differential
Cp = k or = D
∂t ∂x2 ∂t ∂x2 equation.
The equations can be solved on an infinite ∂2t
domain − ∞ < x < ∞, a semi-infinite domain s t (s, x) − f (x) = α
∂x2
0 ≤ x < ∞, or a finite domain 0 ≤ x ≤ L. At a
boundary, the conditions can be a fixed tem- This equation can be solved with Fourier trans-
perature T (0, t) = T 0 (boundary condition of the forms [34, p. 355]
first kind, or Dirichlet condition), or a fixed ∞ ( 1 )
flux −k ∂T ∂x (0, t) = q0 (boundary condition of t (s, x) = √
1
e −
s
|x − y| f ( y) dy
the second kind, or Neumann condition), or a 2 sα α
−∞
combination −k ∂T ∂x (0, t) = h [T (0, t) − T0 ]
(boundary condition of the third kind, or Robin The inverse transformation is [34, p. 357], [40,
condition). p. 53]
The functions T 0 and q0 can be functions of
∞
time. All properties are constant (, Cp , k, D, h), 1 2
T (x, t) = √ e−(x−y) /4αt
f ( y) dy
so that the problem remains linear. Solutions are 2 π αt
−∞
presented on all domains with various boundary
conditions for the heat conduction problem.
∂T ∂2T k Problem 2. Semi-infinite domain, boundary
= α , α=
∂t ∂x2 Cp condition of the first kind, on 0 ≤ x ≤ ∞
T (x, 0) =T0 = constant

Problem 1. Infinite domain, on − ∞ < x < ∞.
T (0, t) =T1 = constant
T (x, 0) =f (x) , initial conditions The solution is

. √ /
T (x, t) bounded T (x, t) =T0 + [T1 −T0 ] 1 − erf x/ 4α t
Solution is via Fourier transforms √
or T (x, t) =T0 + (T1 −T0 ) erfc x/ 4α t
∞
T̂ (ω, t) = T (x, t) eiωx dx
−∞
Problem 3. Semi-infinite domain, boundary ∞ t

2α
condition of the first kind, on 0 ≤ x < ∞ T2 (x, t) = ω sin ωx e−ω
2
α(t−τ )
g (τ ) dτ dω
π
0 0
T (x, 0) =f (x)
The solution for T 1 can also be obtained by
T (0, t) =g (t) Laplace transforms.
The solution is written as t1 =L [T1 ]
Applying this to the differential equation

T (x, t) =T1 (x, t) +T2 (x, t)
∂ 2 t1
where s t1 − f (x) = α , t1 (0, s) = 0
∂x2
T1 (x, 0) =f (x) , T2 (x, 0) = 0 and solving gives

x √
T1 (0, t) = 0, T2 (0, t) =g (t) 1 s/α(x −x)

t1 = √ e− f x dx
sα
Then T 1 is solved by taking the sine transform 0
and the inverse transformation is [34, p. 437],

U1 =Fsω [T1 ] [40, p. 59]
∞.
1 2
T1 (x, t) = √ e−(x−ξ) /4αt
∂U1 4 π αt
= − ω 2 α U1 0
∂t
2
/
−e−(x+ξ) /4αt
f (ξ) dξ
U1 (ω, 0) =Fsω [ f ]
Thus, Problem 4. Semi-infinite domain, boundary

2
conditions of the second kind, on 0 ≤ x < ∞.
U1 (ω, t) = Fsω [ f ] e−ω αt
T (x, 0) = 0
and [34, p. 322]
∂T
∞ −k (0, t) = q0 = constant
2 2 ∂x
T1 (x, t) = Fsω [ f ] e−ω αt
sin ωx dω
π Take the Laplace transform
0
Solve for T 2 by taking the sine transform t (x, s) =L [T (x, t)]
∂2t
U2 =Fsω [T2 ] st = α
∂x2
∂t q0
−k =
∂U2 ∂x s
= − ω 2 α U2 + α g (t) ω
∂t The solution is
√
U2 (ω, 0) = 0 q0 α −x√s/α
t (x, s) = e
ks3/2
Thus,
The inverse transformation is [36, p. 131], [40,
t p. 75]
2
U2 (ω, t) = e−ω α(t−τ )
αω g (τ ) dτ 1
q0 α t −x2 /4αt x
0 T (x, t) = 2 e − x erfc √
k π 4 αt
and [34, p. 435]
Problem 5. Semi-infinite domain, boundary Take the Laplace transform

conditions of the third kind, on 0 ≤ x < ∞
∂2t
s t (x, s) − T0 = α
T (x, 0) =f (x) ∂x2
∂T t (0, s) =t (L, s) = 0
k (0, t) = h T (0, t)
∂x
The solution is
Take the Laplace transform 2 2
T0 sinh α (L − x)
s s
T0 sinh α x
∂2t t (x, s) = − 2 − 2
s t − f (x) = α s sinh s L s sinh αs
L
∂x2 α
∂t T0
k (0, s) = h t (0, s) +
∂x s
The solution is The inverse transformation is [36, p. 220], [40,
∞ p. 96]
t (x, s) = f (ξ) g (x, ξ, s) dξ 2 2 −n2 π2 αt/L2 nπ x
0 T (x, t) = T0 e sin
π n=1,3,5,...
n L
where [36, p. 227]

or (depending on the inversion technique) [34,
- -
2 s/α g (x, ξ, s) = exp − |x − ξ| s/α pp. 362, 438]
√ √ . / L
∞
s − h α/k - T0
+√ √ exp − (x + ξ) s/α T (x, t) = √ [
s + h α/k 4 π αt
0 n=−∞
One form of the inverse transformation is [36, 2 2
/
p. 228] e−[(x−ξ)+2nL] /4αt
− e−[(x+ξ)+2nL] /4αt
dξ
∞ ∞
2 2
T (x, t) = e−β αt
cos [β x − µ (β)] f (ξ)
π
0 0 Problem 7. Finite domain, boundary condi-
tion of the first kind
cos [β ξ − µ (β)] dξdβ
T (x, 0) = 0
µ (β) = arg (β + i h /k)
T (0, t) = 0
Another form of the inverse transformation
T (L, 0) = T0 = constant
when f = T 0 = constant is [36, p. 231], [40, p. 71]
Take the Laplace transform
x 2 2
T (x, t) = T0 erf √ +ehx/k eh αt/k
4 αt ∂2t
s t (x, s) = α
√
∂x2
h αt x
erfc +√
k 4 αt T0
t (0, s) = 0, t (L , s) =
s
The solution is
Problem 6. Finite domain, boundary condi- -
x
tion of the first kind T0 sinh L s/α
t (x, s) = -
s sinh s/α
T (x, 0) =T0 = constant
and the inverse transformation is [36, p. 201],
T (0, t) = T (L, t) = 0 [40, p. 313]
and two directions associated with it, as defined

T (x, t) =
precisely below. The most common examples
∞

are the stress dyadic (or tensor) and the velocity
x 2 (−1)n −n2 π 2 αt/L2 nπ x
T0 + e sin gradient (in fluid flow). Vectors are printed in
L π n=1 n L
boldface type and identified in this chapter by
An alternate transformation is [36, p. 139], [40, lower-case Latin letters. Second-order dyadics
p. 310] are printed in boldface type and are identified in
this chapter by capital or Greek letters. Higher
∞

(2 n + 1) L + x order dyadics are not discussed here. Dyadics
T (x, t) = T0 erf √
n=0 4 αt can be formed from the components of tensors
including their directions, and some of the iden-

(2 n + 1) L − x tities for dyadics are more easily proved by using
− erf √
4 αt tensor analysis, which is not presented here (see
also, → Transport Phenomena, Chap. 1.1.4.).
Vectors are also first-order dyadics.
Problem 8. Finite domain, boundary condi- Vectors. Two vectors u and v are equal if they
tion of the second kind have the same magnitude and direction. If they
have the same magnitude but the opposite di-
T (x, 0) =T0 rection, then u = − v. The sum of two vectors
is identified geometrically by placing the vector
∂T
(0, t) = 0, T (L , t) = 0
v at the end of the vector u, as shown in Fig-
∂x ure 16. The product of a scalar m and a vector
Take the Laplace transform u is a vector m u in the same direction as u but
with a magnitude that equals the magnitude of
∂2t u times the scalar m. Vectors obey commutative
s t (x, s) − T0 = α
∂x2 and associative laws.
∂t u+v=v+u Commutative law for addition
(0, s) = 0, t (L , s) = 0 u + (v + w) = (u + v) + w Associative law for addition
∂x mu=um Commutative law for scalar
multiplication
The solution is
m (n u) = (m n) u Associative law for scalar
-
multiplication
T0 cosh x s/α (m + n) u = m u + n u Distributive law
t (x, s) = 1− -
s cosh L s/α m (u + v) = m u + m v Distributive law
Its inverse is [36, p. 138] The same laws are obeyed by dyadics, as well.
∞

T (x, t) = T0 − T0 (−1)n
n= 0

(2n + 1) L − x (2n + 1) L + x
erfc √ + erfc √
4αt 4αt
Figure 16. Addition of vectors
A unit vector is a vector with magnitude 1.0

5. Vector Analysis and some direction. If a vector has some magni-
tude (i.e., not zero magnitude), a unit vector eu
Notation. A scalar is a quantity having mag- can be formed by
nitude but no direction (e.g., mass, length, time, u
temperature, and concentration). A vector is eu =
|u|
a quantity having both magnitude and direc-
tion (e.g., displacement, velocity, acceleration, The original vector can be represented by the
force). A second-order dyadic has magnitude product of the magnitude and the unit vector.
Dyadics. The dyadic A is written in compo-

u = |u|eu
nent form in cartesian coordinates as
In a cartesian coordinate system the three prin-
A =Axx ex ex + Axy ex ey + Axz ex ez
ciple, orthogonal directions are customarily re-
presented by unit vectors, such as {ex , ey , ez } + Ayx ey ex + Ayy ey ey + Ayz ey ez
or {i, j, k}. Here, the first notation is used (see
Fig. 17). The coordinate system is right handed; + Azx ez ex + Azy ez ey + Azz ez ez
that is, if a right-threaded screw rotated from the
x to the y direction, it would advance in the z di- Quantities such as ex ey are called unit dyadics.
rection. A vector can be represented in terms of They are second-order dyadics and have two di-
its components in these directions, as illustrated rections associated with them, ex and ey ; the
in Figure 18. The vector is then written as order of the pair is important. The components
Axx , . . . , Azz are the components of the tensor
u =ux ex + uy ey + uz ez Aij which here is a 3×3 matrix of numbers that
are transformed in a certain way when variables
The magnitude is undergo a linear transformation. The y x momen-
2 tum flux can be defined as the flux of x mo-
u = |u| = u2x +u2y + u2z mentum across an area with unit normal in the y
direction (→ Fluid Mechanics, Chap. 2.2.; intro-
The position vector is duction to → Transport Phenomena, Chap. 2.2.).
Since two directions are involved, a second-
r =xex + yey + zez order dyadic (or tensor) is needed to represent
with magnitude it, and because the y momentum across an area
with unit normal in the x direction may not be the
- same thing, the order of the indices must be kept
r = |r| = x2 +y 2 +z 2
straight. The dyadic A is said to be symmetric if
Aij = Aji
Here, the indices i and j can take the values x,

y, or z; sometimes (x, 1), ( y, 2), (x, 3) are identi-
fied and the indices take the values 1, 2, or 3. The
dyadic A is said to be antisymmetric if
Aij = −Aji
The transpose of A is
Figure 17. Cartesian coordinate system AT

ij = Aji
Any dyadic can be represented as the sum of

a symmetric portion and an antisymmetric por-
tion.
1
Aij = B ij + C ij , B ij ≡ (Aij + Aji ) ,
2
1
C ij ≡ (Aij − Aji )
2
An ordered pair of vectors is a second-order
dyadic.
Figure 18. Vector components
uv = e i e j ui v j
i j
The transpose of this is


(u v)T = v u A:B = Aij Bji
i j
but
Because the dyadics may not be symmetric, the
order of indices and which indices are summed
u v = v u
are important. The order is made clearer when
The Kronecker delta is defined as the dyadics are made from vectors.
( )
1 if i = j (u v) · (w x) =u (v· w) x =u x (v· w)
δij =
0 if i = j
(u v) : (w x) = (u· x) (v· w)
and the unit dyadic is defined as

The dot product of a dyadic and a vector is
δ = ei ej δij  
i j
A·u = ei  Aij uj 
i j
Operations. The dot or scalar product of The cross or vector product is defined by
two vectors is defined as
c =u×v =a |u||v| sin θ, 0 ≤θ ≤π
u· v =|u| |v| cos θ, 0 ≤θ ≤π where a is a unit vector in the direction of u×v.
where θ is the angle between u and v. The scalar The direction of c is perpendicular to the plane
product of two vectors is a scalar, not a vector. It of u and v such that u, v, and c form a right-
is the magnitude of u multiplied by the projec- handed system. If u = v, or u is parallel to v,
tion of v on u, or vice versa. The scalar product then θ = 0 and u×v = 0. The following laws are
of u with itself is just the square of the magnitude valid for cross products.
of u. u×v =−v×u Commutative law fails for
vector product
u· u = |u2 | =u2 u×(v×w) = (u×v)×w Associative law fails for
vector product
u×(v + w) = u×v + u×w Distributive law for vector
The following laws are valid for scalar products product
ex ×ex = ey ×ey = ez ×ez = 0
u·v=v·u Commutative law for scalar ex ×ey = ez , ey ×ez = ex ,
products ez ×ex = ey
u · (v + w) = u · v + u · w Distributive law for scalar
products
ex · ex = ey · ey = ez · ez = 1  
ex ey ez
ex · ey = ex · ez = ey · ez = 0  
u×v= det ux uy uz 
vx vy vz
If the two vectors u and v are written in com-
ponent notation, the scalar product is = ex (uy vz − vy uz ) + ey (uz vz − ux vz )
u· v =ux vx + uy vy + uz vz + ez (ux vy − uy vx )
If u · v = 0 and u and v are not null vectors, This can also be written as
then u and v are perpendicular to each other
and θ = π/2. u×v = εkij ui vj ek
i j
The single dot product of two dyadics is
where

A ·B = ei ej Aik Bkj 

1 if i, j, k is an even permutation of 123
i j k
εijk = −1 if i, j, k is an odd permutation of 123

0
The double dot product of two dyadics is if any two of i, j, k are equal
Thus ε123 = 1, ε132 =- 1, ε312 = 1,ε112 = 0, for ex- can be formed where λ is an eigenvalue. This
ample. expression is
The magnitude of u×v is the same as the area of
a parallelogram with sides u and v. If u×v = 0 λ3 −I1 λ2 +I2 λ −I3 = 0
and u and v are not null vectors, then u and v
An important theorem of Hamilton and Cay-
are parallel. Certain triple products are useful.
ley [43] is that a second-order dyadic satisfies
(u· v) w =u (v· w) its own characteristic equation.
u· (v× w) = v· (w× u) = w· (u× v) A3 −I1 A2 +I2 A −I3 δ = 0 (14)
Thus A3 can be expressed in terms of δ, A, and

u× (v× w) = (u·w) v − (u·v) w
A2 . Similarly, higher powers of A can be ex-
pressed in terms of δ, A, and A2 . Decomposi-
(u× v) × w = (u·w) v − (v·w) u
tion of a dyadic into a symmetric and an anti-
The cross product of a dyadic and a vector is symmetric part was shown above. The antisym-
defined as metric part has zero trace. The symmetric part
can be decomposed into a part with a trace (the
isotropic part) and a part with zero trace (the
A×u = ei ej εklj Aik ul
i j k l deviatoric part).
The magnitude of a dyadic is A = 1/3 δδ : A + 1/2 [A + AT - 2/3 δδ : A] + 1/2 [A - AT ]
Isotropic Deviatoric Antisymmetric
1 3
4
1 41
|A| =A = (A :A ) = 5
T A2ij
2 2 i j
Differentiation. The derivative of a vector is
There are three invariants of a dyadic. They defined in the same way as the derivative of a
are called invariants because they take the same scalar. Suppose the vector u depends on t. Then
value in any coordinate system and are thus an
intrinsic property of the dyadic. They are the du u (t +∆t) − u (t)
= lim
trace of A, A2 , A3 [41]. dt ∆t→0 ∆t
If the vector is the position vector r (t), then the
I = trA = Aii
i
difference expression is a vector in the direction
of ∆ r (see Fig. 19). The derivative

II = trA2 = Aij Aji
dr ∆r r (t +∆t) − r (t)
i j = lim = lim
dt ∆ t→0 ∆t ∆t→0 ∆t

III = trA3 = Aij Ajk Aki is the velocity. The derivative operation obeys
i j k the following laws.
The invariants can also be expressed as d du dv
(u + v) = +
dt dt dt
I1 = I
d du dv
12 (u· v) = ·v+u·
I2 = I − II dt dt dt
2
d du dv
13 (u×v) = ×v+u×
I3 = I − 3 I · II + 2 III = detA dt dt dt
6
d dϕ du
Invariants of two dyadics are available [42]. Be- (ϕu) = u+ ϕ
dt dt dt
cause a second-order dyadic has nine compo-
nents, the characteristic equation If the vector u depends on more than one vari-
able, such as x, y and z, partial derivatives are
det (λ δ − A) = 0 defined in the usual way. For example,
then
if u (x, y, z) , then
∂u u (x +∆x, y, z) − u (x, y, z) ds2 = dr · dr = dx2 + dy 2 + dz 2

= lim
∂x ∆t→0 ∆x
The derivative dr/dt is tangent to the curve in the
Rules for differentiation of scalar and vector direction of motion
products are
dr
u = dt
∂ ∂u
·v+u·
∂v dr
(u·v) = dt
∂x ∂x ∂x
∂ ∂u ∂v Also,
(u×v) = xv +ux
∂x ∂x ∂x
dr
u=
Differentials of vectors are ds
du= dux ex +duy ey +duz ez
d (u ·v) = du ·v+u ·dv

Differential Operators (see also, → Trans-
port Phenomena, Chap. 1.1.4.). The vector dif-
d (u×v) = du×v+u×dv ferential operator (del operator) ∇ is defined in
cartesian coordinates by
∂u ∂u ∂u
du = dx + dy + dz ∂ ∂ ∂
∂x ∂y ∂z ∇ =ex + ey + ez
∂x ∂y ∂z
The gradient of a scalar function is defined

∂ϕ ∂ϕ ∂ϕ
∇ϕ = ex + ey + ez
∂x ∂y ∂z
and is a vector. If ϕ is height or elevation, the gra-

dient is a vector pointing in the uphill direction.
The steeper the hill, the larger is the magnitude
Figure 19. Vector differentiation of the gradient.
The divergence of a vector is defined by
If a curve is given by r (t), the length of the
curve is [44, p. 373] ∇ ·u =
∂ux ∂uy
+ +
∂uz
∂x ∂y ∂z
b 1
dr dr and is a scalar. For a volume element ∆V , the
L = · dt
dt dt net outflow of a vector u over the surface of the
a
element is
The arc-length function can also be defined:

t 1 u ·ndS
dr dr ∗
s (t) = · dt ∆S
dt∗ dt∗
a
This is related to the divergence by [45, p. 411]
This gives
1
2 2 2 2 ∇ ·u = lim u ·ndS
ds dr dr dx dy dz ∆V →0 ∆V
= · = + + ∆S
dt dt dt dt dt dt
Thus, the divergence is the net outflow per unit
Because volume.
The curl of a vector is defined by
dr = dxex +dyey + dzez
is called the Laplacian operator ∇×(∇ϕ) = 0.

∂ ∂ ∂ The curl of the gradient of ϕ is zero.
∇×u = ex + ey + ez ×
∂x ∂y ∂z
∇ · (∇×u) = 0
(ex ux + ey uy + ez uz )

The divergence of the curl of u is zero. Formulas
= ex
∂uz
−
∂uy
+ey
∂ux
−
∂uz useful in fluid mechanics are
∂y ∂z ∂z ∂x
∇ · (∇v)T = ∇ (∇ ·v)
∂uy ∂ux
+ ez −
∂x ∂y ∇ · (τ ·v) = v · (∇ ·τ ) +τ : ∇v
and is a vector. It is related to the integral
1
v ·∇v= ∇ (v ·v) − v× (∇×v)
u ·ds = us ds 2
C C If a coordinate system is transformed by a rota-
which is called the circulation of u around path tion and translation, the coordinates in the new
C. This integral depends on the vector and the system (denoted by primes) are given by
contour C, in general. If the circulation does not       
depend on the contour C, the vector is said to be x l11 l12 l13 x a1
      
irrotational; if it does, it is rotational. The rela- y  = l21 l22 l23  y  + a2 
tionship with the curl is [45, p. 419] z l31 l32 l33 z a3

1 Any function that has the same value in all coor-
n · (∇×u) = lim u ·ds
∆S→0 ∆S dinate systems is an invariant. The gradient of an
C
Thus, the normal component of the curl equals invariant scalar field is invariant; the same is true
the net circulation per unit area enclosed by the for the divergence and curl of invariant vectors
contour C. fields.
The gradient, divergence, and curl obey a dis- The gradient of a vector field is required in
tributive law but not a commutative or associa- fluid mechanics because the velocity gradient is
tive law. used. It is defined as
∂vj
∇ (ϕ + ψ) = ∇ϕ +∇ψ ∇v= ei e j and
i j
∂xi
∇ · (u + v) = ∇ ·u + ∇ ·v
∂vi
(∇v)T = e i ej
∇× (u + v) = ∇×u+∇×v i j
∂xj
∇ ·ϕ = ϕ∇ The divergence of dyadics is defined

 
∇ ·u = u ·∇ ∂τji
∇ ·τ = ei   and
Useful formulas are [46] i j
∂xj
∇ · (ϕu) = ∇ϕ ·u + ϕ∇ ·u  
∂
∇ · (ϕu v) = ei  (ϕ uj vi )
∇ × (ϕu) = ∇ϕ×u + ϕ ∇ × u ∂xj
i j
∇ · (u×v) = v · (∇×u) − u · (∇×v) where τ is any second-order dyadic.

Useful relations involving dyadics are
∇ × (u×v) = v ·∇u − v (∇ ·u) − u · ∇v+u (∇ ·v)
(ϕ δ : ∇v) = ϕ (∇ ·v)
∇ × (∇ × u) = ∇ (∇ ·u) − ∇2 u
∇ · (ϕ δ) = ∇ϕ
∂2ϕ ∂2ϕ ∂2ϕ
∇ · (∇ϕ) = ∇2 ϕ = 2
+ 2
+ , where ∇2
∂x ∂y ∂z 2
∇ · (ϕτ ) = ∇ϕ · τ + ϕ∇ ·τ
Vector Integration [45, pp. 206 – 212]. If u
is a vector, then its integral is also a vector.

n t:τ = t ·τ ·n = τ : n t
u (t) dt = ex ux (t) dt +ey uy (t) dt
A surface can be represented in the form

f (x, y, z) = c = constant + ez uz (t) dt
The normal to the surface is given by If the vector u is the derivative of another vector,
∇f then
n=
|∇ f | dv dv
u= , u (t) dt = dt = v+constant
provided the gradient is not zero. Operations can dt dt
be performed entirely within the surface. Define If r (t) is a position vector that defines a curve
[47] C, the line integral is defined by

∂ u · dr = (ux dx + uy dy + uz dz)
δ II ≡ δ − n n , ∇II ≡ δ II ·∇, ≡ n ·∇
∂n C C
v II ≡ δ II ·v, vn ≡ n ·v Theorems about this line integral can be written

in various forms.
Then a vector and del operator can be decom- Theorem [44, p. 460]. If the functions appear-
posed into ing in the line integral are continuous in a do-
∂ main D, then the line integral is independent of
v =v II +nvn , ∇ = ∇II + n
∂n the path C if and only if the line integral is zero
The velocity gradient can be decomposed into on every simple closed path in D.
Theorem [44, p. 461]. If u = ∇ϕ where ϕ is
∂v II
∇v= ∇II v II + (∇II n) vn + n∇II vn + n single-valued and has continuous derivatives in
∂n
D, then the line integral is independent of the
∂vn path C and the line integral is zero for any closed
+n n curve in D.
∂n
The surface gradient of the normal is the nega- Theorem [44, p. 460]. If f, g, and h are contin-
tive of the curvature dyadic of the surface. uous functions of x, y, and z, and have continuous
first derivatives in a simply connected domain D,
∇II n = −B then the line integral

The surface divergence is then ( f dx + gdy + hdz)
C
∇II ·v = δ II : ∇v= ∇II ·v II − 2 H vn
is independent of the path if and only if
where H is the mean curvature.
∂h ∂g ∂f ∂h ∂g ∂f
1 = , = , =
H = δ II : B ∂y ∂z ∂z ∂x ∂x ∂y
2
or if f, g, and h are regarded as the x, y, and z
The surface curl can be a scalar components of a vector v:
∇II × v= − εII : ∇v ∇ × v= 0
= − εII : ∇II v II = − n· (∇ × v) , Consequently, the line integral is independent of
the path (and the value is zero for a closed con-
εII =
tour) if the three components in it are regarded
n·ε
as the three components of a vector and the vec-
tor is derivable from a potential (or zero curl).
or a vector The conditions for a vector to be derivable from
a potential are just those in the third theorem. In
∇II × v ≡ ∇II × v II = n∇II × v=n n ·∇ × v
two dimensions this reduces to the more usual
theorem.
Theorem [45, p. 207]. If M and N are continu- volume, divided by the volume. If the vector re-
ous functions of x and y that have continuous first presents the flow of energy and the divergence is
partial derivatives in a simply connected domain positive at a point P, then either a source of en-
D, then the necessary and sufficient condition for ergy is present at P or energy is leaving the region
the line integral around P so that its temperature is decreasing.
If the vector represents the flow of mass and the
(M dx + N dy) divergence is positive at a point P, then either a
C source of mass exists at P or the density is de-
creasing at the point P. For an incompressible
to be zero around every closed curve C in D is fluid the divergence is zero and the rate at which
∂M ∂N fluid is introduced into a volume must equal the
= rate at which it is removed.
∂y ∂x
Various theorems follow from the divergence
If a vector is integrated over a surface with in- theorem.
cremental area d S and normal to the surface n, Theorem. If ϕ is a solution to Laplace’s equa-
then the surface integral can be written as tion

u · dS = u ·ndS ∇2 ϕ = 0
S S
in a domain D, and the second partial deriva-
If u is the velocity then this integral represents tives of ϕ are continuous in D, then the integral
the flow rate past the surface S. of the normal derivative of ϕ over any piece-
wise smooth closed orientable surface S in D is
Divergence Theorem [45], [46]. If V is a zero. Suppose u = ϕ ∇ψ satisfies the conditions
volume bounded by a closed surface S and u of the divergence theorem: then Green’s theo-
is a vector function of position with continuous rem results from use of the divergence theorem
derivatives, then [44, p. 451].

∇ ·udV = n ·udS = u ·ndS = u · dS ∂ψ
ϕ∇2 ψ +∇ϕ · ∇ψ dV = ϕ dS
V S S S ∂n
V S
where n is the normal pointing outward to S. The
normal can be written as and

∂ψ ∂ϕ
n =ex cos (x, n) +ey cos (y, n) +ez cos (z, n) ϕ∇2 ψ − ψ∇2 ϕ dV = ϕ −ψ dS
∂n ∂n
V S
where, for example, cos (x, n) is the cosine of the
angle between the normal n and the x axis. Then Also if ϕ satisfies the conditions of the theorem
the divergence theorem in component form is and is zero on S then ϕ is zero throughout D. If
two functions ϕ and ψ both satisfy the Laplace
∂ux ∂uy ∂uz equation in domain D, and both take the same
+ + dxdydz =
∂x ∂y ∂z values on the bounding curve C, then ϕ = ψ; i.e.,
V
the solution to the Laplace equation is unique.

The divergence theorem for dyadics is
[ux cos (x, n) + uy cos ( y, n) + uz cos (z, n)] dS

S
∇ · τ dV = n · τ dS
If the divergence theorem is written for an incre- V S
mental volume

1
∇ ·u = lim un dS Stokes Theorem [45], [46, p. 106]. Stokes
∆V →0 ∆V
∆S theorem says that if S is a surface bounded by
the divergence of a vector can be called the in- a closed, nonintersecting curve C, and if u has
tegral of that quantity over the area of a closed continuous derivatives then
0 Curvilinear Coordinates. Many of the re-
u ·dr = (∇ × u) ·n dS = (∇ × u) ·dS lations given above are proved most easily by
C S S using tensor analysis rather than dyadics. Once
The integral around the curve is followed in the proven, however, the relations are perfectly gen-
counterclockwise direction. In component nota- eral in any coordinate system. Displayed here are
tion, this is the specific results for cylindrical and spherical
0 geometries. Results are available for a few other
[ux cos (x, s) + uy cos ( y, s) + uz cos (z, s)] ds = geometries: parabolic cylindrical, paraboloidal,
C elliptic cylindrical, prolate spheroidal, oblate

spheroidal, ellipsoidal, and bipolar coordinates
∂uz
−
∂uy
cos (x, n) +
∂ux
−
∂uz [41], [48].
∂y ∂z ∂z ∂x For cylindrical coordinates, the geometry is
S
shown in Figure 20. The coordinates are related
to cartesian coordinates by
∂uy ∂ux
cos ( y, n) + − cos (z, n) dS
∂x ∂y
x = rcosθ r = x2 + y 2
y
Applied in two dimensions, this results in y = rsinθ θ = arctan x
z=z z=z
Green’s theorem in the plane:
0
∂N ∂M The unit vectors are related by
(M dx + N dy) = − dxdy
∂x ∂y
C S
er = cosθex + sinθey ex = cosθer − sinθeθ
The formula for dyadics is eθ = − sinθex + cosθey ey = sinθer + cosθeθ
ez = ez ez = ez
0
n · (∇ × τ ) dS = τ T ·dr
S C Derivatives of the unit vectors are
deθ = − er dθ , der =eθ dθ, dez = 0

Representation. Two theorems give infor-
mation about how to represent vectors that obey Differential operators are given by [41]
certain properties. ∂ eθ ∂ ∂
Theorem [45, p. 422]. The necessary and suf- ∇ =er + + ez ,
∂r r ∂θ ∂z
ficient condition that the curl of a vector vanish
identically is that the vector be the gradient of ∂ϕ eθ ∂ϕ ∂ϕ
∇ϕ = er + + ez
some function. ∂r r ∂θ ∂z

Theorem [45, p. 423]. The necessary and suf- 1 ∂ ∂ϕ 1 ∂ 2ϕ ∂2ϕ
∇2 ϕ = r + 2 +
ficient condition that the divergence of a vector r ∂r ∂r r ∂θ2 ∂z 2
vanish identically is that the vector is the curl of
some other vector. ∂ 2 ϕ 1 ∂ϕ 1 ∂2ϕ ∂2ϕ
= + + 2 +
∂r2 r ∂r r ∂θ2 ∂z 2
Leibniz Formula. In fluid mechanics and 1 ∂ 1 ∂vθ ∂vz
transport phenomena, an important result is the ∇ ·v= (r vr ) + +
r ∂r r ∂θ ∂z
derivative of an integral whose limits of inte-
gration are moving. Suppose the region V (t) is

moving with velocity v s . Then Leibniz’s rule 1 ∂vz ∂vθ ∂vr ∂vz
∇ × v = er − +eθ −
holds: r ∂θ ∂z ∂z ∂r

d ∂ϕ 1 ∂ 1 ∂vr
ϕdV = dV +ez (r vθ ) −
dt ∂t r ∂r r ∂θ
V (t) V (t)

+ ϕv s ·ndS
S
Derivatives of the unit vectors are

1 ∂ 1 ∂τθr ∂τzr τθθ
∇ · τ = er (r τrr ) + + − + ∂er ∂eθ
r ∂r r ∂θ ∂z r = eθ , = − er
∂θ ∂θ

1 ∂ 2 1 ∂τθθ ∂τzθ τθr − τrθ
+eθ r τrθ + + + + ∂er ∂eθ
r2 ∂r r ∂θ ∂z r =eφ sin θ, = eφ cos θ,
∂ϕ ∂ϕ

1 ∂ 1 ∂τθz ∂τzz
+ez (r τrz ) + + ∂eφ
r ∂r r ∂θ ∂z = − er sin θ − eθ cos θ
∂ϕ
∂vr ∂vθ ∂vz Others 0

∇v=er er + e r eθ + e r ez + Differential operators are given by [41]
∂r ∂r ∂r
∂ 1 ∂ 1 ∂
1 ∂vr vθ 1 ∂vθ vr ∇ = er + eθ + eφ ,
+eθ er − +eθ eθ + + ∂r r ∂θ r sin θ ∂ϕ
r ∂θ r r ∂θ r
1 ∂vz ∂vr ∂vθ ∂vz

+ e θ ez + e z er + ez eθ + ez ez
r ∂θ ∂z ∂z ∂z ∂ψ 1 ∂ψ 1 ∂ψ
∇ψ = er + eθ + eφ
∂r r ∂θ r sin θ ∂ϕ

∂ 1 ∂
∇2 v=er (r vr )
∂r r ∂r
1 ∂ ∂ψ 1 ∂ ∂ψ
∇2 ψ = r2 + 2 sin θ +
1 ∂ 2 vr ∂ 2 vr 2 ∂vθ r2 ∂r ∂r r sin θ ∂θ ∂θ
+ + − +
r2 ∂θ2 ∂z 2 r 2 ∂θ
1 ∂2ψ
+
∂ 1 ∂ r 2 sin2 θ ∂ϕ2
+eθ (r vθ )
∂r r ∂r
1 ∂ 2 1 ∂
1 ∂ 2 vθ ∂ 2 vθ 2 ∂vr ∇ ·v= r vr + (vθ sin θ) +
+ 2 2
+ 2
+ 2 + r 2 ∂r r sin θ ∂θ
r ∂θ ∂z r ∂θ
1 ∂vφ
1 ∂ ∂vz 1 ∂ 2 vz ∂ 2 vz +
+ez r + 2 + r sin θ ∂ϕ
r ∂r ∂r r ∂θ2 ∂z 2
For spherical coordinates, the geometry is

shown in Figure 21. The coordinates are related 1 ∂ 1 ∂vθ
∇ × v=er vφ sin θ − +
to cartesian coordinates by r sin θ ∂θ r sin θ ∂ϕ

x = r sinθ cosϕ r = x2 +
y2 + z2
1 ∂vr 1 ∂
y = r sinθ sinϕ θ = arctan x2 + y 2 /z +eθ − r vφ +
y r sin θ ∂ϕ r ∂r
z = r cosθ ϕ = arctan x

1 ∂ 1 ∂vr
+eφ (r vθ ) −
The unit vectors are related by r ∂r r ∂θ
er = sin θcos ϕex + sin θ sin ϕey +cos θez

1 ∂ 2 1 ∂
eθ = cos θcos ϕex +cos θ sin ϕey − sin θez ∇ · τ = er r τrr + (τθr sin θ)
r 2 ∂r r sin θ ∂θ
eφ = − sin ϕex + cos ϕey

1 ∂τφr τθθ + τφφ
+ − +
r sin θ ∂ϕ r
ex = sin θ cos ϕer + cos θ cos ϕeθ − sin ϕeφ

1 ∂ 3 1 ∂
ey = sin θ sin ϕer + cos θ sin ϕeθ + cos ϕeφ +eθ r τrθ + (τθθ sin θ)
r3 ∂r r sin θ ∂θ
ez = cos θer − sin θeθ


1 ∂τφθ τθr − τrθ − τφφ cotθ
+ + +
r sin θ ∂ϕ r

1 ∂ 3 1 ∂
+eφ r τrφ + τθφ sin θ
r3 ∂r r sin θ ∂θ

1 ∂τφφ τφr − τrφ + τφθ cotθ
+ +
r sin θ ∂ϕ r
∂vr ∂vθ ∂vφ

∇v=er er + e r eθ + e r eφ +
∂r ∂r ∂r

1 ∂vr vθ 1 ∂vθ vr
+eθ er − +eθ eθ + +
r ∂θ r r ∂θ r

1 ∂vφ 1 ∂vr vφ
+eθ eφ + eφ er − +
r ∂θ r sin θ ∂ϕ r

1 ∂vθ vφ
+eφ eθ − cotθ +
r sin θ ∂ϕ r
Figure 20. Cylindrical coordinate system
1 ∂vφ vr vθ
+eφ eφ + + cotθ
r sin θ ∂ϕ r r

∂ 1 ∂ 2 1 ∂
∇2 v=er r v r + 2
∂r r 2 ∂r r sin θ ∂θ

∂vr 1 ∂ 2 vr
sin θ + 2 2
∂θ r sin θ ∂ϕ2

2 ∂ 2 ∂vφ
− (vθ sin θ) − 2
r2 sin θ ∂θ r sin θ ∂ϕ

1 ∂ ∂vθ 1 ∂
+eθ r2 +
r2 ∂r ∂r r2 ∂θ

1 ∂ 1 ∂ 2 vθ
(vθ sin θ) + 2 2
sin θ ∂θ r sin θ ∂ϕ2
Figure 21. Spherical coordinate system
2 ∂vr 2 cotθ ∂vφ
+ − 2
r2 ∂θ r sin θ ∂ϕ

1 ∂ ∂vφ 1 ∂ 6. Ordinary Differential Equations
+eφ r2 + 2
r2 ∂r ∂r r ∂θ
as Initial Value Problems

1 ∂ 1 ∂ 2 vφ
vφ sin θ + 2 2 A differential equation for a function that de-
sin θ ∂θ r sin θ ∂ϕ2
pends on only one variable (often time) is called
an ordinary differential equation. The general
2 ∂vr 2 cotθ ∂vθ
+ + 2 solution to the differential equation includes
r2 sin θ ∂ϕ r sin θ ∂ϕ
many possibilities; the boundary or initial con-
ditions are required to specify which of those
are desired. If all conditions are at one point, 1 1

the problem is an initial value problem and can = kt +
c c0
be integrated from that point on. If some of
the conditions are available at one point and For other ordinary differential equations an in-
others at another point, the ordinary differen- tegrating factor is useful. Consider the problem
tial equations become two-point boundary value governing a stirred tank with entering fluid hav-
problems, which are treated in Chapter 7. Initial ing concentration cin and flow rate F, as shown
value problems as ordinary differential equa- in Figure 22. The flow rate out is also F and the
tions arise in control of lumped-parameter mod- volume of the tank is V . If the tank is completely
els, transient models of stirred tank reactors, and mixed, the concentration in the tank is c and the
generally in models where no spatial gradients concentration of the fluid leaving the tank is also
occur in the unknowns. c. The differential equation is then
dc
V = F (cin − c) , c (0) = c0
dt
6.1. Solution by Quadrature
Upon rearrangement,
When only one equation exists, even if it is non- dc F F
linear, solving it by quadrature may be possible. + c = cin
dt V V
For
is obtained. An integrating factor is used to solve
dy this equation. The integrating factor is a function
= f ( y)
dt that can be used to turn the left-hand side into
an exact differential and can be found by using
y (0) = y0 Fréchet differentials [49]. In this case,
the problem can be separated
Ft dc F d Ft
exp + c = exp c
V dt V dt V
dy
= dt
f ( y) Thus, the differential equation can be written as
and integrated:
d Ft Ft F
exp c = exp cin
dt V V V
y t
dy
= dt = t This can be integrated once to give
f ( y )
y0 0
t
Ft F F t
If the quadrature can be performed analytically exp c = c (0) + exp cin t dt
V V V
then the exact solution has been found. 0
For example, consider the kinetics problem or
with a second-order reaction.
Ft
dc c (t) = exp − c0
= − k c2 , c (0) = c0 V
dt
t
To find the function of the concentration versus F F (t − t )
+ exp − cin t dt
time, the variables can be separated and inte- V V
0
grated.
If the integral on the right-hand side can be calcu-
dc
= − kdt , lated, the solution can be obtained analytically.
c2
If not, the numerical methods described in the
1 next sections can be used. Laplace transforms
− = − kt+D
c can also be attempted. However, an analytic so-
lution is so useful that quadrature and an inte-
Application of the initial conditions gives the
grating factor should be tried before resorting to
solution:
numerical solution.
The initial conditions would have to be spec-

ified for variables y1 (0), . . . , yn (0), or equiva-
lently y (0), . . . , y(n−1) (0). The set of equations
is then written as
dy
=f ( y, t)
dt
All the methods in this chapter are described for
a single equation; the methods apply to the multi-
ple equations as well. Taking the single equation
in the form
Figure 22. Stirred tank dy
= f ( y)
dt
multiplying by dt, and integrating once yields
6.2. Explicit Methods
t
n+1 t
n+1
dy
Consider the ordinary differential equation dt = f y t dt
dt
tn tn
dy
= f ( y) This is
dt
Multiple equations that are still initial value t
n+1
problems can be handled by using the same tech- n+1 n dy

y = y + dt
niques discussed here. A higher order differen- dt
tn
tial equation

The last substitution gives a basis for the var-
y (n) +F y (n−1) , y (n−2) , . . . , y , y = 0 ious methods. Different interpolation schemes
for y (t) provide different integration schemes;
with initial conditions using low-order interpolation gives low-order
integration schemes [50], [51].
Gi y (n−1) (0) , y (n−2) (0) , . . . , y (0) , y (0) = 0 Euler’s method is first order
i = 1, . . . , n y n+1 = y n + ∆tf (y n )
can be converted into a set of first-order equa-

tions. By using Adams – Bashforth Methods. The second-
order Adams – Bashforth method is
d(i−1) y d (i−2) dyi−1
yi ≡ y (i−1) = = y = ∆t
dt(i−1) dt dt y n+1 = y n + 3 f ( y n ) − f y n−1
2
the higher order equation can be written as a set
of first-order equations: The fourth-order Adams – Bashforth method is
∆t
dy1 y n+1 = y n + 55 f ( y n ) − 59 f y n−1
= y2 24
dt

dy2 + 37 f y n−2 − 9f y n−3
= y3
dt Notice that the higher order explicit methods re-
dy3 quire knowing the solution (or the right-hand
= y4 side) evaluated at times in the past. Because
dt
these were calculated to get to the current time,
...
this presents no problem except for starting the
dyn evaluation. Then, Euler’s method may have to be
= − F ( yn−1 , yn−2 , . . . , y2 , y1 ) used with a very small step size for several steps
dt
Table 6. Properties of integration methods for ordinary differential equations
Method Error term Order Function evaluations per step Stability limit, λ ∆t≤
Explicit methods
h2
Euler 2 y 1 1 2.0
5 3
Second-order Adams – Bashforth 12 h y 2 1
251 5 (5)
Fourth-order Adams – Bashforth 720 h y 4 1 0.3
Second-order Runge – Kutta
(midpoint) 2 2 2.0
Runge – Kutta – Gill 4 4 2.8
Runge – Kutta – Feldberg y n +1
−z n +1
5 6 3.0
Predictor – corrector methods

Second-order Runge – Kutta 2 2 2.0
Adams, fourth-order 2 2 1.3
Implicit methods, stability limit ∞

Backward Euler 1 many, iterative ∞∗
Trapezoid rule − 12
1
h3 y 2 many, iterative 2∗
Fourth-order Adams – Moulton 4 many, iterative 3∗
∗
Oscillation limit, λ ∆t ≤.
to generate starting values at a succession of time

points. The error terms, order of the method, ∆t n
y n+1 = y n + [ f + f (tn +∆t , y n +∆t f n )]
function evaluations per step, and stability limi- 2
tations are listed in Table 6. The advantage of the The midpoint scheme is another second-order
fourth-order Adams – Bashforth method is that Runge – Kutta method:
it uses only one function evaluation per step and
∆t n ∆t n
yet achieves high-order accuracy. The disadvan- y n+1 = y n +∆t f tn + ,y + f
2 2
tage is the necessity of using another method to
start. A popular fourth-order method is the
Runge – Kutta – Gill method with the formulas
Runge – Kutta Methods. Runge – Kutta
k1 = ∆t f (tn , y n )
methods are explicit methods that use several
function evaluations for each time step. The
∆t n k1
general form of the methods is k2 = ∆t f tn + ,y +
2 2

v
y n+1 = y n + w i ki k3 = ∆t f tn +
∆t n
, y + a k 1 + b k2
i=1 2
with k4 = ∆t f (tn + ∆t, y n + c k2 + d k3 )
 

i−1
1 1
ki = ∆t f tn + ci ∆t , y n + aij kj  y n+1 = y n + (k1 + k4 ) + (b k2 + d k3 )
j=1
6 3
√ √
Runge – Kutta methods traditionally have been 2−1 2− 2
a = , b = ,
writen for f (t, y) and that is done here, too. If 2 2
these equations are expanded and compared with √ √
a Taylor series, restrictions can be placed on the 2 2
c = − , d=1 +
parameters of the method to make it first order, 2 2
second order, etc. Even so, additional parameters Another fourth-order Runge – Kutta method is
can be chosen. A second-order Runge – Kutta given by the Runge – Kutta – Feldberg formu-
method is las [52]; although the method is fourth-order, it
achieves fifth-order accuracy. The popular inte- For other problems the most important criterion
gration package RKF 45 is based on this method. for choosing a method is probably the time the
user spends setting up the problem.
k1 = ∆t f (tn , y n )
The stability of an integration method is best
estimated by determining the rational polyno-
∆t n k1
k2 = ∆t f tn + ,y + mial corresponding to the method. Apply this
4 4
method to the equation

3 3 9
k3 = ∆t f tn + ∆t , y n + k1 + k2 dy
8 32 32 = − λ y , y (0) = 1
dt

12 1932 and determine the formula for rmn :
k4 = ∆t f tn + ∆t , y n + k1
13 2197
y k+1 =rmn (λ ∆t) y k
7200 7296
− k2 + k3
2197 2197 The rational polynomial is defined as

439 pn (z)
k5 = ∆t f tn +∆t , y n + k1 rmn (z) = ≈ e−z
216 qm (z)
and is an approximation to exp (− z), called a
3680 845
− 8 k2 + k3 − k4 Padé approximation. The stability limits are the
513 4104
largest positive z for which

∆t n 8
k6 = ∆t f tn + ,y − k1 + 2 k2
2 27 |rmn (z) | ≤ 1
The method is A acceptable if the inequality
3544 1859 11
− k3 + k4 − k5 holds for Re z > 0. It is A (0) acceptable if the in-
2565 4104 40
equality holds for z real, z > 0 [60]. The method
y n+1 = y n +
25
k1 +
1408
k3 +
2197 1
k4 − k 5
will not induce oscillations about the true solu-
216 2565 4104 5 tion provided
16 6656
z n+1 = y n + k1 + k3 rmn (z) > 0
135 12 825
28 561 9 2
A method is L acceptable if it is A acceptable
+ k4 − k5 + k6 and
56 430 50 55
The value of yn+1 − zn+1 is an estimate of the lim rmn (z) = 0
error in yn+1 and can be used in step-size control z→∞
schemes. For example, Euler’s method gives

Generally, a high-order method should
be used to achieve high accuracy. The y n+1 =y n −λ ∆t y n or y n+1 = (1 −λ ∆t) y n
Runge – Kutta – Gill method is popular be-
cause it is high order and does not require or rmn = 1 − λ∆t
a starting method (as does the fourth-order
Adams – Bashforth method). However, it re- The stability limit is then
quires four function evaluations per time step,
or four times as many as the Adams – Bashforth λ ∆t ≤ 2
method. For problems in which the function The Euler method will not oscillate provided
evaluations are a significant portion of the cal-
culation time this might be important. Given the λ ∆t ≤ 1
speed of computers and the widespread avail-
ability of microcomputers, the efficiency of a The stability limits listed in Table 6 are obtained
method is most important only for very large in this fashion. The limit for the Euler method
problems that are going to be solved many times. is 2.0; for the Runge – Kutta – Gill method it is
2.785; for the Runge – Kutta – Feldberg method the two-step calculation y2 . Then an improved
it is 3.020. The rational polynomials for the solution at the new time is given by
various explicit methods are illustrated in Fig-
2p y 2 − y 1
ure 23. As can be seen, the methods approxi- y =
2p − 1
mate the exact solution well as λ ∆t approaches
zero, and the higher order methods give a better This gives a good estimate provided ∆t is small
approximation at high values of λ ∆t. enough that the method is truly convergent with
LIVE GRAPH order p. This process can also be repeated in
Click here to view the same way Romberg’s method was used for
quadrature (see Section 2.4).
The accuracy of a numerical calculation de-
pends on the step size used, and this is chosen
automatically by efficient codes. For example, in
the Euler method the local truncation error LTE
is
∆t2
LTE = y
2 n
Yet the second derivative can be evaluated by
using the difference formulas as

yn = ∇ ∆t yn = ∆t yn − yn−1 =
Figure 23. Rational approximations for explicit methods ∆t ( fn − fn−1 )

a) Euler; b) Runge – Kutta – 2; c) Runge – Kutta – Gill;
d) Exact curve; e) Runge – Kutta – Feldberg Thus, by monitoring the difference between the
right-hand side from one time step to another, an
In solving sets of equations
estimate of the truncation error is obtained. This
dy error can be reduced by reducing ∆t. If the user
= A y + f , y (0) = y0
dt specifies a criterion for the largest local error es-
all the eigenvalues of the matrix A must be ex- timate, then ∆t is reduced to meet that criterion.
amined. Finlayson [50] and Amundson [53, Also, ∆t is increased to as large a value as pos-
p. 197 – 199] both show how to transform these sible, because this shortens computation time. If
equations into an orthogonal form so that each the local truncation error has been achieved (and
equation becomes one equation in one unknown, estimated) by using a step size ∆t 1
for which single equation analysis applies. For
LTE = c ∆tp1
linear problems the eigenvalues do not change,
so the stability and oscillation limits must be sat- and the desired error is ε, to be achieved using a
isfied for every eigenvalue of the matrix A. When step size ∆t 2
solving nonlinear problems the equations are lin-
earized about the solution at the local time, and ε = c ∆tp2
the analysis applies for small changes in time,
after which a new analysis about the new solu- then the next step size ∆t 2 is taken from
tion must be made. Thus, for nonlinear problems p
LTE ∆t1
the eigenvalues keep changing. =
ε ∆t2
Richardson extrapolation can be used to im-
prove the accuracy of a method. Step forward Generally, things should not be changed too of-
one step ∆t with a p-th order method. Then redo ten or too drastically. Thus one may choose not
the problem, this time stepping forward from the to increase ∆t by more than a factor (such as 2)
same initial point but in two steps of length ∆t/2, or to increase ∆t more than once every so many
thus ending at the same point. Call the solution steps (such as 5) [54]. In the most sophisticated
of the one-step calculation y1 and the solution of codes the alternative exists to change the order
of the method as well. In this case, the trunca- Here, the superscript k refers to an iteration
tion error of the orders one higher and one lower counter. The successive substitution method
than the current one are estimated, and a choice is guaranteed to converge, provided the first
is made depending on the expected step size and derivative of the function is bounded and a
work. small enough time step is chosen. Thus, if it
has not converged within a few iterations, ∆t
can be reduced and the iterations begun again.
6.3. Implicit Methods The Newton – Raphson method (see Section 1.2)
would solve the problem as
By using different interpolation formulas, in- ∂ f
volving yn+1 , implicit integration methods can y n+1, k+1 = ∆t β0 f y n+1,k +∆t β0
be derived. Implicit methods result in a nonlin- ∂y yn+1,k
ear equation to be solved for yn+1 so that itera-
tive methods must be used. The backward Euler y n+1,k+1 − y n+1,k + wn
method is a first-order method: or

y n+1 =y n + ∆t f y n+1 ∂ f
I − ∆t β0 y n+1,k+1 − y n+1, k =
∂y yn+1,k
The trapezoid rule (see Section 2.4) is a second-
order method: ∂ f
∆t β0 f y n+1,k + wn −∆t β0 y n+1,k
∆t ∂y yn+1,k
y n+1 = y n + f ( y n ) + f y n+1
2 For multiple equations, I is the Dirac Kronecker
When the trapezoid rule is used with the finite function δij , and ∂f /∂y is the Jacobian ∂fi /∂yj .
difference method for solving partial differen- As ∆t becomes smaller the conditions for con-
tial equations it is called the Crank – Nicolson vergence are more likely to be satisfied, but if
method. Adams methods exist as well, and the the solution does not converge, ∆t can be re-
fourth-order Adams – Moulton method is duced and the process repeated. In many com-
puter codes, iteration is allowed to proceed only
∆t
y n+1 = y n + 9 f y n+1 + 19 f ( y n ) a fixed number of times (e.g., three) before ∆t
24
is reduced. Because a good history of the func-
tion is available from previous time steps, a good
−5 f y n−1 + f y n−2
initial guess is usually possible.
The properties of these methods are given in Ta- The best software packages for stiff equations
ble 6. The implicit methods are stable for any (see Section 6.4) use Gear’s backward differ-
step size but do require the solution of a set of ence formulas. The formulas of various orders
nonlinear equations, which must be solved it- are [56], [57, p. 263]
eratively. An application to dynamic distillation
problems is given in [55]. 1 : y n+1 = y n +∆t f y n+1
All these methods can be written in the form
4 1 2
2 : y n+1 = y n − y n−1 + ∆t f y n+1

k
k
3 3 3
y n+1 = αi y n+1−i +∆t βi f y n+1−i
i=1 i=0 18 n 9 n−1 2 n−2

3 : y n+1 = y − y + y
or 11 11 11
6
y n+1 = ∆t β0 f y n+1 + wn + ∆t f y n+1
11
where wn represents known information. This
48 n 36 n−1 16 n−2 3 n−3
equation (or set of equations for more than one 4 : y n+1 = y − y + y − y
differential equation) can be solved by using suc- 25 25 25 25
cessive substitution: 12
+ ∆t f y n+1
25
y n+1, k+1 = ∆t β0 f y n+1, k +wn
300 n 300 n− 1 200 n−2

5 : y n+1 = y − y + y ∆t
137 137 137 y n+1 = y n + 9 f ȳ n+1 + 19 f ( y n ) + . . .
24
75 n−3 12 n− 4 The last step can be applied over and over, if de-
− y + y
137 137 sired. The stability properties of these methods
60 are listed in Table 6. Step-size control can also
+ ∆t f y n+1 be employed for these methods.
137
The stability properties of these methods are de-
termined in the same way as explicit methods. 6.4. Stiffness
They are always expected to be stable, no matter
what the value of ∆t is, and this is confirmed in Why is it desirable to use implicit methods that
Figure 24. lead to sets of algebraic equations that must be
LIVE GRAPH solved iteratively whereas explicit methods lead
Click here to view
to a direct calculation? The reason lies in the sta-
bility limits; to understand their impact, the con-
cept of stiffness is necessary. When modeling a
physical situation, the time constants governing
different phenomena should be examined. Con-
sider flow through a packed bed, as illustrated in
Figure 25.
Figure 25. Flow through packed bed
Figure 24. Rational approximations for implicit methods The superficial velocity u is given by
a) Backward Euler; b) Exact curve; c) Trapezoid; d) Euler Q
u =
Predictor – corrector methods can be em- Aϕ
ployed in which an explicit method is used to where Q is the volumetric flow rate, A is the
predict the value of yn+1 . This value is then used cross-sectional area, and ϕ is the void fraction.
in an implicit method to evaluate f ( yn+1 ). The A time constant for flow through the device is
first-order method is merely the Runge – Kutta then
method described above. L ϕAL
tflow = =
n+ 1 n n u Q
ȳ = y +∆t f ( y )
where L is the length of the packed bed. If a
n+1 n ∆t n+1 chemical reaction occurs, with a reaction rate
y = y + f ȳ + f ( yn )
2 given by
Note we do not iterate on yn+1 , as we Moles
= − kc
would in implicit methods. The fourth-order Volume time
Adams predictor – corrector method uses the where k is the rate constant (time−1 ) and c is the
Adams – Bashforth method to provide a pre- concentration (moles/volume), the characteris-
dicted value: tic time for the reaction is
∆t 1
ȳ n+ 1 = y n + [55 f ( y n ) + . . . ] trxn =
24 k
and the Adams – Moulton method to correct it: If diffusion occurs inside the catalyst, the time
constant is
can be found. If a time step larger than the small-

ε R2
tinternal diffusion = est time constant is used, then any phenomena
De
represented by that smallest time constant will
where ε is the porosity of the catalyst, R is the be overlooked – at least transients in it will be
catalyst radius, and De is the effective diffusion smeared over. However, the method will still be
coefficient inside the catalyst. The time constant stable. Thus, if the very rapid transients of part of
for heat transfer is the model are not of interest, they can be ignored
and an implicit method used.
R2 s Cs R2 The idea of stiffness is best explained by con-
tinternal heat transfer = =
α ke sidering a system of linear equations:
where s is the catalyst density, C s is the cata- dy
lyst heat capacity per unit mass, k e is the effec- =A y
dt
tive thermal conductivity of the catalyst, and α
is the thermal diffusivity. The time constants for Let λi be the eigenvalues of the matrix A. This
diffusion of mass and heat through a boundary system can be converted into a system of n equa-
layer surrounding the catalyst are tions, each of them having only one unknown;
the eigenvalues of the new system are the same
R as the eigenvalues of the original system [50,
texternal diffusion =
kg pp. 39 – 42], [53, pp. 197 – 199], [59]. Then the
stiffness ratio SR is defined as [60, p. 32]
s Cs R
texternal heat transfer =
hp maxi |Re (λi ) |
SR =
mini |Re (λi ) |
where k g and hp are the mass-transfer and heat-
transfer coefficients, respectively. The impor- SR = 20 is not stiff, SR = 103 is stiff, and
tance of examining these time constants comes SR = 106 is very stiff. If the problem is nonlin-
from realization that their orders of magnitude ear, the solution is expanded about the current
differ greatly. For example, in the model of an state:
automobile catalytic converter [58] the time con-
stant for internal diffusion was 0.3 s, for internal dyi n
∂fi
= fi [y (tn )] + [ yj − yj (tn )]
heat transfer 21 s, and for flow through the de- dt j=1
∂yj
vice 0.003 s. Flow through the device is so fast
that it might as well be instantaneous. Thus, the The question of stiffness then depends on the
time derivatives could be dropped from the mass eigenvalue of the Jacobian at the current time.
balance equations for the flow, leading to a set Consequently, for nonlinear problems the prob-
of differential-algebraic equations (see below). lem can be stiff during one time period and not
If the original equations had to be solved, the stiff during another. Packages have been devel-
eigenvalues would be roughly proportional to oped for problems such as these. Although the
the inverse of the time constants. The time in- chemical engineer may not actually calculate the
terval over which to integrate would be a small eigenvalues, knowing that they determine the
number (e.g., five) multiplied by the longest time stability and accuracy of the numerical scheme,
constant. Yet the explicit stability limitation ap- as well as the step size employed, is useful.
plies to all the eigenvalues, and the largest eigen-
value would determine the largest permissible
time step. If that eigenvalue was very large, very
small time steps would have to be used, but 6.5. Differential – Algebraic Systems
a long integration would be required to reach
steady state. Such problems are termed stiff, and Sometimes models involve ordinary differential
implicit methods are very useful for them. In that equations subject to some algebraic constraints.
case the stable time constant is not of any inter- For example, the equations governing one equi-
est, because any time step is stable. What is of librium stage (as in a distillation column) are
interest is the largest step for which a solution
dxn
M = V n+1 n+1
y − Ln xn − V n n
y dy
dt F t, y, = 0
dt
+ Ln−1 xn−1 or the variables and equations may be separated
according to whether they come primarily from
xn−1 − xn = E n xn−1 − x∗,n differential or algebraic equations:

N dy
xi = 1 = f (t, y, x) , g (t, y, x) = 0
dt
i=1
Another form is not strictly a differential-
where x and y are the mole fractions in the liquid algebraic set of equations, but the same prin-
and vapor, respectively; L and V are liquid and ciples apply; this form arises frequently when
vapor flow rates, respectively; M is the holdup; the Galerkin finite element is applied:
and the superscript n is the stage number. The
efficiency is E, and the concentration in equilib- dy
A = f ( y)
rium with the vapor is x ∗ . The first equation is dt
an ordinary differential equation for the mass of
Suppose the general problem is to be solved
one component on the stage, whereas the third
by using the backward Euler method. Then, the
equation represents a constraint that the mass
nonlinear differential equation is replaced by the
fractions add to one. As a second example, the
nonlinear algebraic equation for one step:
following kinetics problem can be considered:

y n+1 − y n
dc1 F t, y n+1 , = 0
= f (c1 , c2 ) ∆t
dt
dc2 This equation must be solved for yn+1 . The

= k1 c1 − k2 c22 Newton – Raphson method can be used, and if
dt
convergence is not achieved within a few itera-
The first equation could be the equation for a tions, the time step can be reduced and the step
stirred tank reactor, for example. Suppose both repeated. In actuality, higher order backward-
k 1 and k 2 are large. The problem is then stiff, difference Gear methods are used in the com-
but the second equation could be taken at equi- puter program DASSL [61].
librium. If Differential-algebraic systems are more com-
plicated than differential systems because the so-
c1 2 c2 lution may not always be defined. Pontelides
et al. [62] introduced the term “index” to identify
The equilibrium condition is then
possible problems. The index is defined as the
c22 k1 minimum number of times the equations must
= ≡ K be differentiated with respect to time to convert
c1 k2
the system to a set ofordinary differential equa-
Under these conditions the problem becomes tions. These higher derivatives may not exist,
dc1
and the process places limits on which variables
= f (c1 , c2 ) can be given initial values. Sometimes the ini-
dt
tial values must be constrained by the algebraic
0 = k1 c1 − k2 c22 equations [62]. For a differential-algebraic sys-
tem modeling a distillation tower, the index de-
Thus, a differential-algebraic system of equa- pends on the specification of pressure for the
tions is obtained. In this case, the second equa- column [62]. Several chemical engineering ex-
tion can be solved and substituted into the first to amples of differential-algebraic systems and a
obtain differential equations, but in the general solution for one involving two-phase flow are
case that is not possible. given in [63].
Differential-algebraic equations can be writ-
ten in the general notation
Next Page
6.6. Computer Software the right-hand sides at previous times. An es-

timate is also made for the k-th and (k + 2)-th
Efficient software packages are widely available derivative. Then, the errors in a (k − 1)-th order
for solving ordinary differential equations as ini- method, a k-th order method, and a (k + 1)-th or-
tial value problems. Three of them – RKF 45, der method can be estimated. Furthermore, the
LSODE, and EPISODE – are discussed here. In step size required to satisfy the tolerance with
each of the packages the user specifies the differ- each of these methods can be determined. Then
ential equation to be solved and a desired error the method and step size for the next step that
criterion. The package then integrates in time achieves the biggest step can be chosen, with ap-
and adjusts the step size to achieve the error cri- propriate adjustments due to the different work
terion, within the limitations imposed by stabil- required for each order. The package generally
ity. starts with a very small step size and a first-order
A popular explicit Runge – Kutta package method – the backward Euler method. Then it in-
is RKF 45, developed by Forsythe et al. tegrates along, adjusting the order up (and later
[52, Chap. 6]. The method is based on the down) depending on the error estimates. The
Runge – Kutta – Feldberg formulas (see Section user is thus assured that the local truncation error
6.2). An estimate of the truncation error at each meets the tolerance. A further difficulty arises
step is available. Then the step size can be because the set of nonlinear equations must be
reduced until this estimate is below the user- solved. Usually a good guess of the solution
specified tolerance. The method is thus auto- is available, because the solution is evolving in
matic, and the user is assured of the results. Note, time and past history can be extrapolated. Thus,
however, that the tolerance is set on the local the Newton – Raphson method will usually con-
truncation error, namely, from one step to an- verge. The package protects itself, though, by
other, whereas the user is generally interested only doing a few (i.e., three) iterations. If conver-
in the global trunction error, i.e., the error af- gence is not reached within these iterations, the
ter several steps. The global error is generally step size is reduced and the calculation is redone
made smaller by making the tolerance smaller, for that time step. The convergence theorem for
but the absolute accuracy is not the same as the the Newton – Raphson method (Chap. 1) indi-
tolerance. If the problem is stiff, then very small cates that the method will converge if the step
step sizes are used and the computation becomes size is small enough. Thus, the method is guar-
very lengthy. The RKF 45 code discovers this anteed to work. Further economies are possible.
and returns control to the user with a message The Jacobian needed in the Newton – Raphson
indicating the problem is too hard to solve with method can be fixed over several time steps.
RKF 45. Then if the iteration does not converge, the Jaco-
A popular implicit package is LSODE, a ver- bian can be reevaluated at the current time step.
sion of Gear’s method [56] written by Alan If the iteration still does not converge, then the
Hindmarsh at Lawrence Livermore Laboratory step size is reduced and a new Jacobian is eval-
[64]. Earlier versions of this were GEAR and uated. The successive substitution method can
GEARB [65]. In this package, the user speci- also be used – which is even faster, except that it
fies the differential equation to be solved and may not converge. However, it too will converge
the tolerance desired. Now the method is im- if the time step is small enough.
plicit and, therefore, stable for any step size. Comparisons of the methods and additional
The accuracy may not be acceptable, however, details are provided for chemical engineering
and sets of nonlinear equations must be solved. problems by Finlayson [50, pp. 54 – 56] and
Thus, in practice, the step size is limited but not Carnahan and Wilkes [57]. Generally the
nearly so much as in the Runge – Kutta meth- Runge – Kutta methods give extremely good ac-
ods. In these packages both the step size and the curacy, especially when the step size is kept
order of the method are adjusted by the pack- small for the stability reason. When the com-
age itself. Suppose a k-th order method is be- putation time is comparable for LSODE and
ing used. The truncation error is determined by RKF 45, the RKF 45 package generally gives
the (k + 1)-th order derivative. This is estimated much more accurate results. The RKF 45 pack-
by using difference formulas and the values of age is unsuitable, however, for many chemi-
Previous Page
cal reactor problems because these problems The variable u can be a vector, which makes F a
are so stiff. Other comparisons are available vector, too. Here, F represents a set of equations
by Hull et al. [66], Shampine et al. [67], that can be solved for the steady state:
Byrne et al. [68], and Junce et al. [69]. Other
packages are available through IMSL etc; see F (u, λ) = 0
[54, pp. 291 – 292] and [70, pp. 439, 451]. Gen-
If the Newton – Raphson method is applied,
erally, standard packages must have a high-
order explicit method (usually a version of F su δ us = − F (us , λ)
Runge – Kutta) and a multistep, implicit method
(usually a version of GEAR, EPISODE, or us+1 = us + δu2
LSODE). The package DASSL [61] uses sim-
ilar principles to solve the differential-algebraic is obtained, where
systems. The packages LSODA and LSODAR
∂F
are sister programs to LSODE. They have the Fus = (us )
∂u
feature of switching between stiff and nons-
tiff methods automatically; LSODAR also has is the Jacobian. Look at some property of the
a stopping feature when some condition is sat- solution, perhaps the value at a certain point or
isfied, which can be used for finding roots. the maximum value or an integral of the solu-
[The software described here is available by tion. This property is plotted versus the param-
electronic mail over BITNET. Sending the mes- eter λ; typical plots are shown in Figure 26. At
sage: the point shown in Figure 26 A, the determinant
“mail netlib@ornl.gov”, “send index” of the Jacobian is zero:
will retrieve an index and descriptions of how to
obtain the software. The packages DASSL and det Fu = 0
ODEPACK (containing LSODE . . . LSODAR)
For the limit point,
can be obtained for a nominal fee on a com-
puter tape from Professor W. E. Schiesser, De- ∂F
= 0
partment of Chemical Engineering, Lehigh Uni- ∂λ
versity, Bethlehem, Pennsylvania 18015.] whereas for the bifurcation-limit point
∂F
= 0
6.7. Stability, Bifurcations, Limit Cycles ∂λ
In this section, bifurcation theory is discussed in The stability of the steady solutions is also of
a general way. Some aspects of this subject in- interest. Suppose a steady solution uss ; the func-
volve the solution of nonlinear equations; other tion u is written as the sum of the known steady
aspects involve the integration of ordinary differ- state and a perturbation u :
ential equations; applications include chaos and
fractals as well as unusual operation of some u = uss +u
chemical engineering equipment. An excellent
This expression is substituted into the original
introduction to the subject and details needed to
equation and linearized about the steady-state
apply the methods are given in [71]. For more
value:
details of the algorithms described below and
a concise survey with some chemical engineer- ∂uss ∂u
ing examples, see [72] and [73]. Bifurcation re- + = F uss +u , λ
∂t ∂t
sults are closely connected with stability of the
steady states, which is essentially a transient ∂F
≈ F (uss , λ) + u + . . .
phenomenon. ∂u uss
Consider the problem The result is
∂u ∂u
∂t
= F (u, λ) = Fuss u
∂t
Figure 26. Limit points and bifurcation – limit points

A) Limit point (or turning point); B) Bifurcation-limit point (or singular turning point or bifurcation point)
A solution of the form original equations being real, with no complex

numbers), and this is called a Hopf bifurcation.
u (x, t) = eσt X (x) Numerical methods to study Hopf bifurcation
gives are very computationally intensive and are not
discussed here [71].
σeσt X = F ss σt
ue X To return to the problem of solving for the
steady-state solution: near the limit point or
The exponential term can be factored out and bifurcation-limit point two solutions exist that
(F ss are very close to each other. In solving sets of
u − σ δ) X = 0
equations with thousands of unknowns, the dif-
A solution exists for X if and only if ficulties in convergence are obvious. For some
dependent variables the approximation may be
det |F ss
u − σ δ| = 0 converging to one solution, whereas for another
The σ are the eigenvalues of the Jacobian. set of dependent variables it may be converging
Now clearly if Re (σ) > 0 then u grows with to the other solution; or the two solutions may
time, and the steady solution uss is said to be all be mixed up. Thus, solution is difficult near
unstable to small disturbances. If Im (σ) = 0 it a bifurcation point, and special methods are re-
is called stationary instability, and the distur- quired. These methods are discussed in [72].
bance would grow monotonically, as indicated The first approach is to use natural continu-
in Figure 27 A. If Im (σ) = 0 then the disturbance ation (also known as Euler – Newton continua-
grows in an oscillatory fashion, as shown in Fig- tion). Suppose a solution exists for some param-
ure 27 B, and is called oscillatory instability. The eter λ. Call the value of the parameter λ0 and
case in which Re (σ) = 0 is the dividing point the corresponding solution u0 . Then
between stability and instability. If Re (σ) = 0
and Im (σ) = 0 – the point governing the onset of F (u0 , λ0 ) = 0
stationary instability – then σ = 0. However, this
means that σ = 0 is an eigenvalue of the Jaco- Also, compute uλ as the solution to
bian, and the determinant of the Jacobian is zero.
u uλ = − F λ
F ss
Thus, the points at which the determinant of the
Jacobian is zero (for limit points and bifurcation- at this point [λ0 , u0 ]. Then predict the starting
limit points) are the points governing the on- guess for another λ using
set of stationary instability. When Re (σ) = 0 but
Im (σ) = 0, which is the onset of oscillatory in- u0 =u0 +uλ (λ − λ0 )
stability, an even number of eigenvalues pass
from the left-hand complex plane to the right- and apply Newton – Raphson with this initial
hand complex plane. The eigenvalues are com- guess and the new value of λ. This will be a
plex conjugates of each other (a result of the
Figure 27. Stationary and oscillatory instability

A) Stationary instability; B) Oscillatory instability
much better guess of the new solution than just Exchanging the order of differentiation in the
u0 by itself. first term leads to the ordinary differential equa-
Even this method has difficulties, however. tion
Near a limit point the determinant of the Jaco-
bian may be zero and the Newton method may d ∂y ∂ f ∂y ∂f
= +
fail. Perhaps no solutions exist at all for the cho- dt ∂α ∂y ∂α ∂α
sen parameter λ near a limit point. Also, the The initial conditions on ∂y/∂α are obtained by
ability to switch from one solution path to an- differentiating the initial conditions
other at a bifurcation-limit point is necessary.
Thus, other methods are needed as well: arc- ∂
[ y (0, α) = y0 ] , or
∂y
(0) = 0
length continuation and pseudo-arc-length con- ∂α ∂α
tinuation [72]. The latter method can use the Next, let
arrow matrix LU decomposition described in
Chapter 1. ∂y
y1 = y, y2 =
∂α
and solve the set of ordinary differential equa-
6.8. Sensitivity Analysis tions
Often, when solving differential equations, the dy1
= f ( y1 , α) y1 (0) = y0
solution as well as the sensitivity of the solu- dt
tion to the value of a parameter must be known.
dy2 ∂f ∂f
Such information is useful in doing parameter = ( y1 , α) y2 + y2 (0) = 0
dt ∂y ∂α
estimation (to find the best set of parameters for
a model) and in deciding whether a parameter Thus, the solution y (t, α) and the derivative with
needs to be measured accurately. The differen- respect to α are obtained. To project the impact
tial equation for y (t, α) where α is a parameter, of α, the solution for α = α1 can be used:
is
∂y
dy y (t, α) = y1 (t, α1 ) + (t, α1 ) (α − α1 ) + . . .
= f ( y, α) , y (0) = y0 ∂α
dt
= y1 (t, α1 ) + y2 (t, α1 ) (α − α1 ) + . . .
If this equation is differentiated with respect to
α, then because y is a function of t and α This is a convenient way to determine the sensi-
tivity of the solution to parameters in the prob-
∂ dy ∂ f ∂y ∂f
= + lem.
∂α dt ∂y ∂α ∂α
6.9. Eigenvalues and Roots by Initial The solution is a zero-order Bessel function.
Value Techniques
R (r) = J0 (αk r) because J0 (αk ) = 0
Initial value methods can also be used to find Now a new variable is defined
roots of equations. Doing this requires a code
that stops when the dependent variable (e.g., y) z = αr
takes a certain value, as opposed to stopping
when the independent variable takes a certain and the equation rearranged for R:
value (e.g., t). The RKF 45 code has been mod- d2 R 1 dR dR
ified in this way [74], [75], as has the LSODAR dz 2
+
z dz
+ R = 0,
dz
(0) = 0, R (0) = 1
code. To find the values of t that satisfy
(arbitrary, take = 1)
f (t) = 0
This equation can be solved as an initial value
set problem. The solution is continued until
y = f (t) R=0
and differentiate to get Suppose this occurs for zk . To have
dy df
= R=0
dt dt
Now integrate the problem when
dy df r=1
= ≡ g (t) , y (0) = y0 (arbitrary)
dt dt
choose
until y = 0. The t for which this occurs gives the
root to the equation. Continued integration will αk = z k
give multiple roots.
This technique can also be used to solve cer- The function
tain eigenvalue problems. If separation of vari-
ables is applied to unsteady heat conduction R (αk r) = R (z)
then satisfies the correct differential equation
∂T 1 ∂ ∂T
= r and the appropriate boundary conditions. This
∂t r ∂r ∂r
gives a method of finding the Bessel functions
∂T of order zero.
T (1, t) = 0, (0, t) = 0
∂r When the Graetz problem for heat transfer to
the following is obtained: a fluid flowing in a tube is considered,

∂T 1 ∂ ∂T
T (r, t) = T (t) R (r) 1 − r2 = r
∂t r ∂r ∂r

1 dT 1 d dR
= r = constant = − α2 ∂T
T dt r R dr dr T (1, t) = 0, (0, t) = 0
∂r
Then the function R (r) must satisfy the corresponding eigenvalue problem is

1 d dR
r + α2 R (r) = 0 d2 R 1 dR
r dr dr + + α2 1 − r 2 R (r) = 0,
dr 2 r dr
or
dR
R (1) = 0, (0) = 0
d2 R 1 dR dr
+ + α2 R (r) = 0, R (1) = 0,
dr 2 r dr
Now the initial value methods apparently can-
dR not be used because the transformation is not
(0) = 0 possible.
dr
7. Ordinary Differential Equations

as Boundary Value Problems d (r τ ) = −
∆p
rdr
L
Diffusion problems in one dimension lead to and then integrated to give
boundary value problems. The boundary con-
ditions are applied at two different spatial loca- ∆p r2
rτ = − + c1
tions: at one side the concentration may be fixed L 2
and at the other side the flux may be fixed. Be- Proceeding further requires choosing a consti-
cause the conditions are specified at two differ- tutive relation relating the shear stress and the
ent locations the problems are not initial value velocity gradient as well as a condition specify-
in character. To begin at one position and inte- ing the constant. For a Newtonian fluid
grate directly is impossible because at least one
of the conditions is specified somewhere else and dv
τ = −η
not enough conditions are available to begin the dr
calculation. Thus, methods have been developed where v is the velocity and η the viscosity. Then
especially for boundary value problems. the variables can be separated again and the re-
sult integrated to give
7.1. Solution by Quadrature ∆p r 2

−η v = − + c1 lnr + c2
L 4
When only one equation exists, even if it is non- Now the two unknowns must be specified from
linear, it may possibly be solved by quadrature. the boundary conditions. This problem is a two-
For point boundary value problem because one of
the conditions is usually specified at r = 0 and
dy
= f ( y) the other at r = R, the tube radius. However, the
dt
technique of separating variables and integrating
y (0) = y0 works quite well.
the problem can be separated

dy
= dt
f (y)
and integrated
y t
dy Figure 28. Flow in pipe
= dt = t
f ( y )
y0 0 When the fluid is non-Newtonian, it may not
be possible to do the second step analytically.
If the quadrature can be performed analytically, For example, for the Bird – Carreau fluid [77,
the exact solution has been found. p. 171], stress and velocity are related by
As an example, consider the flow of a non-
Newtonian fluid in a pipe, as illustrated in Fig- η0
τ =
2 (1−n)/2
ure 28. The governing differential equation is 1+λ dv
dr
[76]
1 d ∆p where η 0 is the viscosity at v = 0 and λ the time
(r τ ) = − constant.
r dr L
Putting this value into the equation for stress
where r is the radial position from the center of as a function of r gives
the pipe, τ is the shear stress, ∆ p is the pressure
drop along the pipe, and L is the length over η0 ∆p r c1
= −
2 (1−n)/2
+
which the pressure drop occurs. The variables L 2 r
dv
1+λ
are separated once dr
This equation cannot be solved analytically for which should preferably be zero. Note that the
dv/dr, except for special values of n. For prob- solution depends on s.
lems such as this, numerical methods must be
used. χ (s) = 0
Iteration on s is required to find the solution to

the problem. The condition at x = 0 is satisfied
7.2. Shooting Methods for any s; the differential equation is satisfied
by the integration routine; and all that must be
A shooting method is one that utilizes the tech-
ensured is that the last boundary condition is sat-
niques for initial value problems but allows for
isfied. A successive substitution method would
an iterative calculation to satisfy all the bound-
use
ary conditions. Suppose the nonlinear boundary

value problem sk+1 = sk − m χ sk

d2 y dy
= f x, y, Keller [78] showed that if
dx2 dx
∂f
with the boundary conditions ≤ N
∂y
dy
a0 y (0) − a1 (0) = α, ai ≥ 0 for some N and 0 < m < 2 Γ , where Γ increases
dx
as N increases, then the iteration scheme con-
dy verges as k approaches infinity.
b0 y (1) + b1 (1) = β, bi ≥ 0 Newton’s method of iteration would use
dx

Convert this second-order equation into two χ sk
first-order equations along with the boundary sk+1 = sk − dχ k
ds
s
conditions written to include a parameter s.
The function dχ/ds is determined by integrating
du two more equations obtained by differentiating
= v
dx the original equations with respect to s. If
dv
= f (x, u, v) ∂u (x, s) ∂v (x, s)
dx ζ = , η =
∂s ∂s
u (0) = a1 s − c1 α the additional differential equations are
v (0) = a0 s − c0 α dζ dη ∂ f ∂f
= η, = ζ+ η
dx dx ∂u ∂v
The parameters c0 and c1 are specified by the
analyst such that These equations are integrated along with the
initial conditions
a1 c0 −a0 c1 = 1
ζ (0) = a1 , η (0) =a0
This ensures that the first boundary condition
is satisfied for any value of parameter s. If the Then the derivative is
proper value for s is known, u (0) and u (0) can dχ
be evaluated and the equation integrated as an = b0 ζ (1, s) + b1 η (1, s)
ds
initial value problem. The parameter s should
be chosen so that the last boundary condition is The process can be used when multiple con-
satisfied. Define the function ditions must be satisfied, such as might arise
when more than one dependent variable exists.
du Suppose two equations must be satisfied at one
χ (s) = b0 u (1, s) + b1 (1, s) − β
dx boundary
= b0 u (1, s) + b1 v (1, s) − β χ1 (s1 , s2 ) = 0, χ2 (s1 , s2 ) = 0
Then two variables s1 and s2 are introduced, and This problem can be treated by using initial value
the Newton – Raphson method is applied in the methods also, but the method is highly sensi-
form tive to the choice of the parameter s, as out-
∂χ ∂χ1

lined above. Starting at z = 0 and making small
1
sk+1 − sk1 χ1 sk1 , sk2 changes in s will cause large changes in the so-
∂s1
∂χ2
∂s2
∂χ2
1 = −
∂s1 ∂s2
sk+1
2 − sk2 χ2 sk1 , sk2 lution at the exit, and the boundary condition at
the exit may be impossible to satisfy. By starting
The problem for reaction and diffusion in a at z = 1, however, and integrating backwards, the
catalyst pellet is process works and an iterative scheme converges
in many cases [82]. However, if the problem is
1 d dc
r a−1 = ϕ2 R (c) extremely nonlinear the iterations may not con-
ra−1 dr dr
verge. In such cases, the methods for boundary
dc value problems described below must be used.
(0) = 0, c (1) = 1 (15) Computer software exists for solving two-
dr
point boundary value problems: for example, the
where ϕ is the Thiele modulus. Weisz and Hicks IMSL program DTPTB used DVERK, which
[79] showed how to transform this problem into employs Runge – Kutta integration to integrate
one that can be solved by using initial value the ordinary differential equations [83, p. 301].
methods. The problem can be written as Initial value methods can also be used when
the sensitivity of the solution to parameters must
1 d dc
z a−1 = d2 R (c) be determined. The sensitivity might be desired
z a−1 dz dz
for studying the stability of the equations, es-
dc
(0) = 0, c (b z = 1) = 1
pecially when the solution bifurcates into more
dz than one solution, or it might be required for
by using r = b z and d = b ϕ. For any d, choose parameter estimation. Knowing the sensitivity
an arbitrary c (0) = c0 and integrate until the con- gives clues as to what experimental measure-
centration reaches 1.0. Suppose that occurs at ments are most important for verifying a mathe-
z = z1 . Then, let matical model. As an example, suppose the sen-
sitivity of the solution to Equation (15) with re-
b =
1 d
, ϕ = = d z1 spect to the Thiele modulus squared ϕ2 must be
z1 b known. The variables are defined
and the solution for the problem is obtained with- du
out iteration. We do not know in advance what u (r) = c (r) , v (r) =
dr
ϕ the problem has been solved for, so this tech-
nique is especially useful to solve the problem and the differential equation is written as
for a range of ϕ. Employing this method re-
du
quires a code that stops when the dependent vari- = v
dr
able (here c) equals some value, rather than one
that stops when the independent variable (here dv a−1
= ϕ2 R (u) − v
z) equals some value. dr r
The model for a chemical reactor with axial
Next, the equation is differentiated with respect
diffusion is
to ϕ2 . Then the following variables and equa-
1 dc2 dc tions are added:
− = Da R (c) ,
P e dz 2 dz
∂u ∂v
ζ = , η =
1 dc dc ∂ϕ2 ∂ϕ2
− (0) + c (0) = cin , (1) = 0
P e dz dz
dζ
where Pe is the Péclet number and Da the = η
dr
Damköhler number.
The boundary conditions are due to Danck- dη dR a−1
= R (u) + ϕ2 ζ − η
werts [80] and to Wehner and Wilhelm [81]. dr du r
These can be solved along with the original prob- last equation is chosen to ensure the best accu-
lem (on each iteration) or only after the proper racy.
s is found from the iterations. The result of this
calculation is that we have c (x, ϕ2 ) for some ϕ2
and we also know ∂c/∂ϕ2 at the same value of
ϕ2 . Then,
Figure 29. Finite difference mesh; ∆x uniform

c r, ϕ22 ≈ c r, ϕ21 + ζ r, ϕ21 ϕ22 −ϕ21
The finite difference representation of the
can be used. second derivative can be obtained by adding the
two expressions in Equation (16). Rearrange-
ment and division by ∆x 2 give
7.3. Finite Difference Method d2 c ci+1 − 2 ci + ci−1 d4 c 2 ∆x2
2
= 2
− + . .(20)
.
dx i ∆x dx4 i 4!
To apply the finite difference method, we first
spread grid points through the domain. Figure 29 The truncation error is proportional to ∆x 2 .
shows a uniform mesh of n points (nonuniform To see how to solve a differential equation,
meshes are described below). The unknown, consider the equation for convection, diffusion,
here c (x), at a grid point xi is assigned the sym- and reaction in a tubular reactor:
bol ci = c (xi ). The finite difference method can
1 d2 c dc
be derived easily by using a Taylor expansion of − = Da R (c)
P e dx2 dx
the solution about this point.
To evaluate the differential equation at the i-th
dc d2 c ∆x2 grid point, the finite difference representations
ci+1 = ci + ∆x + 2 + ...
dx i dx i 2 of the first and second derivatives can be used to
give
dc d2 c ∆x2
ci−1 = ci − ∆x + −... (16)
dx i dx2 i 2 1 ci+1 − 2 ci + ci−1 ci+1 − ci−1
− = Da R (ci )
Pe ∆x2 2∆x
These formulas can be rearranged and divided (21)
by ∆x to give
This equation is written for i = 2 to n − 1 (i.e.,
dc ci+1 − ci d2 c ∆x
= − + ... (17) the internal points). The equations would then
dx i ∆x dx2 i 2 be coupled but would involve the values of c1
and cn , as well. These are determined from the
boundary conditions.
dc ci − ci−1 d2 c ∆x
= + +... (18) If the boundary condition involves a deriva-
dx i ∆x dx2 i 2
tive, the finite difference representation of it
which are representations of the first deriva- must be carefully selected; here, three possibili-
tive. Alternatively the two equations can be sub- ties can be written. Consider a derivative needed
tracted from each other, rearranged and divided at the point i = 1. First, Equation (17) could be
by ∆x to give used to write
dc ci+1 − ci−1 d3 c ∆x2 dc c2 − c1
= − (19) = (22)
dx i 2 ∆x dx3 i 3! dx 1 ∆x
If the terms multiplied by ∆x or ∆x 2 are ne- Then a second-order expression is obtained that
glected, three representations of the first deriva- is one-sided. The Taylor series for the point ci+2
tive are possible. In comparison with the Taylor is written:
series, the truncation error in the first two expres-
dc d2 c 4∆x2
sions is proportional to ∆x, and the methods are ci+2 = ci + 2∆x +
dx i dx2 i 2!
said to be first order. The truncation error in the
last expression is proportional to ∆x 2 , and the d3 c 8∆x3
method is said to be second order. Usually, the + + ...
dx3 i 3!
Four times Equation (16) minus this equation, 1 c2 − c 1

− + c1 = cin
with rearrangement, gives P e ∆x
dc −3 ci + 4 ci+1 − ci+2 cn − cn−1

=0
= + O ∆x2 ∆x
dx i 2∆x
plus Equation (21) at points i = 2 through n − 1;
Thus, for the first derivative at point i = 1 second order in ∆x, by using a three-point one-
dc −3 ci + 4 c2 − c3 sided derivative
= (23) 1 −3 c1 + 4 c2 − c3
dx i 2∆x − + c1 = cin
Pe 2 ∆x
This one-sided difference expression uses only
the points already introduced into the domain. cn−2 − 4 cn−1 + 3 cn
= 0
The third alternative is to add a false point, out- 2 ∆x
side the domain, as c0 = c (x = − ∆x). Then the plus Equation (21) at points i = 2 through n − 1;
centered first derivative, Equation (19), can be second order in ∆x, by using a false boundary
used: point
1 c2 − c 0
dc c2 − c0 − + c1 = cin
= P e 2 ∆x
dx 1 2∆x
cn+1 − cn−1
Because this equation introduces a new variable, = 0
2 ∆x
another equation is required. This is obtained by
also writing the differential equation (Eq. 21), plus Equation (21) at points i = 1 through n.
for i = 1. The sets of equations can be solved by us-
The same approach can be taken at the other ing the Newton – Raphson method, as outlined in
end. As a boundary condition, any of three Section 1.2. The form of the equations is impor-
choices can be used: tant, however, because the equations give a tridi-
agonal structure. For the first-order method the
dc cn − cn−1 equations have the form shown in Figure 30 A
=
dx n ∆x and the standard routines for solving tridiagonal
equations suffice. For the second-order method
dc cn−2 − 4 cn−1 + 3 cn with a one-sided three-point derivative the form
=
dx n 2∆x of the equations is shown in Figure 30 B. Now
dc cn+1 − cn−1 the tridiagonal structure is broken. However, if
= the second equation is multiplied by a constant
dx n 2∆x
and added to the first one, a zero can be ob-
The last two are of order ∆x 2 and the last one tained in the third column of the first row. Then
would require writing the differential equation the standard routines for tridiagonal matrices can
(Eq. 21) for i = n, too. be called. Similar manipulations are necessary in
Generally, the first-order expression for the the last row of the matrix to obtain the tridiago-
boundary condition is not used because the er- nal form of the equations. For the second-order
ror in the solution would decrease only as ∆x, method with a false boundary point, the form
and the higher truncation error of the differential of the equations is shown in Figure 30 C. Now,
equation (∆x 2 ) would be lost. For this problem the two additional equations are almost tridiag-
the boundary conditions are onal. With the manipulations described above,
they can be put into a tridiagonal form and the
1 dc
− (0) + c (0) = cin standard routines can be called.
P e dx
Frequently, the transport coefficients (e.g.,
dc diffusion coefficient D or thermal conductivity)
(1) = 0
dx depend on the dependent variable (concentration
or temperature, respectively). Then the differen-
Thus, the three formulations would give first or-
tial equation might look like
der in ∆x
d dc
D (c) =0
dx dx
Figure 30. Equation structure for different boundary conditions

A) First-order method; B) Second-order method with one-sided three-point derivative; C) Second-order method using false
boundary point
This could be written as

The advantage of this approach is that it is eas-
dJ ier to program than a full Newton – Raphson
− = 0 (24)
dx method. If the transport coefficients do not
in terms of the mass flux J, where the mass flux vary radically, the method converges. If the
is given by method does not converge, use of the full
Newton – Raphson method may be necessary.
dc Three ways are commonly used to evaluate
J = − D (c)
dx the transport coefficient at the midpoint. The first
Because the coefficient depends on c the equa- one employs the transport coefficient evaluated
tions are more complicated. A finite difference at the average value of the solutions on either
method can be written in terms of the fluxes at side:
the midpoints, i + 1/2. Thus,
1
D ci+1/2 ≈ D (ci+1 + ci )
Ji+1/2 − Ji−1/2 2
− =0
∆x
The truncation error of this approach is ∆x 2 [84,
Then the constitutive equation for the mass flux Chap. 14]. The second approach uses the aver-
can be written as age of the transport coefficients on either side:
ci+1 − ci 1
Ji+1/2 = − D ci+1/2 D ci+1/2 ≈ [D (ci+1 ) + D (ci )] (25)
∆x 2
If these are combined, The truncation error of this approach is also ∆x 2
[84, Chap. 14], [85, p. 215]. The third approach
D ci+1/2 (ci+1 − ci ) − D ci−1/2 (ci − ci−1 )
= 0 employs an “upstream” transport coefficient.
∆x2

This represents a set of nonlinear alge- D ci+1/2 ≈ D (ci+1 ) , when D (ci+1 ) >D (ci )
braic equations that can be solved with the
Newton – Raphson method. However, in this D ci+1/2 ≈ D (ci ) , when D (ci+1 ) < D (ci )
case a viable iterative strategy is to evaluate the
This approach is used when the transport coef-
transport coefficients at the last value and then
ficients vary over several orders of magnitude
solve
and the “upstream” direction is defined as the

D cki+1/2 ck+1 k+1
i+1 − ci − D cki−1/2 ck+1
i − ck+1
i−1
= 0
∆x2
one in which the transport coefficient is larger.

N +2
The truncation error of this approach is only ∆x y (x) = ai yi (x) (26)
[84, Chap. 14] , [85, p. 253], but this approach is i=1
useful if the numerical solutions show unrealis- Suppose the differential equation is
tic oscillations [84], [85].
If the grid spacing is not uniform the formulas N [ y] = 0
must be revised. The notation is shown in Fig-
ure 31. The finite difference form of Equation Then the expansion is put into the differential
(24) is then equation to form the residual:
Ji+1/2 − Ji−1/2 N +2
− = 0
1
2
(∆xi +∆ xi+1 ) Residual = N ai yi (x)
i=1
and the constitutive relations are
In the collocation method, the residual is set to
ci+1 − ci
Ji+1/2 = − Di+1/2 , zero at a set of points called collocation points:
∆xi+1
N +2

ci − ci−1 N ai yi (xj ) = 0, j = 2, . . . , N + 1
Ji−1/2 = − Di−1/2
∆xi i=1
Combined with Equation (25), this gives the fol- This provides N equations; two more equa-
lowing representation for Equation (24) tions come from the boundary conditions, giving
N + 2 equations for N + 2 unknowns. This proce-
1 1
(Di+1 + Di ) (ci+1 − ci ) dure is especially useful when the expansion is
∆xi+1 +∆xi ∆xi+1
in a series of orthogonal polynomials, and when

1 the collocation points are the roots to an orthog-
− (Di + Di−1 ) (ci − ci−1 ) = 0
∆xi onal polynomial, as first used by Lanczos [87],
[88]. A major improvement was the proposal by
Villadsen and Stewart [16] that the entire so-
lution process be done in terms of the solution at
the collocation points rather than the coefficients
in the expansion. Thus, Equation (26) would be
evaluated at the collocation points
Figure 31. Finite difference grid with variable spacing

N +2
y (xj ) = ai yi (xj ) , j = 1, . . . , N + 2
Rigorous error bounds for linear ordinary dif- i=1
ferential equations solved with the finite dif-
ference method are dicussed by Isaacson and and solved for the coefficients in terms of the
Keller [86, p. 431]. Computer software exists solution at the collocation points:
to solve two-point boundary value problems.

N +2
The IMSL routine DVCPR uses the finite dif- ai = [ yi (xj )]−1 y (xj ) , i = 1, . . . , N + 2
ference method, with a variable step size [83, j=1
p. 301]; FDRXN is given for reaction problems
in [85, p. 335]. Furthermore, if Equation (26) is differentiated
once and evaluated at all collocation points, the
first derivative can be written in terms of the val-
7.4. Orthogonal Collocation ues at the collocation points:
The orthogonal collocation method has found dy

N +2
dyi
(xj ) = ai (xj ) , j = 1, . . . , N + 2
widespread application in chemical engineering, dx i=1
dx
particularly for chemical reaction engineering.
In the collocation method [85], the dependent This can be expressed as
variable is expanded in a series.
N +2 and the set of algebraic equations solved, per-

dy dyi
(xj ) = [ yi (xk )]−1 y (xk ) (xj ) , haps with the Newton – Raphson method. If or-
dx dx
i,k=1 thogonal polynomials are used and the colloca-
tion points are the roots to one of the orthogonal
j = 1, . . . , N + 2 polynomials, the orthogonal collocation method
or shortened to results.
In the orthogonal collocation method the so-
dy
N +2 lution is expanded in a series involving or-
dx
(xj ) = Ajk y (xk ) , thogonal polynomials, where the polynomials
k=1 Pi−1 (x) are defined in Section 2.2.

N +2
N
dyi y = a + b x + x (1 − x)
Ajk = [ yi (xk )]−1 (xj ) ai Pi−1 (x)
i=1
dx i=1
Similar steps can be applied to the second deriva-

N +2
tive to obtain = bi Pi−1 (x) (30)

i=1
d2 y
N +2 which is also
(x j ) = Bjk y (xk ) ,
dx2 k=1

N +2
y = di xi−1
i=1

N +2
d 2 yi
Bjk = [ yi (xk )]−1 (xj ) The collocation points are shown in Fig-
i=1
dx2 ure 32. There are N interior points plus one at
each end, and the domain is always transformed
This method is next applied to the differential to lie on 0 to 1. To define the matrices Aij and
equation for reaction in a tubular reactor, after Bij this expression is evaluated at the colloca-
the equation has been made nondimensional so tion points; it is also differentiated and the result
that the dimensionless length is 1.0. is evaluated at the collocation points.
1 d2 c dc
N +2
− = Da R (c) , y (xj ) = di xi−1
P e dx2 dx j
i=1
dc dc
− (0) = P e [c (0) − cin ] , (1) = 0 (27)
N +2
dx dx dy
(xj ) = di (i − 1) xi−2
j
dx
The differential equation at the collocation i=1
points is
d2 y
N +2
(x ) = di (i − 1) (i − 2) xi−3
1
N +2
N +2
dx2
j j
Bjk c (xk ) − Ajk c (xk ) = Da R (cj ) i=1
Pe k=1 k=1 These formulas are put in matrix notation, where
(28) Q, C, and D are N + 2 by N + 2 matrices.
dy d2 y
and the two boundary conditions are y = Q d, = C d, = Dd
dx dx2

N +2
− Alk c (xk ) = P e (c1 − cin ) , Qji = xi−1
j , Cji = (i − 1) xi−2
j ,
k=1
Dji = (i − 1) (i − 2) xi−3
j

N +2
AN +2,k c (xk ) = 0 (29) In solving the first equation for d, the first and
k=1 second derivatives can be written as
dy
Note that 1 is the first collocation point (x = 0) d = Q−1 y, =C Q−1 y = A y,
and N + 2 is the last one (x = 1). To apply the dx
method, the matrices Aij and Bij must be found d2 y
= D Q−1 y = B y (31)
dx2
Thus the derivative at any collocation point can 1

be determined in terms of the solution at the col- W x2 Pk x2 Pm x2 xa−1 dx = 0,
location points. The same property is enjoyed by 0
the finite difference method (and the finite ele-
ment method described below), and this prop- k ≤ m−1 (33)
erty accounts for some of the popularity of the where the power on xa−1 defines the geom-
orthogonal collocation method. In applying the etry as planar or cartesian (a = 1), cylindrical
method to Equation (27), the same result is ob- (a = 2), and spherical (a = 3). An analogous de-
tained; Equations (28) and (29), with the matri- velopment is used to obtain the (N + 1)×(N + 1)
ces defined in Equation (31). To find the solution matrices
at a point that is not a collocation point, Equa-
tion (30) is used; once the solution is known at
N +1
all collocation points, d can be found; and once y (xj ) = di xj2i− 2

i=1
d is known, the solution for any x can be found.
dy
N +1
(xj ) = di (2 i − 2) x2i−
j
3
dx i=1

N +1

∇2 y (xi ) = di ∇2 x2i−2 |xj
Figure 32. Orthogonal collocation points i=1
To use the orthogonal collocation method, dy

y = Q d, = C d, ∇2 y = D d
the matrices are required. They can be calcu- dx
lated as shown above for small N (N < 8) and
by using more rigorous techniques, for higher Qji = x2i−2
j , Cji = (2 i − 2) x2i−3
j ,
N (see Chap. 2). However, having the matrices
listed explicitly for N = 1 and 2 is useful; this is Dji = ∇2 x2i−2 |xj
shown in Table 7.
For some reaction diffusion problems, the so- dy
d = Q−1 y, = C Q−1 y = A y,
lution can be an even function of x. For example, dx
for the problem ∇2 y=D Q−1 y = B y
d2 c dc In addition, the quadrature formula is
= k c, (0) = 0, c (1) = 1 (32)
dx2 dx
W Q = f , W = f Q−1
The solution can be proved to involve only even
powers of x. In such cases, an orthogonal col- where
location method, which takes this feature into
account, is convenient. This can easily be done 1
N +1
by using expansions that only involve even pow- x2i−2 xa−1 dx = Wj x2i−2
j
j=1
ers of x. Thus, the expansion 0
1

N
= ≡ fi
y x2 = y (1) + 1 − x2 ai Pi−1 x2 2i − 2 + a
i=1
As an example, for the problem
is equivalent to
1 d dc
xa−1 = ϕ2 R (c)
xa− 1 dx dx
N+1
N+1
y x2 = bi Pi−1 x2 = di x2i−2
i=1 i=1 dc
(0) = 0 , c (1) = 1
dx
The polynomials are defined to be orthogonal
with the weighting function W (x 2 ). orthogonal collocation is applied at the interior
points
Table 7. Matrices for orthogonal collocation
the center (a frequent situation because the cen-

ter concentration can be the most extreme one),

N +1
Bji ci = ϕ2 R (cj ) , j = 1, . . . , N it is given by
i=1

N +1

c (0) = d1 = Q− 1 yi
and the boundary condition solved for is i=1
1i
cN +1 = 1 Table 8. Collocation points for orthogonal collocation with symmet-

ric polynomials and W =1
The boundary condition at x = 0 is satisfied au-
Geometry
tomatically by the trial function. After the solu-
tion has been obtained, the effectiveness facor η N Planar Cylindrical Spherical
is obtained by calculating 1 0.5773502692 0.7071067812 0.7745966692
2 0.3399810436 0.4597008434 0.5384693101
1 N
+1 0.8611363116 0.8880738340 0.9061793459
R [c (x)] xa−1 dx Wj R (cj ) 3 0.2386191861 0.3357106870 0.4058451514
0 i=1
η ≡ = 0.6612093865 0.7071067812 0.7415311856
1 N +1
0.9324695142 0.9419651451 0.9491079123
R [c (1)] xa− 1 dx Wj R (1)
0 i=1 4 0.1834346425 0.2634992300 0.3242534234
0.5255324099 0.5744645143 0.6133714327
Note that the effectiveness factor is the average 0.7966664774 0.8185294874 0.8360311073
0.9602898565 0.9646596062 0.9681602395
reaction rate divided by the reaction rate eval- 5 0.1488743390 0.2165873427 0.2695431560
uated at the external conditions. Error bounds 0.4333953941 0.4803804169 0.5190961292
have been given for linear problems [90, p. 356]. 0.6794095683 0.7071067812 0.7301520056
For planar geometry the error is 0.8650633667 0.8770602346 0.8870625998
0.9739065285 0.9762632447 0.9782286581
ϕ2(2N +1)
Error in η =
(2 N + 1)! (2 N + 2) ! The collocation points are listed in Table 8. For
small N the results are usually more accurate
This method is very accurate for small N (and when the weighting function in Equation (33)
small ϕ2 ); note that for finite difference methods is 1 − x 2 . The matrices for N = 1 and N = 2
the error goes as 1/N 2 , which does not decrease are given in Table 9 for the three geometries.
as rapidly with N. If the solution is desired at Computer programs to generate matrices and a
Table 9. Matrices for orthogonal collocation with symmetric polynomials and W =1−x 2
program to solve reaction diffusion problems,

1 1
NP NP
a−1
OCRXN, are available [85, p. 325, p. 331]. 2
BIJ cJ + AIJ cJ =
∆xk J=1 x(k) + uI ∆xk ∆xk J=1
Orthogonal collocation can be applied to dis-
tillation problems. Stewart et al. [91], [92]
developed a method using Hahn polynomials = ϕ2 R (cJ ) , I = 2, . . . , N P − 1
that retains the discrete nature of a plate-to-plate The local points i = 2, . . . , NP − 1 represent the
distillation column. Other work treats problems interior collocation points. Continuity of the
with multiple liquid phases [93]. function and the first derivative between ele-
ments is achieved by taking
7.5. Orthogonal Collocation on Finite
NP
1
Elements AN P,J cJ
∆xk−1 J=1 element k−1
In the method of orthogonal collocation on fi-

1
NP
nite elements, the domain is first divided into
= A1,J cJ
elements, and then within each element orthog- ∆xk J= 1 element k
onal collocation is applied. Figure 33 shows the

domain being divided into NE elements, with at the points between elements. Naturally, the
NCOL interior collocation points within each computer code has only one symbol for the so-
element, and NP = NCOL + 2 total points per lution at a point shared between elements, but
element, giving NT = NE ∗ (NCOL + 1) + 1 total the derivative condition must be imposed. Fi-
number of points. Within each element a local nally, the boundary conditions at x = 0 and x = 1
coordinate is defined are applied:
x − x(k) 1
NP
u = , ∆xk = x(k+1) − x(k) A1,J cJ = 0,
∆xk ∆xk J= 1
The reaction – diffusion equation is written as
in the first element;

1 d a−1 dc d2 c a − 1 dc
x = 2 +
NP
xa− 1 dx dx dx x dx 1
− AN P,J cJ = Bim [cN P − cB ] ,
∆xN E J= 1
= ϕ2 R (c)
in the last element.
and transformed to give These equations can be assembled into an over-
1 d2 c a−1 1 dc all matrix problem
+ = ϕ2 R (c)
∆x2k du2 x(k) + u∆xk ∆xk du
AAc = f
The boundary conditions are typically
The form of these equations is special and is
dc dc
(0) = 0 , − (1) = Bim [c (1) − cB ] discussed by Finlayson [85, p. 116], who also
dx dx
gives the computer code to solve linear equations
where Bim is the Biot number for mass transfer. arising in such problems. Reaction – diffusion
These become problems are solved by the program OCFERXN
1 dc
[85, p. 337]. See also the program COLSYS de-
∆x1 du
(u = 0) = 0, scribed below.
Another way to approach the same problem
in the first element; is to use the Hermite polynomials (see Section
1 dc 2.3). Then the continuity of the first derivative
− (u = 1) = Bim [c (u = 1) − cB ] , between elements is already part of the basis
∆xN E du
set, leading to a smaller set of equations. If cu-
in the last element. The orthogonal collocation bic Hermite polynomials are used, the solution is
method is applied at each interior collocation
point.
Figure 33. Grid for orthogonal collocation on finite elements
identical to that obtained above with the orthog- The series (the trial solution) is inserted into the
onal collocation method when using cubic poly- differential equation to obtain the residual:
nomials (NCOL = 2). This is not usually done

NT
in chemical engineering; the interested reader is 1 d dbi
Residual = ai xa−1
referred to [85, p. 121]. i=1
xa−1 dx dx
The error bounds of DeBoor [94] give the
following results for second-order problems NT

solved with cubic trial functions on finite ele- −ϕ R2
ai bi (x)
i= 1
ments with continuous first derivatives. The er-
ror at all positions is bounded by The residual is then made orthogonal to the set
i of basis functions.
d
≤ constant |∆x|2
dxi (y − yexact ) N T
∞ 1
1 d dbi
The error at the collocation points is more accu- bj (x) ai xa−1
i=1
xa−1 dx dx
rate, giving what is known as superconvergence. 0
di N T

i (y − yexact ) ≤ constant |∆x|4 −ϕ R 2
ai bi (x) xa−1 dx = 0
dx collocation points
i=1
j = 1, . . . , N T (34)
7.6. Galerkin Finite Element Method This process makes the method a Galerkin
method. The basis for the orthogonality condi-
In the finite element method the domain is dition is that a function that is made orthogonal to
vided into elements and an expansion is made each member of a complete set is then zero. The
for the solution on each finite element. In the residual is being made orthogonal, and if the ba-
Galerkin finite element method an additional sis functions are complete, and an infinite num-
idea is introduced: the Galerkin method is used ber of them are used, then the residual is zero.
to solve the equation. The Galerkin method is Once the residual is zero the problem is solved.
explained before the finite element basis set is It is necessary also to allow for the boundary
introduced. conditions. This is done by integrating the first
To solve the problem term of Equation (34) by parts and then inserting
the boundary conditions:
1 d dc
xa−1 = ϕ2 R (c)
xa− 1 dx dx 1
1 d dbi
bj (x) xa−1 xa−1 dx
dc dc xa−1 dx dx
(0) = 0 , − (1) = Bim [c (1) − cB ] 0
dx dx
the unknown solution is expanded in a series of 1 1
d a−1 dbi dbj dbi a−1
known functions {bi (x)}, with unknown coeffi- = bj (x) x dx − x dx
dx dx dx dx
cients {ai }. 0 0

NT
c (x) = ai bi (x)
i=1
1
dbi 1 dbj dbi a−1
= bj (x) xa−1 − x dx dNj 1 dNJ
dx 0 dx dx = , dx = ∆xe du
0 dx ∆xe du
1 in the e-th element. Then the Galerkin method

dbj dbi a−1 is
= − x dx − Bim bj (1) [bi (1) − cB ]
dx dx
0
NP 1
(35) 1 dNJ dNI
− (xe + u∆xe )a−1 du ceI
e
∆xe I=1 du du
Combining this with Equation (34) gives 0
N P
NT

1
dbj dbi a−1 − Bim NJ (1) ceI NI (1) − c1
− x dx ai
i=1
dx dx e I=1
0
N T
1 N P

2
− Bim bj (1) ai bi (1) − cB =ϕ ∆xe NJ (u) R ceI NI (u)
e 0 I=1
i=1
1 N T
(xe + u∆xe )a−1 du (37)

= ϕ2 bj (x) R ai bi (x) xa−1 dx
0 i=1 The element integrals are defined as
j = 1, . . . , N T (36) 1
1 dNJ dNI
e
BJI = − (xe + u∆xe )a−1 du,
∆xe du du
This equation defines the Galerkin method, and 0
a solution that satisfies this equation (for all
N P
j = 1, . . . , ∞) is called a weak solution. For an 1

approximate solution the equation is written FJe = ϕ ∆xe 2
NJ (u) R ceI NI (u)
once for each member of the trial function, 0 I=1
j = 1, . . . , NT . If the boundary condition is

(xe + u∆xe )a−1 du
c (1) =cB
whereas the boundary element integrals are
then the boundary condition is used (instead of
e
Eq. 36) for j = NT , B BJI = − Bim NJ (1) NI (1) ,

NT F FJe = −Bim NJ (1) c1
ai bi (1) = cB
i=1 Then the entire method can be written in the
The Galerkin finite element method results compact notation
when the Galerkin method is combined with
e
a finite element trial function. Both linear and BJI ceI + e
B BJI ceI = FJe + F FJe
e e e e
quadratic finite element approximations are de-
scribed in Chapter 2. The trial functions bi (x) The matrices for various terms are given in Ta-
are then generally written as Ni (x). ble 10. This equation can also be written in the
form

NT
c (x) = ci Ni (x)
i=1
AA c = f
Each Ni (x) takes the value 1 at the point xi and where the matrix AA is sparse. If linear elements
zero at all other grid points (Chap. 2). Thus ci are used the matrix is tridiagonal. If quadratic
are the nodal values, c (xi ) = ci . The first deriva- elements are used the matrix is pentadiagonal.
tive must be transformed to the local coordinate Naturally the linear algebra is most efficiently
system, u = 0 to 1 when x goes from xi to xi + ∆x. carried out if the sparse structure is taken into
Table 10. Element matrices for Galerkin method
account. Once the solution is found the solution but the treatment for differential equations fol-
at any point can be recovered from lows Sincovec [95]. The trial function is taken
as
ce (u) = ceI=1 (1 − u) + ceI=2 u
N
T+ 1
for linear elements
y = a i Si
e 1 i=1
c (u) = ceI=1 2 (u − 1) u −
2
The values of the function and the first and sec-

1 ond derivatives at the knots are listed in Ta-
+ ceI=2 4 u (1 − u) + ceI=2 2 u u−
2 ble 11. The knots are the points between ele-
for quadratic elements ments. If a differential equation
Because the integrals in Equation (36) may be
d2 y dy
complicated, they are usually formed by using = f x, y,
dx2 dx
Gaussian quadrature. If NG Gauss points are
used, a typical term would be must be solved, the derivatives are approximated
1 N P
by

ceI NI (u) (xe + u∆xe )a−1 du
d2 y
NJ (u) R
3 3 3
0 I=1 = ai−1 − 2 ai + ai+1
dx2 i 2 h2 h 2 h2
NP

NG 3
= Wk NJ (uk ) R ceI NI (uk ) = (ai−1 − 2 ai + ai+1 )
2 h2
k=1 I= 1
The differential equation is then satisfied at each
(xe + uk ∆xe )a−1 knot.
For an application of the finite element method
in fluid mechanics, see → Fluid Mechanics, 2 h2
ai−1 − 2 ai + ai+1 =
Chap. 5.2. 3

1 1 3
f xi , ai−1 + ai + ai+1 , (ai+1 − ai−1 )
4 4 4h
7.7. Cubic B-Splines
i = 1, . . . , N T
Cubic B-splines have cubic approximations
within each element, but first and second deriva-
tives continuous between elements. The func-
tions are the same ones discussed in Chapter 2,
The boundary conditions must also be applied. Ej < 0.1 Ea remove node j
If the boundary condition at the left is
0.1 Ea ≤ Ej ≤ 10 Ea keep node j
y (x1 ) =yleft
10 Ea < Ej ≤ 100 Ea add 1 node
it is satisfied by
100 Ea < Ej ≤ 1000 Ea add 2 nodes
N
T +1
y (x1 ) = ai S (x1 ) = a0 S0 (x1 ) + a1 S1 (x1 )
1000 Ea < Ej add 3 nodes
i=0
1 1
n−1
+ a2 S2 (x1 ) = a0 + a1 + a2 = yleft Ea = Ej / (n − 2)
4 4
j=2
Similar considerations apply at the right-hand Finlayson [84, Chap. 7] tried several crite-
side. To preserve the tridiagonal nature of the ria: the residual, the first derivative, the second
equations, the manipulations discussed in Sec- derivative, etc. The first and second derivative
tion 7.3 must be used. worked best and are the easiest so they are de-
scribed. If a finite difference method or a linear
finite element method is used, the truncation er-
Table 11. Function and derivative values at knots of cubic B-spline ror in the method is [96]:
2
x i−2 x i−1 xi xi +1 xi +2 d c
Errorj = C∆x2j 2

Si 0 1
1 1
0
dx j
4 4
Thus, the pointwise value of the second deriva-
Si 0 3
0 − 3
0
4h 4h
tive is used as the criterion. Because the grid
S
i 0 3
2 h2
− 3
h2
3
2 h2
0 points or mesh points are spaced at irregular in-
tervals, an expression must be used for the sec-
ond derivative that accounts for the irregularity.
For the notation shown in Figure 30, the criterion
is then
7.8. Adaptive Mesh Strategies
cj+1 − cj c −c
d2 c xj+1 − xj
− xj − xj−1
j j−1
In many two-point boundary value problems, Ej = ∆x2j = ∆x2j
dx2 1
2
(x j+1 − x j−1 )
the difficulty in the problem is the formation of
a boundary layer region, or a region in which and this should be made uniform throughout
the solution changes very dramatically. In such the domain. The first derivative for the irregu-
cases small mesh spacing should be used there, lar mesh is
either with the finite difference method or the dc cj+1 − cj
=
finite element method. If the region is known a dx j xj+1 − xj
priori, small mesh spacings can be assumed at However, the mean square derivative can also be
the boundary layer. If the region is not known used.
though, other techniques must be used. These  1/2
techniques are known as adaptive mesh tech- xj 2
niques. A simple technique that has proven use-  dc 
Ej =  dx
dx
ful [84, Chap. 7] is presented first, and more xj−1
complicated (and more robust) techniques that
have been implemented are then described. 2
1/2
cj − cj−1 |cj − cj−1 |
The adaptive mesh technique requires some = ∆xj−1 = -
∆xj−1 ∆xj−1
criteria for deciding whether to add or remove
points. The policy is taken as
These adaptive mesh methods work as follows.
An initial mesh is assumed. This might be a uni-
form mesh with only a few points, or it could
have some features of the solution built into it. power of ∆x, and the power is higher for the
Then the problem is solved on this mesh. One higher order methods, which suggests that the
of the criteria is then applied to decide if more error is less. For example, with linear elements
points should be added or if points should be re- the error is
moved. Once an entire new mesh is found, the
points can be smoothed somewhat by using [97] y (∆x) =yexact +c2 ∆x2
1 for small enough (and uniform) ∆x. A computer
xk = (xk + xk+1 )
2 code should be run for varying ∆x to confirm
This ensures that the mesh does not change too this. For quadratic elements, the error is
drastically. Then the old solution is interpolated
onto the new mesh and the problem is resolved. y (∆x) =yexact +c3 ∆x3
The process is continued until the solution is
good enough, which might be defined as mak- If orthogonal collocation on finite elements is
ing the second (or first) derivative smaller than used with cubic polynomials, then
some fixed number over the entire domain.
The adaptive mesh strategy was employed by y (∆x) =yexact +c4 ∆x4
Ascher et al. [98] and by Russell and Chris-
However, the global methods, not using finite el-
tiansen [99]. For a second-order differential
ements, converge even faster [100], for example,
equation and cubic trial functions on finite el-
ements, the error in the i-th element is given by N COL
1
y (N ) = yexact +cN
N COL
Error i = C∆x4i u(4) i
Because cubic elements do not have a nonzero Yet the workload of the methods is also differ-
fourth derivative, the third derivative in adjacent ent. These considerations are discussed in [85].
elements is used [85, p. 166]: Here, only sweeping generalizations are given.
If the problem has a relatively smooth so-
1 d 3 ci 1 d3 ci+1 lution, then the orthogonal collocation method
ai = 3 3
, ai+1 = 3
∆xi du ∆xi+1 du3 is preferred. It gives a very accurate solu-

tion, and N can be quite small so the work is
1 ai − ai−1 ai+1 − ai small. If the problem has a steep front in it,
u(4) i ≈ +
2 1
2
(xi+1 − xi−1 ) 1
2
(xi+2 − xi ] the finite difference method or finite element
method is indicated, and adaptive mesh tech-
Element sizes are then chosen so that the follow-
niques should probably be employed. Consider
ing error bounds are satisfied
the reaction – diffusion problem: as the Thiele
C ∆x4i u(4) i ≤ε for all i modulus ϕ increases from a small value with no
diffusion limitations to a large value with signif-
These features are built into the code COLSYS. icant diffusion limitations, the solution changes
The error expected from a method one order as shown in Figure 34. The orthogonal colloca-
higher and one order lower can also be defined. tion method is initially the method of choice.
Then a decision about whether to increase or For intermediate values of ϕ, N = 3 – 6 must be
decrease the order of the method can be made used, but orthogonal collocation still works well
by taking into account the relative work of the (for η down to approximately 0.01). For large
different orders. This provides a method of ad- ϕ, use of the finite difference method, the finite
justing both the mesh spacing (∆x, sometimes element method, or an asymptotic expansion for
called h) and the degree of polynomial ( p). Such large ϕ is better. The decision depends entirely
methods are called h – p methods. on the type of solution that is obtained. For steep
fronts the finite difference method and finite el-
ement method with adaptive mesh are indicated.
7.9. Comparison
What method should be used for any given prob-
lem? Obviously the error decreases with some
d3 f d2 f
2 3
+f = 0
dη dη 2
df
f = = 0 at η = 0
dη
df
= 1 at η → ∞
dη
Because one boundary is at infinity using a mesh
with a constant size is difficult! One approach is
to transform the domain. For example, let
z = e−η
Then η = 0 becomes z = 1 and η = ∞ becomes

z = 0. The derivatives are
Figure 34. Concentration solution for different values of dz d2 z
Thiele modulus = − e−η = − z, = e−η = z
dη dη 2
df d f dz df
= = −z
7.10. Singular Problems and Infinite dη dz dη dz
Domains 2
d2 f d2 f dz d f d2 z d2 f df
2
= + = z 2 2 +z
If the solution being sought has a singularity, a dη dz 2 dη dz dη 2 dz dz
good numerical solution may be hard to find. The Blasius equation becomes
Sometimes even the location of the singular-
ity may not be known [101, pp. 230 – 238]. One d3 f d2 f df
2 −z 3 3 − 3z 2 2 − z
method of solving such problems is to refine the dz dz dz
mesh near the singularity, by relying on the bet-
d2 f df
ter approximation due to a smaller ∆x. Another +f z2 +z = 0
dz 2 dz
approach is to incorporate the singular trial func-
tion into the approximation. Thus, if the solution The differential equation now has variable coef-
approaches f (x) as x goes to zero, and f (x) be- ficients, but these are no more difficult to handle
comes infinite, an approximation may be taken than the original nonlinearities.
as Another approach is to use a variable mesh,
perhaps with the same transformation. For ex-

N
ample, use z = e−η and a constant mesh size in
y (x) = f (x) + ai yi (x)
i=1
z. Then with 101 points distributed uniformly
from z = 0 to z = 1, the following are the nodal
This function is substituted into the differential points:
equation, which is solved for ai . Essentially, a
new differential equation is being solved for a z = 0., 0.01, 0.02, . . . , 0.99, 1.0
new variable:
η = ∞, 4.605, 3.912, . . . , 0.010, 0
u (x) ≡y (x) −f (x)
∆η = ∞, 0.693, . . . , 0.01
The differential equation is more complicated
but has a better solution near the singularity (see Still another approach is to solve on a finite
[102, pp. 189 – 192], [103, p. 611]). mesh in which the last point is far enough away
Sometimes the domain is infinite. Boundary that its location does not influence the solution
layer flow past a flat plate is governed by the Bla- [105]. A location that is far enough away must
sius equation for stream function [104, p. 117]. be found by trial and error.
8. Partial Differential Equations

n
Partial differential equations are differential α = (α0 , α1 , . . . , αn ) , |α| = αi
equations in which the dependent variable is a i=0
function of two or more independent variables.

These can be time and one space dimension, or ∂ |α|
∂α =
time and two or more space dimensions, or two ∂tα0 ∂xα 1 αn
1 . . . ∂xn
or more space dimensions alone. Problems in- the characteristic equation for P is
volving time are generally either hyperbolic or

parabolic, whereas those involving spatial di- aα σ α = 0, σ = (σ0 , σ1 , . . . , σn )
mensions only are often elliptic. Because the |α|=m
methods applied to each type of equation are
very different, the equation must first be classi- σ α = σ0α0 σ1α1 . . . σn
αn
(38)
fied as to its type. Then the special methods ap-
plicable to each type of equation are described. where σ represents coordinates. Thus only the
For a discussion of all methods, see [106]; for a highest derivatives are used to determine the
discussion oriented more toward chemical engi- type. The surface is defined by this equation plus
neering applications, see [107]. Many chemical a normalization condition:
engineering examples that use some of the meth-
n
ods described below are given in [108]. σk2 = 1
k=0
The shape of the surface defined by Equation

8.1. Classification of Equations (38) is also related to the type: elliptic equations
give rise to ellipses; parabolic equations give rise
A set of differential equations may be hyper- to parabolas; and hyperbolic equations give rise
bolic, elliptic, or parabolic, or it may be of mixed to hyperbolas.
type. The type may change for different param-
eters or in different regions of the flow. This can σ12 σ2
+ 22 = 1 , Ellipse
happen in the case of nonlinear problems; an ex- a 2 b
ample is a compressible flow problem with both
subsonic and supersonic regions. Characteristic σ0 = a σ12 , Parabola
curves are curves along which a discontinuity
σ02 − a σ12 = 0, Hyperbola
can propagate. For a given set of equations, it
is necessary to determine if characteristics ex- If Equation (38) has no nontrivial real zeroes
ist or not, because that determines whether the then the equation is called elliptic. If all the roots
equations are hyperbolic, elliptic, or parabolic. are real and distinct (excluding zero) then the op-
erator is hyperbolic.
Linear Problems. For linear problems, the This formalism is applied to three basic types
theory summarized by Joseph et al. [109] can of equations. First consider the equation arising
be used. from steady diffusion in two dimensions:
∂ ∂ ∂ ∂2c ∂2c
, , ..., + = 0
∂t ∂xi ∂xn ∂x2 ∂y 2
is replaced with the Fourier variables This gives
i ξ0 , i ξ1 , . . . , i ξn
−ξ12 −ξ22 = − ξ21 +ξ22 = 0
If the m-th order differential equation is Thus,

P = aα ∂ α + bα ∂ α
σ12 +σ22 = 1 (normalization)
|α|=m |α|≤m
where σ12 +σ22 = 0 (equation)

Next Page
These cannot both be satisfied so the problem is The roots are real and the equation is hyperbolic.
elliptic. When the equation is When β = 0
∂2u ∂2u ξ12 = 0
− =0
∂t2 ∂x2
and the equation is parabolic.
then First-order quasi-linear problems are written
in the form
−ξ02 +ξ12 = 0

n
∂u
Now real ξ 0 can be solved and the equation is A1 = f , x = (t , x1 , . . . , xn )
l=0
∂x1
hyperbolic
u = (u1 , u2 , . . . , uk ) (39)
σ02 +σ12 = 1 (normalization)
The matrix entries A1 is a k×k matrix whose
−σ02 +σ12 = 0 (equation) entries depend on u but not on derivatives of u.
Equation (39) is hyperbolic if
When the equation is
A = Aµ
∂c ∂2c ∂2 c
=D +
∂t ∂x2 ∂y 2 is nonsingular and for any choice of real λ1 ,
l = 0, . . . , n, l = µ the roots αk of
then
 
σ02 +σ12 +σ22 = 1 (normalization) 

n

det 
αA − λ1 A1 
= 0
l=0
σ12 +σ22 = 0 (equation) l=µ
thus we get are real. If the roots are complex the equation
is elliptic; if some roots are real and some are
σ02 = 1 (for normalization) complex the equation is of mixed type.
Apply these ideas to the convection equation
and the characteristic surfaces are hyperplanes
∂u ∂u
with t = constant. This is a parabolic case. + F (u) = 0
∂t ∂x
Consider next the telegrapher’s equation:
Thus,
∂T ∂2T ∂2T
+β =
∂t ∂t2 ∂x2 det (αA0 − λ1 A1 ) = 0 or det (αA1 − λ0 A0 ) = 0
Replacing the derivatives with the Fourier vari- In this case,

ables gives
n = 1, A0 = 1, A1 =F (u)
i ξ0 −β ξ02 +ξ12 = 0
Using the first of the above equations gives
The equation is thus second order and the type
det (α − λ1 F (u)) = 0, or α = λ1 F (u)
is determined by
Thus, the roots are real and the equation is hy-
−β σ02 +σ12 = 0 perbolic.
The final example is the heat conduction
The normalization condition
problem written as
σ02 +σ12 = 1 ∂T ∂q ∂T
Cp = − , q = −k
∂t ∂x ∂x
is required. Combining these gives
In this formulation the constitutive equation for
1 − (1 + β) σ02 = 0 heat flux is separated out; the resulting set of
equations is first order and written as
Previous Page
∂T ∂q ∂c ∂c ∂2c
Cp + = 0 +u = D (41)
∂t ∂x ∂t ∂x ∂x2
∂T and Burgers viscosity equation

k = −q
∂x ∂u ∂u ∂2u
+u = ν (42)
In matrix notation this is ∂t ∂x ∂x2

where u is the velocity and ν is the kinematic
∂T ∂T
Cp 0 ∂t
0 1 ∂x
0 viscosity. This is a prototype equation for the
∂q + ∂q =
0 0 ∂t
k 0 ∂x
−q Navier – Stokes equations (→ Fluid Mechanics,
Chap. 3.2.). For adsorption phenomena [110,
This compares with
p. 202],
∂u ∂u
A0 + A1 =f ∂c ∂c d f ∂c
∂x0 ∂x1 ϕ + ϕu + (1 − ϕ) = 0 (43)
∂t ∂x dc ∂t
In this case A0 is singular whereas A1 is nonsin- where ϕ is the void fraction and f (c) gives the
gular. Thus, equilibrium relation between the concentrations
in the fluid and in the solid phase. In these exam-
det (αA1 −λ0 A0 ) = 0 ples, if the diffusion coefficient D or the kine-
matic viscosity ν is zero, the equations are hyper-
is considered for any real λ0 . This gives
bolic. If D and ν are small, the phenomenon may
− C λ α be essentially hyperbolic even though the equa-
p 0
= 0 tions are parabolic. Thus the numerical methods
kα 0
for hyperbolic equations may be useful even for
or parabolic equations.
Equations for several methods are given here,
α2 k = 0 as taken from [111]. If the convective term is
treated with a centered difference expression the
Thus the α is real, but zero, and the equation is
solution exhibits oscillations from node to node,
parabolic.
and these vanish only if a very fine grid is used.
The simplest way to avoid the oscillations with
a hyperbolic equation is to use upstream deriva-
8.2. Hyperbolic Equations tives. If the flow is from left to right, this would
give the following for Equations (40):
The most common situation yielding hyperbolic
equations involves unsteady phenomena with dci F (ci ) − F (ci−1 ) ci+1 − 2 ci + ci−1
+ = D
convection. A prototype equation is dt ∆x ∆x2
∂c ∂F (c)
for Equation (42):
+ = 0
∂t ∂x dui ui − ui−1 ui+1 − 2 ui + ui−1
+ ui = ν
Depending on the interpretation of c and F (c), dt ∆x ∆x2
this can represent accumulation of mass and con- and for Equation (43):
vection. With F (c) = u c, where u is the velocity,
dci ci − ci−1 d f dci
the equation represents a mass balance on con- ϕ + ϕ ui + (1 − ϕ) = 0
dt ∆x dc i dt
centration. If diffusive phenomenon are impor-
tant, the equation is changed to If the flow were from right to left, then the for-
mula would be
∂c ∂F (c) ∂2c
+ = D (40) dci F (ci+1 ) − F (ci ) ci+1 − 2 ci + ci−1
∂t ∂x ∂x2 + =D
dt ∆x ∆x2
where D is a diffusion coefficient. Special cases
are the convective diffusive equation If the flow could be in either direction, a local
determination must be made at each node i and
the appropriate formula used. The effect of us- 1 n+1 2 n+1

ci+1 − cn
i+1 + ci − cn
i
ing upstream derivatives is to add artificial or 6 3
numerical diffusion to the model. This can be
1 n+1
ascertained by taking the finite difference form + c − cn
i−1
6 i−1
of the convective diffusion equation

u∆t n ∆t D
dci ci − ci−1 ci+1 − 2 ci + ci−1 = − c − cn
i−1 +
+u =D 2∆x i+1 ∆x2
dt ∆x ∆x2

and rearranging u2 ∆t2
+ i+1 − 2 ci + ci−1
cn n n
2∆x2
dci ci+1 − ci−1
+u
dt 2∆x Leaving out the u2 ∆t 2 terms gives the Galerkin
method. Replacing the left-hand side with
u∆x ci+1 − 2 ci + ci−1
= D+
2 ∆x2 cn+1 − cn
i
i
Thus the diffusion coefficient has been changed gives the Taylor finite difference method, and
from dropping the u2 ∆t 2 terms in that gives the
u∆x centered finite difference method. This method
D to D + might require a small time step if reaction
2
phenomena are important. Then the implicit
Another method often used for hyperbolic equa- Galerkin method (without the Taylor terms) is
tions is the MacCormack method. This method appropriate
has two steps; it is written here for Equation (41).
1 n+1 2
u∆t n ci+1 − cn
i+1 + cin+1 − cn
i
c∗n+1 = cn
i − c − cn 6 3
i
∆x i+1 i
1 n+1
∆t D n + ci−1 − cn
i−1
+ c − 2 cn n
i + ci−1
6
∆x2 i+1
u∆t
1 n u∆t ∗n+1 =− i+1 − ci−1
[1 − θ] cn n
cn+1 = c + c∗n+1 − c − c∗n+1 2∆x
i
2 i i
2∆x i i−1
∆t D ∗n+1 u∆t . n+1 /

+ c − 2 c∗n+1 + c∗n+1 − θ ci+1 − cn+1
i−1
2∆x2 i+1 i i−1 2∆x
The concentration profile is steeper for the Mac- ∆t D

+ [1 − θ] cn
i+1 − 2 ci + ci−1
n n
Cormack method than for the upstream deriva- ∆x2
tives, but oscillations can still be present. The
flux-corrected transport method can be added to ∆t D . n+1 n+1 n+1
/
+ θ c i+1 − 2 c i + c i−1
the MacCormack method. A solution is obtained ∆x2
both with the upstream algorithm and the Mac-
Cormack method; then they are combined to add The Taylor terms are not required because
just enough diffusion to eliminate the oscilla- the implicit time step provides the same effect
tions without smoothing the solution too much. as diffusion.
The algorithm is complicated and lengthy but For the nonlinear Equation (40) the
well worth the effort [111–113]. Taylor – Galerkin method is
If finite element methods are used, an explicit
Taylor – Galerkin method is appropriate. For the
convective diffusion equation the method is
n+1 n+1 Each of these methods tries to avoid oscil-

1 ci+1 − ci+1 1 ci−1 − ci−1
n n
2 cn+1 − cn
+ i i
+ lations that would disappear if the mesh were
6 ∆t 3 ∆t 6 ∆t
fine enough. For the steady convective diffusion
1 ∆t equation these oscillations do not occur provided
= −Fi+1
n n
+ Fi−1 +
2∆x 4∆x2
u∆x
≤ 1
2
(44)
2 2D
dF dF n
+ ci+1 − cn
i
dc i+ 1 dc i For large u, ∆x must be small to meet this con-

dition. An alternative is to use a small ∆x in

2 2
dF dF n regions where the solution changes drastically.
− + ci − cn
dc i dc i−1
i−1 Because these regions change in time, the el-
ements or grid points must move. The crite-
D n ria to move the grid points can be quite com-
+ c − 2 cn n
i + ci− 1
∆x2 i+1 plicated, and typical methods are reviewed in
A stability diagram for the explicit methods [111]. The criteria include moving the mesh in
applied to the convective diffusion equation is a known way (when the movement is known a
shown in Figure 35. Notice that all the methods priori), moving the mesh to keep some prop-
require erty (e.g., first- or second-derivative measures)
uniform over the domain, using a Galerkin or
Co =
u∆t
≤ 1
weighted residual criterion to move the mesh,
∆x and Euler – Lagrange methods which move part
where Co is the Courant number. How much Co of the solution exactly by convection and then
should be less than one depends on the method add on some diffusion after that.
and on r = D ∆t/∆x 2 , as given in Figure 35. The The final illustration is for adsorption in a
MacCormack method with flux correction re- packed bed, or chromatography. Equation (43)
quires a smaller time step than the MacCor- can be solved when the adsorption phenomenon
mack method alone (curve a), and the implicit is governed by a Langmuir isotherm.
Galerkin method (curve e) is stable for all values αc
of Co and r shown in Figure 35 (as well as even f (c) =
1+K c
larger values).
LIVE GRAPH
Similar numerical considerations apply and sim-
Click here to view ilar methods are available [111].
8.3. Parabolic Equations in One

Dimension
In this section several methods are applied to

parabolic equations in one dimension: separa-
tion of variables, combination of variables, fi-
nite difference method, finite element method,
and the orthogonal collocation method. Separa-
tion of variables is successful for linear prob-
lems, whereas the other methods work for linear
or nonlinear problems. The finite difference, the
finite element, and the orthogonal collocation
Figure 35. Stability diagram for convective diffusion methods are numerical, whereas the separation
equation (stable below curve) or combination of variables can lead to analyti-
a) MacCormack; b) Centered finite difference;
c) Taylor finite difference; d) Upstream; e) Galerkin;
cal solutions.
f) Taylor – Galerkin
Analytical Solutions. Consider the diffu- c (x, t) = f (x) + u (x, t)

sion equation
u (0, t) = 0
∂c ∂2c
=D
∂t ∂x2 u (1, t) = 0
with boundary and initial conditions Thus, f (0) = 1 and f (1) = 0 are necessary. Now
the combined function satisfies the boundary
c (x, 0) = 0 conditions. In this case the function f (x) can
be taken as
c (0, t) = 1, c (1, t) = 0
f (x) = 1 −x
A solution of the form
The equation for u is found by substituting for c
c (x, t) =T (t) X (x) in the original equation and noting that the f (x)
drops out for this case; it need not disappear in
is attempted and substituted into the equation,
the general case:
with the terms separated to give
∂u ∂2u
1 dT 1 d2 X =D
= ∂t ∂x2
D T dt X dx2
The boundary conditions for u are
One side of this equation is a function of x alone,
whereas the other side is a function of t alone. u (0, t) = 0
Thus, both sides must be a constant. Otherwise,
if x is changed one side changes, but the other u (1, t) = 0
cannot because it depends on t. Call the constant
− λ and write the separate equations The initial conditions for u are found from the
initial condition
dT d2 X
= − λ D T, = − λX u (x, 0) = c (x, 0) −f (x) = x − 1
dt dx2
The first equation is solved easily Separation of variables is now applied to this
equation by writing
T (t) =T (0) e−λDt
u (x, t) =T (t) X (x)
and the second equation is written in the form
The same equation for T (t) and X (x) is obtained,
d2 X but with X (0) = X (1) = 0.
+ λX = 0
dx2
d2 X
Next consider the boundary conditions. If they + λX = 0
dx2
are written as
X (0) = X (1) = 0
c (1, t) = 1 =T (t) X (1)
Next X (x) is solved for. The equation is an
c (0, t) = 0 =T (t) X (0) eigenvalue problem. The general solution is ob-
mx 2
√ e and finding that m + λ = 0;
tained by using
the boundary conditions are difficult to sat- thus m= ±i λ. The exponential term
isfy because they are not homogeneous, with √
a zero right-hand side. Thus, the problem must e±i λx
be transformed to make the boundary conditions

is written in terms of sines and cosines, so that
homogeneous. The solution is written as the sum
the general solution is
of two functions, one of which satisfies the non-
homogeneous boundary conditions, whereas the √ √
X = B cos λ x +E sin λ x
other satisfies the homogeneous boundary con-
ditions.
The boundary conditions are The Galerkin criterion for finding An is the same
√ √ as the least-squares criterion [114, p. 183]. The
X (1) = B cos λ + E sin λ= 0 solution is then
X (0) = B = 0 ∞
2
π 2 Dt
c (x, t) = 1 − x + An sin n π x e−n
If B = 0, then E = 0 is required to have any solu- n=1
tion at all. Thus, λ must satisfy
This is an “exact” solution to the linear prob-
√
sin λ = 0 lem. It can be evaluated to any desired accuracy
by taking more and more terms, but if a finite
This is true for certain values of λ, called eigen- number of terms are used, some error always oc-
values or characteristic values. Here, they are curs. For large times a single term is adequate,
whereas for small times many terms are needed.
λn = n2 π 2
For small times the Laplace transform method
Each eigenvalue has a corresponding eigenfunc- is also useful, because it leads to solutions that
tion converge with fewer terms. For small times, the
method of combination of variables may be used
Xn (x) =E sin n π x as well. For nonlinear problems, the method of
The composite solution is then separation of variables fails and one of the other
methods must be used.
Xn (x) Tn (t) = E A sin n π x e−λn Dt The method of combination of variables is
useful, particularly when the problem is posed
This function satisfies the boundary conditions in a semi-infinite domain. Here, only one ex-
and differential equation but not the initial con- ample is provided; more detail is given in [114–
dition. To make the function satisfy the initial 116] The method is applied here to the nonlinear
condition, several of these solutions are added problem
up, each with a different eigenfunction, and E A

is replaced by An . ∂c ∂ ∂c ∂ 2 c d D (c) ∂c 2
= D (c) = D (c) +
∞ ∂t ∂x ∂x ∂x2 dc ∂x
2
π 2 Dt
u (x, t) = An sin n π x e−n
n=1
with boundary and initial conditions
The constants An are chosen by making u (x, t) c (x, 0) = 0
satisfy the initial condition.
∞ c (0, t) = 1, c (∞, t) = 0

u (x, 0) = An sin n π x = x − 1
n=1 The transformation combines two variables into
one
The residual R (x) is defined as the error in the
initial condition: x
c (x, t) = f (η) where η = √
∞
4 D0 t

R (x) = x − 1 − An sin n π x
The use of the 4 and D0 makes the analysis below
n=1
simpler. The equation for c (x, t) is transformed
Next, the Galerkin method is applied, and the into an equation for f (η)
residual is made orthogonal to a complete set of
functions, which are the eigenfunctions. ∂c d f ∂η ∂c d f ∂η
= , =
∂t dη ∂t ∂x dη ∂x
1
(x − 1) sin m π xdx 2
∂2c d2 f ∂η d f ∂2η
2
= +
0 ∂x dη 2 ∂x dη ∂x2
∞
1 ∂η x/2 ∂η 1 ∂2η
Am = −- , = √ , = 0
= An sin m π x sin n π xdx = ∂t ∂x 4 D0 t ∂x2
2 4 D0 t3
n=1 0
The result is the theory presented in Chapter 6. The equations

are written as
d df df
K (c) + 2η = 0
dη dη dη D
n+1
dci ci+1 − 2 ci + ci−1
= D 2
= 2
Bij cj
dt ∆x ∆x j=1
K (c) = D (c) /D0
The boundary conditions must also combine. In where the matrix B is tridiagonal. The stability
this case the variable η is infinite when either x is of the integration of these equations is governed
infinite or t is zero. Note that the boundary con- by the largest eigenvalue of B. If Euler’s method
ditions on c (x, t) are both zero at those points. is used for integration,
Thus, the boundary conditions can be combined
D 2
to give ∆t ≤
∆x2 |λ|max
f (∞) = 0 The largest eigenvalue of B is bounded by the
The other boundary condition is for x = 0 or Gerschgorin theorem [119, p. 135].
η = 0,
n
|λ|max ≤ max2<j<n |Bji | = 4
f (0) = 1 i=2
Thus, an ordinary differential equation must be This gives the well-known stability limit
solved rather than a partial differential equation. D 1
When the diffusivity is constant the solution is ∆t ≤
∆x2 2
the well-known complementary error function:
If other methods are used to integrate in time,
c (x, t) = 1 − erf η = erfc η then the stability limit changes according to the
method. It is interesting to note that the eigen-
η 2 values of Equation (45) range from D π 2 /L 2
e−ξ dξ
0 (smallest) to 4 D/∆x 2 (largest), depending on
erf η =

∞ the boundary conditions. Thus the problem be-
e−ξ2 dξ
0 comes stiff as ∆x approaches zero [114, p. 263].
Another way of studying the stability of ex-
This is a tabulated function [117]. plicit equations is to use the positivity theorem.
If the Euler method is applied, the equations can
Numerical Methods. Numerical methods be written in the form
are applicable to both linear and nonlinear prob-
lems on finite and semi-infinite domains. The cn+1
i − cn
i i+1 − 2 ci + ci−1
cn n n
finite difference method is applied by using the = D

∆t ∆x2
method of lines [118]. In this method the same
equations are used for the spatial variations of where
the function, but the function at a grid point
cn n
i =c (xi , t )
can vary with time. Thus the linear diffusion
problem is written as Then the new value is given by
dci ci+1 − 2 ci + ci−1
= D (45) D∆t n D∆t D∆t n
dt ∆x2 cn+1 = c + 1−2 cn
i + c
i
∆x2 i+1 ∆x2 ∆x2 i−1
This can be written in the general form
dc
Theorem. If
=A A c
dt
cn+1 =A cn n n
i+1 +B ci +C ci−1
This set of ordinary differential equations can
be solved by using any of the standard methods. and A, B, and C are positive, and A + B + C ≤ 1,
The stability of explicit schemes is deduced from then the scheme is stable and the errors die out.
Here the theorem requires

1
D∆t e
1−2 >0 CJI = ∆xe NJ (u) NI (u) du
∆x2
0
which gives the same stability condition [114, This set of equations can be written in matrix
p. 217]. form
Implicit methods can also be used. Write a
finite difference form for the time derivative and dc
CC = AAc
average the right-hand sides, evaluated at the old dt
and new times: Now the matrix C C is not diagonal, so that a
set of equations must be solved for each time
cn+1 i+1 − 2 ci + ci−1
cn n n
− cn
i step, even when the right-hand side is evaluated
i
= D (1 − θ) 2
∆t ∆x explicitly. This is not as time-consuming as it
seems, however. The explicit scheme is written
cn+1 n+1
i+1 − 2 ci + cn+1
+Dθ
i−1 as
∆x2
cn+1 − cn
i
Now the equations are of the form C Cji i
= A Aji cn
i
∆t

D∆t θ n+1 D∆t θ n+1 D∆t θ n+1 and rearranged to give
− c i+1 + 1 + 2 ci − c
∆x2 ∆x2 ∆x2 i−1
CCji cn+1
i − cn
i = ∆t AAji cn
i or
D∆t (1 − θ) n
= cn
i + ci+1 − 2 cn n
i + ci−1
∆x2 CC cn+1 − cn = ∆t AAc
and require solving a set of simultaneous equa- This is solved with an L U decomposition (see
tions, which have a tridiagonal structure. Using Section 1.1) that retains the structure of the mass
θ = 0 gives the Euler method (as above); θ = 0.5 matrix C C. Thus,
gives the Crank – Nicolson method; θ = 1 gives
the backward Euler method. The stability limit C C = LU
is given by
At each step, calculate
D∆t 0.5
≤ cn+1 −cn = ∆t U −1 L−1 A A cn
∆x2 1 − 2θ
whereas the oscillation limit is given by This is quick and easy to do because the inverse
of L and U are simple. Thus the problem is re-
D∆t 0.25 duced to solving one full matrix problem and
≤
∆x2 1−θ then evaluating the solution for several right-
If a time step is chosen between the oscillation hand sides. For implicit methods the same ap-
limit and stability limit, the solution will oscil- proach yields
late around the exact solution, but the oscilla- cn+1 − cn
i
tions remain bounded. For further discussion, C Cji i
= A Aji [(1 − θ) cn n
i + θ ci ]
∆t
see [114, p. 218].
The finite element method is handled in a sim- which can be rearranged to give
ilar fashion, as an extension of two-point bound- (CCji − ∆t θ A Aji ) cn+1
i
ary value problems by letting the solution at the
nodes depend on time. For the diffusion equation CCji cn
i + ∆t (1 − θ) AAji ci ≡ fj
n
the finite element method gives
This is again solved as
dceI
e e
CJI = BJI ceI
dt cn+1 =U −1 L−1 f
e I e I
with the mass matrix defined by In both cases the L U decomposition need be
redone only when the time step size is changed.
The method of orthogonal collocation uses a quite useful for hyperbolic or parabolic prob-
similar extension: the same polynomial of x is lems on rectangular domains [121]. The Cheby-
used but now the coefficients depend on time. shev polynomial of degree n is defined by
c (x, t) = a (t) + b (t) x + x (1 − x) Tn (cos θ) = cos n θ

N The first few polynomials are
ai (t) Pi−1 (x)
t=1 T0 (x) = 1, T1 (x) = x, T2 (x) = 2 x2 − 1,
The same spatial derivatives evaluated at the col-
T3 (x) = 4 x3 − 3 x, T4 (x) = 8 x4 − 8 x2 + 1
location points can be derived:
They satisfy the orthogonality condition

N +2
c (x, t) = di (t) xi−1 ;
1
i=1 1 π cn
√ Tn (x) Tm (x) dx = δnm
1 − x2 2

N +2 −1
c (xj , t) = di (t) xi−1
j ; c (t) = Q d (t)
i=1 where the constants are given by
∂c
N +2 c0 = 2, cn = 0 (n < 0) , cn = 1 (n > 0)

= di (t) (i − 1) xi−2 ;
∂x xj xj
i=1 In solving a differential equation for f (x, t), for
example, the function f is expanded in Cheby-
∂c
= C d (t) shev polynomials
∂x
∞

∂c an Tn , |x| ≤ 1
= C Q−1 c ≡ A c f =
∂x n=0
Now both c and ∂c/∂x are functions of time, but Various derivatives are also expanded in Cheby-
the matrix A is constant in time. For the time shev polynomials. For differential operator L,
derivatives, formally
∂c dc (xj , t) dcj ∞

= = Lf = bn Tn , |x| ≤ 1
∂t xj dt dt
n=0
Thus, for diffusion problems
For specific cases [121, p. 160] the relations bet-
dcj
N +2 ween the coefficients of the function (an ) and
= Bji ci , j = 2, . . . , N + 1 the derivatives (bn ) are given by
dt i=1
∞

df
This can be integrated by using the standard Lf = , cn bn = 2 p ap
dx
methods for ordinary differential equations as p=n+1
p+nodd
initial value problems. Stability limits for ex-
plicit methods are available [114, p. 204]. d2 f
∞

The method of orthogonal collocation on fi- Lf = , cn bn = p p2 − n2 ap
dx2 p=n+2
nite elements can also be used, and details are p+neven
provided elsewhere [114, pp. 228 – 230]. An ap-

plication to chemical reactors, where the radial Derivatives can be evaluated even more effi-
direction is handled by using the method of or- ciently by using a recursion relation. When
thogonal collocation on finite elements and the ∞

axial direction is handled by using the method of Sn = p ap
lines (PDECOL), is given by Pirkle et al. [120]. p=n+1
p+nodd
Spectral methods employ Chebyshev poly-
nomials and the fast Fourier transform, and are the following can be used [121, p. 117]:
collocation point the solution can be advanced

forward to the n + 1-th time level.
Sn = Sn+2 + (n + 1) an+1 , 0 ≤ n ≤ N − 1
The advantage of the spectral method is that
SN = 0, SN +1 = 0
it is very fast and can be adapted quite well to
parallel computers. It is, however, restricted in
This recurrence relation is assured by the geometries that can be handled.
Software packages exist that use various dis-
1 dTn+ 1 1 dTn−1 cretizations in the spatial direction and an inte-
2 Tn = − , n>1
n + 1 dx n − 1 dx gration routine in the time variable: PDECOL
In the Chebyshev collocation method, N + 1 col- uses B-splines for the spatial direction and vari-
location points are used ous GEAR methods in time [122, p. 346]; PDE-
PACK and DSS [122, p. 351] use finite differ-
πj ences in the spatial direction and GEARB in
xj = cos , j = 0, 1, . . . , N
N time [123, p. 163]; and REACOL [114, p. 191]
As an example, consider the equation use orthogonal collocation in the radial direc-
tion and LSODE in the axial direction, whereas
∂u ∂u REACFD uses finite difference in the radial di-
+ f (u) = 0
∂t ∂x rection (both codes are restricted to modeling
An explicit method in time can be used chemical reactors).
The maximum eigenvalue for all the methods
un+1 − un ∂u n is given by
+ f (un ) = 0
∆t ∂x
LB
and evaluated at each collocation point |λ|max = (47)
∆x2
un+1
j − un
j ∂u n where the values of LB are as follows:
+ f un
j = 0
∆t ∂x j Finite difference 4
Galerkin, linear elements, lumped 4
The trial function is taken as Galerkin, linear elements 12
Galerkin, quadratic elements 60

N
π pj Orthogonal collocation on finite elements, 36
uj (t) = ap (t) cos , un n
j = uj (t ) (46) cubic
p=0
N
Assume that the values unj exist at some time.

Then invert Equation (46) using the fast Fourier
transform to obtain {ap } for p = 0, 1, . . . , N; then 8.4. Elliptic Equations
calculate Sp
Elliptic equations can be solved with both fi-
Sp = Sp+2 + (p + 1) ap+1 , 0 ≤ p ≤ N − 1 nite difference and finite element methods. One-
dimensional elliptic problems are two-point
SN = 0, SN +1 = 0 boundary value problems and are covered in
Chapter 7. Two- and three-dimensional elliptic
and finally problems are often solved with iterative meth-
2 Sp ods when the finite difference method is used
(1)
ap = and with direct methods when the finite ele-
cp
ment method is used. Thus, two aspects must
Thus, the first derivative is given by be considered: how the equations are discretized
to form sets of algebraic equations and how the
∂u N
(1) π pj algebraic equations are then solved.
= ap (t) cos
∂x j p=0
N The prototype elliptic problem is steady-state
heat conduction or diffusion,
This is evaluated at the set of collocation points
by using the fast Fourier transform again. Once ∂2T ∂2T
k 2
+ = Q
the function and the derivative are known at each ∂x ∂y 2
possibly with a heat generation term per unit from low to high j, the Gauss – Seidel method
volume, Q. The boundary conditions can be can be used:

Dirichlet or 1st kind: T = T 1 on boundary S 1 ∆x2
2 1+ T s+1 s s+1
i,j = T i+1,j + T i−1,j
∆y 2
Neumann or 2nd kind: k ∂T
∂n = q2 on boundary S 2
Robin, mixed, or 3rd kind: ∂n = h (T − T3 ) on

−k ∂T ∆x2 s Qi,j
boundary S 3
+ 2
T i,j+1 + T s+1
i,j−1 − ∆x2
∆y k
This method converges twice as fast as the Ja-

Illustrations are given for constant physical
cobi method. The relaxation method uses
properties k, h, while T 1 , q2 , T 3 are known func-
tions on the boundary and Q is a known function
∆x2 ∆x2
of position. The finite difference formulation is 2 1+ T ∗i,j = T si+1,j + T s+1
i−1,j +
∆y 2 ∆y 2
given by using the following nomenclature
Qi,j
T si,j+1 + T s+1
i,j−1 − ∆x2
Ti,j = T (i ∆x, j ∆y) k
∗
The finite difference formulation is then T s+1
i,j = T i,j + β T i,j − T i,j
s s
Ti+1,j − 2 Ti,j + Ti−1,j If β = 1, this is the Gauss – Seidel method. If

∆x2 β > 1, it is overrelaxation; if β < 1, it is underre-
Ti,j+1 − 2 Ti,j + Ti,j−1 laxation. The value of β may be chosen empiri-
+ = Qi,j (48) cally, 0 < β < 2, but it can be selected theoreti-
∆y 2
cally for simple problems like this [124, p. 100],
Ti,j = T1 for i, j on boundary S1 [114, p. 282]. In particular, the optimal value of
∂T
the iteration parameter is given by
k = q2 for i, j on boundary S2
∂n i,j
− ln (βopt − 1) ≈R
∂T
−k = h (Ti,j − T3 ) for i, j on boundary S3 and the error (in solving the algebraic equation)
∂n i,j
is decreased by the factor (1 − R)N for every N
If the boundary is parallel to a coordinate axis the iterations. For the heat conduction problem and
boundary slope is evaluated as in Chapter 7, by Dirichlet boundary conditions,
using either a one-sided, centered difference or
a false boundary. If the boundary is more irreg- π2
R =
ular and not parallel to a coordinate line, more 2 n2
complicated expressions are needed and the fi- (when there are n points in both x and y direc-
nite element method may be the better method. tions). For Neumann boundary conditions, the
Equation (48) is rewritten in the form value is

∆x2 ∆x2
2 1+ Ti,j = Ti+1,j + Ti− 1,j + π2 1
∆y 2 ∆y 2 R =
2 n2 1 +max [∆x2 /∆y 2 , ∆y 2 /∆x2 ]
Qi,j
(Ti,j+1 + Ti,j−1 ) − ∆x2 These iterative methods are point iterative meth-
k ods. Line iterative methods [124, p. 113] use
The Jacobi method is
∆x2
∆x2 ∆x2 2 1+ T ∗i,j = T ∗i+1,j + T ∗i−1,j
2 1+ T s+1 s s ∆y 2
i,j = T i+1,j + T i−1,j +
∆y 2 ∆y 2
∆x2 s Qi,j
+ T i,j+1 + T si,j−1 − ∆x2
s s 2 Qi,j ∆y 2 k
T i,j+1 +T i,j−1 − ∆x
k
∗
T s+1
i,j = T i,j + β T i,j − T i,j
s s
If the points are located in a regular order, and
the calculations proceed from low to high i, then
The last equation is applied after the solution for where

the entire line (current value of i). Now the value
of R is AeIJ = − k∇NI ·∇NJ dA − h3 NI NJ dC
2 1/2 C3
2π ∆y
R = 1+
n ∆x2
FIe = NI QdA + NI q2 dC − NI h3 T3 dC
for Dirichlet boundary conditions;
C2 C3
2π
R =
n Also, a necessary condition is that
for Neumann boundary conditions.
Line Jacobi converges twice as fast as point Ti =T1 on C1
Jacobi (when ∆x = ∆y), and line successive In these equations I and J refer to the nodes of
overrelaxation converges twice as fast as point the triangle forming element e and the summa-
successive overrelaxation [124, pp. 110, 114]. tion is made over all elements. These equations
The alternating direction method can be em- represent a large set of linear equations. They are
ployed for elliptic problems by using sequences solved simultaneously, with only one iteration,
of iteration parameters [114, pp. 283 – 286], by using either the frontal solution method [129]
[124, pp. 120 – 127]. The method is well suited or various sparse matrix techniques (Chap. 1).
to transient problems.
These are the classical iterative techniques.
Recently, preconditioned conjugate gradient
methods have been developed (see Chap. 1). In
these methods a series of matrix multiplications
are done iteration by iteration; and the steps lend
themselves to the efficiency available in paral-
lel computers. In the multigrid method the prob-
lem is solved on several grids, each more refined
than the previous one. In iterating between the
solutions on different grids, one converges to the
solution of the algebraic equations. A chemical
engineering application is given in [125].
Another way to solve the elliptic equations is
to convert them to parabolic equations and in- Figure 36. Finite elements trial function: linear polynomials
tegrate them to “steady state”. One method of on triangles
doing this, operator splitting, is illustrated for
the Navier – Stokes equations in Section 8.5. If the problem is nonlinear, e.g., with k a func-
The Galerkin finite element method (FEM) is tion of temperature,
useful for solving elliptic problems and is partic-
∂ ∂T ∂ ∂T
ularly effective when the domain or geometry is k (T ) + k (T ) = Q (T )
∂x ∂x ∂y ∂y
irregular. As an example, cover the domain with
triangles and define a trial function on each trian- then the equations must be solved iteratively. Let
gle. The trial function takes the value 1.0 at one T sI be the known temperature at node I. Then
corner and 0.0 at the other corners, and is linear Equation (49) can be used with
in between (see Fig. 36). These trial functions on
each triangle are pieced together to give a trial AeIJ (T e ) = − k (T e ) ∇NI ·∇NJ dA
function on the whole domain. General treat-
ments of the finite element method are available
[126–128]. For the heat conduction problem the − h3 NI NJ dC
method gives [114] C3

AeIJ T eJ = FIe (49)
e J e J

aI + aJ + aK = 1
FIe (T e ) = NI Q (T e ) dA + NI q2 dC
C2
bI + bJ + bK = 0

− NI h3 T3 dC cI + cJ + cK = 0
C3
k
or AeIJ = − (bI bJ + cI cJ )
4∆

AeIJ (T e,s ) T e,s+1
J = FJe (T e,s ) e
FIJ =
Q
(aI + bI x̄ + cI ȳ) =
Q∆
e J e J 2 3
This is a successive substitution method. The xI + x J + x K yI + y J + y K

x̄ = , ȳ = ,
Newton – Raphson method can also be used in 3 3
the form
2
aI + bI x̄ + cI ȳ = ∆
3
AeIJ (T e,s ) T e,s+1
J
e J One nice feature of the finite element method

is the use of natural boundary conditions. In
dAe
+ IJ
(T e,s ) T e,s+1 − T e,s this problem the natural boundary conditions are
K K
e K
dTK the Neumann or Robin conditions. When using
Equation (49), the problem can be solved on a
dF e domain that is shorter than needed to reach some
= FIe (T e,s ) + I
e K
dTK limiting condition (such as at an outflow bound-
ary). The externally applied flux is still applied
/
(T e,s ) T e,s+1 − T e,s at the shorter domain, and the solution inside
K K
the truncated domain is still valid. Examples are
The integrals in these formulas can be calcu- given in [111] and [130]. The effect of this is to
lated analytically when the physical properties allow solutions in domains that are smaller, thus
are constant. The results are given for a triangle saving computation time and permitting the so-
with nodes I, J, and K in counterclockwise order. lution in semi-infinite domains. Use of the col-
Within an element, location method on finite elements is discussed
in [106, pp. 330 – 339].
T = NI (x, y) TI + NJ (x, y) TJ + NK (x, y) TK The methods can also be combined by us-
ing one method for one direction and another
NI =
aI + bI x + cI y method for the other direction. Klein [131,
2∆ p. 603] treated two-dimensional reactors using
orthogonal collocation in the radial direction and
a I = x J yK − x K yJ
a shooting method in the axial direction. Pirkle
bI = yI − yK et al. [132] were able to derive an equivalent
one-dimensional model of a chemical reactor to
cI = x K − x J avoid solving the two-dimensional problem. De-
greve et al. [133] used an adaptive mesh cal-
plus permutation on I, K, J culation for combustion problems (see also the
  examples in [111]).
1 xI yI A general-purpose package for general two-
 
2 ∆ = det 1 xJ yJ  = 2 (area of triangle) dimensional domains and rectangular three-
1 xK yK dimensional domains is ELLPACK [116,
p. 348]. This package allows choice of a vari-
ety of methods: finite difference, Hermite col-
location, spline Galerkin, collocation, and oth-
ers. Comparisons of the various methods are
available [134]. The program FISHPAK solves
the Helmholtz equation in multiple dimensions

when the domain is separable (because fast n+1/2
T i,j − Tn
methods like FFT are used) [122, p. 346]. Cp
i,j
=
∆t/2
k n+1/2 n+1/2 n+1/2

8.5. Parabolic Equations in Two or 2
T i+1,j − 2 T i,j + T i−1,j
∆x
Three Dimensions
k n
+ i,j + T i,j−1 − Q
T i,j+1 − 2 T n n
Computations become much more lengthy with ∆y 2
two or more spatial dimensions, for example, the and then another ∆t/2 using an implicit method
unsteady heat conduction equation
n+1/2
T n+1 − T i,j
∂T ∂2T ∂2T Cp
i,j
=
Cp = k + −Q ∆t/2
∂t ∂x2 ∂y 2
or the unsteady diffusion equation k n+1/2 n+1/2 n+1/2

2
T i+1,j − 2 T i,j + T i−1,j
∆x
∂c ∂2c ∂2c
∂t
=D
∂x2
+
∂y 2
− R (c) k n+1
+ T i,j+1 − 2 T n+1 n+1
i,j + T i,j−1 −Q
∆y 2
In the finite difference method an explicit tech-
nique would evaluate the right-hand side at the This method is second order in ∆t errors
n-th time level: [O (∆t 2 )] and reduces the approximate compu-
tational burden from n4 to 6 n2 .
T n+1
i,j − Tn
i,j
The method of operator splitting is also use-
Cp ful when different terms in the equation are best
∆t
evaluated by using different methods or as a
k n technique for reducing a larger problem to a se-
= T i+1,j − 2 T n n
i,j + T i−1,j
∆x2 ries of smaller problems. Here the method is il-
k n lustrated by using the Navier – Stokes equations.
+ i,j + T i,j−1 − Q
T i,j+1 − 2 T n n
In vector notation the equations are
∆y 2
When Q = 0 and ∆x = ∆y, the time step is lim- ∂u

+ u ·∇u = f − ∇p + µ∇2 u
ited by ∂t
The equation is solved in the following steps
∆x2 Cp ∆x2
∆t ≤ or
4k 4D u∗ − un
= − un ·∇un + f + µ∇2 un
∆t
These time steps are smaller than for one-
dimensional problems. For three dimensions, 1
the limit is ∇2 pn+1 = ∇ ·u∗
∆t
∆x2 un+1 − u∗
∆t ≤ = − ∇p
6D ∆t
To avoid such small time steps, which become This can be done by using the finite difference
smaller as ∆x decreases, an implicit method [135, p. 162] or the finite element method [136].
could be used. This leads to large sparse matri- In the finite element method, the need to solve
ces, rather than convenient tridiagonal matrices. large sets of equations simultaneously must be
These can be solved, but the alternating direction eliminated. To do this, the matrices multiply-
method is also useful [124, pp. 57 – 63]. This re- ing time derivatives are approximated by mov-
duces a problem on an n×n grid to a series of 2 n ing all terms to the diagonal (called lumping).
one-dimensional problems on an n-grid. Here, The effects of this have been examined in detail
step forward ∆t/2 by using the Crank – Nicolson in [137].
method
9. Integral Equations [138–141]

t
If the dependent variable appears under an inte- 1 1 2
T (x, t) = √ g (s) √ e−x /4(t−s) ds
gral sign an equation is called an integral equa- π t−s
0
tion; if derivatives of the dependent variable ap-
pear elsewhere in the equation it is called an inte- Suppose the problem is generalized so that the
grodifferential equation. This chapter describes boundary condition is one involving the solution
the various classes of equations, gives informa- T , which might occur with a radiation boundary
tion concerning Green’s functions, and presents condition or heat-transfer coefficient. Then the
numerical methods for solving integral equa- boundary condition is written as
tions.
∂T
= − G (T, t) , x = 0, t > 0
∂x
9.1. Classification The solution to this problem is

t
Volterra integral equations have an integral with 1 1
T (x, t) = √ G (T (0, s) , s) √
a variable limit, whereas Fredholm integral π t−s
0
equations have a fixed limit. Volterra equations
are usually associated with initial value or evolu- 2
e−x /4(t−s)
ds
tionary problems, whereas Fredholm equations
are analogous to boundary value problems. The If T (t) is used to represent T (0, t), then
terms in the integral can be unbounded, but still
yield bounded integrals, and these equations are t
1 1
said to be weakly singular. A Volterra equation T (t) = √ G (T (s) , s) √ ds
π t−s
of the second kind is 0
t Thus the behavior of the solution at the boundary

y (t) = g (t) + λ K (t, s) y (s) ds (50) is governed by an integral equation. Nagel and
a Kluge [142] use a similar approach to solve for
adsorption in a porous catalyst.
whereas a Volterra equation of the first kind is The existence and uniqueness of the solution
t
can be proved. One example is the following:
y (t) = λ K (t, s) y (s) ds
Theorem [140, p. 30]. If K (t, s) is continu-
a
ous in 0 ≤ s ≤ t ≤ α and g (t) is continuous in
0 ≤ t ≤ α, then the integral equation (Eq. 50)
Equations of the first kind are very sensitive to possesses a unique continuous solution for
solution errors so that they present severe nu- 0 ≤ t ≤ α. More general theorems are also avail-
merical problems. able [140, p. 32]. The solution to the integral
An example of a problem giving rise to a equation can be obtained by using a Picard or
Volterra equation of the second kind is the fol- successive substitution method (this is how the
lowing heat conduction problem: existence theorem is proved).
∂T ∂2T t
Cp = k , 0 ≤ x < ∞, t > 0
∂t ∂x2 yn (t) = g (t) + λ K (t, s) yn−1 (s) ds
a
∂T
T (x, 0) = 0, (0, t) = − g (t) ,
∂x Sometimes the kernel is of the form
∂T K (t, s) =K (t − s)
lim T (x, t) = 0, lim = 0
x→∞ x→∞ ∂x
If this is solved by using Fourier transforms the Equations of this form are called convolution
solution is equations and can be solved by taking the
Laplace transform. For the integral equation
t t
Y (t) = G (t) + λ K (t − τ ) Y (τ ) dτ y (t) = y (0) + F (s, y (s)) ds
0 0
t which is a nonlinear Volterra equation. The gen-

∗
K (t) Y (t) ≡ K (t − τ ) Y (τ ) dτ eral nonlinear Volterra equation is
0
t
the Laplace transform is y (t) = g (t) + K (t, s, y (s)) ds (53)
0
y (s) = g (s) + k (s) y (s)
A successive substitution method for its solution
is
k (s) y (s) =L [K (t) ∗ Y (t)]
t
Solving this for y (s) gives
yn+1 (t) = g (t) + K [t, s, yn (s)] ds
g (s) 0
y (s) =
1 − k (s)
Theorem [140, p. 55]. If g (t) is continuous,
If the inverse transform can be found, the inte- the kernel K (t, s, y) is continuous in all variables
gral equation is solved. and satisfies a Lipschitz condition
A Fredholm equation of the second kind is
|K (t, s, y) − K (t, s, z) | ≤ L |y − z|
b
y (x) = g (x) + λ K (x, s) y (s) ds (51) then the nonlinear Volterra equation has a unique
a continuous solution.
Nonlinear Fredholm equations have special
whereas a Fredholm equation of the first kind is names. The equation
b 1
K (x, s) y (s) ds = g (x) f (x) = K [x, y, f ( y)] dy
a
0
The limits of integration are fixed, and these is called the Urysohn equation [139, p. 208]. The
problems are analogous to boundary value prob- special equation
lems. An eigenvalue problem is a homogeneous
equation of the second kind. 1
f (x) = K [x, y] F [y, f ( y)] dy
b 0
y (x) = λ K (x, s) y (s) ds (52)
a is called the Hammerstein equation [139,
p. 209]. Iterative methods can be used to solve
Solutions to this problem occur only for spe- these equations, and these methods are closely
cific values of λ, the eigenvalues. Usually the tied to fixed point problems. A fixed point prob-
Fredholm equation of the second or first kind lem is
is solved for values of λ different from these,
which are called regular values. x = F (x)
Nonlinear Volterra equations arise naturally
from initial value problems. For the initial value and a successive substitution method is
problem
xn+1 =F (xn )
dy
= F (t, y (t)) Local convergence theorems prove the process
dt
convergent if the solution is close enough to the
both sides can be integrated from 0 to t to obtain answer, whereas global convergence theorems
are valid for any initial guess [139, p. 229 – 231]. dy

The successive substitution method for nonlin- = − λ y, y (0) = 1
dt
ear Fredholm equations is
the stability results are identical to those for ini-
1 tial value methods. In particular, using the trape-
yn+1 (x) = K [x, s, yn (s)] ds zoid rule for integral equations is identical to
0 using this rule for initial value problems. The
method is A-stable.
Typical conditions for convergence include that The next highest quadrature method is Simp-
the function satisfies a Lipschitz condition. son’s rule. When expressed for three points, each
∆t apart, this is
t
i+2
9.2. Numerical Methods for Volterra ∆t
y (s) ds = [ y (ti ) + 4 y (ti+1 ) + y (ti+2 )]
Equations of the Second Kind 3
ti
Volterra equations of the second kind are anal- ti+1 = ti +∆t, ti+2 = ti + 2∆t
ogous to initial value problems. An initial value
problem can be written as a Volterra equation of When applied to an integral equation in the first
the second kind, although not all Volterra equa- two intervals,
tions can be written as initial value problems ∆t
[140, p. 7]. Here the general nonlinear Volterra yi+2 = g (ti+2 ) + {K (ti+2 , ti , yi )
3
equation of the second kind is treated (Eq. 53).
The simpliest numerical method involves replac- + 4 K (ti+2 , ti+1 , yi+1 )
ing the integral by a quadrature using the trape-
zoid rule. + K (ti+2 , ti+2 , yi+2 )}
( This is the equation for yi+2 , but now there is
1
yn ≡ y (tn ) = g (tn ) +∆t K (tn , t0 , y0 ) no equation for yi+1 . This is obtained by sub-
2
dividing the region from ti to ti+1 with another

n−1
1 point at ti+1/2 . Then an integral equation can be
+ K (tn , ti , yi ) + K (tn , tn , yn ) written as
i=1
2
∆t
This equation is a nonlinear algebraic equation yi+1 = g (ti+1 ) + {K (ti+1 , ti , yi )
3
for yn . Since y0 is known it can be applied to
solve for y1 , y2 , . . . in succession. For a single + 4 K ti+1 , ti+1/2 , yi+1/2
integral equation, at each step one must solve a
single nonlinear algebraic equation for yn . Typ- + K (ti+1 , ti+1 , yi+1 )}
ically, the error in the solution to the integral To obtain yi+1/2 a quadratic interpolation is used
equation is proportional to ∆t µ , and the power through the original three points:
µ is the same as the power in the quadrature error
[140, p. 97]. 3 3 1
yi+1/2 = yi + yi+1 − yi+2
The stability of the method [140, p. 111] can 8 4 8
be examined by considering the equation Now two equations must be solved for the two
points yi+1 and yi+2 . In this block-by-block
t method [140, p. 114], the solution proceeds to
y (t) = 1 − λ y (s) ds solve for two unknowns at a time, block by
0 block.
whose solution is Explicit Runge – Kutta methods have an
analogous formula for integral equations.
y (t) = e−λt When solving nonstiff differential equations,
Runge – Kutta methods are fast and efficient un-
Since the integral equation can be differentiated til the time step is very small to meet the stability
to obtain the initial value problem
requirements. Then implicit methods are used, functional form of p is included in the quadrature
even though the set of simultaneous algebraic rule. For example, the integral
equations must be solved. This time-consuming
step can be justified only for stiff problems. b
When solving integral equations, however, the I = p (s) ψ (s) ds
time-consuming part of the calculation is the re- a
peated approximation of the integrals; thus the where p is singular at some points. Each quadra-
effort needed to solve the algebraic equations is ture method corresponds to some method of in-
not as large a fraction of the total effort for interpolating the solution. That interpolation is
tegral methods. Thus, implicit methods, like the written as
trapezoid rule given above, tend to be preferred

for integral equations [140, p. 124]. ψ (t) = ai ψi (t)
Predictor-corrector methods can be used,
however. Using fourth-order Adams – Moulton Integrals of the form
and Adams – Bashforth methods gives
b
∆t p (s) ψi (s) ds
ȳn+1 = gn+1 + [55 K (tn+1 , tn , yn )
24 a
− 59 K (tn+1 , tn−1 , yn−1 ) must be integrated exactly. Then methods can be

constructed to handle weakly singular problems.
+ 37 K (tn+1 , tn−2 , yn−2 ) The product trapezoid rule and product
Simpson’s rule are contained in the follow-
− 9 K (tn+1 , tn−3 , yn−3 )]
ing algorithm. Subdivide the interval into
and n equal subintervals of length ∆t, having
points at t 0 , t 1 , . . . , tn . Within each subinter-
∆t val, introduce a further subdivision with points
yn+1 = gn+1 + [9 K (tn+1 , tn+1 , ȳn+1 )
24 ti ≤ ti0 < ti1 < . . . tim ≤ ti+1 . Approximate the
+ 19 K (tn+1 , tn , yn )
function with a polynomial of degree m in
each subinterval using a Lagrangian interpola-
− 5 K (tn+1 , tn−1 , yn−1 ) tion (see Section 2.2).

m
+ K (tn+1 , tn−2 , yn−2 )] ψ (t) = lij (t) ψ (tij ) , ti0 ≤ t ≤ tim
i=0
(t − ti0 ) . . . (t − ti,j−1 ) (t − ti,j+1 ) . . . (t − tim )

lij =
(tij − ti0 ) . . . (tij − ti,j−1 ) (tij − ti,j+1 ) . . . (tij − tim )
Inserting this approximation into the integral

The next situation that must be addressed is gives
how to solve problems when the kernel is infi-
nite at certain points, i.e., when the problem has
n−1 m
I = wij ψ (tij )
a weak singularity. Clearly the formulas given i=0 j=0
above would be unsuitable when the kernel is
infinite at the quadrature point. To handle prob- where
lems like this, product equations are employed.
t
The problem is written as i+2
wij = p (s) lij (s) ds

t ti
y (t) = g (t) + p (t, s) K [t, s, y (s)] ds
0 If the following integrals can be calculated

where the kernel K is Lipschitz continuous and
sµ p (s) ds, µ = 0, 1, . . . , m
the singular behavior is contained in p. Then, the
then the weights can be found explicitly. where

An example is the function as piecewise con-
t
i+1
stant [140, p. 132]. Then the integrals are 1
αn,i+1 = (ti+1 − s) p (tn , s) ds,
t
∆t
i+1 ti
K [tn , s, y (s)] p (s) ds =
t
i+1
ti
1
βn,i+1 = (s − ti ) p (tn , s) ds
t
∆t
i+1 ti
K [tn , ti , y (ti )] p (s) ds
The numerical version of the integral equation
ti
is
In using this expression the numerical form of
the integral equation is yn = gn + αn K [tn , t0 , y (t0 )]
−1

n−1 N
y n = gn + wni K [tn , ti , yi ] , n = 1, 2, . . . + (αn,i+1 + βni ) K [tn , ti , y (ti )]
i=0 i=1
where the weights are + βnn K [tn , tn , y (tn )]

t
i+1 Higher order methods can be solved block by
wni = p (s) ds block in a similar fashion.
ti Volterra equations of the first kind are not
well posed, and small errors in the solution can
When the function p (s, t) = (s − t)−1/2 , the have disastrous consequences [140, p. 71]. Only
weights are lowest order methods have been recommended
.√ - / for problems of the first kind [140, p. 151].
wni = 2 tn − ti − tn − ti+1
By starting with y0 = g (0) successive values of

y1 , y2 , etc. can be calculated. This corresponds
9.3. Numerical Methods for Fredholm,
to the Euler method of integration and is only Urysohn, and Hammerstein Equations
accurate to O (∆t). To improve the accuracy, the of the Second Kind
Richardson extrapolation techniques described
in Section 6.2 can be used. Whereas Volterra equations could be solved
Next, consider the product trapezoid rule from one position to the next, like initial value
[140, p. 135]. The kernel is approximated by differential equations, Fredholm equations must
piecewise linear functions be solved over the entire domain, like bound-
ary value differential equations. Thus, large sets
s − ti of equations will be solved and the notation is
K [t, s, y (s)] = K [t, ti+1 , y (ti+1 )]
∆t designed to emphasize that.
ti+1 − s The methods are also based on quadrature
+ K [t, ti , y (ti )] , ti ≤ s ≤ ti+1 formulas. For the integral
∆t
Then the integration formula is b
I (ϕ) = ϕ ( y) dy
tn a
p (tn , s) K [tn , s, y (s)] ds = αn1 K [tn , t0 , y (t0 )]
0
a quadrature formula is written:
−1

n

N
I (ϕ) = wi ϕ ( y i )
+ (αn,i+1 + βni ) K [tn , ti , y (ti )] i=0
i=1
Then the integral Fredholm equation can be
+ βnn K [tn , tn , y (tn )] rewritten as

n
b b
f (x) − λ wi K (x, yi ) f ( yi ) = g (x) ,
K (x, y) f (y) dy= K (x, y) [f (y) − f (x)] dy
i=0
a a
a ≤ x ≤ b (54)
b b
If this equation is evaluated at the points x = yj , + K (x, y) f (x) dy = K (x, y) [f (y)
a a

n
f ( yj ) − λ w i K ( yj , y i ) f ( y i ) = g ( y i )
i=0
−f (x)] dy + f (x) H (x)
is obtained, which is a set of linear equations to where

be solved for { f ( yj )}. The solution at any point
is then given by Equation (54). b
Because the quadrature method is often de- H (x) = K (x, y) f (x) dy
fined on subintervals, the equation is rewritten a
in terms of information obtained on the subin- is a known function. The integral equation is then
tervals. The finite element notation is a natu- replaced by
ral notation. On a subinterval with points yI =1 ,
yI =2 , . . . the quadrature formula is
n
f (x) = g (x) + wi K (x, yi ) [ f ( yi )
xi+2 1 i=0

NP
ϕ ( y) dy = ∆x ϕ (u) du = wI ϕ ( yI )
I=1
− f (x)] + f (x) H (x)
xi 0
An element diagonal matrix is then constructed: In matrix notation this is

 
w1 0 . 0 (I − λM ) f = g
0 . 0 
 w2 
D=  and the matrix M is the same as K D except for
. . . . 
0 0 . wn the diagonal elements, which are

and the element kernel Mii = Hi − Kik wk
e
KiJ = K (xi , xe +∆ xe uJ ) The product quadrature can be used to handle
weak singularities, as with Volterra equations
The numerical version of the integral equation (see [138, p. 540] for an example).
is then Collocation methods can be applied as well

NP [138, p. 396]. To solve integral Equation (51)
fi − λ e
KiJ e
DJJ f eJ = gi expand f in the function
e J=1

n
In matrix notation this can be written as f= ai ϕi (x)
i=0
(I −λK D) f =g
Substitute f into the equation to form the resid-
The structure of this matrix is typically dense, ual
because the kernel is nonzero even when the

n
n b
points x and y are in different elements. Thus,
ai ϕi (x) − λ ai K (x, y) ϕi ( y) dy
the economies obtained by using sparse matrix
i=0 i=0 a
routines to solve differential equations do not
always hold for integral equations. = g (x)
A common type of integral equation has a sin-
gular kernel along x = y. This can be transformed Evaluate the residual at the collocation points
to a less severe singularity by writing
b
n

n
n
w i K ( yi , y i ) f ( y i ) = λ f ( y j ) ,
ai ϕi (xj ) − λ ai K (xj , y) ϕi ( y) dy i=1
i=0 i=0 a
i = 0, 1, . . . , n
= g (xj )
leads to the matrix eigenvalue problem
The expansion can be in piecewise polynomials,
K D f =λf
leading to a collocation finite element method,
or global polynomials, leading to a global ap-
proximation. If orthogonal polynomials are used
then the quadratures can make use of the ac-
curate Gaussian quadrature points to calculate 9.5. Green’s Functions
the integrals. Galerkin methods are also possi-
Integral equations can arise from the formula-
ble [138, p. 406]. Mills et al. [143] consider
tion of a problem by using Green’s function.
reaction – diffusion problems and say the choice
For example, the equation governing heat con-
of technique cannot be made in general because
duction with a variable heat generation rate is
it is highly dependent on the kernel.
represented in differential forms as
When the integral equation is nonlinear, iter-
ative methods must be used to solve it. Con- d2 T Q (x)
= , T (0) = T (1) = 0
vergence proofs are available, based on Ba- dx2 k
nach’s contractive mapping principle. Consider In integral form the same problem is [138,
the Urysohn equation, with g (x) = 0 without loss pp. 57 – 60]
of generality: 1
1
b T (x) = G (x, y) Q ( y) dy
k
f (x) = F [x, y, f ( y)] dy 0
a
−x (1 − y) x ≤ y
The kernel satisfies the Lipschitz condition G (x, y) =
−y (1 − x) y ≤ x
maxa≤x,y≤b |F [x, y, f ( y)] − F [x, z, f (z)] | Green’s functions for typical operators are given
below.
≤ K | y − z| For the Poisson equation with solution decay-
ing to zero at infinity
Theorem [139, p. 214]. If the constant K is ∇2 ψ = − 4π
< 1 and certain other conditions hold, the suc-
the formulation as an integral equation is
cessive substitution method
ψ (r) = (r 0 ) G (r, r 0 ) dV0
b
fn+1 (x) = F [x, y, fn ( y)] dy, n = 0, 1, . . . V
a where Green’s function is [144, p. 891]

converges to the solution of the integral equa- 1
G (r, r 0 ) = in three dimensions
tions. r
= − 2 ln r in two dimensions
2
9.4. Numerical Methods for Eigenvalue where r = (x − x0 )2 + ( y − y0 )2 + (z − z0 )2
Problems
in three dimensions
Eigenvalue problems are treated similarly to 2
Fredholm equations, except that the final equa- and r = (x − x0 )2 + ( y − y0 )2
tion is a matrix eigenvalue problem instead of a
set of simultaneous equations. For example, in two dimensions
For the problem Green’s function for the differential operators

are [146]
∂u
= D ∇2 u, u = 0 on S,
∂t
a = 1
with a point source at x0 , y0 , z0
1 + Sh 2
− x, y ≤ x
G (x, y, Sh) =
Green’s function is [145, p. 355] 1 + Sh − y,
2
x<y
1
u = a = 2
8 [π D (t − τ )]3/2

2
Sh
− lnx, y ≤ x
2
−[(x−x0 ) +(y−y0 ) +(z−z0 ) 2 2
]/4D(t−τ ) G (x, y, Sh) =
e 2
Sh
− lny, x<y
When the problem is

a = 3
∂c
= D∇2 c 2
+ 1
− 1, y ≤ x
∂t G (x, y, Sh) = Sh x
2
Sh
+ 1
y
− 1, x<y
c = f (x, y, z) in S at t = 0
Green’s functions for the reaction diffusion
c = ϕ (x, y, z) on S, t > 0 problem were used to provide computable error
bounds by Ferguson and Finlayson [146].
the solution can be represented as [145, p. 353]
If Green’s function has the form

c = (u)τ =0 f (x, y, z) dxdydz
u (x) v ( y) 0 ≤ y ≤ x
K (x, y) =
u ( y) v (x) x ≤ y ≤ 1
t
∂u
+D ϕ (x, y, z, τ ) dSdt the problem
∂n
0
1
When the problem is two dimensional, f (x) = K (x, y) F [ y, f ( y)] dy
1 2 2 0
u = - e−[(x−x0 ) +(y−y0 ) ]/4D(t−τ )
4 π D (t − τ ) may be written as

x
c = (u)τ =0 f (x, y) dxdy
f (x) − [u (x) v ( y) − u ( y) v (x)] ·
0
t
∂u
+D ϕ (x, y, τ ) dCdt F [ y, f ( y)] dy = α v (x)
∂n
0
where
For the following differential equation and
boundary conditions 1
α = u ( y) F [ y, f (y)] dy
1 d dc
xa−1 = f [x, c (x)] , 0
xa−1 dx dx
Thus, the problem ends up as one directly for-
dc 2 dc
(0) = 0, (1) + c (1) = g mulated as a fixed point problem:
dx Sh dx
where Sh is the Sherwood number, the problem f = Φ (f )
can be written as a Hammerstein integral equa-
tion: When the problem is the diffusion – reaction
one, the form is
1
c (x) = g − G (x, y, Sh) f [ y, c ( y)] y a−1 dy
0

x ∂ψ ∂ϕ
ϕ −ψ dS = 0
c (x) = g − [u (x) v ( y) − u ( y) v (x)] ∂n ∂n
S
0
Consider the two-dimensional case. Since the
f [ y, c (y)] y a−1 dy − α v (x) function ψ is singular at a point, the integrals
must be carefully evaluated. For the region
1 shown in Figure 37, the domain is S = S 1 + S 2 ;
α = u ( y) f [ y, c ( y)] y a−1 dy a small circle of radius r 0 is placed around the
0 point P at x 0 , y0 . Then the full integral is
Dixit and Taularidis [147] solved problems
∂ln r ∂ϕ
ϕ − lnr dS
involving Fischer – Tropsch synthesis reactions ∂n ∂n
S
in a catalyst pellet using a similar method.

θ=2π
∂lnr0 ∂ϕ
+ ϕ − lnr0 r0 dθ = 0
9.6. Boundary Integral Equations and ∂n ∂n
θ=0
Boundary Element Method
As r 0 approaches 0,
The boundary element method utilizes Green’s lim r0 lnr0 = 0
theorem and integral equations. Here, the r0 →0
method is described briefly for the following and

boundary value problem in two or three dimen-
sions
θ=2π
∂ lnr0
lim ϕ r0 dθ = − ϕ (P ) 2 π
r0 →0 ∂n
∂ϕ
∇2 ϕ = 0, ϕ = f1 on S1 , = f2 on S2 θ=0
∂n
Thus for an internal point,
Green’s theorem (see page 58) says that for any
1 ∂ lnr ∂ϕ
functions sufficiently smooth ϕ (P ) = ϕ − lnr dS (55)
2π ∂n ∂n
S
∂ψ ∂ϕ
ϕ∇2 ψ − ψ∇2 ϕ dV = ϕ −ψ dS
∂n ∂n If P is on the boundary, the result is [148, p. 464]
V S

1 ∂ lnr ∂ϕ
Suppose the function ψ satisfies the equation ϕ (P ) = ϕ − lnr dS
π ∂n ∂n
S
∇2 ψ = 0 Putting in the boundary conditions gives

In two and three dimensions, such a function is ∂ lnr ∂ϕ
π ϕ (P ) = f1 − lnr dS
2 ∂n ∂n
2 2 S1
ψ = ln r, r = (x − x0 ) + ( y − y0 )

∂lnr
in two dimensions + ϕ − f2 lnr dS (56)
∂n
2 S2
1
ψ = , r = (x − x0 )2 + ( y − y0 )2 + (z − z0 )2
r This is an integral equation for ϕ on the bound-
ary. Note that the order is one less than the orig-
in three dimensions inal differential equation. However, the integral
where {x 0 , y0 } or {x 0 , y0 , z0 } is a point in the equation leads to matrices that are dense rather
domain. The solution ϕ also satisfies than banded or sparse, so some of the advan-
tage of lower dimension is lost. Once this inte-
∇2 ϕ = 0
gral equation (Eq. 56) is solved to find ϕ on the
boundary, it can be substituted in Equation (55)
so that to find ϕ anywhere in the domain.
Next Page
Thus, for an internal point,

∂lnr ∂ϕ
2 π ϕ (P ) = ϕ − lnr dS
∂n ∂n
S

+ g lnr dA (57)
A
and for a boundary point,

∂lnr ∂ϕ
π ϕ (P ) = ϕ − lnr dS
Figure 37. Domain with singularity at P ∂n ∂n
S
In the boundary finite element method, both
the function and its normal derivative along the + g lnr dA (58)
boundary are approximated. A
N
∂ϕ ∂ϕ
N
If the region is nonhomogeneous this method
ϕ = ϕj Nj (ξ) , = Nj (ξ)
∂n j=1 ∂n j can be used [148, p. 475], and it has been ap-
j=1
plied to heat conduction by Hsieh and Shang
One choice of trial functions can be the piece- [149]. The finite element method can be ap-
wise constant functions shown in Figure 38. The plied in one region and the boundary finite ele-
integral equation then becomes ment method in another region, with appropriate
  matching conditions [148, p. 478]. If the prob-
N
 ∂lnri ∂ϕj  lem is nonlinear, then it is more difficult. For ex-
π ϕi = ϕj dS − lnri  ds
j=1
∂n ∂n ample, consider an equation such as Poisson’s
sj sj
in which the function depends on the solution as
The function ϕj is of course known along s1 , well
whereas the derivative ∂ϕj /∂n is known along
s2 . This set of equations is then solved for ϕi and ∇2 ϕ =g (x, y, ϕ)
∂ϕi /∂n along the boundary. This constitutes the
boundary integral method applied to the Laplace Then the integral appearing in Equation (58)
equation. must be evaluated over the entire domain, and the
solution in the interior is given by Equation (57).
For further applications, see [150] and [151].
10. Optimization
10.1. Introduction
The design and operation of chemical processes

involve making decisions that commonly have
Figure 38. Trial function on boundary for boundary finite a large economic impact. In most cases, select-
element method ing the appropriate decisions is a complex pro-
cess. Chemical processes tend to exhibit strong
If the problem is Poisson’s equation
interactions among units as well as many dif-
∇2 ϕ = g (x, y) ferent types of trade-offs. Furthermore, how to
select decisions that satisfy design or product
Green’s theorem gives specifications is not always obvious. A clear
need exists for the use of systematic techniques
∂lnr ∂ϕ
ϕ − lnr dS + g lnr dA = 0
∂n ∂n
S A
Previous Page
to model the decision making in chemical pro- Different types of optimization problems
cesses. The methods of optimization, or more arise depending on the nature of the functions
precisely, mathematical programming, are con- involved in Equation (59). The simplest case,
cerned with this objective. when no constraints are involved, gives rise
In its most general form, an optimization to unconstrained nonlinear optimization prob-
problem can be modeled as follows: lems. An example in chemical engineering of
this problem type is the fitting of parameters for
min F = F (z) thermodynamic correlations. When both equal-
ity and inequality constraints are involved, a
such that h (z) = 0 nonlinear programming (NLP) problem must
be solved. These problems are used to model
g (z) ≤ 0 (59) the optimization of sizes and operating condi-
where F represents a specified objective functions of flow sheets operating at steady state.
tion that is to be minimized. The case of maxi- The particular case when all the functions and
mization can be modeled by minimizing the neg- constraints are linear gives rise to linear pro-
ative of the objective. The functions h and g re- gramming (LP) problems. Linear programming
present equality and inequality constraints that problems are used in the planning and schedul-
must be satisfied as the minimum of the func- ing of refinery operations. At the other extreme,
tion F is determined. These constraints define when differential equations are involved in the
the feasible region for the allowable choices of model, a variational or optimal control problem
variables z. Also, any inequality constraint can exists. Such problems are encountered in the de-
be rearranged in the above form. termination of optimal temperature profiles in
In Equation (59) the variables z are often con- batch reactors. Finally, when a subset of the vari-
tinuous in nature because they are used mainly ables is restricted to take discrete (e.g., 0 – 1) val-
to model flow, pressure, temperature, and size. ues, a mixed-integer optimization problem ex-
However, in a number of cases, some of these ists. Such formulations are used to synthesize
variables can be restricted to take only discrete the configuration of a process flow sheet.
values. This arises when in modeling choices This chapter presents on overview of the fore-
of standard sizes or logical choices that are re- mentioned optimization problems. Section 10.2
presented by Boolean variables 0 – 1. The ob- presents the optimality conditions for nonlinear
jective function F is assumed to be a scalar unconstrained and constrained continuous vari-
function typically representing total cost or net able optimization problems, introducing con-
present value. When several objective functions strained derivatives and the closely related La-
are specified (e.g., minimize cost, maximize re- grange theory. The next section presents both
liability), these objectives are commonly com- basic and state-of-the-art algorithms for these
bined into one function, or else one is selected problems. Because of their importance as prob-
for optimization whereas the others are specified lem classes, individual sections covering linear
as constraints by stating values they are to attain. programming, mixed-integer programming, and
The equations h (z) = 0 are commonly linear or the optimization of variational problems com-
nonlinear algebraic equations when steady-state plete this chapter.
processes are being modeled. However, in deal-
ing with distributed or dynamic models, ordi-
nary or partial differential equations might be 10.2. Conditions for Optimality
involved. The inequalities g (z) ≤ 0, correspond In this section, conditions are presented by
to algebraic functions, many of which are sim- which a candidate point for the solution of the
ply lower and upper bounds on the variables. Fi- optimization problem (Eq. 59) can be tested to
nally, the objective function and the constraints see if it is indeed optimal. Generally, local tests
may be given explicitly as equations, or they may are developed, which can tell only if the candi-
be given as implicit functions when computed date point is a minimum point for the objective
through procedures (e.g., by calling a subrou- function among all points in a small but finite
tine or by running a process simulator). neighborhood of points around it.
To prove that a point is the global optimum

F (u) = F (û) + ∇T
u F |û (u − û)
requires stating something about the structure
of the overall problem. A sufficient condition is 1
that the problem is convex, a property that can + (u − û)T ∇uu F |û (u − û) + . . .
2
be proved for certain classes of problems (e.g., In the neighborhood of û where ∆u = u − û is
linear and some geometric programming prob- sufficiently small that all higher order terms are
lems). For a convex problem, all local optimum negligible, F (u) will increase if the matrix of
points (if many exist) are connected to each other second partial derivatives ∇uu F evaluated at û
(form a flat spot) and must be the global opti- is positive definite. Because ∇uu F is symmet-
mum. ric, all of its eigenvalues are real numbers, and
An intuitive feel for the concept of a con- it will be positive definite if and only if all of
vex problem can be gained by visualizing an its eigenvalues are greater than zero. Thus a set
objective function F (z1 , z2 ) plotted above two of sufficient conditions that F has a local mini-
variables, z1 and z2 . Constraints of the form mum at û is that ∇T u F is zero and that ∇uu F is
g (z1 , z2 ) ≤ 0 and h (z1 , z2 ) = 0 limit the allowed positive definite at û.
values of z1 and z2 . A three-dimensional vol-
ume is defined by joining vertically all allowed Equality Constrained Problems – Con-
values of z1 and z2 to their respective values of strained Derivatives. The necessary conditions
F. If any two points in this three-dimensional for minimizing a scalar objective function F
volume are joined by a straight line and that line written in terms of n variables z and subject to m
always stays within the volume, the problem is equality constraints h (z) = 0 are more complex.
convex; otherwise, it is not. A nonlinear equal- A formal definition of the problem is
ity constraint in z1 and z2 makes the problem
nonconvex. Min {F (z) | h (z) = 0, z ∈Ren , h : Ren → Rem }
Assume the candidate point ẑ is to be tested to

Local Minimum Point for Unconstrained see if it could be an optimum point. Linearizing
Problems. The first problem for which optimal- the m equality constraints around ẑ yields
ity conditions are presented is for the minimiza-
tion of a scalar objective function F of r indepen- h (ẑ+∆z) = h (ẑ) +∇T
z h|ẑ ∆z
dent variables ui , i = 1, 2, . . . r, where the vari- where ∆z = z − ẑ. Require that the move ∆z be
ables u are unconstrained, i.e., selected in such a way that to a first-order ap-
proximation, the equality constraints remain at
Min {F (u) u ∈ Rer }
zero, i.e., ∆h = h (ẑ + ∆z) − h (ẑ) = 0 (this is con-
If F is sufficiently smooth (is continuous and straining the allowed move). Therefore, m con-
has continuous first and second derivatives), a straints have been written which must be satis-
necessary condition for optimality is that F is fied for any move away from ẑ.
stationary with respect to all variations in the in- Next partition the variables ∆z into a set of
dependent variables u at the candidate point û, m dependent variables ∆x and n − m = r inde-
i.e., pendent variables ∆u, and rewrite the previous
equations in terms of these partitioned variables.
∂F
= 0, i = 1, 2, . . . r or ∇T T
u F = 0 at u = û ∆h = ∇T
x h|ẑ ∆x + ∇u h|ẑ ∆u = 0
T
∂ui
The point û may, however, be a minimum, max- These equations are solved for the dependent
imum, or saddle point. variables ∆x in terms of the independent vari-
Sufficient conditions are harder to state. They ables ∆u:
require that any local move away from the op- . /−1
∆x= − ∇T
x h|ẑ ∇T
u h|ẑ ∆u = 0 (60)
timal point û must give rise to an increase in
the objective function. Here, F is expanded in a Because the inverse of the Jacobian matrix
Taylor series locally around the candidate point ∇T x h |ẑ must be formed, we are constrained
û up to second-order terms: to partition the variables ∆z into variables ∆x
and ∆u in such a way that this Jacobian matrix within that row. Pivot using any of the variables
will be nonsingular. Only the values of the inde- z, and rearrange the variables and equations so
pendent variables ∆u can be changed arbitrarily they are in the order in which they were piv-
because Equation (60) provides us with the cor- oted. Figure 39 shows the structure of the re-
responding values for the dependent variables sult. The pivoted variables become the depen-
∆x. dent variables x. Because one could pivot with
The objective function F (z) can also be lin- these variables, the Jacobian matrix ∇T x h |ẑ will
earized in terms of the partitioned variables be nonsingular, as required. The remaining un-
pivoted variables are selected to be the indepen-
∆F = ∇T
x F |ẑ ∆x + ∇u F |ẑ ∆u
T
dent variables u. Finally, and most conveniently,
the nonzero portion of the last row beneath the
and ∆x can be replaced by using Equation (60): variables u contains the numerical evaluation
( . /−1 ) for the constrained derivatives given in Equation
∆F = ∇T
u F | ẑ − ∇ T
x F |ẑ ∇T
x h|ẑ ∇T
u h ∆u (61). The numbers here are exact, as if the ma-
trix operations in Equation (61) had been carried
T r out.
dF dF
= ∆u = ∆ui (61)
du ∆h=0 i=1
dui ∆h=0
The terms in the braces { } are in the form of a

row vector, one term for each variable ∆ui . Each
tells how the objective function F will change
if an infinitesimal change is made in the corre-
sponding independent variable ∆ui while cor-
responding changes in the variables x are be-
ing computed such that the equality constraints
remain satisfied. These terms are called con-
strained derivatives.
Necessary conditions for optimality are now
written directly: F should be stationary with re-
spect to any infinitesimal move in the indepen-
dent variables u. The coefficients in these equa- Figure 39. Computing constrained derivatives by Gaussian
elimination
tions must be zero, i.e.,

dF Equality Constrained Problems – Lagrange
= 0, i = 1, 2, . . . r
dui ∆h=0 Multipliers. Look at exactly the same opti-
Partitioning the variables z into a legal set of mization problem given in the last section, again
dependent and independent variables, and at the with a point ẑ, and consider what conditions are
same time computing these constrained deriva- necessary for ẑ to be an optimum point. A scalar
tives by performing the forward elimination step function is formed by adding to the objective
of a Gauss elimination for solving linear equa- function each of the equality constraints multi-
tions, are rather easy. The following m + 1 equa- plied by an arbitrary multiplier and partitioning
tions are written in the m = n + r variables z. The the variables as shown above.
Jacobian should be evaluated at ẑ, i.e., it should
m
L (x, u, λ) = F (x, u) + λi hi (x, u)
be an array of numbers:
i=1
∇T
z h|ẑ ∆z = 0 m rows = F (x, u) + λT h (x, u)
z F |ẑ ∆z = 0 1 row
∇T This function is termed the Lagrange function
and the multipliers are called Lagrange multi-
Next a forward Gauss elimination is performed pliers. At any point where the functions h (z) are
on this Jacobian. The eliminations are done zero, the Lagrange function equals the objective
in the last row (∇T
z F ∆z = 0) without pivoting function.
Next, the stationarity conditions for L are Thus, with the multiplier, an estimation can be
written with respect to all the variables of which made of how the objective function will change
it is a function, x, u, and λ. for a small change in the value of a constraint.
For example, suppose a chemical process
∇T
z L |ẑ =∇x F |ẑ + λ ∇hx |ẑ = 0
T T T
flow sheet has been optimized, subject to a con-
straint that held the sulfur dioxide concentration
u L |ẑ =∇u F |ẑ + λ ∇hu |ẑ = 0
∇T T T T
leaving in the stack gas at 1 ppm. In solving with
the Lagrange formulation, the multiplier would
λ L |ẑ =h (x, u)
∇T T
= 0 have been evaluated for that constraint. Then an
The first equation is solved for the Lagrange estimate could be made of the cost of decreasing
multipliers the concentration to 0.95 ppm by simply apply-
ing Equation (64) rather than by resolving. (If
. /−1 this change could be tied to projected human
λT = − ∇T
x F ∇hx
T
(62)
mortality rates downstream of the emission, our
and this result is used to eliminate the multipliers multiplier would allow calculation of how many
from the second equation. dollars would have to be spent to save another
life per year.)
. /
u L = ∇u F − ∇x F ∇hx ∇hu = 0
∇T T T T T
(63)
Equality and Inequality Constrained
The results are examined. The third stationarity Problems – Kuhn – Tucker Multipliers. In
equation for the Lagrange function with respect this section, the following problem is consid-
to the Lagrange multipliers simply states that ered:
the equality constraints must be zero. Equation
Min {F (z) |h (z) = 0, g (z) ≤ 0,
(63) states that ∇u L is equal to the constrained
derivatives for the problem, which can be seen by
where z ∈ Ren , F : Ren → Re1 ,
comparing them to Equation (61). These should
be zero. Thus the necessary conditions for op- h : Ren → Rem , g : Ren → Rep }
timality, derived in the last section, have been
reproduced rather nicely. Now, p inequality constraints g (z) ≤ 0 are be-
These Lagrange multipliers are very inter- ing added to the equality constrained problem
esting variables. They are often referred to as considered in the last two sections. A Lagrange
shadow prices, adjoint variables, or dual vari- function can be written, as before:
ables, depending on the context. The notion of
a shadow price is that the multiplier λi tells one L (z, λ, µ) ≡ F (z) +λT h (z) +µT g (z)
the marginal cost of requiring the constraint hi to Here, to the Lagrange function is added each of
be held at zero. If hi is moved slightly away from the inequality constraints gi (z), multiplied by
zero at a point that is currently the solution for a so-called Kuhn – Tucker multiplier µi . The
the optimization problem, and reoptimization is necessary conditions for optimality are then
performed (which will result in all the other con- stated and interpreted. These conditions are
straints being held at zero), consider how the ob- called the (Karush-)Kuhn – Tucker conditions
jective function will change. The perturbation in for inequality-constrained optimization prob-
the Lagrange function L is given by lems.
∆L = ∆F + λi ∆hi = 0 ∇T
z L |ẑ =∇z F |ẑ + ∇z h|ẑ λ + ∇z g|ẑ µ= 0
T T T
(65a)
which is zero because, as above, L (and not the ∇T
λ L = h (z) = 0 (65b)
objective Function F ) is at a stationary point at
the optimum. Solving for the change in the ob- g (z) ≤ 0 (65c)
jective function yields
µi g i (z) = 0, i = 1, 2, . . . p (65d)
∆F = −λi ∆hi = −λi hi (64)
µi ≥ 0, i = 1, 2, . . . p (65e)
The conditions in Equation (65 d) are called

complementary slackness conditions. Each one
says that either the constraint gi (z) = 0 or its cor-
responding multiplier µi is zero (or both can be
zero). Intuitively, this makes sense. If the con-
straint gi (z) = 0, it is behaving like an equality
constraint, and its Kuhn – Tucker multiplier µi
can be thought of as a Lagrange multiplier that
can be nonzero. In this case the inequality is be- Figure 40. Special case where necessary conditions do not
ing treated exactly like an equality constraint. If, hold
on the other hand, the constraint is away from
zero, it is not a part of the problem. It can be Kuhn – Tucker Sufficiency Conditions.
removed from the Lagrange function by simply Sufficiency conditions can be stated which
setting its corresponding Kuhn – Tucker multi- will assure that an optimum that meets the
plier to zero. Kuhn – Tucker conditions is indeed a local min-
If the objective function is to be minimized, imum point. The matrix of second derivatives
then Kuhn and Tucker [152] showed that of the Lagrange function with respect to all the
the multipliers must be positive, conditions variables z evaluated at ẑ must be generated and
(Eq. 65 e). Because a Kuhn – Tucker multiplier used in a test to guarantee that all moves away
is a Lagrange multiplier for an inequality con- from ẑ which remain feasible with respect to the
straint that is being treated as an equality con- constraints will lead to an increase in the ob-
straint, the interpretation that it is a shadow price jective function. This test is formidable and is
can be used to understand this condition. If gi (z) seldom done.
is currently zero, then a feasible change would
be for it to become negative (gi (z) ≤ 0). From
Equation (64), if the multiplier for the constraint 10.3. Strategies of Optimization
is negative, this change will increase the objec-
tive function F which says the constraint should The theory covered in Section 10.2 explains how
be kept at zero. If the multiplier is negative, this to decide if a point is an optimum point – or bet-
change will decrease the objective function F. ter, if a point cannot be an optimum point. This
The constraint should be released; the point ẑ is section explores how to find such a candidate
almost certainly not a minimum point. point. This is rather like being blindfolded and
starting a walk to find the lowest point in a val-
Constraint Qualifications. In special cases
ley below. One can imagine being fooled by lo-
the necessary conditions above do not hold. For
cal optima (multiple low points); running into a
example, if two nonlinear inequality constraints
fence that is not allowed to be crossed (inequality
form a cusp as shown in Figure 40 and the op-
constraint) but that might be hung on to; being
timum is exactly at that point as shown, then
required to find the solution along a trail (equal-
(1) both constraints are needed to define the op-
ity constraint) that can perhaps be found only by
timum, but (2) they are locally colinear at that
groping, bumping into a cliff (discontinuities),
point. Thus the equation
and so forth.
∇F + µ1 ∇g1 + µ2 ∇g2 = 0 The simplest strategy to finding the minimum
of a function is to place a grid of points through-
which states that the gradient of the objective
out the feasible space and evaluate the objective
function can be written as a linear combination
function at every grid point. The point yield-
of the gradients of the constraints, can be untrue
ing the highest value for the objective function
at this point, as Figure 40 illustrates. By prov-
would be chosen as the solution. Although this is
ing that the constraints have to be independent at
simple, with 20 variables over which to search
the solution, one can be assured that this prob-
and a rather coarse grid of 10 points in each
lem will not occur (but proving this condition
direction, 1020 function evaluations would be
will hold for a general nonlinear problem is not
easy).
required to solve the problem. At 1 µs per eval- (each trial point requires the product to be manu-
uation, more than four million years would be factured and judged). When a successful point
necessary to carry out these evaluations. Clearly, is located, throw out the worst point and include
nothing but the smallest problem can be solved the new one in the complex of points. Repeat
with this approach. the cycle until the points in the complex are so
Most strategies limit themselves to finding close together that the differences among them
a local minimum point in the vicinity of the are uninteresting. A series of steps that success-
starting point for the search. This would be like fully uses the doubled step size starts to take
the person with a blindfold moving only in the quite large steps in a generally downhill direc-
downhill direction until reaching a spot that ap- tion. When the step size must be reduced for a
peared locally level. Such a strategy will find series of successive steps, the complex of points
the global optimum if the problem is convex. It will come quite close together and signal that
will work if the roughness that makes the prob- the optimum is near.
lem nonconvex does not lead to local minimum The method works adequately but, as might
points along the search path. be expected, takes an enormous number of steps
relative to methods discussed next that work
Pattern Search. Occasionally a problem is when a reasonably behaved mathematical model
confronted for which no mathematical model is available. It also collapses into searching only
is available for assessing the objective function in a subspace if it encounters any sort of ridge
value. For example, in trying to improve a recipe along the way. This method should thus be
where the objective is that the product looks and restarted frequently by setting up a new com-
smells nice: the recipe can be varied by adjusting plex of points around the current best point.
the relative amounts of materials used in mak-
ing it, by changing the temperature at which it Quadratic Fit – Unconstrained Case. An
is processed, and so forth. Manufacturing sev- often effective method for optimization is to con-
eral examples and handing them to a panel of vert the problem into an unconstrained one and
judges may lead to a preference ordering only. solve it by using a sequence of quadratic approx-
For this type of problem, pattern search meth- imations to it. Suppose a computer program is
ods can be used to find the better conditions for available that can be run to give the value of the
manufacturing the product. Only the ideas be- objective function F, if it is supplied with values
hind this approach are described here. Details of for a set of independent variables u.
one approach to implement it can be found in Assume that F can be approximated by the
[153]. quadratic function in the variables u
One pattern search method called the com-
plex method is as follows. First, a “complex” 1 T
F ≈ a +bT u + u Qu
of at least r + 1 different points is formed, at 2
which to manufacture the product by picking a where a is a scalar, b a vector, and Q an r×r
range of suitable values for the r independent symmetric positive definite matrix. If a, b, and
variables in manufacturing process. The prod- Q are known then the minimum could be found
uct is manufactured at each of these points. Next by finding a stationary point for this equation:
judges are asked to decide which product is the
worst. For each independent variable, form the ∇T
u F = b +Q u = 0
average value at which it was run in the com-
plex. Draw a line from the coordinates of the or
worst point through the average point and con-
tinue on that line a distance twice that between u = −Q−1 b (66)
these two points. Choose that point as the next
test point if it is feasible and if it is better than the However, a, b, and Q are not known. They con-
worst point (the product will have to be manu- tain q = 1 + r + r (r + 1)/2 unknown coefficients
factured at that point and judged). If not feasible in a, b, and Q. If the computer program were
and better, back off on the distance past the aver- run q times, q equations could be generated in
age point until a feasible, better point is located these unknown coefficients which could then be
solved to estimate their values from the follow- three equations. Thus, the program would have
ing set of linear equations (note that the values to be run at least three times to estimate the co-
for F i and ui are known, the coefficients are to efficients b and Q.
be computed):
Quadratic Fit – Equality-Constrained
1 1T
F 1 = a + b T u1 + u Q u1 Case. To solve the following equality-
2
constrainted optimization problem
1 2
F 2 = a + b T u2 + u Q u2 Min {F (z) | h (z) = 0, z ∈Ren , h : Rn → Rm }
2
1 qT proceed as follows:
F q = a + b T uq + u Q uq
2
1) Partition the variables z into dependent vari-
The points at which to run the code must be ables x and independent variables u.
selected to ensure that these equations are not 2) Guess values for the variables uk , k = 0,
singular. Once an estimate for a, b, and Q is where k is the iteration counter.
available, Equation (66) gives the next point at 3) Solve equation h (x, u) for xk given the val-
which to evaluate the variables u. The newest ues guessed for uk . These will be m equa-
point is then included in the set and the oldest tions in m unknowns. Solving in general
removed, giving again q points at which to eval- will require an iterative procedure (e.g., the
uate a, b, and Q. If removal of the oldest point Newton – Raphson method).
leads to a singular set of equations, a different 4) Use Equation (62) to solve for the Lagrange
point must be selected for removal. An approach multipliers λk . If the Newton – Raphson
to this is to keep all the older equations, with the method is used to solve the equations, the
new ones added to the top of the list. Then piv- Jacobian matrix ∇T x h |ẑ will already have
oting can be done by proceeding down the list been generated at the point zk = xk , uk found
until a nonsingular set of q equations has been in previous step.
found. The older equations will not be used un- 5) Substitute λk to form Equation (63), which
less they have to be. In addition, clever schemes, in general will not be zero; ∇u Lk computed
to be considered in the section on quasi-Newton will be the constrained derivatives of F with
methods, can be used to minimize the effort to respect to the independent variables uk .
carry out the pivoting from one step to the next
because only a single equation has been changed This effectively creates a method for com-
for each step. puting F (u) and ∇T u F (u) if u is given. Now
If gradients as well as objective function val- directly apply the ideas in the last section for
ues are provided by the computer model, the pro- using the quadratic fit method to solve uncon-
cess is even more efficient. The following equa- strained optimization problems for the case in
tions are written a sufficient number of times to which derivatives are available. In other words,
allow one to estimate b and Q: generate a table of u values at which to compute
∇T u F (u) sufficient in number that b and Q can
∇T 1 1 be estimated for a quadratic fit. These can be es-
u F = b + Qu
timated by using Equation (67). Then the next
∇T 2
u F = b + Qu
2
(67) value is estimated for the independent variables
u by using Equation (66), and so forth.
Again, past equations are kept on a stack, and This method is termed a reduced gradient
newer ones are placed at the top. Then, pivot- method and is one of the more effective ap-
ing from the top down until a nonsingular set of proaches for solving equality-constrained opti-
equations exists provides a scheme for estimat- mization problems.
ing b and Q and for deleting older equations as
the iterations proceed. Quasi-Newton Updates. The above ap-
For a problem with three independent vari- proach on quadratic fit for finding an optimum
ables u, 3 + 3 (4)/2 = 9 unknown coefficients ex- point is a secant method which is a form of
ist. Each numerical experiment would supply quasi-Newton method. Approaches based on
the Newton method have a number of advan- developed by Davidon [154] and analyzed by
tages. Most important is that convergence near Fletcher and Powell [155]; this rank 2 for-
the solution is very fast (i.e., at a superlinear or, mula can be stated as follows:
for the Newton method itself, quadratic rate). If
the matrix of second partial derivatives of the γ sT s γT
Qk+1 = sT Qk s I − T Qk I − T
objective function ∇Fuu (termed the Hessian γ s γ s
matrix) remains positive definite, the Newton
γ γT
method can be made globally convergent by +
choosing a stepsize α between 0 and 1 along γTs
the Newton direction that will guarantee a de- That Qk +1 satisfies the secant relationship and
crease of the objective function and movement is symmetric as long as Qk is can be shown, as
toward the optimum. However, if the Hessian can the fact that Qk +1 is positive definite as long
matrix becomes singular or indefinite, a modifi- as Qk is positive definite and γ T s > 0. This for-
cation of Newton’s method must be considered. mula can be derived conceptually by using the
Moreover, Newton’s method itself requires the following variational problem [156].
evaluation of second derivatives for the Hes-

sian matrix and the solution of a set of linear Min W 1/2 Qk+1 − Qk W 1/2 2F
equations similar to Equation (66):
T
∇uu F uk d = −∇u F uk such that Qk+1 = Qk+1
where d = uk+1 − uk at each iteration k. Qk+1 s = γ

Now develop efficient update formulas for the
approach where gradients are available. Assume Here, the weighting matrix W must satisfy the
that the next point to test as the optimum point inverse secant relationship W γ = s. Also, the
is uk+1 by solving equations similar to those Frobenius norm squared ( · 2 F ) is the sum of
above for d (or by Eq. 66). Evaluate the gradient squares of the matrix elements. The DFP for-
of F with respect to u, ∇Fu (uk+1 ) at that point mula can also be represented by an inverse rela-
by running the model. The goal is to update the tionship where Hk = (Qk −1 and
estimate of the Hessian matrix at uk+1 . Proceed
as follows: s sT Hk γ γTHk
H k+1 = H k + T
−
Second derivative information may be ap- s γ γT Hk γ
proximated by application of a secant relation-
In this way the quasi-Newton search direction
ship (also known as the quasi-Newton condi-
d k =− Hk ∇u F (uk ) is evaluated directly by a
tion):
simple matrix multiplication, rather than by
Qk+1 s =γ solving a system of linear equations.
An alternative to the DFP update was disco-
where s = uk+1 − uk , γ = ∇F k+1 − ∇F k , and vered in 1970 independently by Broyden,
Q is the same matrix as in the above section on Fletcher, Goldfarb, and Shanno (BFGS)
quadratic fit (see Eq. 66). In one dimension, this [157–160]. Matrix and inverse formulas for this
condition is sufficient for construction of Q. For BFGS update are given as
multiple dimensions, additional conditions must
be specified, and here conditions are imposed Qk s sT Qk γ γT
Qk+1 = Qk − + T
that are desirable for the optimization problem, T
s Q sk γ s
such as symmetry and positive definiteness of
Q. s γT γ sT s sT
H k+1 = I − Hk I − +
Although detailed derivation of quasi- γT s sT γ sT γ
Newton update formulas is beyond the scope of
As with the DFP formula, symmetry conditions
this chapter, considering two of the most pop-
and the secant relation can easily be verified.
ular quasi-Newton methods and the concepts
Similarly, these updates remain positive definite
underlying their derivation is constructive. The
as long as γ T s > 0. Conceptually, this update
older update formula (the DFP formula) was
can be derived by the following variational prob- 10.4. Successive Quadratic

lem: Programming (SQP)

Min W 1/2 H k+1 − H k W 1/2 2F Because the solution of the nonlinear program-
ming problem is a stationary point represented
T
H k+1 = H k+1 by a set of optimality conditions (i.e., the
Kuhn – Tucker conditions), a straightforward al-
ternative to the reduced gradient approach can
H k+1 γ = s
be derived by considering a Newton method ap-
where the weighting matrix W satisfies W s = γ. plied directly to these conditions. The advantage
Note the similarities in the BFGS and DFP for- of this formulation is that, as with any Newton-
mulas. From the variational formulations and the type method, convergence is rapid near the so-
update formulas themselves the two updates are lution. However, advantage must be taken of the
seen to complement each other. The BFGS up- special structure of the optimality conditions to
date, in fact, is often referred to as the comple- ensure convergence from a poor starting point.
mentary DFP formula. A concise derivation of this method can be de-
Once either Qk +1 or Hk +1 has been updated, veloped by considering the Kuhn – Tucker con-
d can be computed for the next move. Again, at ditions as written below:
this new point, the model is run to obtain the
gradient of F with respect to u, update Qk +2 or ∇Z L (z, µ, λ) = ∇F +∇g A µ + ∇h λ = 0
Hk +2 , etc.
g A (z) = 0
Both quasi-Newton methods exhibit super-
linear convergence on unconstrained optimiza-
h (z) = 0
tion problems and have been very successful in
solving moderate-sized (e.g., n < 100 variables) Assume, for the moment, that the active inequal-
optimization problems. However, extensive nuities gA are known at the solution and that their
merical testing has shown that the BFGS up- corresponding multipliers are positive. Apply-
date is consistently more reliable and efficient ing Newton’s method to these conditions from
for these problems. More information about the- an initial guess (xi , µi , λi ) leads to the solution
oretical properties, numerical experience, and of the following system of linear equations to
implementation details of these quasi-Newton determine the search direction:
methods can be found in [161] and [162].    
∇zz L z i , ui , λi ∇gA z i ∇h z i z − zi
 i T  
Inequality-Constrained Problems. To ∇g A z 0 0  µ − µ 
i
i T
solve inequality-constrained problems, we must ∇h z 0 0 λ−λ i
develop a strategy that can decide which of the

 
inequality constraints should be treated as equal- ∇zz L z i , ui , λi
 i 
ities. The problem often is split into two phases: = − g A z 
i
phase 1 where the objective is to find a point ∇h z
that is feasible with respect to the equality and
inequality constraints, and phase 2 where the op- An equivalent linear system written only in
timum is sought while feasibility is maintained. terms of the search direction for z and the mul-
Many optimization strategies are based on this tipliers is given by
idea and are called feasible path approaches. The    
sequential quadratic programming approach dis- ∇zz L z i , ui , λi ∇gA z i ∇h z i d
 T   
cussed in Section 10.4, in contrast, does not ∇g A z i 0 0  µ
i T
worry about any of the constraints being feasi- ∇h z 0 0 λ
ble except after the final iteration. It is termed an  
infeasible path approach and is one of the most ∇z F z i
 i 
effective approaches in terms of computational = − gA z 

efficiency for large problems. h zi
This system of linear equations, however, may solution. Moreover, quadratic programs can be
not have a solution. A sufficient condition for solved quite efficiently with numerous finite step
a unique Newton direction is that the matrix of algorithms including primal projection methods
constraint derivatives is of full rank (linear inde- [165], dual projection methods [166], or modi-
pendence of constraints) and the Hessian matrix fied simplex methods [167], [168].
of the Lagrange function (∇zz L (z, µ, λ) pro- Finally, to ensure convergence of this algo-
jected into the space of the linearized constraints rithm from poor starting points, a step size α
is positive definite. Moreover, under these con- is chosen along the search direction so that the
ditions the linearized system actually represents point at the next iteration (zi+1 = zi + α d ) is
the solution of the following quadratic program- closer to the solution of the NLP.
ming problem: Line search criteria for determining α usu-
T 1 ally consist of obtaining a sufficient decrease for
Min ∇F z i d + dT ∇zz L z i , µi , λi d some merit function that consists of the objective
d 2
function and the violated constraints. Examples
T of these merit functions include the exact penalty
such that g A z i +∇g A z i d = 0
function [153], augmented Lagrange functions
T [169] and the watchdog hybrid function [170].
h z i + ∇h z i d = 0
For many problems, performance of these line
Note that the quadratic program still requires search methods is similar and generally quite
second derivatives for construction of the Hes- good. However, all of these line search methods
sian matrix. can experience difficulties, and much research
The question of choosing the active set of focuses on their development and improvement.
inequalities, mentioned above, was resolved by In numerous numerical comparisons (e.g.,
Wilson in 1963 simply by adding all of the in- [169] and [171]) successive quadratic program-
equality constraints to the quadratic program. ming requires consistently fewer function evalu-
Because a quadratic program is solved at ev- ations than other NLP algorithms, including re-
ery iteration, the active set that minimizes the duced gradient methods described above. How-
quadratic program is updated and therefore be- ever, for larger problems the cost of creating and
comes the active set at the solution to the non- storing a large, dense Hessian matrix and of solv-
linear program. Also, a solution of zero to the ing large quadratic programs can be prohibitive.
linear system for the search direction implies To adapt SQP to deal with larger problems,
satisfaction of the Kuhn – Tucker conditions for two approaches are available. On one hand,
the nonlinear program. quadratic programming algorithms can be de-
Problems with calculating second derivatives veloped that take advantage of problem spar-
as well as maintaining positive definiteness of sity, especially in the matrix of constraint deriva-
the Hessian matrix can be avoided by approxi- tives. Also, the structure of the Hessian matrix
mating this matrix by Bi using a positive definite must be exploited, either by providing second-
quasi-Newton formula (such as BFGS). Here, derivative information directly or by implement-
gradients of the Lagrange function are used to ing structured quasi-Newton updating formulas.
calculate γ in the update formula [163], [164]. These approaches have met with some success
The resulting quadratic program, which gener- on process optimization problems [172]. How-
ates the search direction at each iteration i, there- ever, several problems still remain, including
fore becomes loss of positive definiteness in the Hessian ma-
T 1 trix and the determination of a systematic step-
Min ∇F z i d + dT B i d size adjustment strategy.
d 2
Many process problems, however, consist
T of large complex models (i.e., many nonlinear
such that g z i + ∇g z i d ≤ 0
equality constraints) and relatively few indepen-
T dent variables. Moreover, for these problems the
h z i + ∇h z i d = 0
approximation of the sparse, indefinite Hessian
Because this problem has linear constraints and a matrix by a large, dense positive definite matrix
strictly convex objective function, it has a unique
may not be appropriate. Also, from the second-    

Y T Bi y Y TBiZ R dY
order optimality conditions, the small Hessian  T i   
Z B Y Z TBiZ 0  dZ 
matrix projected into the constraint space (the
RT 0 0 λ
constrained second derivatives for the indepen-
dent variables) is generally dense and positive  
definite at the solution. Consequently, Berna Y T ∇F
 T 
et al. [173] proposed the use of decomposition = − Z ∇F 
algorithms to exploit these problem characteris- h
tics. Problems with a few thousands of depen- Note that the range space direction dY can now
dent and a few tens of independent variables be determined directly from the bottom row.
were solved. The more recent algorithms that ex- Moreover, the null space direction dZ is inde-
ploit these problem characteristics are presented pendent of the multipliers λ. Consequently, the
here. multipliers can be estimated by R λ = −Y T ∇F
Consider the linear equations that repre- because the other terms become unimportant as
sent the optimality conditions of an equality- both dZ and dY approach zero. As suggested
constrained quadratic programming subprob- initially by Murray and Wright [175], the
lem: Y T BZ term in the second row could be ignored

because it becomes unimportant for small dY .
Bi ∇h d ∇F z i
= − i With these simplifications, the linear system of
∇hT 0 λ h z
equations becomes uncoupled, and null steps,
To simplify the notation the inequality con- range steps, and multipliers can be determined
straints are omitted (if the active ones are known, independently as follows:
they can also be combined within the set of
RT dY = − h
equalities). By performing an orthonormal fac-
torization of the m columns of ∇h, an n×m
Z T B i Z = − Z T ∇F
matrix Y is obtained that spans the range space
of the linearized constraints. Orthogonal to the
columns of Y, an orthonormal n×(n − m) ma- R λ = − Y T ∇F
trix Z is developed, whose columns span the
d=Y dY +ZdZ
null space of the linearized constraints. These
orthonormal matrices have the following prop-
erties [174]: Nocedal and Overton [176] proved that
the convergence rate of this procedure is super-
Y T Y = I m Y T ∇h = R linear at every second iteration; this represents
a slight deterioration from the “ideal” conver-
Z T Z = I n−m Y T Z = 0 ∇hT Z = 0
gence rate of the original SQP method. How-
Also, the following orthonormal matrix Q: ever, testing on a set of small problems shows no

loss in performance with this approach. Further

[Y Z] 0 testing on small problems as well as evaluation
Q= Q QT =I n+m
0 Im of a number of strategies for handling inequal-
ity constraints were reported by Gurwitz and
is constructed, and the Q P optimality conditions Overton [177].
are multiplied through by Q to transform this Vasantharajan and Biegler [178] ex-
system to tended this approach to deal with general in-

equality constraints. Here, the null space step is
Bi ∇h d ∇F determined by a small quadratic program, which
QT Q QT = − QT
∇hT 0 λ h represents a slight modification of the uncou-
pled linear equations given above. Multipliers
which upon multiplication becomes for the inequality constraints are also determined
from the quadratic program, and the equation
for λ is modified slightly. They also developed

a factorization of Y and Z that allows the ap-
plication of sparse matrix methods. Although
columns of Y and Z are no longer orthonor-
mal, the overall search direction predicted by the
range and null space algorithm still remains the
same. The range and null space decomposition
of SQP has been very efficient and reliable in
solving large nonlinear programming problems.
Vasantharajan et al. [179] demonstrated this
approach on process optimization problems of
up to 1000 variables. Their results showed it to
be competitive with recent implementations of
MINOS and very reliable for difficult, nonlinear
problems. Figure 41. Feasible region for linear programming problem
The observations in the above example on

10.5. Linear Programming the nature of the optimal solution for linear pro-
grams can be generalized. Consider first the gen-
A very important special case of the nonlinear eral form of a linear program as given by
programming problem arises when both the ob- min F = cT z
jective function and the constraints are linear.
This case gives rise to a linear programming such that Az = b
problem which, due to its special properties, can
be solved much more efficiently than general z≥0 (68)
nonlinear programs.
To provide some insight into the nature of this where z is an n vector of continuous variables, c
problem, consider the following linear program- is an n vector of coefficients, A is an m×n matrix
ming optimization problem: (m < n), and b is an m vector of right-hand sides.
Note that any linear program can be written in
min F = − z1 − 3 z2
the form of Equation (68). As an example, con-
sider the above problem. The inequalities can
such that z1 + z2 ≤ 4 be converted to equalities by introducting slack
variables and rewriting the constraints as
z1 + 2 z2 ≤ 6
z1 +z2 +z3 = 4
z1 ≥ 0, z2 ≥ 0
z1 + 2z2 + z4 = 6
The feasible region and the contours for this where z3 und z4 are nonnegative slack variables.
problem are shown in Figure 41. The feasible Thus, the example can be expressed in the form
region is convex because the inequalities de- of Equation (68):
fine a polyhedral set. Also, because the objec-  
tive function is linear, it corresponds to a convex z1
z 
function. The unique minimum value of the ob-  2
min F = [−1 − 3 0 0]  
z3 
jective function of F = − 9 is located at the point
z4
z1 = 0, z2 = 3 ( point B). This point corresponds
to a vertex in the feasible region given by the  
intersection of the constraints z1 + 2, z2 = 6 and
z1
1 1 1 0  
 z2  4
z1 = 0. The two inequality constraints to which   =
1 2 0 1  z3  6
these correspond are said to be active at this
z4
point.
z 1 , z 2 , z3 , z 4 ≥ 0 (69)
Inequalities that are greater or equal to zero Bz B = b

can similarly be converted into equations by
the use of nonnegative slack variables. For ex- or
ample, 6 z1 − 3 z2 ≥ 9, can be converted into

1 0 z1 4
6 z1 − 3 z2 − z3 = 0, where z3 is a slack variable. =
0 1 z2 6
10.5.1. Basic Properties In this way the basic variables z3 = 4, z4 = 6

correspond precisely to nonzero slacks for the
The linear programming problem (Eq. 68) has two inequalities that are inactive at that point.
the following basic properties, which are stated As another example, consider vertex B for
without proof (see [180], [181], for details). which z1 = 0, z2 = 3, and for which the second in-
equality is active (i.e., slack z4 = 0). In this case,
Property 1. The linear program (Eq. 68) has z2 = z4 = 0 are the nonbasic variables and thus the
a unique minimum value for the objective func- basic equations are given by
tion. Otherwise the problem is either unbounded

or infeasible. 1 1 z1 4
=
As mentioned previously, the uniqueness of 2 0 z2 6
the optimal objective function value follows
from the fact that Equation (68) corresponds to for which z2 = 3, z3 = 1. Note that at vertex B,
a convex programming problem. Note, however, z2 = 3, and the first constraint has a slack of 1.
that although the minimum value of the objec-
tive function is unique, the values of the opti- Property 3. The minimum of Equation (68)
mum variables may not be. For illustration, as- is located at an extreme point of the feasible
sume that the objective function in the example space. Furthermore, at that extreme point the fol-
is replaced by F = − z1 − 2 z2 . From Figure 41, it lowing inequality is satisfied:
can easily be verified that the minimum F = − 6
occurs at the two vertices z1 = 0, z2 = 3 and at −cT
BB
−1
N ≥0
N + cT T
(71)
z1 = z2 = 2, as well as at any point that is a linear
combination of these two points (i.e., boundary where cB and cN are coefficients of the objec-
of z1 + 2, z2 = 2 ≤ 6 in the feasible region). tive for the basic and nonbasic variables, respec-
Note also that if Equation (68) has no finite tively.
solution, it is either unbounded or infeasible. An As was illustrated with the example problem,
example of the former arises if the two inequal- the optimum was indeed located at the vertex
ities in the problem are deleted. An example point which is also predicted by property 2. The
of the latter arises if the constraint z1 + z2 ≥ 5 is reason why an interior point z̄ (nonvertex) will
added to the problem. generally be nonoptimal is that such a point can
always be expressed as a linear combination of
Property 2. A vertex or extreme solution in extreme points, that is,
Equation (68) corresponds to a partition of those
equations which has the form z̄ = αi z i (72)
i
Bz B + N z N = b (70)
where zi is an extreme point,
and αi is a scalar
with zB ≥ 0 and zN = 0, where B is an m×m between 0 and 1 for which αi = 1. Therefore,
nonsingular matrix denoted as the basis, N is

an (n − m)×m matrix, zB is an m vector of ba- cT z̄ = cT αi z i
sic variables, zN is an n − m vector of nonbasic i
variables.
This equation can clearly not be satisfied for
Again for illustration purposes, consider ver-
0 < αi < 1 if cT z < cT zi . Thus, the optimum
tex A in Figure 41 for the problem where
will always correspond to an extremepoint.
z1 = z2 = 0. If these two variables are selected as
nonbasic, then from Equations (69) and (70),
As for Equation (71), recall that the reduced (T 1)

gradient g R in a linearly constrained optimiza- F zT B zT
N Right-hand
tion problem is given by side
Objective row 1 −cT
B −cT
N 0
−1
R = − ∇x F [∇x h]
gT T
∇u h + ∇u F T (73)
Constraint row 0 B N b
Because the dependent variables x correspond
to the basic variables zB , ∇x F T = cT
B , ∇x h = B. To update this, premultiply the constraint
Also, because the independent variables corre- rows by B−1 and add to the objective row the
spond to the nonbasic variables zN , ∇u F T = cTN, product of cB T times the new constraint; that is,
∇u h = N. Thus, the reduced gradient in Equa-
tion (68) is given by (T 2 )
F zT
B zT
N Right-
−1
hand
gT
R = − cT
BB N + cT
N side
−1
N − cT
T
Thus, Equation (68) can be expressed in the Objective row 1 0 cT
B B N cBB
space of the non-basic (reduced) variables zN Constraint row 0 I B−1 N b̄
as
. /
min F = −cT −1
N + cT
where b̄ = N−1 b. Note that the entry in the
BB N zN
objective row for zT N displays the information
such that − z N ≤ 0
of the negative of the reduced gradient. Thus, at
the optimum each of these components must be
From the Kuhn – Tucker conditions presented nonpositive.
earlier, In general, the simplex algorithm proceeds as
follows. First, an initial basis is selected. This is
−1
−cT
BB N − µ = 0
N + cT T T
trivial for the case in which the constraints are
of the form A z ≤ b where b > 0, because then
−z N ≤ 0, µ ≥ 0 , µT z N = 0 the initial basis to be selected can be the slack
Thus, because the multipliers µ ≥ 0, Equation variables for which B = I. Otherwise, one has to
(71) holds. resort to the use of artificial variables and a two-
phase procedure [181]. Second, the optimality
condition is verified by checking if
10.5.2. Simplex Algorithm
−1
cT
BB ni − cT
Ni ≤ 0
The simplex algorithm [182] exploits the basic
properties described in the previous section by for each nonbasic variable zNi . If this condition
searching only among the vertex points in the is not satisfied, move to a new vertex which re-
feasible space. It verifies whether Equation (73) quires the selection of a new basis. This is ac-
holds to identify the optimum solution. Rather complished as follows:
than enumerating all possible vertices, the al- 1) Introduce in the basis the nonbasic variable
gorithm proceeds by moving sequentially from zNj with largest positive value for the above
one vertex to another, ensuring that the objective optimality condition. This ensures a move
function value decreases. to a neighboring vertex that will lead to the
To explain the essence of the simplex algo- largest decrease in the objective per unit of
rithm, rewrite the objective function of the equa- distance moved.
tion 2) Remove from the basis the basic variable zBr
that will become zero as a step is taken along
F − cT z = 0
the j-th component of the reduced gradient.
Then, for a given selection of the basis, the The r-th basic variable can be determined
problem can be presented through the following by computing the smallest step size a from
tableau [see the above equations and Equation among all the basic variables zBi :
(72)]:
F z1 z2 z3 z4 Right-hand side
a = min {bi /yij } = br /yrj ≥ 0 −9 −1/2 0 0 −3/2
where yij is the i-th in row in the vector 0 1/2 0 1 −1/2 1
B−1 nj which corresponds to the j-th column 0 1/2 1 0 1/2 3

of the nonbasic variables.
3) Pivot on the r-th row and the j-th column of Then, because the elements of the negative of
the tableau to obtain the identity matrix for the reduced gradient (− 1/2, − 3/2) (variables z1
the basic variables. and z4 are the nonbasic variables) are negative,
To illustrate the application of the simplex stop. Thus, the optimal solution is given at z1 = 0,
algorithm, construct the tableau for the example z2 = 3, and z3 = 1 (slack for first constraint), z4 = 0
problem. From Equation (69), (second constraint is active) with F = − 9.
Finally, note that most commercial codes for
F z1 z2 z3 z4 Right-hand side LP (MPSX, SCICONIC, MINOS) are based on
1 1 3 0 0 0 extensions of the simplex algorithm and can typ-
ically handle problems with up to 15 000 con-
0 1 1 1 0 4
straints. The new interior point methods (see
0 1 2 0 1 6 [159] for a review) seem to offer the potential
of solving larger problems more efficiently.
If the initial basis z3 and z4 is chosen, the
point is feasible because z1 = z2 = 0 (nonbasic)
and z3 = 4, z4 = 6 (vertex A in Fig. 41). Further- 10.6. Mixed-Integer Programming
more, because the matrix in the basis corre-
sponds to the identity matrix, the tableau has the Up to this point, this chapter has assumed that
form of (T 2). The entries in the first row under only continuous variables are involved in the op-
z1 and z2 correspond to the negative of the re- timization problems. A number of important ap-
duced gradient. Select z2 as the variable to enter plications, however, require that all or a subset
the basis because it has the largest negative re- of the variables be constrained to take only in-
duced gradient, − 3. Now compute the step size teger or discrete values. Simple examples occur
a: in modeling the number of batches to be pro-
duced or discrete sizes to be selected for a piece
a = min {4/1, 6/2} = 6/2 = 3
of equipment. Another example is modeling the
selection of process units in a flow sheet (i.e.,
Because this corresponds to the right-hand side yes or no decisions).
element that is the value of z4 , select z4 as the When an optimization problem involves both
variable to leave the basis. The second constraint discrete and continuous variables, it is called a
will become active as its slack variable z4 is set mixed-integer programming problem. This sec-
to zero when it becomes nonbasic. Notice from tion considers the case in which the objective
Figure 41 that a = 3 along the direction (0, 1) function and constraints are linear (MILP) first
corresponds to the boundary of the second con- and then the case in which nonlinearities are in-
straint; a = 4 would lead to the boundary of the volved (MINLP). Also, for convenience, assume
first constraint, which would then violate the sec- that all the discrete variables are of the 0 – 1 type.
ond constraint.
By selecting z2 as the variable to enter the Mixed-Integer Linear Programming
basis and z4 as the one to leave it, one pivots (MILP). Assume a linear programming prob-
on the entry with the value of “2” in the column lem in which a subset of the variables y is re-
beneath z2 in the bottom row above. This then stricted to take only 0 or 1 values. This then
leads to the following new tableau: gives rise to the MILP problem:
binary tree such as the example shown in Fig-

min F = cT z + bT y ure 42. At each node of the tree the solution of
the linear program is considered subject to inte-
such that Az + By ≤ d
ger constraints for the subset of the y variables
that are fixed in previous branches. For example,
z≥0, y ∈ {0, 1} (74)
in node A the root of the tree involves the solu-
A first approach to solve this MILP problem is tion of the relaxed LP, whereas node B involves
to solve a linear programming problem for ev- the solution of the LP with fixed y1 = 0, y2 = 1 and
ery combination of 0 – 1 variables and pick as with 0 ≤ y3 ≤ 1.
the solution the 0 – 1 combination with the low-
est value for the objective function. The major
drawback with such an approach is that the num-
ber of 0 – 1 combinations can be very large. For
example, an MILP problem with ten 0 – 1 vari-
ables would require the solution of 210 = 1024
linear programs, whereas a problem with fifty
0 – 1 variables would require the solution of
250 = 1.13×1015 programs. This approach is, in
general, computationally infeasible. Figure 42. Binary tree for three 0 – 1 variables
A second alternative is to relax the 0 – 1 re-
quirements and treat the variables y as contin- To avoid enumeration of all the nodes in the
uous with bounds 0 ≤ y ≤ 1. The problem with binary tree, the following basic properties can
such an approach, however, is that except for few be exploited. Let k denote a descendent node of
special cases (e.g., assignment problems), there another node l in the tree (e.g., k = B, l = A) and
is no guarantee that the variables y will take inlet (P k ) and (P l ) denote the corresponding LP
teger values at the relaxed LP solution. As an subproblems. Then the following properties can
example, consider the pure integer program be easily established:
1) If (P l ) is infeasible then (P k ) is also infea-
min F = − 1.2y1 −y2 sible.
2) If (P k ) is feasible than (P l ) is also feasi-
such that 1.2y1 + 0.5y2 ≤ 1 ble, and (F l )∗ ≤ (F k )∗ . That is, the optimal
value of the objective of subproblem (P l )
y1 , y2 = 0.1
corresponds to a lower bound of the optimal
By relaxing y1 and y2 to be continuous the so- value of the objective for subproblem (P k ).
lution yields y1 = 0.715, y2 = 0.285, F = 1.148. It 3) If the optimal solution of subproblem (P k )
might then be tempting to simply round the vari- is such that all y = 0 or 1, then (F k )∗ ≥ F ∗ .
ables to the nearest integer value, namely y1 = 1, That is, the optimal objective of subproblem
y2 = 0. This point is an infeasible solution be- (P k ) corresponds to an upper bound of F ∗ ,
cause it violates the first constraint. In fact, the the optimal MILP solution.
optimal solution is y1 = 0, y2 = 1, F = − 1. Thus, These properties can be used to fathom nodes
solving the MILP problem by relaxation of the in the tree within an enumeration procedure. The
y variables will in general not lead to the cor- question of how actually to enumerate the tree
rect solution. Note, however, that the relaxed LP involves the use of branching nodes. It is not
has the property that its optimal objective value necessary to follow the order of the index of
provides a lower bound to the integer solution. the variables y for branching as might be im-
To obtain the solution to Equation (73), the plied in Figure 42. A simple alternative is to
most common approach is the branch and bound branch instead on the 0 – 1 variable that is closest
method [183], where the basic objective is to per- to 0.5. Alternatively, a priority ordering for the
form an enumeration without having to examine 0 – 1 variables can be specified, or else a more
all the 0 – 1 combinations. The basic idea is to sophisticated scheme can be used, such as the
represent all the 0 – 1 combinations through a penalties described in [184]. After solving the
LP at a node in the tree, decide which node to

examine next. Here the two primary alternatives
are to use a depth-first (last in – first out) or a
breadth-first (best second rule) enumeration. In
the former case, one of the branches of the most
recent node is expanded first: if all of them have
been examined, backtrack to another node. In
the latter case, the two branches of the node with
the lowest bound are expanded successively; in
this case, no backtracking is required. Although
the depth-first enumeration requires less storage,
the breadth-first enumeration generally requires
examination of fewer nodes.
In summary, the branch and bound method
consists of first solving the relaxed LP prob-
lem. If all the integer variables y take integer Figure 43. Branch and bound search
values, stop. Otherwise, proceed to enumerate
the nodes in the tree according to some prespec-
ified branching rules. At each node the corre- Mixed-Integer Nonlinear Programming
sponding LP subproblem is solved. (Typically (MINLP). Consider now the case of the non-
the dual problem is updated because it requires linear optimization problem involving both con-
less work. The dual problem for an LP is not tinuous and 0 – 1 variables (MINLP, Eq. 75)
discussed in this chapter.) By making use of the
properties stated above, either the node is fath- min F = F (z, y)
omed (i.e., terminate looking at it and all nodes
emanating from it) if the LP for it is infeasible or such that h (z, y) = 0
if its lower bound is greater or equal to its upper
g (z, y) ≤ 0
bound) or it is kept open for further examination.
As an example, consider the following MILP z∈Ren y ∈ {0, 1}m (75)
problem involving one continuous variable and
three 0 – 1 variables: This mixed-integer nonlinear program can in
principle also be solved with the branch and
min F = z +y1 + 3y2 + 2y3 bound method presented in the previous sec-
tion. The major difference here would be that
such that − z + 3y1 + 2y2 + y3 ≤ 0 the examination of each node would require the
solution of a nonlinear program rather than the
− 5y1 − 8y1 − 3y3 ≤ −9 solution of an LP. Provided the solution of each
NLP subproblem is unique, similar properties as
z ≥ 0, y1 , y2 , y3 = 0.1
in the case of the MILP would hold with which
The branch and bound enumeration using a the rigorous global solution of the MINLP can
breadth-first enumeration is shown in Figure 43, be guaranteed.
where the number in the circles represents the An important drawback of the branch and
order in which 9 out of the 15 nodes in the tree bound method for MINLP is that solution of the
are examined to find the optimum. Note that the NLP subproblems is much more expensive, and
relaxed solution (node 1) has a lower bound of they cannot be updated readily as in the case
F = 5.8 and that the optimum is found in node 9 of the MILP. Therefore, to reduce the compu-
where F = 8, y1 = 0, y2 = y3 = 1, and z = 3. tational expense involved in solving many NLP
subproblems, two other methods can be used:
generalized Benders decomposition [185] and
outer-approximation [186].
In both these methods the MINLP (Eq. 75) is
assumed to be linear in the 0 – 1 variables and
nonlinear in the continuous variables z; that is,

MINLP (Eq. 76)
min F = f (z) +cT y
such that h (z) = 0
g (z) + B y ≤ 0
z ∈ Ren , y ∈ {0, 1}m (76) where α is the largest linear approximation of

the objective function subject to linear approx-
The basic idea in both methods is to solve an
imations of the feasible region obtained from
alternating sequence of NLP subproblems and
the solution of the K NLP subproblems; T k is
MILP master problems. The NLP subproblems
a diagonal matrix whose entries t kii = sign (λki ),
are solved by optimizing the continuous vari-
where λki is the Lagrange multiplier of equation
ables z for a given fixed value of y, and their
hi at iteration k and is used to relax the equations
solution yields an upper bound to the optimal so-
in the form of inequalities [187].
lution of Equation (76). The MILP master prob-
Note that in both master problems the pre-
lems consist of a linear approximation that is
dicted linear bounds F K K
GB , and F OA increase
refined as iterations proceed, and they have the
monotonically as iterations K proceed, because
objective of predicting new values of the binary
the linear approximations are refined by accu-
variables y as well as a lower bound on the op-
mulating the Lagrangian (in Eq. 77) or lineariza-
timal solution. The alternate sequence of NLP
tions (in Eq. 78) of previous iterations. Also, in
subproblems and MILP master problems is con-
both cases, rigorous lower bounds can only be
tinued up to the point where the predicted lower
ensured when certain convexity conditions hold
bound of the MILP master is greater than or
[185], [186].
equal to the best upper bound obtained from the
In comparing the two methods, the lower
NLP subproblems.
bounds predicted by the outer-approximation
The MILP master problem in generalized
method are always greater or equal to the
Benders decomposition is given at any iteration
lower bounds predicted by generalized Benders
K by Equation (77):
decomposition. Hence, the outer-approximation
K method requires the solution of fewer NLP
FGB = min α
subproblems and MILP master problems. On
such that
the other hand, the MILP master in the outer-
approximation method is more expensive to
T . /
α≥ f z k +cT y + µk g z k +B y
solve, so the generalized Benders method may
require less time if the NLP subproblems are in-
k = 1, 2, . . . K
expensive to solve. For a more extensive discus-
sion and computational experience in chemical
α ∈ Re1 , y ∈ {0, 1}m (77) engineering applications, see [187–189].
where α is the largest Lagrangian approxima-

tion obtained from the solution of the K NLP 10.7. Solution of Dynamic Optimization
subproblems; zk and µk correspond to the op- Problems
timal solution and multiplier of the k-th NLP
subproblem; F KGB corresponds to the predicted This section deals with the solution of optimiza-
lower bound at iteration K. tion problems that include differential equa-
In the case of the outer-approximation tions as well as algebraic constraints. In addi-
method, the MILP master problem is given by tion to parametric decision variables, they can
Equation (78) include control profiles that are functions of
time. Differential – algebraic models appear in
all aspects of process engineering. Optimiza-
tion problems that include these models are ex- Optimality conditions for the above problem
tremely common, covering problems as funda- formulation can be derived in a manner simi-
mental as the design of a single catalyst pel- lar to nonlinear programming problems. Here, a
let to the optimal design and operation of an Lagrange function is formed that consists of the
entire chemical plant. However, solving even objective function and the weighted sum of the
the simplest and smallest of these optimiza- constraints evaluated at each point in time. This
tion problems is typically difficult and time- weighted sum is expressed more concisely as an
consuming. Consequently, the development of integral and the resulting function can be written
efficient methods for these problems represents as
an interesting research area with a wealth of im-
portant and challenging applications. L (x, u, p, µ, ν, λ) = F x tf
The general optimization problem under con-
sideration can be represented by Equation (79): tf 6
+ λT ( f (x, u) − ẋ)
0
Min F p, x tf
p,x(t),u(t)
7
+µT g (x, u) + ν T h (x, u) dt
such that h (p, u (t) , x (t)) = 0

hf p, x tf = 0 +µT
f g f x tf + νT
f hf x tf
To express this function entirely in terms of pa-

g (p, u (t) , x (t)) ≤ 0 rameters and state and control variables, the fol-
lowing transformation is applied:
g f p, x tf ≤ 0
tf
T
ẋ (t) = f (p, u (t) , x (t)) λT ẋ dt = λ tf x tf − λ (0)T x (0)
0
x (0) = x0
tf
pL ≤ p ≤ pU − λ̇T x dt
0
uL ≤ u (t) ≤ uU
and the Lagrange function becomes
. T
xL ≤ x (t) ≤ xU (79)
L (x, u, p, µ, ν, λ) = F x tf − λ tf x tf
where F is the objective function; g, g f represent
/
the design inequality constraint vector; h, hf the + µT
f g f x tf + νT
f hf x tf
design equality constraint vector; p is a param-
eter, decision variable vector; x (t) the state pro- tf 6
file vector; u (t) the control profile vector; pL , T
+λ (0) x (0) + λT f (x, u)
pU are the parameter variable bounds; xL , xU 0
the state profile bounds; and uL , uU the control
7
profile bounds. Note that algebraic constraints +λT x + µT g (x) + ν T h (x) dt
have been classified into conditions at final time
tf as well as constraints that must be enforced Note that multipliers λ, µ, and ν have been in-
over the time domain. Also, although the model troduced, which correspond to f (x, u, p) − ẋ,
is given as an initial value problem for conve- g (x, u, p), and h (x, u, p), and that all are func-
nience, general ordinary differential equations tions of t. Because the multipliers λ perform a
can be handled in a straightforward manner. Fi- special function for the sensitivity of the differ-
nally, note the distinction between continuous ential equations, they are denoted as adjoint vari-
variables p ( parameters that do not vary with ables. On the other hand, multipliers µf and ν f ,
time) and u (t) (time-varying control profiles) as which correspond to the final time conditions, do
decision variables. not vary with time and function in the same man-
ner as multipliers in nonlinear programming.
Stationary conditions of this Lagrange func- between 0 and 1. Note that a new parameter pf ,
tion can be given as follows with respect to x (t), whose value is determined as part of the opti-
u (t), and p. In addition, complementarity and mization, is introduced to represent final time.
nonnegativity conditions relating to the inequal- By writing the problem with τ substituted for t,
ity constraints and feasibility conditions make differential equations are merely rewritten as
up the balance of the optimality conditions given dx
below: dτ
= pf f (x, u) ; x (0) = x0
x (t) : λ̇ + ∇x f λ + ∇x g µ (t) + ∇x h ν (t) = 0 and final conditions are evaluated at τ = 1.

Finally, a large body of literature appears for
x tf : ∇xf F − λf +∇xf g f µf + ∇xf hf ν f = 0 this problem in which the algebraic constraints
H and the profile bounds are deleted. For this
u (t) : ∇u f λ + ∇u g µ (t) + ∇u h ν (t) = 0 case, the Hamiltonian is defined as λT f and
the resulting simplified optimality conditions are
/ f
t
. denoted as the Euler – Lagrange equations:
p : ∇p F + ∇p g T µ
f f +∇ p hT
ν f + [∇p f λ
∂H ∂f
0 = λ= 0
∂u ∂u
+∇p g µ + ∇p h ν] dt = 0
∂H
λ̇ = − = ∇xf f λ
µT ∂x
f g f = 0 µ, µf ≥ 0 g, g f ≤ 0

λ tf = − ∇xf F
µT g= 0 h, hf = 0 ẋ = f (x, u) , x (0) = x0
To illustrate these optimality conditions, the sim-
The derivation of these conditions is very similar
ple example given below is considered:
to the Kuhn – Tucker conditions for the nonlin-

ear programming problem. The additional dif- Min x2 tf
ferential equations encountered for λ are known
as adjoint equations and, in this case, have fi- such that ẋ1 = − 2x1 + u2 − u
nal conditions associated with them. In the same
manner as for nonlinear programs, second-order ẋ2 = x1
conditions can also be derived, based on con-
strained projections of the second variations of x1 (0) = 1
the Lagrange functions. A detailed derivation of
x2 (0) = 1 tf = 1
these conditions is given in [190].
Moreover, several straightforward modifica- Here, the optimal control profile over a 1-h pe-
tions can be made to extend this problem. For riod must be determined for this dynamic sys-
example, if some or all initial conditions are tem. This problem has no algebraic side condi-
not specified, they can be represented by pa- tions and no parameters. The Lagrange function
rameters p0 that are determined as part of the for this system is given by
optimization. In this case, an additional term
νT tf
0 (x (0) − p0 ) is appended to the Lagrange 8 2
function, and the corresponding stationary con- L = x2 tf + λ1 u − u − 2x1 − ẋ1
0
dition with respect to p0 becomes
x0 : ν0 − λ0 = 0 +λ2 (x1 − ẋ2 )} dt =

p0 : ν0 = 0 x2 tf + λ1 tf x1 tf + λ2 tf x2 tf
λ0 = 0, an additional boundary condition for − λ1 (0) x1 (0) − λ2 (0) x2 (0)
the adjoint equations tf

8 2
+ λ1 u − u − 2x1
In addition, if final time tf is not specified for
0
this problem, t can be normalized by τ = t/pf
7 to u (t), Bryson and Denham [191] proposed a

+λ̇1 x1 + λ2 x1 + λ̇2 x2 dt steepest descent method. Lasdon, Mitter, and
Warren [192] and Lasdon [193] accelerated
and the stationary conditions with respect to
this approach by proposing conjugate gradient
x (t), x (1.0), and u (t) are given by:
and variable metric methods, respectively, for
these types of problems. Finally, a Newton-type
x1 : λ̇1 = 2λ1 − λ2 λ1 (1) = 0
extension to optimal control problems is pre-
x2 : λ̇2 = 0 λ2 (1) = 1
sented in [194].
These methods work best on problems with
u: λ (2u − 1) = 0 initial value ordinary differential equation mod-
els without state variable and final time con-
The adjoint variables λ1 and λ2 can be deter- straints. For these simple problems, solutions
mined directly from the adjoint equations and have been reported that require from several
the associated final conditions. These are dozen to several hundred model (and adjoint
equation) evaluations [195], [196]. Moreover,
λ1 (t) = {1 − exp (2t − 2)} /2 any additional constraints in this problem re-
quire the search for appropriate multiplier val-
λ2 (t) = 1 ues, µ and ν, which often requires an outer loop
Because λ1 is zero only at t = 1, the station- in the solution algorithm and can easily lead
ary condition for u (t) is satisfied only when to a prohibitive number of model evaluations,
u = 0.5. Consequently, it can be verified that even for small systems. Consequently, the con-
u (t) = 0.5 minimizes x2 (1). trol vector iteration methods are limited to the
Solution of the differential – algebraic op- simplest optimal control problems.
timization problem becomes especially diffi- Instead, the optimal control problem can be
cult in the presence of state variable inequality approached as a nonlinear programming prob-
and equality constraints. Because many process lem which results after the control variable is
problems are constrained, optimization prob- discretized. Here, the ordinary differential equa-
lems of this type are not considered frequently. tion model is solved repeatedly in an inner loop
Methods for tackling these problems can be di- while parameters representing u (t) are updated
vided into three basic types: on the outside. Initially, the updating was per-
formed by direct search or “hill climbing” algo-
1) iterative methods based on variational con- rithms and could become costly for large prob-
ditions; lems. Use of more sophisticated methods, on the
2) feasible path nonlinear programming meth- other hand, must lead to a consideration of how
ods; and gradients can be calculated efficiently from the
3) simultaneous nonlinear programming meth- differential equation model.
ods. Using this nonlinear programming approach
(also termed the feasible path approach), denote
The analytical approach to solving small de- up as the vector of parameters representing u (t).
sign problems, such as the above example, natu- For example, if u (t) is assumed piecewise con-
rally leads to iterative algorithms based on vari- stant over a variable distance, include ui and ti
ational conditions. Based on the optimality con- in up . The original optimization problem then
ditions derived above, control vector iteration becomes the following nonlinear programming
algorithms were proposed that involve the so- problem:
lution of model equations forward in time, ad-
joint equations backward in time, and intermit- Min F (up , p)
up ,p
tent updating of the control profile to minimize
the Hamiltonian function, λT f (x, u) (or which such that h (up , p) = 0
make dH/du = 0). Methods that are analogous
to those for solving unconstrained optimization g (up , p) ≤ 0
problems can be applied here. For example, us-
ing the gradient of the Hamiltonian with respect
These equations are very similar to the optimal-

pL ≤ p ≤ p U ity conditions derived above.
Gradients with respect to up can also be
p ≤ up ≤ up
uL
calculated through sensitivity equations derived
and the ordinary differential equation model: from the ordinary differential equation model.
Here, for continuous state variable profiles, the
ẋ (t) = f (p, up , x (t)) sensitivity equations with respect to parameters
p, for example, are
x (0) = x0
∂ ∂ dx ∂f
{ẋ = f (x, u)} → =
xK+1 ti−1,f = xio i = 2, N E ∂p ∂p dt ∂p

∂x ∂f
xK+1 tN E,f = xf +
∂p ∂x
xL ≤ xil ≤ xU which, upon changing orders of differentiation
and defining s = ∂x/∂p, leads to
uL ≤ uil ≤ uU
ṡ = ∂f /∂p + s (∂f /∂x)
pL ≤ p ≤ p U
Either approach results in gradient calcula-
is solved.
tions with costs proportional to problem size;
Note that the independent variable, time, dis-
effort for evaluating gradients with adjoint ap-
appears from this problem, and constraints im-
proaches is proportional to the number of (objec-
posed at final time appear naturally in the above
tive and constraint) functions evaluated at final
problem; other constraints that must be enforced
time, whereas effort for sensitivity equations is
over time have to be treated in a more complex
proportional to the number of parameters up and
manner. For example, they can be converted to
p. Consequently, the choice of gradient calcula-
final time constraints by integrating the square
tion approach depends on the structure of the
of the constraint violations and forcing these to
particular feasible path problem. Nevertheless,
be less than a tolerance at the final time.
both Carcotsios and Stewart [197] and Sar-
To solve the nonlinear program, gradients can
gent and Sullivan [198] demonstrated that
be calculated in a number of ways with respect
gradient calculation approaches can be acceler-
to up from the ordinary differential equation
ated considerably by tailoring the ordinary dif-
model. The easiest, but least efficient and ac-
ferential equation solver to include sensitivity or
curate, way is simply to resolve the model for
adjoint equations.
each perturbation of the parameters. Sensitivity
The feasible path approach has been very
information can also be obtained by solving the
successful in solving large process problems.
adjoint equations
However, this approach still requires repeated
solution of the process model (and sensitivi-
λ̇i =∇x f (x, u) λi , i = 0, m
ties). For large processes or for processes that
λ0 =∇xf F ; λi = ∇xf g fi or ∇xf hfi
require the solution of rigorous underlying pro-
cedures, this approach can become expensive.
and evaluating parameteric sensitivities by using Moreover, for stiff or otherwise difficult sys-
the following relation: tems, this approach is only as reliable as the
ordinary differential equation solver. The feasi-
tf . / ble path approach also offers only indirect ways
∂F
= ∇p f T λ0 dt of handling time-dependent constraints. Finally,
∂p
0 the optimal solution with this approach is only
as good as its control-variable parameterization,
tf which often can only be improved by a priori
∂g fi ∂hfi
or = ∇p f T λi dt information about the specific problem. Conse-
∂p ∂p
0 quently, a simultaneous nonlinear programming
Next Page
approach is also considered as an alternative so-

K
lution method. uK (τ ) = ul ψl (τ )
Instead of parameterizing the control pro- l=1
file and solving the system as a nonlinear pro-
gram, the simultaneous approach begins with
K
(τ − τk )
K
(τ − τk )
ϕl (τ ) = , ψl (τ ) =
a parameterization of both the control and the (τl − τ k ) (τl − τk )
k=0,l k=1,l
state variable profiles, and solves a mathemat-
ical programming problem consisting of alge- where x K +1 > (τ ) and uK are (K + 1)-th order
braic equations. However, early application of (degree < K + 1) and K-th order polynomials,
the simultaneous approach suffered from two respectively. (Here the notation k = 0, l refers to
drawbacks. First, simultaneous approaches lead the index k starting at zero but not equal to l.)
to much larger nonlinear programs than feasi- The state variables are one order higher than
ble path approaches. Consequently, nonlinear the controls because they have explicit interpo-
programming methods must be very efficient lation coefficients defined at the beginning of
to compete with smaller feasible path formula- each element. With this representation of x (t)
tions. Here, a trade-off occurs between the ex- and u (t) this approach is extended to piecewise
pense of repeated ordinary differential equation polynomials and orthogonal collocation on NE
model solution and solution of a larger nonlin- finite elements (of length ∆αi ) is applied. The
ear program. Second, care must be taken in the differential equations are now represented by the
formulation to yield an accurate algebraic repre- following nonlinear algebraic equations:
sentation of the differential equations.
Recently, the SQP algorithm, described in a
K
R (til , ∆αi ) = xij ϕj (τl ) − ∆αi f (p, uil ) = 0
previous section, and orthogonal colloction have
j=0
been applied successfully to a number of optimal
control problems; this approach shows consid- l = 1, . . . K, i = 1 , . . . N E
erably better performance than control vector it-
eration methods. Moreover, through appropriate with
discretization of the differential equations, this
simultaneous approach can handle constraints xi,0 = x0 and xK+1 ti−1,f = xi0 i = 2, N E
on state and control profiles directly. Moreover,
by using the range and null space decomposition where til represent shifted roots of Legendre
technique for SQP, very efficient solutions can polynomials over the i-th element length and
be achieved with the simultaneous approach. ti−1, f is the time at the end of the (i − 1)-th el-
Because their approximation and stability ement. Note that state profiles satisfy continuity
properties are well studied, various ordinary dif- conditions across finite elements ∆αi , whereas
ferential equation solution methods can be ap- this property is not enforced for control profiles.
plied directly to discretize the differential equa- Substituting this representation of the ordinary
tions to algebraic constraints. Here, implicit differential equation model into the dynamic op-
Runge – Kutta methods are considered, which timization problem with ∆αi fixed, leads to the
coincidentally also include the method of or- following nonlinear programming problem:
thogonal collocation. By defining state and con-
Min F p, xf
trol profiles at τi ε [0,1] [e.g., the shifted roots of p,xil ,uil
orthogonal (Legendre) polynomials], these pro-
files are parameterized as Lagrange-form poly- such that h (p, uil , xil ) = 0
nomials over τ ε [0,1]:
g (p, uil , xil ) ≤ 0

K
xK+1 (τ ) = xl ϕl (τ ) R (til , ∆αi ) = 0
l=0
i = 1, . . . N E, l = 1 , . . . K
xi0 = x0
Previous Page
By taking advantage of the orthogonal prop- namic optimization problems with control pro-
erties of the polynomial representation, the files, the optimality conditions form a set of
Kuhn – Tucker conditions of this nonlinear pro- differential – algebraic equations that may lead
gram can be shown to be parameterizations of to different approximation and stability proper-
the optimality conditions of the dynamic prob- ties for the same discretization method.
lem. Therefore, the only requirement is that Difficulties in solving differential – algebraic
∆α be chosen appropriately (i.e., be sufficiently equation systems normally occur when the dis-
small for accurate approximation of the differ- cretized system of algebraic equations becomes
ential equations) and that the breakpoints for the singular. This can occur, for example, if time-
optimal control profile can be located. dependent equalities (h) and active inequalities
Choosing the element lengths to render an (g) are not functions of u (t). Although solu-
accurate discretization of the differential equations to the differential – algebraic equation sys-
tions can also be performed automatically by the tem (and the optimization problem) do exist, in-
nonlinear programming problem. For example, stabilities and loss of accuracy may result un-
the element lengths ∆αi could be made deci- less the discretization is of reasonably high order
sion variables, and a measure of the approxi- and has very strong stability properties. Brenan
mation error could be included as an inequality and Petzold [199] and Logsdon and Biegler
constraint. Here, a suitable approximation mea- [200] mention that collocation formulas can deal
sure is the residual of the differential equation with these difficult systems, but the orthogonal
evaluated at a noncollocation point t̄ within each colloction method may have to be modified be-
element, i.e., | R (t̄, ∆αi ) | ≤ ε for some ε toler- fore it can be applied.
ance. Consequently, to deal with dynamic opti-
For dynamic optimization problems without mization problems with control profiles, it is
control profiles and with a sufficiently large necessary to determine the difficulty of the sys-
number of elements, this simultaneous nonlinear tem (a straightforward analysis can be found in
programming approach can be shown to yield [199] and [201]) to see if an appropriately ac-
accurate solutions to difficult dynamic optimiza- curate and stable discretization (e.g., orthogo-
tion problems. Therefore, the choice of approach nal collocation, implicit Runge – Kutta, etc.) is
for parameter optimization problems depends on available. If one cannot be found, then the only
the difficulty of solving the ordinary differential recourse may be to parameterize the control pro-
equation model. If the model and its sensitiv- file and settle for a suboptimal solution. The
ity information can be determined quickly, then advantage of this, however, is that the meth-
a feasible path approach is probably more effi- ods described above for parameter problems can
cient than a simultaneous strategy. On the other be applied directly without any difficulties due
hand, if the model is expensive and difficult to to discretization of differential – algebraic equa-
solve at intermediate points, and if state variable tion systems.
constraints must be enforced over time, then a
simultaneous approach with an efficient nonlin-
ear programming strategy should be considered. 11. Probability and Statistics
Here, the advantage of this approach is that the [202–205]
ordinary differential equation model is solved
only once and state variable constraints can be The models treated thus far have been determin-
enforced directly. istic, that is, if the parameters are known the
For problems with control profiles, on the outcome is determined. In many situations, all
other hand, one must be especially careful the factors cannot be controlled and the outcome
about the stability properties of the ordinary dif- may vary randomly about some average value.
ferential equation discretization. Without con- Then a range of outcomes has a certain proba-
trol profiles, stability properties of the ordi- bility of occurring, and statistical methods must
nary differential equation discretization are de- be used. This is especially true in quality control
termined by properties of the corresponding of production processes and experimental mea-
ordinary differential equation solver (e.g., im- surements. This chapter presents standard sta-
plicit Runge – Kutta methods). However, for dy- tistical concepts, sampling theory and statistical
decisions, and factorial design of experiments is used in calculating the sample variance
or analysis of variances. Multivariant linear and

n
nonlinear regression is treated in Chapter 2. ( yi − ȳ)2
2 i=1
s =
n−1
11.1. Concepts and the sample standard deviation

3
4
Suppose N values of a variable y, called y1 , 4 n
4 ( y − ȳ)2
5 i=1 i
y2 , . . . , yN , might represent N measurements of s =
the same quantity. The arithmetic mean E ( y) is n−1
The value n − 1 is used in the denominator be-

N
yi cause the deviations from the sample average
i=1 must total zero:
E ( y) =
N

n
The median is the middle value (or average of ( yi − ȳ) = 0
the two middle values) when the set of numbers i=1
is arranged in increasing (or decreasing) order. Thus, knowing n − 1 values of yi − ȳ and the fact
The geometric mean ȳG is that there are n values automatically gives the n-
th value. Thus, only n − 1 degrees of freedom
ȳG = (y1 y2 . . . yN )1/N
ν exist. This occurs because the unknown mean
The root-mean-square or quadratic mean is E ( y) is replaced by the sample mean y derived
from the data.
3
2 4N If data are taken consecutively, running totals
4
Root − mean − square = E ( y2 ) =5 yi2 /N can be kept to permit calculation of the mean and
i=1 variance without retaining all the data:
The range of a set of numbers is the difference
n
n
n
between the largest and the smallest members in ( yi − ȳ)2 = y12 − 2 ȳ yi + (ȳ)2
i=1 i=1 i=1
the set. The mean deviation is the mean of the
deviation from the mean.
n
ȳ = yi /n

N
i=1
|yi − E ( y) |
i=1
Mean − deviation = Thus,
N
The variance is
n
n
n, y12 , and yi
i=1 i=1

N
( yi − E ( y))2 are retained, and the mean and variance are com-
2 i=1
var ( y) = σ = puted when needed.
N
Repeated observations that differ because of
and the standard deviation σ is the square root experimental error often vary about some cen-
of the variance. tral value in a roughly symmetrical distribution
3 in which small deviations occur more frequently
4 N
4 than large deviations. In plotting the number of
4 ( y − E ( y))2
5 i=1 i
σ = times a discrete event occurs, a typical curve is
N obtained, which is shown in Figure 44. Then the
If the set of numbers {yi } is a small sample from probability p of an event (score) occurring can
a larger set, then the sample average be thought of as the ratio of the number of times
it was observed divided by the total number of

n events. A continuous representation of this prob-
yi
i=1 ability density function is given by the normal
ȳ =
n distribution
1 2 2
p ( y) = √ e−[y−E(y)] /2σ . (80)
σ 2π
This is called a normal probability distribution

function. It is important because many results
are insensitive to deviations from a normal dis-
tribution. Also, the central limit theorem says
that if an overall error is a linear combination of Figure 45. Area under normal curve
component errors, then the distribution of errors
tends to be normal as the number of components
increases, almost regardless of the distribution of For a small sample, the variance can only be
the component errors (i.e., they need not be nor- estimated with the sample variance s2 . Thus, the
mally distributed). Naturally, several sources of normal distribution cannot be used because σ is
error must be present and one error cannot pre- not known. In such cases Student’s t-distribu-
dominate (unless it is normally distributed). The tion, shown in Figure 46 [202, p. 70], is used:
normal distribution function is calculated eas- y0 ȳ − E ( y)
ily; of more value are integrals of the function, p ( y) = n/2 , t = √
t2 s/ n
which are given in Table 12; the region of inter- 1+ n−1
est is illustrated in Figure 45.
and y0 is chosen such that the area under the
Table 12. Area under normal curve ∗ curve is one. The number ν = n − 1 is the degrees
z 2 /2
of freedom, and as ν increases, Student’s t-distri-
F (z) = √12 π e−z dz bution approaches the normal distribution. The
0

z F (z) z F (z) normal distribution is adequate (rather than the
0.0 0.0000 1.5 0.4332
t-distribution) when ν > 15, except for the tails
0.1 0.0398 1.6 0.4452 of the curve which require larger ν. Integrals of
0.2 0.0793 1.7 0.4554 the t-distribution are given in Table 13, the re-
0.3 0.1179 1.8 0.4641
gion of interest is shown in Figure 47.
0.4 0.1554 1.9 0.4713
0.5 0.1915 2.0 0.4772
0.6 0.2257 2.1 0.4821
0.7 0.2580 2.2 0.4861
0.8 0.2881 2.3 0.4893
0.9 0.3159 2.4 0.4918 Table 13. Percentage points of area under Students t-distribution ∗
1.0 0.3413 2.5 0.4938
1.1 0.3643 2.7 0.4965 ν α=0.10 α=0.05 α=0.01 α=0.001
1.2 0.3849 3.0 0.4987
1.3 0.4032 4.0 0.499968 1 6.314 12.706 63.657 636.619
1.4 0.4192 5.0 0.4999997 2 2.920 4.303 9.925 31.598
3 2.353 3.182 5.841 12.941
∗
Table gives the probability F that a random variable will fall 4 2.132 2.776 4.604 8.610
in the shaded region of Figure 45. For a more complete table 5 2.015 2.571 4.032 6.859
(in slightly different form), see [207, Table 26.1]. 6 1.943 2.447 3.707 5.959
7 1.895 2.365 3.499 5.408
8 1.860 2.306 3.355 5.041
9 1.833 2.262 3.250 4.781
10 1.812 2.228 3.169 4.587
15 1.753 2.131 2.947 4.073
20 1.725 2.086 2.845 3.850
25 1.708 2.060 2.787 3.725
30 1.697 2.042 2.750 3.646
∞ 1.645 1.960 2.576 3.291
∗
Table gives t values such that a random variable will fall in
the shaded region of Figure 47 with probability α. For a
one-sided test the confidence limits are obtained for α/2. For
a more complet table (in slightly different form), see [207,
Table 26.10].
Figure 44. Frequency of occurrence of different scores

Figure 46. Student’s t-distribution.

For explanation of ν see text
where
dF =p dx
is the probability of x being between x and x + dx.

The probability density function satisfies
p (x) ≥ 0
∞
p (x) dx = 1
−∞
Figure 47. Percentage points of area under Student’s t-dis-
tribution The Bernoulli distribution applies when the out-
Other probability distribution functions are come can take only two values, such as heads or
useful. Any distribution function must satisfy the tails, or 0 or 1. The probability distribution func-
following conditions: tion is
0 ≤ F (x) ≤ 1 p (x = k) =pk (1 −p)1−k , k = 0 or 1
F (−∞) = 0, F (+∞) = 1 and the mean of a function g (x) depending on x

is
F (x) ≤ F (y) when x ≤ y
E [g (x)] =g (1) p +g (0) (1 −p)
The probability density function is
The binomial distribution function applies when
dF (x)
p (x) = there are n trials of a Bernoulli event; it gives the
dx
probability of k occurrences of the event, which 


0 x<a
occurs with probability p on each trial x−a
F (x) = a<x<b
 b−a
1 b<x
p (x = k) =
The mean and variance are
n!
pk (1 − p)n−k a+b
k! (n − k)! E (x) =
2
(b − a)2
var (x) =
E (x) =n p 12
The normal distribution is given by Equation
var (x) = np (1 − p)
(80) with variance σ 2 .
The hypergeometric distribution function ap- The log normal probability density function is
plies when there are N objects, of which M are of
1 (logx − µ)2
one kind and N − M are of another kind. Then p (x) = √ exp −
xσ 2π 2 σ2
the objects are drawn one by one, without re-
placing the last draw. If the last draw had been and the mean and variance are [206, p. 89]
replaced the distribution would be the binomial
distribution. If x is the number of objects of type σ2
E (x) = exp µ+
M drawn in a sample of size n, then the proba- 2
bility of x = k is
var (x) = exp σ 2 − 1 exp 2 µ + σ 2
p (x = k) =
M ! (N − M )! n! (N − n) !
k! (M − k)! (n − k)! (N − M − n + k) ! N !
11.2. Sampling and Statistical Decisions
Two variables can be statistically dependent or
nM independent. For example, the height and diam-
E (x) =
N eter of all distillation towers are statistically in-
dependent, because the distribution of diameters
N −n
var (x) = n p (1 − p) of all columns 10 m high is different from that
N −1
of columns 30 m high. If yB is the diameter and
The Poisson distribution is yA the height, the distribution is written as
λk p (yB |yA = constant) , or here

p (x = k) = e−λ
k!
p (yB |yA = 10) =p (yB |yA = 30)
with a parameter λ. The mean and variance are
A third variable yC , could be the age of the oper-
E (x) =λ ator on the third shift. This variable is probably
unrelated to the diameter of the column, and for
var (x) =λ the distribution of ages is
The simplest continuous distribution is the uni- p ( yC | yA ) =p ( yC )
form distribution. The probability density func-
tion is Thus, variables yA and yC are distributed inde-
pendently. The joint distribution for two vari-

1
a <x<b ables is
p = b−a
0 x < a, x > b
p (yA , yB ) =p ( yA ) p ( yB | yA )
and the probability distribution function is if they are statistically dependent, and
p ( yA , yB ) =p ( yA ) p ( yB ) and the variance of Y is
if they are statistically independent. If a set of σ 2 (Y ) = σ 2 ( yA ) +σ 2 ( yB )

variables yA , yB , . . . is independent and identi-
cally distributed, More generally, consider the random variables
y1 , y2 , . . . with means E ( y1 ), E ( y2 ), . . . and
p ( yA , yB , . . .) =p ( yA ) p ( yB ) . . . variances σ 2 ( y1 ), σ 2 ( y2 ), . . . and correlation
coefficients ij . The variable
Conditional probabilities are used in hazard
analysis of chemical plants. Y = α1 y1 +α2 y2 + . . .
A measure of the linear dependence between
variables is given by the covariance has a mean
Cov ( yA , yB ) = E {[ yA − E ( yA )] [( yB − E ( yB ))]} E (Y ) = α1 E ( y1 ) +α2 E ( y2 ) + . . .

N
and variance [202, p. 87]
[ yAi − E ( yA )] [ yBi − E ( yB )]
=
i=1
n
N σ 2 (Y ) = α2i σ 2 ( yi )
i=1
The correlation coefficient is

n
n
Cov ( yA , yB ) +2 αi αj σ ( yi ) σ ( yj ) ij
( y A , yB ) = i=1 j=i+1
σ A σB
If yA and yB are independent, then or

Cov ( yA , yB ) = 0. If yA tends to increase when
n
yB decreases then Cov ( yA , yB ) < 0. The sample σ 2 (Y ) = α2i σ 2 ( yi )
correlation coefficient is [205, p. 484] i=1

n
n
n
( yAi − ȳA ) ( yBi − ȳB ) +2 αi αj Cov ( yi , yj ) (80)
i=1
r ( yA , yB ) = i=1 j=i+1
(n − 1) sA sB
If the variables are uncorrelated and have the
If measurements are for independent, identi- same variance, then
cally distributed observations, the errors are in-

dependent and uncorrelated. Then ȳ varies about
n
2
E ( y) with variance σ 2 /n, where n is the number σ (Y ) = α2i σ2
i=1
of observations in ȳ. Thus if something is mea-
sured several times today and every day, and the This fact can be used to obtain more accurate
measurements have the same distribution, the cost estimates for the purchased cost of a chem-
variance of the means decreases with the num- ical plant than is true for any one piece of equip-
ber of samples in each day’s measurement n. Of ment. Suppose the plant is composed of a num-
course, other factors (weather, weekends) may ber of heat exchangers, pumps, towers, etc., and
cause the observations on different days to be that the cost estimate of each device is ± 40 %
distributed nonidentically. of its cost (the sample standard deviation is 20 %
Suppose Y , which is the sum or difference of of its cost). In this case the αi are the numbers
two variables, is of interest: of each type of unit. Under special conditions,
such as equal numbers of all types of units and
Y = yA ± yB comparable cost, the standard deviation of the
plant costs is
Then the mean value of Y is
σ
σ (Y ) = √
E (Y ) =E ( yA ) ± E ( yB ) n
√
and is then ± (40/ n) %. Thus the standard de-
viation of the cost for the entire plant is the stan-
dard deviation of each piece of equipment di-
vided by the square root of the number of units.
Under less restrictive conditions the actual num-
bers change according to the above equations,
but the principle is the same.
Suppose modifications are introduced into
the manufacturing process. To determine if the
Figure 48. Two-sided statistical decision
modification causes a significant change, the
mean of some property could be measured be- The same type of decisions can be made
fore and after the change; if these differ, does for other distributions. Consider Student’s t-dis-
it mean the process modification caused it, or tribution. At a 95 % level of confidence, with
could the change have happened by chance? This ν = 10 degrees of freedom, the t values are
is a statistical decision. A hypothesis H 0 is de- ± 2.228. Thus, the sample mean would be ex-
fined; if it is true, action A must be taken. The pected to be between
reverse hypothesis is H 1 ; if this is true, action
B must be taken. A correct decision is made if s
ȳ ± tc √
action A is taken when H 0 is true or action B n
is taken when H 1 is true. Taking action B when with 95 % confidence. If the mean were outside
H 0 is true is called a type I error, whereas taking this interval, the hypothesis would be rejected.
action A when H 1 is true is called a type II error. The chi-square distribution is useful for ex-
The following test of hypothesis or test of amining the variance or standard deviation. The
significance must be defined to determine if the statistic is defined as
hypothesis is true. The level of significance is
the maximum probability that an error would be n s2
χ2 = 2
accepted in the decision (i.e., rejecting the hy- σ
pothesis when it is actually true). Common lev-
els of significance are 0.05 and 0.01, and the test ( y1 − ȳ)2 + ( y2 − ȳ)2 + . . . + ( yn − ȳ)2
=
of significance can be either one or two sided. If σ2
a sampled distribution is normal, then the prob- and the chi-square distribution is
ability that the z score
2
y − ȳ p ( y) = y0 χν−2 e−χ /2
z =
sy ν = n − 1 is the number of degrees of freedom
is in the unshaded region is 0.95. The value given and y0 is chosen so that the integral of p ( y) over
in Table 12 for F = 0.475 is z = 1.96. Because a all y is 1. The probability of a deviation larger
two-sided test is desired, F = 0.95/2 = 0.475. If than χ2 is given in Table 14; the area in ques-
the test was one-sided, at the 5 % level of signif- tion, in Figure 49. For example, for 10 degrees of
icance, F = 0.45 or z = 1.645. In the two-sided freedom and a 95 % confidence level, the critical
test (see Fig. 48), if a single sample is chosen values of χ2 are 0.025 and 0.975. Then
and z <− 1.96 or z > 1.96, then this could hap- √ √
s n s n
pen with probability 0.05 if the hypothesis were <σ <
χ0.975 χ0.025
true. This z would be significantly different from
the expected value (based on the chosen level or
of significance) and the tendency would be to √ √
s n s n
reject the hypothesis. If the value of z was bet- <σ <
20.5 3.25
ween − 1.96 and 1.96, the hypothesis would be
accepted. with 95 % confidence.
Table 14. Percentage points of area under chi-square distribution with ν degrees of freedom ∗
ν α=0.995 α=0.99 α=0.975 α=0.95 α=0.5 α=0.05 α=0.025 α=0.01 α=0.005
1 7.88 6.63 5.02 3.84 0.455 0.0039 0.0010 0.0002 0.00004

2 10.6 9.21 7.38 5.99 1.39 0.103 0.0506 0.0201 0.0100
3 12.8 11.3 9.35 7.81 2.37 0.352 0.216 0.115 0.072
4 14.9 13.3 11.1 9.49 3.36 0.711 0.484 0.297 0.207
5 16.7 15.1 12.8 11.1 4.35 1.15 0.831 0.554 0.412
6 18.5 16.8 14.4 12.6 5.35 1.64 1.24 0.872 0.676
7 20.3 18.5 16.0 14.1 6.35 2.17 1.69 1.24 0.989
8 22.0 20.1 17.5 15.5 7.34 2.73 2.18 1.65 1.34
9 23.6 21.7 19.0 16.9 8.34 3.33 2.70 2.09 1.73
10 25.2 23.2 20.5 18.3 9.34 3.94 3.25 2.56 2.16
12 28.3 26.2 23.3 21.0 11.3 5.23 4.40 3.57 3.07
15 32.8 30.6 27.5 25.0 14.3 7.26 6.26 5.23 4.60
17 35.7 33.4 30.2 27.6 16.3 8.67 7.56 6.41 5.70
20 40.0 37.6 34.2 31.4 19.3 10.9 9.59 8.26 7.43
25 46.9 44.3 40.6 37.7 24.3 14.6 13.1 11.5 10.5
30 53.7 50.9 47.0 43.8 29.3 18.5 16.8 15.0 13.8
40 66.8 63.7 59.3 55.8 39.3 26.5 24.4 22.2 20.7
50 79.5 76.2 71.4 67.5 49.3 34.8 32.4 29.7 28.0
60 92.0 88.4 83.3 79.1 59.3 43.2 40.5 37.5 35.5
70 104.2 100.4 95.0 90.5 69.3 51.7 48.8 45.4 43.3
80 116.3 112.3 106.6 101.9 79.3 60.4 57.2 53.5 51.2
90 128.3 124.1 118.1 113.1 89.3 69.1 65.6 61.8 59.2
100 140.2 135.8 129.6 124.3 99.3 77.9 74.2 70.1 67.3
∗
Table value is χ2 α ; χ2 < χ2 α with probability α. For a more complete table (in slightly different form), see [207, Table 26.8].
If the samples have different variances, the

relevant statistic for the t-test is
x̄ − ȳ
t = -
var (x) /N1 + var ( y) /N2
The number of degrees of freedom is now taken

approximately as
2
Figure 49. Percentage points of area under chi-squared var(x) var( y)
+
distribution with ν degrees of freedom N1 N2
ν=
[var (x)/N1 ]2 [var( y)/N2 ]2
N1 − 1
+ N2 − 1
Tests are available to decide if two distribu-
tions that have the same variance have differ- There is also an F-test to decide if two distri-
ent means [205, p. 465]. Let one distribution be butions have significantly different variances. In
called x, with N 1 samples, and the other be called this case, the ratio of variances is calculated:
y, with N 2 samples. First, compute the standard
error of the difference of the means: F =
var (x)
3 var ( y)
4
4N
4 (xi − x̄)2 + ( yi − ȳ)2
1 N2
4 where the variance of x is assumed to be larger.
5 i=1 i=1 1 1
sD = + Then, a table of values is used to determine
N1 + N 2 − 2 N1 N2
the significance of the ratio. The table [207,
Next, compute the value of t Table 26.9] is derived from the formula [205,
p. 169]
x̄ − ȳ
t = ν ν1
sD 2
Q (F |ν1 , ν2 ) = Iν2 /(ν2 +ν1 F ) ,
2 2
and evaluate the significance of t using Student’s
t-distribution for N 1 + N 2 − 2 degrees of free- where the right-hand side is an incomplete beta
dom. function.
11.3. Error Analysis in Experiments Thus, the variance of the desired quantity Y can
be found. This gives an independent estimate
Suppose a measurement of several quantities is of the errors in measuring the quantity Y from
made and a formula or mathematical model is the errors in measuring each variable it depends
used to deduce some property of interest. For upon.
example, to measure the thermal conductivity
of a solid k, the heat flux q, the thickness of the
sample d, and the temperature difference across 11.4. Factorial Design of Experiments
the sample ∆T must be measured. Each mea- and Analysis of Variance
surement has some error. The heat flux q may be
the rate of electrical heat input Q̇ divided by the Statistically designed experiments consider, of
area A, and both quantities are measured to some course, the effect of primary variables, but they
tolerance. The thickness of the sample is mea- also consider the effect of extraneous variables,
sured with some accuracy, and the temperatures the interactions among variables, and a measure
are probably measured with a thermocouple, to of the random error. Primary variables are those
some accuracy. These measurements are com- whose effect must be determined. These vari-
bined, however, to obtain the thermal conduc- ables can be quantitative or qualitative. Quanti-
tivity, and the error in the thermal conductivity tative variables are ones that may be fit to a model
must be determined. The formula is to determine the model parameters. Curve fitting
d of this type is discused in Chapter 2. Qualitative
k = Q̇ variables are ones whose effect needs to be
A∆T
known; no attempt is made to quantify that ef-
If each measured quantity has some variance, fect other than to assign possible errors or mag-
what is the variance in the thermal conductiv- nitudes. Qualitative variables can be further sub-
ity? divided into type I variables, whose effect is de-
Suppose a model for Y depends on vari- termined directly, and type II variables, which
ous measurable quantities, y1 , y2 , . . . Suppose contribute to performance variability, and whose
several measurements are made of y1 , y2 , . . . effect is averaged out. For example, in studying
under seemingly identical conditions and sev- the effect of several catalysts on yield in a chem-
eral different values are obtained, with means ical reactor, each different type of catalyst would
E (y1 ), E (y2 ), . . . and variances σ 21 , σ 22 , . . . Next be a type I variable, because its effect should be
suppose the errors are small and independent of known. However, each time the catalyst is pre-
one another. Then a change in Y is related to pared, the results are slightly different, because
changes in yi by of random variations; thus, several batches may
∂Y ∂Y exist of what purports to be the same catalyst.
dY = dy1 + dy2 + . . .
∂y1 ∂y2 The variability between batches is a type II vari-
able. Because the ultimate use will require us-
If the changes are indeed small, the partial ing different batches, the overall effect including
derivatives are constant among all the samples. that variation should be known, because know-
Then the expected value of the change is ing the results from one batch of one catalyst
N
precisely might not be representative of the re-
∂Y
E (dY ) = E (dyi ) sults obtained from all batches of the same cat-
∂yi
i=1 alyst. A randomized block design, incomplete
Naturally E (dyi ) = 0 by definition so that block design, or Latin square design, for exam-
E (dY ) = 0, too. However, since the errors are ple, all keep the effect of experimental error in
independent of each other and the partial deriva- the blocked variables from influencing the ef-
tives are assumed constant because the errors are fect of the primary variables. Other uncontrolled
small, the variances are given by Equation (81) variables are accounted for by introducing ran-
domization in parts of the experimental design.
N
To study all variables and their interaction re-
∂Y 2
σ 2 (dY ) = σi2 (81) quires a factorial design, involving all possible
i=1
∂yi
combinations of each variable, or a fractional

factorial design, involving only a selected set.
nt
Statistical techniques are then used to determine St = ( yti − ȳt )2
the important variables, the important interac- i=1
tions and the error in estimating these effects. Since each treatment has nt experiments, the
The discussion here is a brief overview of [202]. number of degrees of freedom is nt − 1. Then
If only two methods exist for preparing some the sample variances are
product, to see which treatment is best, the sam-
pling analysis discussed in Section 11.2 can be St
s2t =
used to deduce if the means of the two treatments nt − 1
differ significantly. With more treatments, the
analysis is more detailed. Suppose the experi- The within-treatment sum of squares is
mental results are arranged as shown in Table 15,
k
i.e., several measurements for each treatment. SR = St
The objective is to see if the treatments differ sig- t=1
nificantly from each other, that is, whether their
and the within-treatment sample variance is
means are different. The samples are assumed to
have the same variance. The hypothesis is that SR
s2R =
the treatments are all the same, and the null hy- N −k
pothesis is that they are different. Deducing the
statistical validity of the hypothesis is done by Now, if no difference exists between treatments,
an analysis of variance. a second estimate of σ 2 could be obtained by
calculating the variation of the treatment aver-
Table 15. Estimating the effect of four treatments ages about the grand average. Thus, the between-
treatment mean square is computed:
Treatment 1 2 3 4
− − − − ST k
− − − − s2T = , ST = nt ( ȳt − ȳ)2
k−1
− − − − t= 1
− − −
− − Basically the test for whether the hypothesis is
− true or not hinges on a comparison between the
within-treatment estimate s2 R (with νR = N − k
Treatment − − − − degrees of freedom) and the between-treatment
average estimate s2 T (with νT = k − 1 degrees of free-
Grand −
average dom). The test is made based on the F distri-
bution for νR and νT degrees of freedom [207,
Table 26.9], [202, p. 636].
The data for k = 4 treatments are arranged in Next consider the case in which randomized
Table 15. Each treatment has nt experiments, blocking is used to eliminate the effect of some
and the outcome of the i-th experiment with variable whose effect is of no interest, such as
treatment t is called yti . The treatment average the batch-to-batch variation of the catalysts in
is the chemical reactor example. With k treatments

nt and n experiments in each treatment, the results
yti
i=1 from n k experiments can be arranged as shown
ȳt =
nt in Table 16; within each block, various treat-
and the grand average is ments are applied in a random order. The block
average, the treatment average, and the grand

k
average are computed as before. The following
nt ȳt
k
ȳ =
t=1
, N = nt quantities are also computed for the analysis of
N t= 1 variance table:
Next, the sum of squares of deviations is com-
puted from the average within the t-th treatment
Table 16. Block design with four treatments and five blocks
sider a 23 factorial design, with 3 variables and
2 levels for each. The experiments are indicated
Treatment 1 2 3 4 Block in Table 17. The main effects are calculated by
average determining the difference between results from
Block 1 − − − − − all high values of a variable and all low values of
Block 2 − − − − − a variable; the result is divided by the number of
Block 3 − − − − −
Block 4 − − − − −
experiments at each level. For example, for the
Block 5 − − − − − first variable, calculate
Effect of variable 1 = [( y2 + y4 + y6 + y8 )
Treatment − − − − grand
average average
− [( y1 + y3 + y5 + y7 )]] /4
Note that all observations are being used to sup-

Name Formula Degrees ply information on each of the main effects and
of freedom
Average SA = n k ȳ 2 1 each effect is determined with the precision of a

n
fourfold replicated difference. The advantage of
Blocks SB = k ( ȳt − ȳ)2 n-1
i=1 a one-at-a-time experiment is the gain in preci-

k
Treatments ST = n ( ȳt − ȳ)2 k-1 sion if the variables are additive and the measure
t=1
Residuals SR = (n-1)(k-1) of nonadditivity if it occurs [202, p. 313].

t
n
( yti − ȳi − ȳt + ȳ)2
t=1 i=1 Table 17. Two-level factorial design with three variables

t
n
2
Total S= yti N=nk Run Variable 1 Variable 2 Variable 3
t=1 i=1
1 − − −
The key test is again a statistical one, based 2 + − −
3 − + −
on the value of 4 + + −
5 − − +
ST −
s2T /s2R , where s2T = 6 + +
k−1 7 − + +
8 + + +
SR
and s2R =
(n − 1) (k − 1)
Interaction effects between variables 1 and 2
and the F distribution for νR and νT degrees of are obtained by comparing the difference bet-
freedom [202, p. 636]. The assumption behind ween the results obtained with the high and low
the analysis is that the variations are linear [202, value of 1 at the low value of 2 with the differ-
p. 218]. Ways to test this assumption as well as ence between the results obtained with the high
transformations to make if it is not true are pro- and low value 1 at the high value of 2. The 12-
vided in [202], where an example is given of how interaction is
the observations are broken down into a grand
average, a block deviation, a treatment deviation, 12 interaction = [( y4 − y3 + y8 − y7 )
and a residual. For two-way factorial design, in
which the second variable is a real one rather − [( y2 − y1 + y6 − y5 )]] /2
than one you would like to block out, see [202,
p. 228]. The key step is to determine the errors associated
To measure the effects of variables on a single with the effect of each variable and each interac-
outcome, a factorial design is appropriate. In a tion so that the significance can be determined.
two-level factorial design, each variable is con- Thus, standard errors need to be assigned. This
sidered at two levels only, a high and low value, can be done by repeating the experiments, but it
often designated as a + and a −. The two-level can also be done by using higher order interac-
factorial design is useful for indicating trends tions (such as 123 interactions in a 24 factorial
and showing interactions; it is also the basis for design). These are assumed negligible in their ef-
a fractional factorial design. As an example, con- fect on the mean but can be used to estimate the
standard error [202, pp. 319 – 328]. Then calcu- Because the total differential can be written as
lated effects that are large compared to the stan-
dard error are considered important, whereas ∂z ∂z
dz = dx + dy (83)
those that are small compared to the standard ∂x y ∂y x
error are considered due to random variations for path independence

and are unimportant.

In a fractional factorial design, only part of ∂ ∂z ∂ ∂z
=
the possible experiments is performed. With k ∂y ∂x y ∂x ∂y x
variables, a factorial design requires 2k experi-
or
ments. When k is large, the number of experi-
ments can be large; for k = 5, 25 = 32. For k this ∂2z ∂2z
large, Box et al. [202, p. 376] do a fractional = (84)
∂y ∂x ∂x ∂y
factorial design. In the fractional factorial de-
sign with k = 5, only 16 experiments are cho- is needed.
sen. Cropley [208] gives an example of how to Various relationships can be derived from
combine heuristics and statistical arguments in Equation (83). If z is constant,
application to kinetics mechanisms in chemical
∂z ∂z
engineering. 0 = dx + dy
∂x y ∂y x z
Rearrangement gives
12. Multivariable Calculus Applied
∂z ∂y ∂z (∂y/∂x)z
to Thermodynamics = − = − (85)
∂x y ∂x z ∂y x (∂y/∂z)x
Many of the functional relationships required Alternatively, if Equation (83) is divided by dy
in thermodynamics are direct applications of while some other variable w is held constant,
the rules of multivariable calculus. In this short

chapter, those rules are reviewed in the context ∂z ∂z ∂x ∂z
= + (86)
of the needs of thermodynamics. These ideas ∂y w ∂x y ∂y w ∂y x
were expounded in one of the classic books on
chemical engineering thermodynamics [209]. Dividing both the numerator and the denomina-
tor of a partial derivative by dw while holding a
variable y constant yields
12.1. State Functions
∂z (∂z/∂w)y ∂z ∂w
= = (87)
∂x y (∂x/∂w)y ∂w y ∂x y
State functions depend only on the state of the
system, not on its past history or how one got In thermodynamics the state functions include
there. If z is a function of two variables x and the internal energy U, the enthalpy H, and the
y, then z (x, y) is a state function, because z is Helmholtz and Gibbs free energies A and G, re-
known once x and y are specified. The differen- spectively, which are defined as follows:
tial of z is
H = U +pV
dz =M dx +N dy
A = U − TS
By the theorem in page 57 the line integral
G = H − T S = U + pV − T S = A + pV
(M dx + N dy)
C where S is the entropy, T the absolute temper-
ature, p the pressure, and V the volume. These
is independent of the path in x – y space if and
are also state functions, in that the entropy is
only if
specified once two variables (e.g., T and p) are
∂M ∂N specified. Likewise V is specified once T and p
= (82)
∂y ∂x are specified, and so forth.
12.2. Applications to Thermodynamics

∂H
All of the following applications are for closed Cp =
∂T p
systems with constant mass. If a process is re-
versible and only p – V work is done, one form If entropy and enthalpy are taken as functions of
of the first law states that changes in the internal T and p, the total differentials are
energy are given by the following expression
∂S ∂S
dS = dT + dp
∂T p ∂p T
dU = T dS − pdV (88)

∂H ∂H
If the internal energy is considered a function of dH = dT + dp
S and V , then ∂T p ∂p T

∂U ∂U ∂H
dU = dS + dV = Cp dT + dp
∂S V ∂V S
∂p T
This is the equivalent of Equation (83) and If the pressure is constant,

∂S
∂U ∂U dS = dT and dH = Cp dT
T = , p = − ∂T p
∂S V ∂V S
Because the internal energy is a state function, When enthalpy is considered a function of S and
Equation (84) is required: p, the total differential is
dH = T dS + V dp
∂2U ∂2U
=
∂V ∂S ∂S ∂V When the pressure is constant, this is
which here is
dH = T dS

∂T ∂p
=− (89) Thus, at constant pressure
∂V S ∂S V

∂S
This is one of the Maxwell relations and is dH = Cp dT = T dS = T
∂T
dT
p
merely an expression of Equation (84).
The differentials of the other energies are which gives

∂S Cp
dH = T dS +V dp (90) =
∂T p T
dA = − S dT − pdV (91) When p is not constant, using the last Maxwell
relation gives
dG = − S dT + V dp (92)
Cp ∂V
dS = dT − dp (96)
From these differentials, other Maxwell rela- T ∂T p
tions can be derived in a similar fashion by ap-
Then the total differential for H is
plying Equation (84).

∂V
∂T ∂V dH = T dS + V dp = Cp dT − T dp + V dp
= (93) ∂T p
∂p S ∂S p
Rearranging this, when H (T, p), yields
∂S ∂p
= (94)
∂V T ∂T V
∂V
∂S ∂V dH = Cp dT + V − T dp (97)
= − (95) ∂T p
∂p T ∂T p
This equation can be used to evaluate enthalpy
The heat capacity at constant pressure is defined differences by using information on the equation
as of state and the heat capacity:
Type 2 (30 possibilities).

T2
∂α ∂G
H (T2 , p2 ) − H (T1 , p1 ) = Cp (T, p1 ) dT General : , Specific :
∂b c ∂T V
T1
Using Equation (92) gives
p2

∂V ∂G ∂p
+ V −T dp (98) = −S + V
∂T p T2 ,p ∂T ∂T
p1 V V
The same manipulations can be done for inter- Using the other equations for U, H, A, or S gives
nal energy: the other possibilities.

∂S Cv Type 3 (15 possibilities plus reciprocals).
= (99)
∂T V T
∂a ∂V
General : , Specific :
∂b α ∂T S

(∂V /∂T )p Cv
dS = − dV + dT (100) First the derivative is expanded by using Equa-
(∂V /∂p)T T tion (85), which is called expansion without in-
troducing a new variable:

(∂V /∂T )p ∂V ∂S ∂V (∂S/∂T )V
dU = Cv dT − p+T dV =− =−
(∂V /∂p)T ∂T S ∂T V ∂S T (∂S/∂V )T
Then the numerator and denominator are evalu-

ated as type 2 derivatives, or by using Equations
(99) and (100):
12.3. Partial Derivatives of All
Thermodynamic Functions ∂V Cv /T
=−
∂T S − (∂V /∂T )p (∂p/∂V )T
The various partial derivatives of the thermody-
namic functions can be classified into six groups. ∂V
Cv ∂p T
In the general formulas below, the variables U, = (102)
T ∂V
H, A, G, or S are denoted by Greek letters, ∂T p
whereas the variables V, T, or p are denoted by
Latin letters. These derivatives are important for reversible,
adiabatic processes (e.g., in an ideal turbine or
compressor) because the entropy is constant.
Type 1 (3 possibilities plus reciprocals).
Similar derivatives can be obtained for isen-
thalpic processes, such as a pressure reduction
∂a ∂p
General : , Specific : at a valve. In that case, the Joule – Thomson co-
∂b c ∂T V
efficient is obtained:
Equation (85) yields

∂T 1 ∂V
∂p ∂V ∂p = −V + T
=− = ∂p H Cp ∂T p
∂T V ∂T p ∂V T
(∂V /∂T )p
− (101) Type 4 (30 possibilities plus reciprocals).
(∂V /∂p)T

This relates all three partial derivatives of this ∂α ∂G
General : , Specific :
type. ∂β c ∂A p
Now, expand through the introduction of a new

variable using Equation (87):

∂G ∂G ∂T (∂G/∂T )p ∂S ∂V ∂p Cp
= = =− +
∂A p ∂T p ∂A p (∂A/∂T )p ∂T V ∂T p ∂T V T
This operation has created two type 2 deriva- Substitution for (∂p/∂T )V and rearrangement
tives. Substitution yields give

∂G S ∂V ∂p
= Cp − C v = T
∂A S + p (∂V /∂T )p ∂T p ∂T V
p
2
∂V ∂p
= −T
∂T ∂V
Type 5 (60 possibilities). p T
Use of this equation permits the rearrangement

∂α ∂G
General : , Specific : of Equation (102) into
∂b β ∂p A
Cp
Starting from Equation (92) for dG gives ∂V (∂V /∂T )2p + T
(∂V /∂p)T
=
∂T S (∂V /∂T )p
∂G ∂T
= −S +V
∂p A ∂p A
The ratio of heat capacities is
The derivative is a type 3 derivative and can be Cp T (∂S/∂T )p
=
evaluated by using Equation (85). Cv T (∂S/∂T )V

∂G (∂A/∂p)T Expansion by using Equation (85) gives
= S +V
∂p A (∂A/∂T )p
Cp − (∂p/∂T )S (∂S/∂p)T
=
The two type 2 derivatives are then evaluated: Cv − (∂V /∂T )S (∂S/∂V )T
and the ratios are then
∂G S p (∂V /∂p)T
= +V
∂p A S + p (∂V /∂T )p
Cp ∂p ∂V
=
These derivatives are also of interest for free ex- Cv ∂V S ∂p T
pansions or isentropic changes. Using Equation (85) gives

Type 6 (30 possibilities plus reciprocals). Cp ∂p ∂T ∂V
= −
Cv ∂V S ∂p V ∂T p
∂α ∂G
General : , Specific : Entropy is a variable in at least one of the partial
∂β γ ∂A H
derivatives.
Equation (87) is used to obtain two type 5 deriva-
tives.
13. References
∂G (∂G/∂T )H
=
∂A H (∂A/∂T )H
General References
These can then be evaluated by using the proce- 1. J. J. Dongarra, C. B. Moler, J. R. Bunch, G. W.
dures for type 5 derivatives. Stewart: Linpack User’s Guide, SIAM,
The difference in molar heat capacities (Cp – Philadelphia 1979.
Cv ) can be derived in similar fashion. Using 2. G. Forsyth, C. B. Moler: Computer Solution of
Lineart Algebraic Systems, Prentice-Hall,
Equation (98) for Cv yields
Englewood Cliffs 1967.

∂S
Cv = T
∂T V
Specific References
3. E. Isaacson, H. B. Keller, Analysis of
To evaluate the derivative, Equation (86) is used Numerical Methods, J. Wiley and Sons, New
to express dS in terms of p and T : York 1966.
4. S. C. Eisenstat, M. H. Schultz, A. H. Sherman: 20. N. R. Amundson: Mathematical Methods in

“Algorithms and Data Structures for Sparse Chemical Engineering, Prentice-Hall,
Symmetric Gaussian Elimination,” SIAM J. Englewood Cliffs, N.J. 1966.
Sci. Stat. Comput. 2 (1981) 225 – 237. 21. J. H. Perry: Chemical Engineers’ Handbook,
5. V. A. Barker (ed.): Sparse Matrix Techniques – 6th ed., McGraw-Hill, New York 1984.
Copenhagen 1976, Lecture Notes in 22. D. S. Watkins: “Understanding the QR
Mathematics 572, Springer Verlag, Berlin – Algorithm,” SIAM Rev. 24 (1982) 427 – 440.
Heidelberg – New York – Tokyo 1977. 23. G. F. Carey, K. Sepehrnoori: “Gershgorin
6. J. R. Bunch, D. J. Rose (ed.): Sparse Matrix Theory for Stiffness and Stability of Evolution
Computations, Academic Press, New York Systems and Convection-Diffusion,” Comp.
1976. Meth. Appl. Mech. 22 (1980) 23 – 48.
7. I. S. Duff (ed.): Sparse Matrices and Their 24. M. Abranowitz, I. A. Stegun: Handbook of
Uses, Academic Press, New York 1981. Mathematical Functions, National Bureau of
8. I. S. Duff: Direct Methods for Sparse Matrices, Standards, Washington, D.C. 1964.
25. W. H. Press, B. P. Flannery, S. A. Teukolsky,
Charendon Press, Oxford 1986.
W. T. Vetterling: Numerical Recipes,
9. J. R. Rice: Matrix Computations and
Cambridge University Press, Cambridge 1986.
Mathematical Software, McGraw-Hill, New
26. J. C. Daubisse: “Some Results about
York 1983.
Approximation of Functions of One or Two
10. H. S. Price, K. H. Coats, “Direct Methods in
Variables by Sums of Exponentials, ” Int. J.
Reservoir Simulation,” Soc. Pet. Eng. J. 14
Num. Meth. Eng. 23 (1986) 1959 – 1967.
(1974) 295 – 308. 27. L. Lapidus, J. H. Seinfeld: Numerical Solution
11. A. Bykat: “A Note on an Element Re-Ordering of Ordinary Differential Equations, Academic
Scheme,” Int. J. Num. Methods Egn. 11 Press, New York 1971.
(1977) 194 –198. 28. B. A. Finlayson: Nonlinear Analysis in
12. M. R. Hesteness, E. Stiefel: “Methods of Chemical Engineering, McGraw-Hill, New
conjugate gradients for solving linear York 1980.
systems,” J. Res. Nat. Bur. Stand 29 (1952) 29. J. M. Ortega, W. G. Poole Jr.: An Introduction
409 – 439. to Numerical Methods for Differential
13. S. C. Eisenstat: “Efficient Implementation of a Equations, Pitman, Marshfield, Mass. 1981.
Class of Preconditioned Conjugate Gradient 30. R. Courant, D. Hilbert: Methods of
Methods,” SIAM J. Sci. Stat. Comput. 2 Mathematical Physics, vol. 1,
(1981) 1 – 4. Wiley-Interscience, New-York 1953.
14. M. R. Hestenes: Conjugate Gradient Methods 31. E. Hille: Analytic Function Theory, Ginn and
in Optimization, Springer-Verlag, Berlin – Co., Boston 1959.
Heidelberg – New York – Tokyo 1980. 32. H. F. Weinberger: A First Course in Partical
15. A. McIntosh: Fitting Linear Models: an Differential Equations, Blaisdell, Waltham,
Application of Conjugate Graduent Mass. 1965.
Algorithms, Springer Verlag, Berlin – 33. R. V. Churchill: Operational Mathematics,
Heidelberg – New York – Tokyo 1982. McGraw-Hill, New York 1958.
16. W. H. Press, B. P. Flannery, S. A. Teukolsky, 34. H. F. Weinberger: A First Course in Partial
W. T. Vetterling: Numerical Recipes, Differential Equations, Blaisdell, Waltham,
Cambridge University Press, Cambridge 1986. Mass. 1965.
17. B. A. Finlayson: Nonlinear Analysis in 35. W. H. Press, B. P. Flanner, S. A. Teukolsky,
Chemical Engineering, McGraw-Hill, New W. T. Vetterling: Numercial Recipes,
York 1980. Cambridge Univ. Press, Cambridge 1986.
36. R. V. Churchill: Operational Mathematics,
18. R. W. H. Sargent: “A Review of Methods for
McGraw-Hill, New York 1958.
Solving Non-linear Algebraic Equations,” in
37. J. T. Hsu, J. S. Dranoff: “Numerical Inversion
R. S. H. Mah, W. D. Seider (eds.): Foundations
of Certain Laplace Transforms by the Direct
of Computer-Aided Chemical Process Design,
Application of Fast Fourier Transform (FFT)
American Institute of Chemical Engineers,
Algorithm,” Comput. Chem. Eng. 11 (1987)
New York 1981.
101 – 110.
19. J. D. Seader: “Computer Modeling of 38. M. Abramowitz, I. A. Stegun: Handbook of
Chemical Processes,” AIChE Monogr. Ser. 81 Mathematical Functions, National Bureau of
(1985) no. 15. Standards, Washington, D.C. 1964.
39. E. Kreyszig: Advanced Engineering Chemical Process Design, American Institute

Mathematics, 4th ed., J. Wiley and Sons, New of Chemical Engineers, New York 1981,
York 1979. pp. 225 – 340.
40. H. S. Carslaw, J. C. Jaeger: Conduction of Heat 58. N. B. Ferguson, B. A. Finlayson: “Transient
in Solids, 2nd ed., Clarendon Press, Oxford – Modeling of a Catalytic Converter to Reduce
London 1959. Nitric Oxide in Automobile Exhaust,” AIChE J
41. R. B. Bird, R. C. Armstrong, O. Hassager: 20 (1974) 539 – 550.
Dynamics of Polymeric Liquids, 2nd ed., 59. I. M. Smith, J. L. Siemienivich, I. Gladwell: “A
Appendix A, Wiley-Interscience, New York Comparison of Old and New Methods for
1987. Large Systems of Ordinary Differential
42. R. S. Rivlin, J. Rat. Mech. Anal. 4 (1955) Equations Arising from Parabolic Partial
681 – 702. Differential Equations,” Num. Anal. Rep.
43. N. R. Amundson: Mathematical Methods in no. 13, Department of Engineering, University
Chemical Engineering; Matrices and Their of Manchester, 1975.
Application, Prentice-Hall, Englewood Cliffs, 60. J. D. Lambert: Computational Methods in
N.J. 1966. Ordinary Differential Equations, J. Wiley and
44. E. Kreyszig: Advanced Engineering Sons, New York 1973.
Mathematics, 4th ed., J. Wiley and Sons, New 61. L. R. Petzold: “A description of DASSL: a
York 1979. Differential-Algebraic System Solver,” Sandia
45. I. S. Sokolnikoff, E. S. Sokolnikoff: Higher Nat. Lab. Rech. Rep. SAND 82-8637; also in
Mathematics for Engineers and Physicists, R. S. Stepleman et al. (eds.): IMACS Trans. on
McGraw-Hill, New York 1941. Scientific Computing, vol. 1, North Holland
46. M. R. Spiegel: Vector Analysis, Schaum Publ. Co, Amsterdam 1983, pp. 65 – 68.
Publishing, New York 1959. 62. C. C. Pontelides, D. Gritsis, K. R. Morison,
47. L. E. Scriven: personal communication. R. W. H. Sargent: “The Mathematical
48. P. M. Morse, H. Feshbach: Methods of Modelling of Transient Systems Using
Theoretical Physics, McGraw-Hill, New York Differential-Algebraic Equations,” Comput.
1953. Chem. Eng. 12 (1988) 449 – 454.
49. B. A. Finlayson: The Method of Weighted 63. G. A. Byrne, P. R. Ponzi:
Residuals and Variational Principles, “Differential-Algebraic Systems, Their
Academic Press, New York 1972. Applications and Solutions,” Comput. Chem.
50. B. A. Finlayson: Nonlinear Analysis in Eng. 12 (1988) 377 – 382.
Chemical Engineering, McGraw-Hill, New 64. A. C. Hindmarsh: “LSODE and LSODE, Two
York 1980. New Initial Value Ordinary Differential
51. L. Lapidus, J. H. Seinfeld: Numerical Solution Equations Solvers,“ ACM SIGNUM Newsletter
of Ordinary Differential Equations, Academic 15 (1980) 10 –11.
Press, New York 1971. 65. A. C. Hindmarsh: “GEARB: Solution of
52. G. Forsythe, M. Malcolm, C. Moler: Computer
Ordinary Differential Equations Having
Methods for Mathematical Computation,
Banded Jacobian,” Computer Documentation,
Prentice-Hall, Englewood Cliffs, N.J. 1977.
UCID-30 059, Rev. 1, Lawrence Livermore
53. N. R. Amundson: Mathematical Methods in
Laboratory, University of California, 1975.
Chemical Engineering, Prentice-Hall,
66. T. E. Hull, W. H. Enright, B. M. Fellen, A. E.
Englewood Cliffs, N.J. 1966.
Sedgwick: “Comparing Numerical Methods
54. J. R. Rice: Numerical Methods, Software, and
for Ordinary Differential Equations,” SIAM J.
Analysis, McGraw-Hill, New York 1983.
Num. Anal. 9 (1972) 603 – 637.
55. M. B. Bogacki, K. Alejski, J. Szymanowski:
67. L. F. Shampine, H. A. Watts, S. M. Davenport:
“The Fast Method of the Solution of Reacting
“Solving Nonstiff Ordinary Differential
Distillation Problem,” Comput. Chem. Eng. 13
Equations – The State of the Art,” SIAM Rev.
(1989) 1081 – 1085.
18 (1976) 376 – 411.
56. C. W. Gear: Numerical Initial-Value Problems
68. G. Byrne, A. Hindmarsh, K. R. Jackson, H. G.
in Ordinary Differential Equations,
Brown: “A Comparison of Two ODE Codes:
57. B. Carnahan, J. O. Wilkes: “Numerical GEAR and EPISODE,” Comput. Chem. Eng.
Solution of Differential Equations – An 1 (1977) 133 – 147.
Overview,” in Foundations of Computer-Aided
69. G. Junce, V. Lauric, R. Mihail: “A Comparison 83. J. R. Rice: Numerical Methods, Software, and
Between the Insensitive Runge – Kutta, The Analysis, McGraw-Hill, New York 1983.
Semi-Implicit Extrapolation and the Backward 84. B. A. Finlayson: Numerical Methods for
Differencing Methods in Solving the ODE Problems with Moving Fronts, Ravenna Park
Systems Which Describe the Radical Publishing Inc., Seattle 1990.
Hydrocarbon Pyrolysis,” Comput. Chem. Eng. 85. B. A. Finlayson: Nonlinear Analysis in
13 (1989) 1075 – 1079. Chemical Engineering, McGraw-Hill, New
70. W. F. Ramirez: Computational Methods for York 1980.
Process Simulations, Butterworths, Boston 86. E. Isaacson, H. B. Keller: Analysis of
1989. Numerical Methods, J. Wiley and Sons, New
71. M. Kubicek, M. Marek: Computational York 1966.
Methods in Bifurcation Theory and Dissipative 87. C. Lanczos: “Trigonometric Interpolation of
Structures, Springer Verlag, Berlin – Empirical and Analytical Functions,” J. Math.
Heidelberg – New York – Tokyo 1983. Phys. (Cambridge Mass.) 17 (1938) 123 – 199.
72. T. F. C. Chan, H. B. Keller: “Arc-Length 88. C. Lanczos: Applied Analysis, Prentice-Hall,
Continuation and Multi-Grid Techniques for Englewood Cliffs, N.J. 1956.
Nonlinear Elliptic Eigenvalue Problems,” 89. J. Villadsen, W. E. Stewart: “Solution of
SIAM J. Sci. Stat. Comput. 3 (1982) 173 – 194. Boundary-Value Problems by Orthogonal
73. M. F. Doherty, J. M. Ottino: “Chaos in Collocation,” Chem. Eng. Sci. 22 (1967)
Deterministic Systems: Strange Attractors, 1483 – 1501.
Turbulence and Applications in Chemical 90. M. L. Michelsen, J. Villadsen: “Polynomial
Engineering,” Chem. Eng. Sci. 43 (1988) Solution of Differential Equations”
139 – 183. pp. 341 – 368 in R. S. H. Mah, W. D. Seider
74. K. L. Hiebert, L. F. Shampine: “Implicity (eds.): Foundations of Computer-Aided
Defined Output Points for Solutions of Chemical Process Design, Engineering
Ordinard Differential Equations,” Sandia Nat. Foundation, New York 1981.
Lab. Tech. Rep. SAND 80-180 (1980); 91. W. E. Stewart, K. L. Levien, M. Morari:
SAND 84-0812; SAND 83-2560. “Collocation Methods in Distillation,” in A. W.
75. H. Stern, B. A. Finlayson: On Terminating the Westerber, H. H. Chien (eds.): Proceedings of
Integration of ODE’s Based on the Value of the the Second Int. Conf. on Foundations of
Dependent Variable, Unpublished report, Computer-Aided Process Design, Computer
April, 10, 1985, University of Washington. Aids for Chemical Engineering Education
76. R. B. Bird, W. E. Stewart, E. N. Lightfoot: (CACHE), Austin Texas, 1984, pp. 535 – 569.
Transport Phenomena, J. Wiley and Sons, 92. W. E. Stewart, K. L. Levien, M. Morari:
New York 1960. “Simulation of Fractionation by Orthogonal
77. R. B. Bird, R. C. Armstrong, O. Hassager: Collocation,” Chem. Eng. Sci. 40 (1985)
Dynamics of Polymeric Liquids, 2nd ed., 409 – 421.
Wiley-Interscience, New York 1987. 93. C. L. E. Swartz, W. E. Stewart: “Finite-Element
78. H. B. Keller: Numerical Methods for Steady State Simulation of Multiphase
Two-Point Boundary-Value Problems, Distillation,” AIChE J. 33 (1987) 1977 – 1985.
Blaisdell, New York 1972. 94. C. deBoor, B. Swartz: “Collocation at
79. P. B. Weisz, J. S. Hicks: “The Behavior of
Gaussian Points,” SIAM J. Num. Anal. 10
Porous Catalyst Particles in View of Internal
(1973) 582 – 606.
Mass and Heat Diffusion Effects,” Chem. Eng.
95. R. F. Sincovec: “On the Solution of the
Sci. 17 (1962) 265 – 275.
Equations Arising From Collocation With
80. P. V. Danckwerts: “Continuous Flow Systems,”
Cubic B-Splines,” Math. Comp. 26 (1972)
Chem. Eng. Sci. 2 (1953) 1 – 13.
893 – 895.
81. J. F. Wehner, R. Wilhelm: “Boundary
96. P. M. Prenter, Splines and Variational
Conditions of Flow Reactor,” Chem. Eng. Sci.
Methods, J. Wiley and Sons, New York 1975.
6 (1956) 89 – 93.
82. V. Hlavácek, H. Hofmann: “Modeling of 97. C. E. Pearson: “On a Differential Equation of
Chemical Reactors-XVI-Steady-State Axial Boundary Layer-Type,” J. Math. Phys.
Heat and Mass Transfer in Tubular Reactors. (Cambridge Mass.) 47 (1968) 351 – 358.
An Analysis of the Uniqueness of Solutions,” 98. U. Ascher, J. Christiansen, R. D. Russell: “A
Chem. Eng. Sci. 25 (1970) 173 – 185. Collocation Solver for Mixed-Order Systems
of Boundary-Value Problems,” Math. Comp. 114. B. A. Finlayson: Nonlinear Analysis in

33 (1979) 659 – 679. Chemical Engineering, McGraw-Hill, New
99. R. D. Russell, J. Christiansen: “Adaptive Mesh York 1980.
Selection Strategies for Solving 115. W. F. Ames: “Recent Developments in the
Boundary-Value Problems,” SIAM J. Num. Nonlinear Equations of Transport Processes,”
Anal. 15 (1978) 59 – 80. Ind. Eng. Chem. Fundam. 8 (1969) 522 – 536.
100. P. G. Ciarlet, M. H. Schultz, R. S. Varga: 116. W. F. Ames: Nonlinear Partial Differential
“Nonlinear Boundary-Value Problems I. One Equations in Engineering, Academic Press,
Dimensional Problem,” Num. Math. 9 (1967) New York 1965.
394 – 430. 117. M. Abramowitz, I. A. Stegun: Handbook of
101. W. F. Ames: Numerical Methods for Partial Mathematical Functions, National Bureau of
Differential Equations, 2nd ed., Academic Standards, Washington, D.C. 1964.
Press, New York 1977. 118. M. B. Carver: “Methods of Lines Solution of
102. J. F. Botha, G. F. Pinder: Fundamental Differential Equations. Fundamental
Concepts in The Numerical Solution of Principles and Recent Extensions” in
Differential Equations, Wiley-Interscience, Foundations of Computer-Aided Chemical
New York 1983. Process Design, vol. 1, Engineering
103. W. H. Press, B. P. Flanner, S. A. Teukolsky, Foundation, New York 1981, pp. 369 – 402.
W. T. Vetterling: Numerical Recipes, 119. E. Isaacson, H. B. Keller: Analysis of
Cambridge Univ. Press, Cambridge 1986. Numerical Methods, J. Wiley and Sons, New
104. H. Schlichting, Boundary Layer Theory, 4th York 1966.
ed. McGraw-Hill, New York 1960. 120. J. C. Pirkle, I. E. Wachs, J. E. Sobel:
105. B. Carnahan, H. A. Luther, J. O. Wilkes: “Numerical Methods for Simulation of
Applied Numercial Methods, J. Wiley and Fixed-Bed Reactors for Complex Exothermic
Sons, New York 1969. Reactions” in Foundations of Computer-Aided
106. L. Lapidus, G. F. Pinter: Numerical Solution of Chemical Process Design, vol. 2, Engineering
Partial Differential Equations in Science and Foundation, New York 1981, pp. 401 – 429.
Engineering, Wiley-Interscience, New York 121. D. Gottlieb, S. A. Orszag: Numerical Analysis
1982. of Spectral Methods: Theory and Applications,
107. B. Carnahan, J. O. Wilkes: “Numerical SIAM, Philadelphia, PA 1977.
Solution of Differential Equations – An 122. J. R. Rice: Numerical Methods, Software, and
Overview” in Foundations of Computer-Aided Analysis, McGraw-Hill, New York 1983.
Chemical Process Design, vol. 1, Engineering 123. M. E. Davis: Numerical Methods and
Foundation, New York 1981, pp. 225 – 340. Modeling for Chemical Engineers, J. Wiley
108. W. F. Ramirez: Computational Methods for and Sons, New York 1984.
Process Simulation, Butterworths, Boston 124. D. W. Peaceman: Fundamentals of Numerical
1989. Reservoir Simulation, Elsevier, Amsterdam
109. D. D. Joseph, M. Renardy, J. C. Saut: 1977.
125. G. Juncu, R. Mihail: “Multigrid Solution of
“Hyperbolicity and Change of Type in the
the Diffusion-Convection-Reaction Equations
Flow of Viscoelastic Fluids,” Arch. Rational
which Describe the Mass and/or Heat Transfer
Mech. Anal. 87 (1985) 213 – 251.
from or to a Spherical Particle,” Comput.
110. H. K. Rhee, R. Aris, N. R. Amundson:
Chem. Eng. 13 (1989) 259 – 270.
First-Order Partial Differential Equations,
126. G. Strang, G. J. Fix: An Analysis of the Finite
Element Method, Prentice-Hall, Englewood
111. B. A. Finlayson: Numerical Methods for
Cliffs, N.J. 1973.
Problems with Moving Fronts, Ravenna Park
127. E. B. Becker, G. F. Carey, J. T. Oden: Finite
Publishing Inc., Seattle 1990.
Elements. An Introduction, vol. 1,
112. D. L. Book: Finite-Difference Techniques for
Vectorized Fluid Dynamics Calculations,
128. J. E. Akin: Finite Element Analysis for
Springer Verlag, Berlin – Heidelberg – New
Undergraduates, Academic Press, New York
York – Tokyo 1981.
1986.
113. G. A. Sod: Numerical Methods in Fluid 129. P. Hood, “Frontal Solution Program for
Dynamics, Cambridge University Press, Unsymmetric Matrices,” Int. J. Num. Methods
Cambridge 1985. Eng. 10 (1976) 379 – 399; 11 (1977) 1202.
130. M. W. Chang, B. A. Finlayson: “On the Proper Their Numerical Treatment by Means of
Boundary Condition for the Thermal Entry Integro-Differential Equations,” Comput.
Problem,” Int. J. Num. Methods Eng. 15 Chem. Eng. 13 (1989) 1025 – 1030.
(1980) 935 – 942. 143. P. L. Mills, S. Lai, M. P. Duduković, P. A.
131. H. H. Klein: “Computer Modeling of Chemical Ramachandran: “A Numerical Study of
Process Reactors,” in A. W. Westerberg, H. H. Approximation Methods for Solution of Linear
Chien (eds.): Proceedings of the Second and Nonlinear Diffusion-Reaction Equations
International Conference on Foundations of with Discontinuous Boundary Conditions,”
Computer-Aided Process Design, Computer Comput. Chem. Eng. 12 (1988) 37 – 53.
Aids for Chemical Engineering Education 144. P. M. Morse, H. Feshbach: Methods of
(CACHE), Austin, Texas 1984, pp. 571 – 661. Theoretical Physics, vol. I, McGraw-Hill, New
132. J. C. Pirkl Jr., S. C. Reyes, P. S. Hagan, H. York 1953.
Kheshgi, W. E. Schiesser: “Solution of 145. H. S. Carslaw, J. C. Jaeger: Conduction of Heat
Dynamic Distributed Parameter Model of in Solids, 2nd ed., Clarendon Press, Oxford
Nonadiabatic, Fixed-Bed Reactor,” Comput. 1959.
Chem. Eng. 11 (1987) 737 – 747. 146. N. B. Ferguson, B. A. Finlayson: “Error
133. J. Degreve, P. Dimitriou, J. Puszynski, V. Bounds for Approximate Solutions to
Hlavacek: “Use of 2-D-Adaptive Mesh in Nonlinear Ordinary Differential Equations,”
Simulation of Combustion Front Phenomena,” AIChE J. 18 (1972) 1053 – 1059.
Comput. Chem. Eng. 11 (1987) 749 – 755. 147. R. S. Dixit, L. L. Taularidis: “Integral Method
134. E. N. Houstis, W. F. Mitchell, T. S. of Analysis of Fischer – Tropsch Synthesis
Papatheodoros: “Performance Evaluation of Reactions in a Catalyst Pellet,” Chem. Eng.
Algorithms for Mildly Nonlinear Elliptic Sci. 37 (1982) 539 – 544.
Problems,” Int. J. Num. Methods Eng. 19 148. L. Lapidus, G. F. Pinder: Numerical Solution
(1983) 665 – 709. of Partial Differential Equations in Science
135. R. Peyret, T. D. Taylor: Computational and Engineering, Wiley-Interscience, New
Methods for Fluid Flow, Springer Verlag, York 1982.
Berlin – Heidelberg – New York – Tokyo 1983. 149. C. K. Hsieh, H. Shang: “A Boundary
136. P. M. Gresho, S. T. Chan, C. Upson, R. L. Lee: Condition Dissection Method for the Solution
“A Modified Finite Element Method for of Boundary-Value Heat Conduction Problems
Solving the Time-Dependent, Incompressible with Position-Dependent Convective
Navier – Stokes Equations,” Int. J. Num. Coefficients,” Num. Heat Trans. Part B: Fund.
Method. Fluids 4 ‘Part 1. Theory”, 16 (1989) 245 – 255.
pp. 557 – 589; “Part 2: Applications,” 150. C. A. Brebbia, J. Dominguez: Boundary
pp. 619 – 640 (1984). Elements – An Introductory Course,
137. P. M. Gresho, S. Chan: “A New Semi-Implicit Computational Mechanics Publications,
Method for Solving the Time-Dependent Southhampton 1988.
Conservation Equations for Incompressible 151. J. Mackerle, C. A. Brebbia (eds.): Boundary
Flow,” Proc. Num. Methods in Laminar and Element Reference Book, Springer Verlag,
Turbulent Flow, Pineridge Press, Ltd., Berlin – Heidelberg – New York – Tokyo 1988.
Swansea, U.K. 1985. 152. H. W. Kuhn, A. W. Tucker: “Nonlinear
138. C. T. H. Baker: The Numerical Treatment of Programming” in J. Neyman (ed.): Proc.
Integral Equations, Clarendon Press, Oxford Second Berkeley Symp. Mathematical
1977. Statistics and Probability, Univ. California
139. L. M. Delves, J. Walsh (eds.): Numerical
Press, Berkeley, CA, 1951, pp. 402 – 411.
Solution of Integral Equations, Clarendon
153. T. Umeda, A. Ichikawa, Ind. Eng. Chem.
Press, Oxford 1974.
Process Des. Dev. 10 (1971) 229.
140. P. Linz: Analytical and Numerical Methods for
154. W. C. Davidon: “Variable Metric Methods for
Volterra Equations, SIAM Publications,
Minimization,” AEC R & D Report ANL-5990,
Philadelphia 1985.
(rev.) Argonne, Illinois 1959.
141. M. A. Golberg (ed.): Numerical Solution of
155. R. Fletcher, M. J. D. Powell: “A Rapidly
Integral Equations, Plenum Press, New York
Converging Descent Method for
1990.
142. G. Nagel, G. Kluge: “Non-Isothermal Minimization,” Comput. J. 6 (1963) 163.
Multicomponent Adsorption Processes and
156. R. Fletcher: Practical Methods of Notes in Economics 187, Springer Verlag,

Optimization, Wiley-Interscience, New York Berlin – Heidelberg – New York – Tokyo 1981.
1987. 172. A. Lucia, A. Kumar: “Distillation
157. C. G. Broyden: “The Convergence of a Class Optimization,” Comput. Chem. Engl. 12
of Double Rank Minimization Algorithms,” J. (1988) no. 12, 1263.
Inst. Math. Its. Appl. 6 (1970) 76. 173. T. J. Berna, M. H. Locke, A. W. Westerberg: “A
158. R. Fletcher: “A new approach to variable New Approach to Optimization of Chemical
metric algorithms,” Comput. J. 13 (1970) 317. Processes,” AIChE J. 26 (1980) 37 – 43.
159. D. Goldfarb: “A Family of Variable Metric 174. P. E. Gill, W. Murray, M. Wright: Practical
Methods Derived by Variational Means,” Optimization, Academic Press, New York
Math. Comp. 24 (1970) 23. 1981.
160. D. Goldfarb, M. J. Todd: “Linear 175. W. Murray, M. Wright: “Projected Lagrangian
Programming,” chap. II, in G. L. Nemhauser, Methods Based on the Trajectories of Penalty
A. H. G. Rinnoy Kan, M. J. Todd (eds.): and Barrier Functions,” SOL Report 78-23,
Optimization, North Holland Publ. Co, Stanford University 1978.
Amsterdam 1989. 176. J. Nocedal, M. L. Overton: “Projected Hessian
161. D. F. Shanno: “Conditioning of Quasi-Newton Updating Algorithms for Nonlinearly
Methods for Function Minimization,” Math. Constrained Optimization,” SIAM J. Numer.
Comp. Co 24 (1970) 647. Anal. 22 (1985) 821.
162. J. E. Dennis, J. J. More: “Quasi-Newton 177. C. B. Gurwitz, M. L. Overton: “SQP Methods
Methods, Motivation and Theory,” SIAM Rev. Based on Approximating a Projected Hessian
21 (1977) 443. Matrix,” SIAM J. Sci. Stat. Comput. 10 (1989)
163. S.-P. Han: “A Globally Convergent Method for no. 4, 631.
Nonlinear Programming,” J. Opt. Theo. 178. A. Vasantharajan, L. T. Biegler: “Large-Scale
Applics., 22 (1977) 297. Decomposition Strategies for Successive
164. M. J. D. Powell: “A Fast Algorithm for Quadratic Programming,” Comput. Chem.
Nonlinearly Constrained Optimization Eng. 12 (1988) no. 11, 1087.
Calculations,” Lecture Notes in Mathematics 179. S. Vasantharajan, J. Viswanathan, L. T.
630, Springer Verlag, Berlin – Heidelberg– Biegler: “Large Scale Development of
New York – Tokyo 1977. Reduced Successive Quadratic Programming,”
165. P. Gill, W. Muray: “Numerically Stable CORS/TIMS/ORSA Meeting, Vancouver, BC,
Methods for Quadratic Programming,” Math. May, 1989.
180. V. Chvatal: Linear Programming, Freeman,
Prog., 14 (1978) 349.
New York 1983.
166. D. Goldfarb, A. Idnani: “A Numerically Stable
181. K. G. Murty: Linear Programming, J. Wiley
Dual Method for Solving Strictly Convex
& Sons, New York 1983.
Quadratic Programs,” Math. Prog. 27 (1983) 182. G. Dantzig: Linear Programming and
1. Extensions, Princeton University Press,
167. P. Wolfe: “The Simplex Method for Quadratic
Princeton 1963.
Programming,” Econometrica 27 (1959) no. 3, 183. G. L. Nemhauser, L. A. Wolsey: Integer and
382. Combinatorial Optimization, J. Wiley & Sons,
168. C. E. Lemke: “A Method of Solution for New York 1988.
Quadratic Programs,” Manag. Science 8 184. R. S. Garfinkel, G. L. Nemhauser: Integer
(1962) 442. Programing, J. Wiley & Sons, New York
169. K. Schittkowski: “The Nonlinear 1972.
Programming Algorithm of Wilson, Han and 185. A. M. Geoffrion: “Generalized Benders
Powell with an Augmented Lagrangian Type Decomposition,” J. Optim. Theory Appl. 10
Line Search Function,” Num. Math. 38 (1982) (1972) 237.
83. 186. M. A. Duran, I. E. Grossmann: “An
170. R. M. Chamberlain, C. Lemarechal, H. C. Outer-Approximation Algorith for a Class of
Pedersen, M. J. D. Powell: “The Watchdog Mixed-Integer Nonlinear Programs,” Math.
Technique for Forcing Convergence in Prog. 36 (1986) 307.
Algorithms for Constrained Optimization,” 187. G. R. Kocis, I. E. Grossmann: “Relaxation
Math. Prog. Study 16 (1982). Strategy for the Structural Optimization of
171. W. Hock, K. Schittkowski: “Test Examples for Process Flowsheets,” Ind. Eng. Chem. Prod.
Nonlinear Programming Codes,” Lecture Res. Dev. 27 (1987) no. 8, 1869.
188. I. E. Grossmann: “MINLP Optimization 199. K. E. Brenan, L. R. Petzold: The Numerical

Strategies and Algorithms for Process Solution of Higher Index
Synthesis”, in J. J. Siirola, I. E. Grossmann, G. Differential/Algebraic Equations by Implicit
Stephanopoulos (eds.): Proceedings of Runge – Kutta Methods, UCRL-95 905,
FOCAPD ‘89 Conference, Elsevier, preprint, Lawrence Livermore National
Amsterdam 1989. Laboratories, Livermore, Ca. 1986.
189. J. Viswanathan, I. E. Grossmann: “Combined 200. J. S. Logsdon, L. T. Biegler: “Accurate
Penalty Function and Outer-Approximation Solution of Differential-Algebraic
Method for MINLP Optimization,” Paper MD Optimization Problems,” Ind. Eng. Chem. Res.
18.5, CORS/TIMS/ORSA Meeting, Vancouver 28 (1989) 1628.
1989. 201. L. R. Petzold: “Differential/Algebraic
190. A. E. Bryson, Y.-C. Ho: Applied Optimal Equations Are Not ODEs,” SIAM J. Sci. Stat.
Control, Hemisphere Publishing, Washington, Comput. 3 (1982) 367 – 385.
D.C. 1975. 202. G. E. P. Box, W. G. Hunter, J. S. Hunter:
191. A. E. Bryson, W. F. Denham, J. Appl. Mech. Statistics for Experimenters, J. Wiley and
29 (1962) 247. Sons, New York 1978.
192. L. S. Lasdon, S. K. Mitter, A. D. Warren, IEEE 203. E. Kreyszig: Advanced Engineering
Trans. Autom. Control AC-12 (1967) 132. Mathematics, 4th ed., J. Wiley and Sons, New
193. L. S. Lasdon, IEEE Trans. Autom. Control
York 1979.
AC-15 (1970) 268.
204. J. L. Devore: Probability and Statistics for
194. L. Lapidus, R. Luus: Optimal Control of
Engineering and the Sciences, Brooks/Cole,
Engineering Processes, Blaisdell, Waltham,
Monterery, California 1987.
MA 1967.
195. D. I. Jones, J. W. Finch: “Comparison of 205. W. H. Press, B. P. Flannery, S. A. Teukolsky,
Optimization Algorithms,” Int. J. Control 40 W. T. Vetterling: Numerical Recipes. The Art
(1984) 747. of Scientific Computing, Cambridge
196. S. N. Rao, R. Luus: “Evaluation and University Press, Cambridge 1986.
Improvement of Control Vector Iteration 206. B. W. Lindgren: Statistical Theory,
Procedures,” Can. J. Chem. Eng. 50 (1972) Macmillan, New York 1962.
777. 207. M. Abramowitz, I. A. Stegun: Handbook of
197. M. Caracotsios, W. E. Stewart: “Sensitivity Mathematical Functions, U.S. Government
Analysis of Initial Value Problems with Mixed Printing Office, Washington, D.C. 1964.
ODE’s and Algebraic Equations,” Comput. 208. J. B. Cropley: “Heuristic Approach to Comples
Chem. Eng. 9 (1985) 359 – 365. Kinetics,” ACS Symp. Ser. 65 (1978)
198. R. W. H. Sargent, G. R. Sullivan: “The 292 – 302.
Development of an Efficient Optimal Control 209. O. A. Hougen, K. M. Watson, R. A. Ragatz:
Package,” Proceedings of the 8th IFIP Chemical Process Principles, 2nd ed., part II,
Conference on Optimization Techniques Pt. 2, “Thermodynamics,” J. Wiley and Sons, New
Würzburg 1977. York 1959.
Mathematical Modeling 165
Mathematical Modeling
See also → Mathematics in Chemical Engineering
Henning Bockhorn, Technische Hochschule, Darmstadt, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . 169 3.3.2.1. Models with Constraints on the

1.1. Terminology . . . . . . . . . . . . . 169 Parameters . . . . . . . . . . . . . . 192
1.2. Application Areas 3.3.2.2. Models Based on Differential
of Mathematical Modeling Equations . . . . . . . . . . . . . . . 193
in Industrial Chemistry 4. Models Based on Transport
and Chemical Engineering . . . 169 Equations for Probability
1.3. Limitations of Mathematical Density Functions . . . . . . . . . 194
Models . . . . . . . . . . . . . . . . 170 4.1. Terminology . . . . . . . . . . . . . 195
2. Construction and Classification 4.1.1. One-Dimensional Distribution
of Mathematical Models . . . . . 171 and Probability Density Functions 195
2.1. Construction of Mathematical 4.1.2. Multidimensional Distribution
Models . . . . . . . . . . . . . . . . 171 and Probability Density Functions 198
2.2. Classification of Mathematical 4.1.3. Conditional Probability Density
Models . . . . . . . . . . . . . . . . 172 Functions . . . . . . . . . . . . . . . 199
3. Empirical Models . . . . . . . . . 175 4.2. Transport Equations for Single-
3.1. Linear Empirical Models . . . . 176 Point Probability Density
3.1.1. Linear Empirical Models with One Functions . . . . . . . . . . . . . . 199
Variable . . . . . . . . . . . . . . . . 176 4.2.1. General form of the Transport
3.1.1.1. Parameter Estimation (Linear Re- Equations for Probability Density
gression) . . . . . . . . . . . . . . . 176 Functions . . . . . . . . . . . . . . . 200
3.1.1.2. Assessment of Estimated Parame- 4.2.2. Limitations of Single-Point
ter Values . . . . . . . . . . . . . . . 177 Probability Density Functions . . 203
3.1.1.3. Sensitivity Analysis . . . . . . . . 178
4.3. Examples of Calculating
3.1.1.4. Example of a Linear Model . . . . 179
Probability Density Functions . 204
3.1.1.5. Concluding Remarks . . . . . . . . 181
4.3.1. Solutions for Deterministic Sys-
3.1.2. Linear Empirical Models with
tems . . . . . . . . . . . . . . . . . . 205
Several Variables . . . . . . . . . . 181
4.3.1.1. Age (Residence Time) Distribu-
3.1.2.1. Parameter Estimation . . . . . . . 182
tions in Chemical Reactors . . . . 205
3.1.2.2. Assessment of Estimated Parame-
ter Values . . . . . . . . . . . . . . . 183 4.3.1.2. Size Distribution in Continuously
Operating Crystallizers . . . . . . 209
3.1.2.3. Concluding Remarks . . . . . . . . 184
3.2. Nonlinear Empirical Models . . 184 4.3.2. Solutions for Statistical Systems . 209
3.2.1. Parameter Estimation (Nonlinear 4.3.2.1. Closure of the Transport Equation
Regression) . . . . . . . . . . . . . . 184 for Probability Density Functions 210
3.2.1.1. Transformation of the Model into 4.3.2.2. Solution Methods of the Transport
Linear Form . . . . . . . . . . . . . 185 Equation for Probability Density
3.2.1.2. Direct Search Methods . . . . . . . 186 Functions . . . . . . . . . . . . . . . 213
3.2.1.3. Gradient Methods . . . . . . . . . . 187 4.3.2.3. Example: Combustion of Propane
3.2.2. Assessment of Estimated Parame- in a Turbulent Diffusion Flame . 214
ter Values . . . . . . . . . . . . . . . 189 5. Models Based
3.2.3. Example of a Nonlinear Model . 190 on Physicochemical Principles
3.2.4. Concluding Remarks . . . . . . . . 191 (Transport Phenomena) . . . . . 216
3.3. Further Calculation Methods 5.1. Application of the Principle of
and Model Types . . . . . . . . . . 191 Conservation of Momentum . . 217
3.3.1. Further Methods of Parameter Es- 5.1.1. Laminar Tube Flow . . . . . . . . . 217
timation . . . . . . . . . . . . . . . . 191 5.1.2. Turbulent, Nonreactive Free Jets . 218
3.3.2. Other Types of Models . . . . . . . 192 5.1.2.1. Models for Reynolds Stresses . . 219
166 Mathematical Modeling
5.1.2.2. Solution Method of the Result- 5.3.1.3. Examples of Simultaneous Mass

ing System of Partial Differential and Heat Transfer: Dynamic Mod-
Equations . . . . . . . . . . . . . . . 221 els . . . . . . . . . . . . . . . . . . . 232
5.1.2.3. Example: Turbulent Flow of Ni- 5.3.1.4. Examples of Simultaneous Mass
trogen in Air . . . . . . . . . . . . . 224 and Heat Transfer: Static Models 233
5.2. Applications of the Principle of 5.3.2. Mass Transfer with Chemical Re-
Conservation of Enthalpy . . . . 224 actions . . . . . . . . . . . . . . . . . 237
5.2.1. Heat Conduction . . . . . . . . . . 225 5.3.3. Chemical Reactions in the Homo-
5.2.2. Heat Transfer . . . . . . . . . . . . 226 geneous Phase . . . . . . . . . . . . 239
5.3.3.1. Isothermal Reactors with
5.2.2.1. Exact Solution for a Boundary
Frictionless Flow, Constant
Layer Problem . . . . . . . . . . . . 226
Density, and Reactions Without
5.2.2.2. General Principles of Modeling Volume Changes . . . . . . . . . . 240
Heat Transfer . . . . . . . . . . . . 228 5.3.3.1.1. Stability of Isothermal Reactors . 243
5.3. Applications of the Law 5.3.3.1.2. Sensitivity Analysis . . . . . . . . 248
of Conservation of Mass . . . . . 229 5.3.3.2. Nonisothermal Reactors . . . . . . 249
5.3.1. Mass Transfer without Chemical 5.3.3.2.1. Heterogeneous Catalytic Reac-
Reaction . . . . . . . . . . . . . . . . 230 tions . . . . . . . . . . . . . . . . . . 249
5.3.1.1. Exact Solution for a Boundary 5.3.3.2.2. Stability Analysis of Nonisother-
Layer Problem . . . . . . . . . . . . 230 mal Reactors . . . . . . . . . . . . . 256
5.3.1.2. General Principles for Modeling 5.3.3.2.3. Use on Statistical Processes . . . 261
Mass Transfer . . . . . . . . . . . . 231 6. References . . . . . . . . . . . . . . 266
Symbols E statistical error in vector notation

Ea activation energy
a general coefficient, temperature conduc-
f dimensionless flow function, mixture
tivity
fraction (normalized mass fraction of an
a general matrix
element in a mixture)
A chemical component
F cross-sectional area, feed flow of a liquid,
A general coefficient, source term in mo-
value of the F-distribution
mentum conservation equation
F distribution function of a statistical vari-
b general coefficient, general model param-
able
eter (estimate)
g acceleration due to gravity
b general model parameter in vector nota-
G mass flow of gas
tion (estimate)
h enthalpy
B chemical component
h step size in vector notation
B general coefficient
∆hv specific latent heat of vaporization
B general matrix
H Heaviside step function, height
Bi Biot number
Ha Hatta number
Bo Bodenstein number
HTU height of one transfer unit
c concentration, general coefficient
I unit matrix
c general matrix
Iu , IΦ , Ip class of integrals
cp specific heat capacity
j total flux of a scalar quantity
C chemical component
J flux of scalar quantities per unit area
C model parameter in turbulence models
J Jacobi matrix
C 1 , C 2 , C 3 , C 4 integration constants
k general parameter, rate coefficient, total
D chemical component
heat-transfer coefficient, turbulence en-
D diameter, diffusion coefficient
ergy
DR tube diameter
K “adsorption” coefficient
DaI , DaII Damköhler number (of 1st and 2nd
Kp class of integrals
kind)
E statistical event
L length, likelihood function, mass flow of W residence time distribution function,

liquid, number of grid nodes in the x- probability, velocity in a turbulent (sta-
direction, size, transport operator tistical) flow
Le Lewis number x distance, general independent variable
m deterministic moment, mass fraction, x distance in vector notation, i.e., x =
number of occurrences of an event (x 1 , x 2 , x 3 ); x = (x, y, z), general indepen-
M number of grid nodes in the y- or r- dent variable in vector notation
direction X partial derivatives of expected values with
Mi molecular mass respect to model parameters in matrix no-
n number of data sets, number of units tation
Nu Nusselt number y general dependent variable
NTU number of transfer units y general dependent variable in vector no-
O order of magnitude tation
p general parameter, pressure, statistical Y general statistical variable
weight Y general statistical variable in vector nota-
p statistical weight in vector notation tion
P chemical component
P probability density function of a statisti-
cal variable Greek Symbols
Pe Péclet number α age, general coefficient, heat-transfer co-
Pr Prandtl number efficient, normalized mass fraction, sig-
q general parameter, number of indepen- nificance level
dent variables in multivariable models, β general coefficient, general model param-
volumetric flow rate eter, mass-transfer coefficient, normal-
Q general function ized mass fraction
r general parameter, radial distance, rate of β general model parameter in vector nota-
reaction tion
R gas constant, radius, ratio of enthalpies of βr acceleration factor
vaporization βH Prater number
Re Reynolds number γ Arrhenius number, correlation coeffi-
s specific surface area, general parameter, cient, scaling factor
estimate for standard deviation γr reciprocal Arrhenius number
S sink flow of a liquid, source term in con- δ Dirac delta function
servation equation, surface area δ film thickness, Kronecker symbol
s2r mean square deviation about regression ε dissipation rate, intergranular volume,
s2 ε mean square deviation of data set normalized rate coefficient, statistical er-
s2 Ȳi mean square deviation about Ȳi ror
Sc Schmidt number ζ phase shift
Sh Sherwood number η effectiveness factor, normalized distance,
t time, value of student t-variable similarity coordinate
T temperature η expected values in vector notation
u velocity θ general variable, normalized age, normal-
u velocity in vector notation, i.e., ized residence time, normalized temper-
u = (u1 , u2 , u3 ); u = (u, v, w) ature
U velocity in a turbulent (statistical) flow Θ general statistical variable, source term in
U velocity in a turbulent (statistical) flow scalar quantities equation
in vector notation, i.e., U = (U 1 , U 2 , U 3 ); κ permeability, normalized rate coefficient
U = (U, V, W ) λ eigenvalues, Lagrangian multipliers,
V volume mean free path, scaling factor, thermal
w residence time distribution, velocity conductivity, wavelength
µ dynamic viscosity, normalized mass frac-
tion
µt apparent turbulent viscosity summation according to the Einstein

µn nth moment of a probability density func- summation convention
tion l number of elements in a difference equa-
ν frequency, kinematic viscosity, stoichio- tion
metric coefficient L liquid phase
ξ general variable L total length
Ξ general statistical variable m mean
π normalized mass fraction m mass
density, scaling factor n north
σ standard deviation o upper limit
σϕ turbulent Schmidt/Prandtl numbers p pressure, pressure-related
τ normalized time, residence time, tur- Ph phase boundary
bulent time scale, viscous stress qs quasi-steady-state
τN cooling time r reaction, reflected
ϕ general variable, normalized mass frac- ref reference
tion s south
Φ general variable, general statistical vari- S surface
able t turbulent
Φ general variable and general statisti- T temperature
cal variable in vector notation, sum of tot total
squares of deviations u lower limit
ΦK Thiele modulus u velocity
ψ general variable w west
Ψ general variable, general statistical vari- W wall
able, stream function Wi inner wall
Ψ general variable and general statistical Wo outer wall
variable in vector notation x local
Ω general function, general operator α a component
ε dissipation rate
ϕ variable
Subscripts
ω chemical component, summation accord-
a, b reference states a and b ing to the Einstein summation convention
A ambient, chemical component 0 initial, reference state
ad adiabatic
B chemical component
Bf bifurcation Superscripts
c central ∗ transformed or normalized variable or pa-
C cooling rameter
Cat catalyst ’ scaled variable
diff diffusion ∼
weighted or normalized variable
e east, end, expansion −
mean
eff effective ˆ calculated model response
ext external A, B, C, D chemical component
G gas phase eq equilibrium
h enthalpy f fluctuating
i component of a vector, chemical compo- G gas phase
nent h enthalpy
int internal L liquid phase
j component of a vector, chemical compo- m mass
nent (n) number of iterations
k component of a vector, chemical com- T transpose of a vector or matrix
ponent, contraction, turbulence energy,
1. Introduction tion and optimization of existing processes and

(2) the design of new or improved ones. In this
1.1. Terminology article the term process means a sequence of op-
erations or treatments and transformations per-
Models are used in almost every branch of sci- formed on specific materials.
ence and technology. It is difficult to encompass For the first task engineers and scientists must
the many meanings of the term “model” with one obtain exact information about the particular
single definition. The classical definition is “An process under consideration. Qualitative aspects
object M (an object, physical or ideal system, or and criteria must be quantified. The basic vari-
process) is a model if analogies exist between M ables and parameters of the relationships which
and another object O that permit conclusions to describe the individual parts of the process must
be made about O” [1]. This definition describes be worked out. The individual parts of the pro-
the representation of the object O and presup- cess must be combined. Mathematical models
poses its isolation from the whole of reality. Thus are very important in this respect.
a model represents reality or a part of it. Since For the second task mathematical models
only certain conclusions are required, the model help in applying existing processes to new or
is reduced to parts or individual aspects of real- modified plants and in the definition of safer,
ity. The restriction to analogies between model more economically viable operating conditions.
M and object O results in limited conformity of Data for the construction of new plants cannot be
their function, structure, and behavior. The re- obtained from an operating process by running
presentation of the object O by the model M may it to its technical limits; this entails a high degree
have limited accuracy and the model M can be of risk. In contrast, a mathematical model of a
based on a different scale than the object O. The process is easy to manipulate. Unusual operating
model is satisfactory as long as important vari- conditions can easily be simulated. The plant can
ables and phenomena are correctly represented even be modeled under hazardous conditions to
for the specific context or investigation. define the limits of operating parameters or risk
An adequate model according to the above areas.
definition can rarely explain reality in the form The main applications of mathematical mod-
of a theory. Information that has been lost in els in industrial chemistry are summarized as
the representation cannot be retrieved from the follows:
model. Attempts at theoretically interpreting the
object O with the help of model M must there- 1) Simple Experimentation. By means of math-
fore be discussed according to the aspect, scale, ematical models, existing processes can be
and accuracy of the representation. investigated more quickly, economically,
Analogies between model M and object O and thoroughly than in operating industrial
can be established in the form of mathemati- plants. Mathematical models can simulate
cal equations. A mathematical model therefore the plant in time lapse or slow motion. The
represents a set of algebraic and/or differential results from the model are therefore available
and/or integral equations which are used to de- more quickly or have a higher time resolu-
scribe the behavior of the object O. The terms tion.
variables and parameters are used in this arti- 2) Repetition of Experiments. Simulation of
cle in accordance with their definitions given in processes with mathematical models allows
mathematical relationships, and not as defined the influence of variations in variables or pa-
in process control, see for example [2]. rameters to be investigated. Errors can eas-
ily be implanted into or removed from the
model. In a running industrial process, this
1.2. Application Areas of Mathematical type of empirical sensitivity analysis has the
Modeling in Industrial Chemistry and disadvantage that it requires a high degree of
Chemical Engineering technical effort and entails a high degree of
risk.
The two major tasks facing engineers and sci- 3) Sensitivity Analysis. With a mathematical
entists in industrial chemistry are (1) the opera- model, sensitivity analysis does not have to
be carried out on an empirical basis by repe- The number of theoretical plates necessary
tition of tests with systematic changes of the for solving a separation problem (e.g., the num-
variables and parameters. Sensitivity analy- ber of theoretical plates of a rectification col-
sis as a mathematical tool allows calculation umn) can usually be calculated more accurately
of the gradients of dependent variables with than the effectiveness factor of a separation plate
respect to the model parameters. in a real piece of equipment. The latter value de-
4) Control and Operation. Mathematical mod- pends on the fluid dynamics of the system and
els can be used as an economical way of es- on the operating conditions of the column. How-
timating the stability of industrial processes ever, the inaccuracy in the estimate of the ef-
or subsystems as a prerequisite for effective fectiveness factor strongly affects the commer-
control or operation. Again, use of the in- cial viability of a separation process with a large
dustrial process for direct experimentation number of theoretical plates.
must be ruled out because of the high risk Another example concerns the kinetic data
involved. for industrial processes that are mainly derived
5) Optimization. Description of a complex sys- from laboratory experiments. On a laboratory
tem in terms of a mathematical model allows scale, side reactions may be much less notice-
optimization objectives for the process to be able than in an industrial plant. Lack of infor-
developed. The optimization objectives can mation about side reactions can lead to rate data
easily be adjusted in accordance with chang- that are unsuitable for industrial process design.
ing requirements. Optimum values of oper- A further problem is the impurities of the reac-
ating variables or parameters can also be de- tants used in an industrial plant; impurities can
termined easily. lead to changes in the reaction rate that cannot
6) Extrapolation. A suitable mathematical be predicted with the pure chemicals used in lab-
model can be used to test extreme operat- oratory experiments.
ing conditions that are not possible or prac- The accuracy required for the individual pa-
tical in the running process. Surfaces of op- rameters of the model depends on the sensitiv-
erating variables and parameters can then be ity with which the results of the model respond
constructed and the optimum conditions for to changes in these parameters (see Sections
running the plant can be extrapolated. Ex- 3.1.1.3 and 5.3). Those parameters which exert
trapolability must, however, always be dis- the greatest influence on the results of the model
cussed in the light of the limits of the model must be determined with the greatest accuracy.
and the part of the object O being modeled. A second restriction in the use of mathe-
matical models lies in the mathematical tools
that are available for solving the resulting sys-
tem of equations. Complex structures can of-
1.3. Limitations of Mathematical ten be formulated mathematically. However, the
Models mathematical and numerical methods required
to solve the resulting system of equations are ei-
Mathematical models have some significant lim- ther not yet developed or are beyond the capacity
itations. The first is the type, quantity, and accu- of available computers. The rapid development
racy of the available data. The success and re- of supercomputers in recent years has enabled
sults of mathematical models depend largely on increasingly complex problems to be solved.
the information about the object O being mod- A further restriction concerns the interpreta-
eled. A mathematical model cannot be better tion of the results of the model and the extrapola-
than the physical or chemical data on which it bility of the representation. This limitation is il-
is based. In many cases available data are not lustrated in the simple example in Figure 1. The
sufficient and engineers and scientists have to solid curve shows the dynamics of a physico-
obtain sufficient data for a model by experimen- chemical quantity. The object could be, for ex-
tal analysis. The alternative is to simplify the ample, an intermediate in consecutive chemical
model adequately. The two following examples reactions, ϕ represents its concentration:
illustrate the associated problems. k1
ϕ= ψ0 [exp (−k1 t) − exp (−k2 t)] (1)
k2 − k1
where ψ 0 is the initial concentration of starting sists of setting up a consistent set of mathemat-
compound from which ϕ is formed, t is the time, ical relationships. In the ideal case these would
and k 1 and k 2 are the rate coefficients of two be identical to the relationships between the pro-
consecutive first-order reactions, k 1 = k 2 . The cess variables. Often, only certain phenomena
available data cover the range 0 < t < t 1 and are of particular interest can be incorporated in the
shown in Figure 1 as squares. An obvious em- model due to the complexity of the real process.
pirical model based on these data is ϕ = kt and is The strategy of analysis used for developing
given by the dashed line. In fact the object is re- mathematical models generally contains the fol-
presented by this model in the range k 1 t 1 and lowing steps (see also [3–10]):
k 2 t 1. If the exponential functions in Equa-
tion (1) are developed for the above condition, 1) Formulation of the problem and compilation
it follows that: of objectives and decision criteria
2) Investigation of the process and its classi-
ϕ≈
k1
ψ0 [(k2 − k1 ) t] =k1 ψ0 t (2)
fication with the aim of splitting it up into
k2 − k 1 subsystems ( process elements)
3) Determination of the relationships between
the subsystems
4) Analysis of the variables and relationships
between the variables for the individual pro-
cess elements
5) Setting up of mathematical relationships
with variables and parameters; data acqui-
sition
6) Investigation of the representation of the pro-
cess by the model; comparison of the simu-
lation with real process data
7) Installation of the model; interpretation and
Figure 1. Relationship between a model and object with collation of the results
limited data
For further evaluation of the model the above
It can be seen that for the range covered by steps can be complemented by:
experimental data (0 < t < t 1 ), an analogy exists
between the model and the object and the phe- 1) Sensitivity analysis of the model: identifica-
nomenon of interest is also adequately repro- tion of the parameters with strong and weak
duced within this region. The representation has influences on the response of the model
a coarser scale, i.e., ϕ = kt instead of ϕ = k 1 ψ0 t. 2) Model simplification
However, the model does not explain the physi-
If the above steps are compiled in a flow dia-
cochemical characteristics of the object – an in-
gram, then steps 4 – 9 must be repeated, possibly
termediate in a system of consecutive chemical
several times, until the interpretation of the re-
reactions. Finally, extrapolation of this model
sults of the model still makes sense within the
beyond the range covered by the available data
framework of the formulated objectives and ex-
leads to a false representation.
pected solutions to the problem.
Industrial processes are very complex. The
success of mathematical models in describing
2. Construction and Classification of them often depends on whether they can be sub-
Mathematical Models divided into process elements. The entire pro-
cess can then be built up from the individual
2.1. Construction of Mathematical elements if the relationships between them have
Models been worked out. Subdivision into process ele-
ments is not necessarily based on the physical
Based on the terminology used in Section 1.1, principles of the entire process. For example, a
the construction of a mathematical model con- nonideal tubular reactor can be simulated by a
series of ideal stirred tank reactors although such used to formulate models and to solve the re-
units may not exist in the industrial process. A sulting systems of equations.
packed absorption column can be represented by For this reason further formalization of the
a number of theoretical plates even though mass steps for building mathematical models and a
transfer occurs continuously and does not result further division into individual steps will be
in stepwise attainment of phase equilibrium. avoided. The following section examines the
By correct treatment and adjustment of the classification of models based on the physical
process elements, modeling strives to represent background of the model, the type of system of
the entire process as accurately as possible on equations, and the necessary methods for their
the basis of simple, established principles of the solution.
individual elements.
Industrial processes are not only very com-
plex, they can also consist of a number of qual- 2.2. Classification of Mathematical
itatively different process elements. A chemical Models
process may, for example, encompass process
elements for the preparation of the reactants, Mathematical models can be classified accord-
the chemical reactor, heat exchangers, and fi- ing to their physical background, the type of sys-
nally process elements for separation and pos- tems of equations, and the corresponding meth-
sibly processing of the product. The different ods of solution. Alternatives are discussed in [3],
qualities of the process elements require differ- [8–12]. Figure 2 shows three classes of mod-
ent mathematical models depending on the phys- els with different physical backgrounds: models
ical or physicochemical principles on which they based on physicochemical principles, probabil-
are based. An industrial heat exchanger is repre- ity density function ( pdf ) models, and empirical
sented by a different type of model from that re- models.
quired for a rectification column, the latter has a The first category comprises models based
different mathematical description from a chem- mainly on the mathematical formulation of
ical reactor, and so on. Due to the underlying transport phenomena. Use of this principle re-
physicochemical principles, mathematical mod- quires that the process can be subdivided into
eling and the construction of mathematical mod- process elements that can be described by the
els employ a wide variety of mathematical meth- laws governing the transport of mass, momen-
ods and methods of solution. For example, the tum, and energy, i.e., their conservation princi-
design of distillation columns with models based ples.
on theoretical plates leads to a system of linear Such models are subdivided into determinis-
equations which is often solved graphically. The tic and statistical models. Deterministic models
representation of a nonideal reactor by a series or model elements have a determined value or
of ideal stirred tank reactors leads to a system set of values for each variable or parameter for
of algebraic equations which can be highly non- any given set of conditions. In contrast, the vari-
linear depending on the chemical reaction under ables and parameters used in statistical models
consideration. Finally, a reactor model for a ho- (or elements of statistical models) are statisti-
mogeneous, turbulent-flow reactor based on the cal quantities. They can only be given with a
modeled Navier–Stokes equations leads to a sys- certain probability or in terms of moments of
tem of coupled partial differential equations that probability density functions. If, for example,
can be solved by various methods. the probability density function P (Y ) holds for
Mathematical modeling is used to formulate the statistical variable Y , then P (Y ) dY is the
widely differing physical and physicochemical probability for the variable lying in the range
phenomena: transfer of heat, mass, and momen- dY around Y . Normally the full statistical infor-
tum, as well as chemical reactions in homoge- mation is not necessary for technical purposes;
neous and heterogeneous systems. Mathemati- therefore statistical variables are often described
cal modeling is thus used in the design of mass- by moments of the probability density functions.
transfer operations, calculation of heat exchang- These moments are defined as
ers, chemical reaction engineering, and finally
process control. A wide range of methods are
Figure 2. Classification of mathematical models according to their physical principles
cases is, however, more complicated. The trans-

+∞ port equations used to describe a statistical pro-
µn ≡ Y n P (Y ) dY
cess by means of statistical moments contain,
−∞
for example, a number of statistical hypothe-
ses and model assumptions for their closure but
For example the first moment the character of the model equations does not
change. For these reasons statistical models are

+∞
classified as shown in Figure 3. Methods for re-
µ1 ≡ Y P (Y ) dY presenting statistical processes will be discussed
−∞ in Chapter 5.
is the mean value of the statistical variable Y , A further subdivision of models based on
the second moment about the mean value is its physicochemical principles according to the
variance Var (Y ): type of model equations is shown in Fig-
ure 4. The complexity of the method of so-

+∞ lution decreases from right to left. The di-
µ2 ≡ (Y − µ1 )2 P (Y ) dY , etc. vision is based on the most commonly used
−∞ types of models but is by no means definitive.
Thus, multidimensional models can be formu-
A statistical mathematical model is the math- lated in the form of algebraic relationships; mod-
ematical description of a process, e.g., in terms els which can be described by algebraic rela-
of the moments defined above. Figure 3 shows tionships do not have to be steady-state mod-
some possibilities for statistical processes. Nor- els. Steady-state models describe processes in
mally a deterministic process leads to determin- which the accumulation terms (the changes in
istic results (Fig. 3 A). If a statistical error is the variables over time) disappear. Nonsteady-
added to the process results (Fig. 3 B), it leads to state models include changes in the variables
a statistical result. The same result is obtained over time. In models with constant variables, the
if the deterministic process becomes unstable properties and state are not functions of space
(Fig. 3 C); a simple example for this is buoyancy- so that the system is homogeneous. Description
driven turbulence. If the input process variables with locally distributed variables considers local
are statistical variables then the results of the changes in the dependent variables. (The nomen-
process are also statistical variables (Fig. 3 D). clature of process analysis does not make the
Figure 3 shows that the macroscopic phenomena distinction between variables and parameters in-
in statistical processes change but that the physi- troduced in Section 1.1; the latter two types of
cochemical background of the process and hence models are then classified as models with con-
of the process model remains the same. The prin- stant or concentrated parameters or as models
ciples of the conservation of mass, momentum, with distributed parameters [10], [13–15].) Fig-
and energy are also valid for statistical variables; ure 4 also shows that the description of pro-
the mathematical overhead for handling these cesses by differential equations and difference
equations is frequently equivalent. Differential give the probability that the dependent variables
equations must normally be solved by numerical at a fixed distance x = (x 1 , x 2 , x 3 ) and time t lie
methods. In order to achieve this they are trans- in the range dΦ1 , . . . , dΦn around the values
formed into difference equations. These meth- Φ1 , . . . , Φn as P (Φ1 , . . . , Φn ; x, t) dΦ1 , . . . , dΦn .
ods, which are really mathematical tools, have These models provide the complete statistical in-
their physical analogy in the description of pro- formation for statistical processes or give distri-
cesses with models based on finite changes (see bution functions of particular process variables.
Sections 4.3.1 and 5.3.3.1). They are closely related to the description of sta-
tistical processes by the statistical moments dis-
cussed above, the difference is that the transport
equations for the probability density functions
are formulated.
Classical examples for models based on
transport equations for probability density func-
tions are to be found in statistical mechanics
and kinetic gas theory. This concept was in-
troduced in industrial systems to describe flow
and mixing in nonideally mixed reactors [16].
One-dimensional models which represent the
“macromixing” in a chemical reactor in terms of
age (residence time) distributions are often suf-
ficient to allow estimation of its behavior. Other
simple pdf models are used in other areas, for
example to model the crystal size distribution in
crystallization, the activity distribution of cata-
lyst pellets, or the age and size distribution of
microbiological cultures [17]. This concept has
been used to describe reacting turbulent flow
[18], [19].
Many industrial processes cannot be de-
scribed with pdf models or models based on
physicochemical principles because of their
complexity. In these cases empirical models are
used. In such cases the response of the process
to variation of one or more process variables is
known and the model correlates the process re-
sults. The simplest example of this is the fitting
Figure 3. Statistical and deterministic processes
of a polynomial to experimental data. Another
example in process control is the description of
a process response in the form of transfer func-
Models based on transport equations for tions in the time or frequency domain. Empirical
probability density functions generally give their models are statistical (Fig. 3 B) because the nec-
results in the form of functionals P (Φ1 , . . . , Φn ). essary data have to be obtained experimentally
These are defined in such a way that the and contain statistical errors. Empirical models
probability of finding the dependent variables have only limited value for describing processes
(Φ1 , . . . , Φn ) in the small range dΦ1 , . . . , dΦn or process elements, e.g., if predictions are to be
around the functions Φ1 (x, t), . . ., Φn (x, t) is made outside the range covered by experimental
P (Φ1 , . . . , Φn ) dΦ1 , . . . , dΦn . Probability den- data or if a theoretical approach is to be verified.
sity functions P (Φ1 , . . . , Φn ; x, t) that are de- In spite of this empirical mathematical models
fined analogously for given values of the inde- are still preferred in many cases.
pendent variables x, t are more common. They Discussion on mathematical modeling in the
following sections is based on the classification
Figure 4. Classification of deterministic models based on physicochemical principles according to the type of resulting
equations
of mathematical models shown in Figures 3 and 3. Empirical Models

4. Empirical models will be discussed first, fol-
lowed by models based on the transport equa- The fundamental variables of a process are
tions for probability density functions, and fi- known, for example, from a series of experi-
nally models based on physicochemical princi- ments. If, however, the complexity of the pro-
ples (transport phenomena). Presentation of the cess prevents the formulation of a model on the
important principles of mathematical modeling basis of physicochemical principles, the process
will be given priority over a complete descrip- can be described by empirical models. The fit-
tion. ting of a polynomial or a similar function to a
Nonstandard numerical and mathematical set of measured values is the simplest empirical
methods required for solving the resulting set of model. An empirical model represents a general
equations for the developed mathematical mod- relationship:
els are discussed in more depth. More detailed
classifications of industrial processes or process y=f (x, β) (3)
variables can be found in the literature [2], [10],
[13–15]. Relevant aspects of such classifications where y is the vector of the dependent variables
will be discussed where necessary. (model responses, process responses), x is the
Mathematical modeling of physical or physi- vector of the independent variables (model vari-
cochemical phenomena or industrial processes ables, process variables), and β is the vector of
is a concept that is applied to many other the parameters from which the functional rela-
disciplines. Aspects of mathematical model- tionship is constructed. This relationship is em-
ing related to other topics of engineering are pirical and must be found on the basis of existing
described elsewhere in this handbook, e.g., experimental data. In the following sections em-
→ Transport Phenomena; → Fluid Mechanics; pirical models will be introduced through sev-
→ Computational Fluid Dynamics. eral examples.
3.1. Linear Empirical Models A process based on these assumptions is

shown in Figure 5 and is discussed as an ex-
If Equation (3) can be represented by the relation ample in Section 3.1.1.4.
y = βx (4)
the model is linear. Equation (4) is linear with

respect to both its parameters and its indepen-
dent variables. This implies that the first deriva-
tives with respect to the components of the pa-
rameter vector and the vector of the independent
variables disappear. The simplest relationship of
type (4) is a linear model with one dependent
variable:
y = β0 +β1 x (5)
where the estimates b0 and b1 of the parameters

Figure 5. Representation of the statistical process described
β 0 and β 1 have to be determined from experi- in Section 3.1.1
mental data. This will be outlined briefly in the
following. Only the essential steps of the cal-
culation will be presented. Detailed derivations
and proofs are given in [2], [4], [5], [7], [20]. 3.1.1.1. Parameter Estimation (Linear
Regression)
3.1.1. Linear Empirical Models with One Estimates b0 and b1 of the parameters β 0 and β 1
Variable are found by minimizing the sum of the squares
of the deviations between the observed values
The determination of the estimates of the param- Yi and the expected values of Ȳi , Ȳi , i.e., the
eters β 0 and β 1 will be discussed in detail for a variance
linear model with one dependent variable. This

n
9 : 2 !
model is based on the following assumptions: Ȳi − Ȳi = Min (7)
i=1
1) The dependent variable is a random variable
so that the model in Equation (5) can be given This is known as least squares estimation.
in the following form: The problem can also be posed in other ways.
For the overdetermined system of equations for
9 : β 0 and β 1
Ȳi = Ȳi − εi = β0 +β1 (xi − x̄) (6)
where Ȳi is the mean value of the dependent Ȳ1 −β0 −β1 (x1 −x̄) = 0 (8a)
variables of n data sets with repeated mea-
surements at xi ; εi is the random error in Ȳi . Ȳ2 −β0 −β1 (x2 −x̄) = 0 (8b)
Hence (Ȳi − Ȳi ) = εi has an expected value
of zero and a constant variance. The angular ..
.
brackets denote the expected values or math-
ematical expectation.
Ȳn −β0 −β1 (xn −x̄) = 0 (8n)
2) The variance of Yi is also constant, has a nor-
mal distribution, and is equal to the variance the estimated values b0 and b1 have to be found
of εi . that reduce the residuals on the left-hand sides
3) The observations of Y are statistically inde- to as close to zero as possible.
pendent so that the random errors εi are also The problem is the minimization of the sum:
statistically independent.
4) The variable x is not a random variable.
3.1.1.2. Assessment of Estimated Parameter

n
9 : 2
Φ= pi Ȳi − Ȳi Values
i=1

n
2 Although the estimation of the parameter values
= pi Ȳi − β0 − β1 (xi − x̄) (9) is important, the quality of the empirical model is
i=1
of particular interest (see points 6 and 7, Section
where pi are statistical weights determined by 2.1). The first assessment of the empirical model
the number of measurements made for each data is the test of the hypothesis Ȳi = β 0 + β 1 (xi −x̄).
set, i.e., the number of measured values of the For this the mean square deviations
dependent variables at each value of the inde-
1 2
n
pendent variable x. If Equation (9) is partially s2r = pi Ȳi − Ŷi (13)
differentiated with respect to the parameters β 0 n − 2 i=1
and β 1 and the derivatives set to zero, rearrange-
ment gives the normal equations and
pi
n 2

n
n
n Yij − Ȳi
pi Ȳi = b0 pi + b1 pi (xi − x̄) (10a) i=1 j=1
s2ε = (14)
i=1 i=1 i=1 n
pi − n
i=1
and
are formed. Equation (13) represents the mean

n
n
pi Ȳi (xi − x̄) =b0 pi (xi − x̄) square of the residuals, i.e., the mean square de-
i=1 i=1 viations from the regression line. Equation (14)

n represents the mean square deviations within the
+b1 pi (xi − x̄)2 (10b) data sets; it is a measure of the random error
i=1
which occurs in the experiments at the points xi .
in which the parameters β 0 and β 1 are replaced The hypothesis Yi = β 0 + β 1 (xi − x̄) is con-
by their estimated values b0 and b1 . Since firmed if the mean squares of the residuals are
significantly smaller than the mean deviations

n
within the data sets. The hypothesis can be ver-
pi (xi − x̄) ≡ 0 (11)
i=1
ified by means of the F-test [4], [5], [20–23].
If, for a preset confidence number (1 − α), for
the coupling between Equations (10 a) and (10 b) example, 0.95
disappears and they can be solved separately for
b0 and b1 : (n−2),

pi −n
s2r i
>F (1−α) (15)

n s2ε
pi Ȳi
b0 =
i=1

n = Ȳ (12a) then the mean squares of the residuals are sig-
pi nificantly greater than the mean square devia-
i=1
tions within one data set, and the hypothesis

is

(n−2), pi −n

n not valid. In Equation (15) F (1−α) i
pi Ȳi (xi − x̄)
b1 =
i=1
(12b) is the value of the F-distribution for the con-

(1 − α) and
n
pi (xi − x̄)2 fidence number the degrees of free-
i=1
dom (n−2), pi − n . In the positive case
By forming the second partial derivatives, it can i
easily be shown that Equations (10 a) and (10 b) both s2r and s2ε are good estimates for σ 2Ȳi , the
actually represent a minimum of the sum Φ. variance in Ȳi . If the hypothesis is valid, the vari-
The simple uncoupled form only arises using ance of Ȳi is required for the calculation of the
the scaled form given in Equation (6). variances of the estimated values of the model
parameters and their confidence intervals. The
variances as given by their definitions are
9 :
2
σȲ An analogous procedure is adopted for β 1 .
Var b0 = b0 − β0 = i (16) The Student t-variable is then
pi
i
b1 − β1 b1 − β1
t= = 1/2 (21)
(cf. Eq. 12 a) and sb1
2 /
σȲ pi (xi − x̄)2
2 i i
9 : σȲ
Var (b1 ) = (b1 − β1 )2 = i
(17)
pi (xi − x̄) 2 This quantity also has a t-distribution with

i pi − 2 degrees of freedom. As before, the
i
(cf. Eq. 12 b). The variance of the model re- confidence interval for β 1 becomes:
sponse Ŷi calculated from the linear model is
given by

pi −2 pi −2
i i
b1 − t(1−α/2) sb1 ≤ β1 ≤ b1 + t(1−α/2) sb1 (22)
Var Ŷi = Var b0 + (xi − x̄)2 Var (b1 )
  Confidence intervals for the expected values
 1 (xi − x̄)2  Ȳi are defined in a similar fashion. Since the Ȳi

2
= σȲ +  (18) values are assumed to have a normal distribution
i pi pi (xi − x̄)2
i i around Ȳi , the t-variable can be expressed in
the form
since b0
and b1 are statistically independent.
9 :
Equation (18) shows that the variance of Yi is de- Ȳi − Ȳi
pendent on x and shows a minimum at x̄. A first t= =
sȲi
assessment of the linear model defined by the es- 9 :
Ȳi − Ȳi
timated parameter values b0 and b1 is achieved
1/2 (23)
by means of the calculated variances. σȲi /
1 +
(x − x̄)2

i
pi pi (xi − x̄)2
In addition to the variances, which are a mea- i i
sure of the scatter of the estimated values, the
confidence limits of the estimated values are which
again
has a t-distribution with

used and can be calculated from the variances pi − 2 degrees of freedom. In analogy
for further assessment. Since b0 and b1 are lin- i
ear combinations of Yi (cf. Eq. 12), they also with Equations (20) and (22) the confidence
have a normal distribution about β 0 and β 1 re- interval for Ȳi is as follows:
spectively because of the assumed normal distri-

pi −2 pi −2
bution of Yi . Under these conditions the Student i 9 : i
Ŷi − t(1−α/2) sȲi ≤ Ȳi ≤ Ŷi + t(1−α/2) sȲi
t-variable can be formed [4], [5], [21–23]:
(24)
b − β0 b0 − β0
t= 0 = 1/2 (19) Further discussion and illustration of the method
sb
0 σȲi / pi of parameter estimation and assessment are
i
given in Section 3.1.1.4.

This has a t-distribution with pi − 2 de-
i 3.1.1.3. Sensitivity Analysis
grees of freedom. Estimates of the confidence
interval can be obtained using the t-distribution In addition to the analysis of the variances of β 0 ,
in the following form: β 1 , and Ȳi , the sensitivity of the linear empirical

model Ȳi = β 0 + β 1 (xi −x̄) can help in interpret-

pi −2 pi −2 ing the results obtained from the model as well
b0 − t(1−α/2) sb ≤ β0 ≤ b0 +t(1−α/2)
i i
sb (20) as in the design of experiments for establishing
0 0
an empirical model. The sensitivity of the model

With known σ 2 Ȳi the interval in which the ex- may be described in various ways. In order to se-
pected value β 0 lies is given. Values of the t-dis- lect experiments and methods of measurement
tribution can be found in statistics books [4], [5], for verification of the fundamental variables of
[21–23]. the process, it is useful to have a measure of the
sensitivity of the sum of the squares of the de-

9 :
viations and of the estimated parameter values ∂ Ȳi ∂β0 β
with respect to Yi . Sensitivity can be regarded as 9 : / = 9 0: (29)
Ȳi β0 Ȳi
the relative change in the sum of squares of the
deviations ∂Φmin /Φmin or the relative change and
in the estimated parameter values ∂bi /bi for a 9 :
∂ Ȳi ∂β1 β1
relative change ∂ Ȳi /Ȳi in Ȳi . Since 9 : / = 9 : (xi − x̄) (30)
Ȳi β1 Ȳi

n 2 are obvious and can be derived directly from
Φmin = pi Ȳi − Ŷi (25)
i=1
Equation (6). For more complex models there
are other more subtle relationships for deciding
(cf. Section 3.1.1.1), the sensitivity of Φmin with the degree of complexity of the experiments re-
respect to Ȳi is: quired for the model development. This type of
sensitivity analysis will be discussed in detail
∂Φmin ∂ Ȳi 2 Ȳi pi Ȳi − Ŷi later (Section 5.3.3.1).
/ = n
2 (26)
Φmin Ȳi
pi Ȳi − Ŷi
i=1
3.1.1.4. Example of a Linear Model
Hence, relative change in a value Ȳi causes a
change in the minimum of the sum of squares, The determination of the model parameters will
which increases as the deviation between Ȳi and now be illustrated using a simple example of a
the model solution Ŷi becomes larger and as the linear model with one dependent variable, as de-
minimum becomes smaller. fined in Section 3.1.1.1.
The sensitivity of the estimated parameter As an example we will consider the corre-
values b0 and b1 to changes in Ȳi can be ob- lation of the mean heat-transfer coefficients for
tained simply and directly from Equations (12 a) hot air at the wall of a pipe with turbulent flow
and (12 b): (Table 1). The gas velocity (indicated by x in Ta-
ble 1) is varied and can be precisely adjusted so
∂b0 ∂ Ȳi 1 pi Ȳi that it can be regarded as a deterministic variable.
/ = (27)
b0 Ȳi pi b0 The measured values (the mean heat-transfer co-
i
efficients denoted by Y ) are statistical quantities
and which satisfy the assumptions presented in Sec-
tion 3.1.1. Table 1 also contains all conversions
∂b1 ∂ Ȳi 1 pi Ȳi (xi − x̄) necessary for linear regression.
/ = (28)
b1 Ȳi (xi − x̄)2 b1 According to Equations (12 a) and (12 b), the
estimated values for the parameters of the lin-
The sensitivity obtained from Equations (27)
ear model Ȳi = β 0 + β 1 (xi − x̄) are b0 = 15.002
and (28) is equally simple to interpret. The more
and b = 1.282. To test the hypothesis, the mean
reliable the measured value is, i.e., the larger
square deviations s2r and s2ε are first obtained
pi becomes in comparison to pi , the more from Equations (13) and (14): s2r = 7.749/3
i
rapidly b0 changes with Ȳi . The same applies to = 2.583 and s2ε = 7.613/9 = 0.846. The ratio of the
b1 , here the interval (xi − x̄) at which the values mean square deviations is then 3.05. The asso-
are measured has an additional weight. ciated F-value [4] is F 3.9 0.95 = 3.86, so that the
Finally, an estimate of the sensitivity of the hypothesis is valid for a significance level of
model with respect to its parameters is a sensible 0.05. To obtain an estimated value s2Ȳi for σ 2Ȳi it
measure to evaluate the experimental effort re- is better to use the combined square deviations
quired in the model assessment. This sensitivity from s2r and s2ε :
is defined by the relative change in the expected pi
n 2
value Ȳi , ∂Ȳi /Ȳi , caused by a change of Yij − Ŷi
i=1 j=1 7.613 + 7.746
∂βi /β i in the model parameter. For the linear s2Ȳ = = = 1.28
i n
9+3
model described here formulation of the prob- pi − 2
i=1
lem is trivial since the solutions
The variances of the estimated values of the

(xi −x̄)
0.00
2.50
5.00
−5.00
−2.50
model parameters can be obtained using Equa-
tions (16) and (17):
= 7.746
1.28
Var b0 = = 9.14 × 10−2
14
2
1.28
= 6.20 × 10−3
pi Ȳi − Ŷi
Var (b1 ) =
206.25
(Ȳi −Ŷi )2
and finally the xi -dependent variance of the

model responses Ŷi are given by Equation (18).
0.248
0.146
0.001
0.247
1.517
i

1 1
Y − Ȳi 2 = 7.613 Var Ŷi = 1.28 + (xi − x̄)2
14 206.25
= 9.14 × 10−2 + 6.20 × 10−3 (xi − x̄)2

The individual confidence intervals of the ex-

(Y −Ȳi )2
pected values of these three quantities can

be calculated for a significance level of
1.020
0.739
0.029
0.941
0.032
0.640
0.846
0.846
0.828
0.828
0.336
0.010
0.518
0.004

i
0.05

using

Equations (20), (22), and (24)

pi −2
pi (xi − x̄)2 = 206.25
i
(t0.975 = 2.179, [4]):
b0 −0.658 ≤β0 ≤b0 +0.658
and
pi (xi −x̄)2
75.00
18.75
0.00
12.50
100.00
b1 −0.171 ≤β1 ≤b1 +0.171

The individual confidence intervals for Ȳi are

pi Ȳi (xi − x̄) = 264.45
also dependent on xi because of the dependence

of the variance on xi :
. /1/2
Ŷi − 1.99 × 10−1 +1.35 × 10−2 (xi − x̄)2
pi (xi −x̄) Ȳi
9 :
≤ Ȳi ≤ Ŷi + 1.99 × 10−1
0.00
88.55
403.60
−136.35
− 91.35
Table 1. Example of linear regression, model with one independent variable
+1.35 × 10 −2 (xi − x̄) 2 1/2

i
9.09
12.18
15.04
17.71
20.18
The results of the regression analysis are illus-

Ȳi
trated in Figure 6: the regression line, the confi-

Ȳ = 15.002
dence intervals of the parameters, and the con-

fidence intervals for the expected values of the
11.21
12.36
12.98
14.12
15.96
16.80
18.62
19.60
20.08
20.90
20.16
8.08
9.95
9.26
model responses are shown. In spite of the veri-

Y
fication of the hypothesis, the results of the lin-

x̄ = 13.00
ear regression are only moderately satisfactory

8.00
10.50
13.00
15.50
18.00
due to the relatively large scatter of the measure-

xi
ments. Sensitivity analysis emphasizes this. For

pi = 14
example, for data set number 5 from Table 1

∂Φmin ∂ Ȳ5 2 × 20.28 × 4 × 1.231

/ = = 25.66
i
pi
Φmin Ȳ5 7.746

n= 5
A change in the measured value Ȳ 5 of 1 % causes

Data set
a change of 25.55 % in Φmin . Similarly high sen-

sitivities arise with

not differ in principle from that presented so far:

∂b0 ∂ Ȳ5 1 4 × 20.18 more complex calculations may be required and
/ = · = 0.384 further hypotheses or statistical rules may be
b0 Ȳ5 14 15.002
needed. For discussion of these special cases,
and the reader is referred to the literature [4], [5],
[7], [20].
∂b1 ∂ Ȳ5 1 4 × 20.18 × 5
/ = · = 1.526 Standardized computer programs are avail-
b1 Ȳ5 206.25 1.282
able for linear regression by least squares esti-
so that the experimenter concerned with this task mations for models with one dependent variable
would be well advised to repeat the experiments [26]. The solution of linear equations required
with a more precise measurement technique. In for linear regression is also available through
fact other experiments for this example give the program libraries for numerical problems or for
relationship problems in linear algebra. Most of these li-

braries are readily available [26–32], so that
ξ/8 (Re − 1000) P r DR 2/3 special-purpose computer programs can easily
Nu = - 1+
1 + 12.7 ξ/8 P r2/3 − 1 L be assembled for particular requirements.
where ξ = (1.82 log Re−1.64)−2 [24], [25]: this
relationship does not produce a linear depen-
3.1.2. Linear Empirical Models with Several
dency Nu = f (Re) and hence a linear model ap-
Variables
pears to be inadequate.
LIVE GRAPH In the case of linear empirical models with sev-
Click here to view
eral independent variables, similar problems to
those in Section 3.1.1 arise. Thus in the follow-
ing, only the generalized notation will be dis-
cussed.
The linear relationship for a model with sev-
eral independent variables is given by
y = βx (31)
and in extended notation
y = β0 +β1 x1 +β2 x2 +...+βq xq (32)
Figure 6. Results of linear regression for the example dis- so that the problem is extended to q variables
cussed in Section 3.1.1.4 and (q + 1) parameters. The same assumptions
Arrows indicate the confidence intervals of the parameters,
square symbols denote measured values, and the dashed hold as in Section 3.1.1, so that the model given
lines the confidence intervals of the expected values. by Equation (31) can be written in the form
9 : q
Ȳi = Ȳi − εi = β0 + βj (xij − x̄j ) (33)
j=1
3.1.1.5. Concluding Remarks
The (q+1) model parameters are calculated from
The assumptions stated in Section 3.1.1 are not the measured values defined at the n data points
always appropriate; for example, the random er- in the same way as in Section 3.1.1.
ror of the measurements may be a function of the In matrix notation Equation (33) reads
independent variables. In addition, the random
errors may be statistically dependent on each 9 :
Ȳ =Ȳ −E=βx (34)
other and, in a given process, both the depen-
dent and the independent variables can be sta- with the abbreviations
tistical quantities. Estimation of the model pa-
rameters by linear regression in such cases does
so that for a minimum to occur

9 :   
Ȳi β0 T
9Ȳ2 :   β1  x p Ȳ −βx = 0 (38)
9 :    
Ȳ = 
..
 , β = .  ,
 . 
.  .  Further differentiation shows that Equation (38)
9 :
Ȳn βq actually represents a minimum. After rearrange-
ment the normal equation
and
T T
  x px b= x p Ȳ (39)
1 (x11 − x̄1 ) · · · (x1q − x̄q )
1 (x21 − x̄1 ) · · · (x2q − x̄q ) 
  is obtained.
x = 
.. .. .. .. p

. . . .  In Equation (39) the parameters βi are re-
1 (xn1 − x̄1 ) · · · (xnq − x̄q ) placed by their estimated values. Equation (39)
is the matrix equivalent of Equations (9 a, b). So-
The first step is the same as for models with lution of Equation (39) for the parameters gives
only one independent variable – the estimation
. T /−1
of model parameters β. b= x px x p Ȳ
T
(40)
Inversion of the matrix (x )T p x ≡ a is required

3.1.2.1. Parameter Estimation for the solution. A condition for this is that the
determinant is not equal to zero, or in other
As in Section 3.1.1.1, the estimates of the pa-
words that matrix a is nonsingular. Numerical
rameters β are found by minimizing the sum of
problems related to ill-conditioned matrices a
squares of the deviations between the observed
can be avoided by suitably scaling or normal-
values Ȳi and the expected values Ȳi (i.e., the
izing the independent variables or by suitable
sum of the variances):
experimental design. This can be illustrated by
9 : T 9 : ! a simple example. From measurements at
Ȳ − Ȳ p Ȳ − Ȳ =Min (35)
 
By using Equation (34), the sum of squares of 9.5
 
the deviations can be formulated as x= 10.0 ,
10.5
T
Φ= Ȳ − βx p Ȳ −βx (36)
a relationship of the form y = β 0 + β 1 x will be in-
which has to be differentiated with respect to all vestigated. Estimation of the model parameters
the elements of vector β and then set to zero. involves inversion of the matrix
In Equation (36) p once again represents the
number of repeated measurements or, in general T 3.0 30.0
terms, the statistical weights. In matrix notation a≡x px=
30.0 300.5
 
p1 0 ··· 0 As can be easily verified,
0 p2 ··· 0 
 
p=
.. .. .. .. 
. . . .  Det (a) = 3.0 × 300.5 − 30.0 × 30.0
0 0 ··· pn = 901.5 − 900.0 = 1.5
Differentiation yields However, because of the spread of the measured

 ∂Φ
 values, the matrix is ill-conditioned for inver-
∂β
 ∂Φ0  sion since Det (a) = 0 if only the first two digits
 ∂β1  are significant. If it is scaled instead and we use
∂Φ  
= . =
∂β .  y = β 0 + β 1 (x−x̄) then
. 
∂Φ
∂βq T 3.0 0
. T / a≡ x px =
2 ∂ Ȳ − βx p Ȳ − βx 0 0.5
(37)
∂β or Det (a) = 3.0 × 0.5 − 0 = 1.5
The result is the same. The problem of subtrac- calculated model solutions that depends on the
tion of large numbers which arises from the de- estimated values b0 and b1 results.
sign of the experiments is thereby avoided. As
can be seen from the numbers given above, the
problem of handling differences between large
numbers is aggravated if the empirical model is
in the form of a polynomial, i.e.,
y = β0 +β1 x1 + β2 x2
with x1 =x, x2 =x2 etc.
Numerical problems with the inversion of a are

also avoided if the main diagonal of a can be
occupied predominantly through proper normal-
ization of the independent variables. This tech-
Figure 7. Geometrical illustration of the normal equations
nique can be demonstrated using the simple ex- for a linear model
ample of measured values at
 
The set of estimated values b0 and b1 that
5.0 10.0 gives the shortest distance between the end
5.0 20.0
  points of the vectors Ȳ and Ŷ now has to be
x=  
10.0 10.0 found. Obviously the shortest distance Ȳ − Ŷ is
10.0 20.0 given by the normal from the end of Ȳ onto the
If the variables are normalized in the form surface of the calculated model solution. The
normal Equations (10) and (39) fix b such that
x̃i1 =
xi1 − 7.5 the vector of the residuals Ȳ − Ŷ passes through
2.5 the end point of Ȳ and is perpendicular to the
xi2 − 15.0 surface of values calculated from the model.
and x̃i2 = then
5.0
 
1.0 −1.0 −1.0
1.0 −1.0 1.0 
  3.1.2.2. Assessment of Estimated Parameter
x̃ =  
1.0 1.0 −1.0 Values
1.0 1.0 1.0
The approach used to assess the estimated pa-
With a ≡ (x̃ )T px̃ this leads to the occupation of rameter values is the same as that in Section
the main diagonal only with 3.1.1.2, and so will only be briefly discussed. To
  test the hypothesis Ȳ = β x , the mean square
4.0 0 0
  deviations from the regression line must be ob-
a= 0 0.4 0  ,
0 0 4.0
tained. If Ȳ−Ȳ is represented by E then
T
so that inversion does not cause any problems. E pE
s2r = (41)
The variables normalized in this form n−q−1
are or-
thogonal since x 0 xi1 = x 0 xi2 = xi1 xi2 where s2r is the sum of squares of the residuals
= 0. Ill-conditioning of a can therefore be divided by the number of degrees of freedom.
avoided by planning the experiment in a man- The number of degrees of freedom is the number
ner which allows simple orthogonalization of the of data points minus the number of conditions
dependent variables. constraining the minimization, in this case the
A brief geometric explanation of the normal number of parameters. The mean square devia-
equations will now be given. Figure 7 shows the tions for the individual data points are calculated
vector Ȳ = (Ȳ 1 , Ȳ 2 , Ȳ 3 ) in the space of measured from Equation (19), so that the F-test can be con-
values. Since the relationship y = β 0 + β 1 (x−x̄) ducted using the ratio s2r /s2ε . The variances of the
is linear in its parameters, a plane surface for the
parameters and the model solutions can be cal- [33]. Programs can be easily constructed to fit
culated by means of the estimated values s2Ȳi of users’ requirements with the aid of modules
σ 2Ȳi which are obtained from s2r and/or s2ε in the from extensive program libraries for matrix and
case of a positive F-test. The covariances of the linear algebra [27–32].
parameters are
9 : 3.2. Nonlinear Empirical Models
Cov (b) = (b − β)T (b − β) =σȲ
2
a−1 (42)
i
If a−1 is denoted as c, then the variances of the In nonlinear models the relationship from Equa-
estimated parameter values can be obtained from tion (3) cannot be represented by Equation (4).
the diagonal elements of c with estimated values The derivatives of the model equation with re-
s2Ȳi for σ 2Ȳi : spect to the parameters are themselves func-
tions of the parameters. The nonlinear model
s2bk =s2Ȳ ckk (43) y = f (x, β) is once again based on several as-
i
sumptions:
With

1) The dependent variable is a random variable
T
Var Ŷi = Var x b =x Var (b) x for which n data sets of measured values Ȳi
T are available. The model can therefore be re-
2
=σȲ x c x (44) presented in the form
i
and s2Ȳi for σ 2Ȳi , the following is obtained: 9 :

Ȳ =Ȳ − E=f (x, β) (46)
2
sŶ = sȲi x c (x )T (45) where E once again represents the random
i
error in Ȳi , so that Ȳ − Ȳ = E. The expected
so that, as in Section 3.1.1.2 (Eqs. 20, 22, and
value of the random error is zero and its vari-
24), the confidence intervals for b and Ŷi are
ance is constant (independent of x).
obtained.
2) The random variable Y has a normal distri-
More detailed methods for the assessment of
bution about Ȳi and has the same variance as
the estimated parameter values for models with
several independent variables are treated in [4], εi .
3) Both the random variable and the random
[5], [20].
error are statistically independent.
4) The variables x are not random variables.
3.1.2.3. Concluding Remarks The empirical nonlinear statistical model can
be represented analogously to that in Figure 5,
The sensitivity analysis for empirical models whereby the relationship is nonlinear and is char-
with several independent variables will not be acterized by several independent variables. As
discussed. The relationships presented in Sec- with the linear model, the first task consists of
tion 3.1.1.3 can be used, and so need not be re- estimating the model parameters using the ex-
peated. The basic rules of linear regression were perimental process data.
illustrated using an example with one indepen-
dent variable, a further example for a model with
several independent variables will not be given. 3.2.1. Parameter Estimation (Nonlinear
Cases which do not comply with the assump- Regression)
tions presented here are described in the liter-
ature; for example, processes with random er- Estimation of the model parameters β involves
rors which are not normally distributed or with the now familiar task of defining the estimated
random errors which depend on x are discussed values b such that the sum of squares of the de-
in [4], [7]. Standardized computer programs are viations between the values Ȳi observed at the
available for the treatment of empirical linear n data points and the estimated values Ȳi is a
models with several independent variables or for minimum. [ In the following, the equations are
multiple linear or polynomial regression [26], expressed in a simplified form, without repeated
Next Page
measurements, i.e., with unit statistical weights 3.2.1.1. Transformation of the Model into
p, Det ( p) = 1]: Linear Form
9 : T 9 : ! The simplest method of estimating parameters
Ȳ − Ȳ Ȳ − Ȳ = Min (47)
in nonlinear regression is transformation of the
A geometric representation of this task is model equations into linear form to avoid the
shown in Figure 8. The end point of the vector problem of solving the nonlinear equations de-
Ȳ = (Ȳ 1 , Ȳ 2 , Ȳ 3 ) in the space of measured values scribed above. Certain types of nonlinear mod-
should be linked by the shortest possible dis- els can be transformed into linear form but this
tance with the end point of the vector Ŷ. This is may involve several problems; this will now be
once again given by the normal to the surface of briefly illustrated.
model responses in the parameter space, which The relationship
in this case is curved because of the nonlinearity
of the relationship y = f (x, β). y = β0 xβ1 β2
1 x2 (49)
e.g., the rate of a complex chemical reaction,

can be transformed into linear form by taking
logarithms:
logy= logβ0 +β1 logx1 +β2 logx2 (50)
The transformed model is therefore
logȲi −εi = logβ0 +β1 logxi1 + β2 logxi2 (51)
The previously presented methods of regression

analysis for testing hypotheses and calculating
the confidence intervals of the parameters or
model solutions presume that the additive errors
εi and random variables have normal distribu-
tions. For the nonlinear model of Equation (49),
the additive error must be multiplicative:
1 β2
Ȳi =β0 xβ
i1 xi2 εi (52)
and, like the random variable Yi , must have

Figure 8. Geometrical illustration of the normal equation
for a nonlinear model
a log-normal distribution to satisfy the above-
mentioned presumptions. This is not always the
Partial differentiation of the sum of squares case and must be experimentally verified.
of the deviations Another example is the relationship of the
T form
Φ= Ȳ −f (x, β) Ȳ −f (x, β) (48)
β1 β2 x
y= (53)
with respect to the parameters and then setting (1+β2 x)2
the derivatives to zero produces a system of non-
linear normal equations. This is the main differ- which represents, for example, the rate
ence from linear regression in which a system of of a heterogeneous catalytic reaction
linear equations in β is obtained for the normal (Hougen – Watson – Langmuir – Hinshelwood
equations. This can be easily verified by analyz- kinetics). Transformation into a linear model
ing the sums of squares (Eqs. 9, 36, and 48). gives
Nonlinear regression is therefore the solution 1/2
x 1 β2
of a system of nonlinear equations for β. y
=
(β1 β2 )1/2
+
(β1 β2 )1/2
x (54)
The additive statistical error εi in the linear

model for the estimation of the parameters
Previous Page
(Eq. 54) is not identical to the random error of Simplex methods are more effective, espe-
the nonlinear model (Eq. 53). Inverse transfor- cially with large numbers of parameters. For a
mation of Equation (54) gives: twoparameter problem (Fig. 10), a regular Sim-
β1 β2 x β1 β2 √ plex is an equilateral triangle which, starting
y= + yε2 − 2 yxε (55) (0)
(1+β2 x) 2
(1+β2 x) 2 from estimated values bi , is placed at a point on
which contains an additive random error that is the surface of Φ in the parameter space. During
dependent on x, y, β 1 , and β 2 . the search, Φ is evaluated at each of the three
vertices, and the triangle is reflected about the
side opposite the largest value of Φ. If there is
3.2.1.2. Direct Search Methods no further reduction in Φ after reflection, then
the Simplex is reduced in size to allow more ac-
Another way of circumventing the problem of
curate localization of the minimum.
solving nonlinear equations is to use direct
search methods. For this the normal equations
are not derived from the sum of squares of the
deviations (Eq. 48), instead the minimum of the
function Φ is sought directly. Vectorial search
methods [34], Simplex methods [35], and Sim-
plex methods with variable Simplex geometry
[36] are the most commonly used direct search
methods. The structure of these methods is pre-
sented schematically for a model with two pa-
rameters in Figure 9.
Figure 10. Representation of the Simplex method

The numbers represent the number of reflection
Simplexes with variable geometry are ob-

tained by expanding after successful reflec-
tion or contracting after unsuccessful reflection.
An example is given in Figure 11 for a two-
parameter problem. The reflection algorithm
is
bir = (1+γr ) bic −γr bimax
Figure 9. Representation of direct search methods where bir , bi max , and bic are the coordinates of
The first digits in the parentheses indicate the number of it- the reflected Simplex point, of the Simplex point
eration. The second digits denote the number of successive with the largest sum of squares of deviations,
variation of βi . For example, (02) on the β 1 axis means the
initial guess of β 1 and the second variation and of the midpoint of the side lying opposite
it, respectively; γ r is the reflection factor. The
Vectorial search methods start from esti- expansion algorithm is
(0)
mated values bi for the parameters βi . The
direction of the search vector is established bie =γe bir + (1−γe ) bic
from successive calculations of Φ by varying
the estimated values bi . The direction of the where bie are the coordinates of the expanded
vector leading to a reduction in Φ is used to Simplex point and γ e is the expansion factor.
calculate improved estimates of bi . If there is no After unsuccessful expansion or reflection, con-
further reduction in Φ along the search vector, traction is achieved with the algorithm
the direction is redefined and the minimum of
Φ is located by reducing the step size (Fig. 9). bik = (1−γk ) bic +γk bimax
where bik and γ k have analogous meanings to nonlinear systems of equations. Here the non-
those in reflection or expansion. linear Equation (58) is expanded around an es-
timated solution into a Taylor series, which is
truncated after the first term. For Equation (58)
this leads to the expansion of η about η (0) at
b(0) , hence
(0)
∂η
η = η (0) + ∆b(0) (59)
∂β
with ∆b(0) = β − b(0) . A system of linear equa-

tions for the new variable ∆b(0) then arises, so-
lution of which leads to an improved estimated
value for the parameters:
b(1) =b(0) +∆b(0) (60)

Figure 11. Representation of the Simplex method with vari-
able geometry
If this procedure is applied to Equation (58),
The numbers represent the number of reflection, expansion, substitution of Equation (59) into Equation (58)
or contraction gives
T

(0) (0)
∂η ∂η
2 ∂ Ȳ − η (0) − β ∆b (0)
β
∆b(0)
3.2.1.3. Gradient Methods
∂∆b(0)
Discussion of the methods for solving nonlinear =0 (61)
systems of equations arising from the minimum
conditions for Φ will be limited to two methods. This gives the following system of equations for
Further methods are described in the literature ∆b(0) :
on nonlinear optimization [5], [7], [20], [37–39] (0) (0)
(see also → Mathematics in Chemical Engineer- XT X B (0) = X T E (62)
ing, Chap. 10.).
Through use of the abbreviation which employs the abbreviations
9 : ∂η
Ȳ ≡η=f (x, β) (56) X ≡ , E ≡ Ȳ − η , and B ≡ ∆b
∂β
the sum of the squares of the deviations (Eq. 48)
can be written as Equation (62) is similar to Equation (39). In
Equation (62) B (0) is the dependent variable,
T
Φ= Ȳ −η Ȳ −η (57) whereas Equation (39) represents a system of
equations for the parameters themselves. (Since
The condition for the minimum with respect to there are no repeated measurements according
the parameters β then becomes: to the assumptions in Section 3.2.1 the statisti-
 ∂Φ
 cal weights for all measured points are equal, p
∂β
 ∂Φ1 
is replaced by the unit matrix). The solution of
 ∂β2  Equation (62) for B (0) gives
∂Φ  
= . =
∂β . 
.  (0) −1 (0)
∂Φ B (0) = XT X XT E (63)
∂βq
. T /
2 ∂ Ȳ − η Ȳ − η
=0 (58)
By using Equation (60) an improved set of pa-
∂β rameters is obtained and the method is iterated
The first method discussed here is based on the until a previously defined convergence condition
Newton – Raphson method for the solution of of B (n) or Φ is satisfied.
With the second method for the estimation where I is the unit matrix and λ is a scaling fac-
of parameters from nonlinear empirical models, tor. When λ = 0 Equation (62) is obtained. As
the sum of squares itself is linearized. Expansion λ → ∞, then B ≈ X T E/λ which, with the iden-
tity λ =
−gradΦ
(n)
of Equation (48) around b(0) into a Taylor series leads to the method of
h(n)
truncated after the first term gives steepest descent for calculating B. By fitting λ
q using Marquardt’s method, the essential charac-
∂Φ (0) (0)

teristics of both methods can be combined, [4],
Φ ≈ (Φ)(0) + βj − bj (64)
j=1
βj [7], [40].
The direction of search used to calculate im- Numerical Problems Connected with Gra-
proved estimated values from the relation dient Methods. Iterative solution of Equation
(62) or the method of steepest descent can give
b(n+1) =b(n) +hT ∆b(n) (65)
rise to problems, one of them being the initial
(h is a vector of the step size) can be defined by guesses b(0) . Under certain conditions, the se-
the gradient of Φ; grad Φ is a vector that is nor- lection of b(0) leads to a neighboring minimum
mal to the surface of Φ in the parameter space in Φ, or is so unfavorable that iteration does
and indicates the direction of the steepest ascent not lead to convergence. The first of these prob-
in Φ at the point b. Conversely, the vector − grad lems requires a more precise investigation of the
Φ shows the direction of the steepest descent of sum of the squares of the deviations or repetition
Φ. For parameter estimation the components of of the calculation with various initial values for
the vectors at b(0) b(0) . In order to avoid divergence of the iterative
method (especially with poorly chosen b(0) ),
(0) (0)
∂Φ ∂Φ only the direction of the vector B (0) should be
−gradΦ = − δβ1 − δβ2 −
∂β1 ∂β2 used; new estimated values for β are then cal-
(0) culated using Equation (65) with a reduced step
∂Φ
... − δβq (66) size in place of Equation (60). In Equation (65),
∂βq
h has the character of a user-selected damping
are calculated. For this the vector −grad Φ, nor- factor, which can be adjusted during each itera-
malized by its absolute value is used: tion in accordance with the evolution of Φ. With
favorable conditioning of the nonlinear equation
−gradΦ
= (67) system, this factor can also be used to accelerate
−gradΦ convergence.
(0) (0) (0) Another problem lies in the mathematical
− ∂β
∂Φ
δβ1 − ∂β ∂Φ
δβ2 − ... − ∂β ∂Φ
δβq
1
1 2 q form of the model. For example, for a model
(0)2 (0)2 (0)2
− ∂β∂Φ
+ − ∂β∂Φ
+...+ − ∂β ∂Φ consistent with Equation (53) it is easy to show
1 2 q
that η, as well as the partial derivatives ∂η/∂β1
In Equations (66) and (67), δβi denotes the unit and ∂η/∂β2 , are unbounded if β 2 x = −1. The
vectors in the direction of βi . The components of only way to circumvent this problem is to con-
the normalized vector (Eq. 67) produce the term strain the range of the estimated values of the
∆b in Equation (64) from which the iteration parameters on the basis of the physicochemical
formula (Eq. 65) can proceed. characteristics of the process.
Both methods (solution of the system of non- The sum of the squares of the deviations can
linear normal equations and the method of steep- contain terms of differing orders of magnitude,
est descent) can, under certain conditions of the which lead to very different gradients in the
sum of squares Φ, lead to unfavorable trajecto- direction of the individual parameters. In such
ries over the surface of Φ in the parameter space cases scaling of the parameters is always ad-
[40]. To deal with this, according to Marquardt visable, whereby the individual components in
a diagonal matrix is added to the coefficient ma- Equation (66) are brought to the same order of
trix (X T X) in Equation (62): magnitude by linear transformation.
Transformations of the independent variables

X T X +λI B=X T E λ≥0 (68) are necessary if interactions exist between indi-
vidual parameters. This is the case, for example,

with a simple Arrhenius type of rate coefficient ∂k ∗ ∗ k
of a chemical reaction = eE T = ∗
∂k0∗ k0
k = k0 e−Ea /RT and
where E a is the activation energy, R the universal ∂k ∗ ∗

= − k0∗ T ∗ eE T =kT ∗
gas constant, and T the temperature. ∂E ∗
If the exponential function is expanded so that Hence
2  2 ∗
1
Ea 1 Ea
k∗2
iki2 − k1∗ iki T i
k ≈ k0 − k0 + k0 − ··· X X T
= 01 2 ∗ 0 2 
RT 2 RT − k∗ iki T i i ki T ∗i
0
it becomes clear that k 0 has a multiplicative ef-
fect on the other parameter E a . Minima of the Since Ti ∗ can be positive or negative, the diag-
sum of squares can thus be found for various onal elements of the matrix dominate, and in
combinations of k 0 and E a that do not make
1
sense in physical terms. In such cases either the Det XT X = ki2 (ki T ∗i )2
k0∗2
range of allowable estimated values of the pa- i i
rameters is restricted on the basis of the physi- 2 

cochemical process characteristics, or the matrix
− ki2 T ∗i 
(X T X ) is brought into a form in which the diag- i
onal elements dominate through transformation
of the independent variables. The smaller the the first term in the square brackets always dom-
off-diagonal elements of the matrix (X T X ) are inates. The danger of the matrix (X T X ) be-
compared to the diagonal elements, the smaller ing singular (which would prevent solution of
the interaction between the parameters becomes. Eq. 63) is thus overcome.
This can be demonstrated for the above example
of the simple Arrhenius type of rate coefficient
in which T is the independent variable. Since 3.2.2. Assessment of Estimated Parameter
Values
∂k Ea k ∂k k0 −Ea k
= e− RT = and = − e RT =
∂k0 k0 ∂ (Ea /R) T T Several methods have been developed to assess
 k 2 the estimated parameter values from nonlinear

1
iki2 −k1
i Ti
 k0
2
0
i2  empirical models [20], [41], [42]. A method
then XT X =  ki 
− k1 iT
2
k
i Ti
2
which is similar to the approach used in Sec-
0 i i
tions 3.1.1.2 and 3.1.2.2 will be presented here.
Therefore The nonlinear model is linearized around the
estimated values b in the parameter space, i.e.,

1 k 2 2 is expanded into a Taylor series truncated after
T
Det X X = 2 ki2 i
the first term. The approximate variances and
k0 i i
Ti
covariances of the parameters are then given by
2  (cf. Eqs. 42 and 59):
k2
− i  −1
i
Ti Cov (b) ≈ X T X 2
σȲ (69)
i
which can become singular under certain condi- Each element of X is calculated either analyt-
tions, since all terms in the square brackets are ically or numerically from the value of b indi-
positive for all regions of the measured ki and cated by the minimum. If the hypothesis is valid,
Ti . s2r can once again be used as an estimated value
If the transformation
∗ ∗
T ∗ = (T−T̄ )/T is ∗used, for σȲ2 i (Eq. 41). If repeated measurements are
we obtain k = k ∗0 e E T with k ∗0 = k 0 /e E and available, the hypothesis Ȳi = f (x, β) can be
E ∗ = Ea /RT̄ . For the transformed model tested beforehand. The approximate variances
of the estimated values of the parameters are ob- Φ with each iteration. Figure 12 shows the es-
tained from the diagonal elements of (X T X )−1 : (n) (n)
timated values b0 and b1 and the sum of
squares of the deviations Φ plotted against the
(n)
s2bk ≈ s2Ȳ ·ckk (70)
i number of iterations n. The method is regarded
as convergent when Φ(n−1) − Φ(n) ≤ 10−4 .
using the abbreviation c = (X T X )−1 . The ap- LIVE GRAPH
proximate confidence intervals can be estimated Click here to view
from this as described in Section 3.1.1.2.
The variances of the model solutions are ob-
tained from the linearized model according to

q
∂ Ŷ
s2Ŷ ≈ s2bj
i
j=1
∂b j

q q
∂ Ŷ ∂ Ŷ
+ Cov (bi bj )
i=1 j=1,i=j
∂bi ∂bj

q q
∂ Ŷ ∂ Ŷ
≈ sŶ cij (71)
i
i=1 j=1,i=j
∂bi ∂bj Figure 12. Results of nonlinear regression for the example
discussed in Section 3.2.3
so that the approximate confidence intervals of
For the region of the experimentally adjusted
the expected values can also be estimated.
gas velocities, the calculated results b0 = 1.257
and b1 = 0.9626 produce a smaller minimum
in Φ, Φmin = 0.332, than the linear regression
3.2.3. Example of a Nonlinear Model
with Φmin = 7.746 (Fig. 6). The improved qual-
ity of the regression is obvious from the value
The estimation of the parameters of a nonlinear
of the mean square deviations about the regres-
empirical model will be demonstrated by further
sion function (s2r = 0.1105) so that the F-test is
discussion of the process presented in Section
fulfilled to a higher level of significance. If the
3.1.1.4. Because of the relatively large scatter of
combined squared deviations s2r and s2ε are used
the measured values within the individual data
to estimate σȲ2 i , s2Ȳi = 0.996 is obtained; the im-
sets, the result of the linear regression is merely
tolerable in spite of a positive test of the hypoth- provement seen in Figure 12 also results in a
esis Ȳi = β 0 + β 1 (xi − x̄). The assessment of the smaller variance in the estimated parameter val-
estimated parameters gives large individual con- ues b0 and b1 and in the model solution Ȳi . From
fidence intervals for the parameters and the ex- Equations (70) and (71) the model linearized in
pected values. Furthermore, the sum of squares the minimum of Φ gives
and the estimated parameter values show a high
s2b0 ≈ 0.996 × 5.21 × 10−2 = 5.03 × 10−2
sensitivity to the measured values Ȳi .
The same process will now be tested with a
s2b1 ≈ 0.996 × 4.51 × 10−3 = 4.3 × 10−3
second approximation using a model of the form
. 2
9 : s2Y i ≈ 0.996 x0.9626 5.21 × 10−2 −3.6lnxi
Ȳi =β0 xβ
i
1
(72) i
/
The data for nonlinear regression are given in Ta- +7.13 × 10−3 (lnxi )2
ble 1. The Newton − Raphson method is used to
solve the system of nonlinear equations (Eq. 58).
The relation Ȳi = β 0 x βi 1 with b1 ≤ 1 reflects
The results from the application of the linear
the true dependency better (see Section 3.1.1.4).
model Ȳi = β 0 + β 1 (xi − x̄) are used as an ini-
(0)
tial guess for b0 and b1 , hence b0 = 1.282,
(0) (n)
b1 = 1. The step size hi (Eq. 65) is adjusted
automatically according to the improvement in
3.2.4. Concluding Remarks such that the likelihood function becomes a max-
imum. With one observation the likelihood func-
The treatment of nonlinear empirical models is tion L for the parameters is the probability den-
conducted as in Sections 3.1.1 and 3.1.2 using sity function in which the variables Ȳ and x are
a relatively simple model to obtain the simplest viewed as parameters and the parameters β0 , β1 ,
formulation possible. The principles of nonlin- and σȲ2 i are viewed as variables.
ear regression and some of the resulting prob-
lems can be clarified using this simple model. L β0 ,β1 , σȲ
2
; Ȳ1 , x1 = P Ȳ1 ,x1 ;β0 ,β1 ,σȲ
2
(73)
i i
For cases in which the assumptions listed in the With n statistically independent observations
introduction to Section 3.2 do not hold, more ad- the likelihood function is the product of the in-
vanced literature should be consulted, [4], [5], dividual functions:
[7], [20]. Many computer programs are avail-
able for routine problems of parameter estima- L β0 ,β1 ,σȲ
2
; Ȳ1 , x1 ... Ȳn ,x̄n
i
tion with nonlinear empirical models (e.g., for
n
gradient methods [27], for Marquardt’s method = L β0 ,β1 ,σȲ
2
; Ȳi ,xi
i
i=1
[43], or for direct search methods [44]). The in-
dividual steps of the Newton − Raphson method =P Ȳ1 ,x1 ;β0 ,β1 ,σȲ
2
i
·P Ȳ2 ,x2 ;β0 ,β1 ,σȲ
2
i
(see Sections 3.1.1.5 and 3.1.2.3) can be ob-
...P Ȳn ,xn ;β0 ,β1 ,σȲ2
(74)
tained as modules from readily available pro- i
gram libraries [26–32]. To define β0 ,

β1 , and σȲ2 i ,
L must now be max-
imized. The logarithms of Equation (74) are
taken giving the following relations for the pa-
3.3. Further Calculation Methods and rameters:
Model Types
n
∂ P Ȳi ,xi ;β0 ,β1 , σȲ
2
∂lnL i=1 i
The discussion on the quantitive definition of = =0 (75a)
∂β0 ∂β0
empirical models (Sections 3.1 and 3.2) referred
to the minimization of the sum of squares of the
deviations as well as to simple models based on
n
∂ P Ȳi ,xi ;β0 ,β1 , σȲ
2
Equations (5) and (46). The section on empiri- ∂lnL i=1 i
= =0 (75b)
cal models will now be concluded with a short ∂β1 ∂β1
discussion of other methods of parameter esti-

n
mation for empirical models and other types of ∂ P Ȳi ,xi ;β0 ,β1 , σȲ
2
models. ∂lnL i=1 i
2
= 2
=0 (75c)
∂σȲ ∂σȲ
i i
3.3.1. Further Methods of Parameter For the linear problem Ȳi = β 0 + β 1 (xi −x̄)
Estimation where the random variable Y is assumed to have
a normal distribution, it can easily be shown that
Further methods of defining the parameters of Equations (9) for defining β 0 and β are obtained
empirical models include the maximum likeli- from Equation (75) since

hood method. P Ȳi ,xi ;β0 ,β1 ,σȲ
2
A statistical empirical model can be de-
i

scribed with the use of the probability density 1 1 9 : 2

= 2 ·exp − 2 Ȳi − Ȳi pi (76)
function P (x, y) (Section 2.2 and Fig. 5). If a 2πσ 2 Ȳi
2σȲ
i
model for the process can be represented in the
form Ȳi = β 0 + β 1 (xi − x̄) (Section 3.1.1), the Detailed discussion of this method can be found
probability density function is defined by the in [4], [22].
parameters β 0 , β 1 , and σȲ2 i , hence P (Ȳ , x ; β0 , Further search algorithms are discussed
in more advanced literature on optimiza-
β1 , σȲ2 i ). The problem of estimating the param-
tion, → Mathematics in Chemical Engineering,
eters now consists of defining β0 , β1 , and σȲ2 i Chap. 10., [5], [7], [38], [39].
3.3.2. Other Types of Models

q
!
In addition to the models described by Equa- Φ+ λi (gi ) = Φ∗ = Min (80)
tions (5) and (46), empirical models in which un- i=1
derlying conditions constrain the parameters are For constraints given in Equation (77 b) the
frequently encountered in industrial chemistry. penalty function is gi = 0 for bj ≥ kj and
Furthermore the functional relationship may not gi = (bj − kj )2 for bj ≤ kj . Here the scaling fac-
be in the simple form of algebraic equations tors λ and are set to 1 and 2, respectively.
(Eqs. 5, 32, and 46) but in the form of differ- Similarly constraints in the form
ential equations or transfer functions.
gi (Y , x, β) = 0, i= 1, ...q (81)
3.3.2.1. Models with Constraints on the can be handled in the form of penalty functions
Parameters which are added to the sum of squares of the
deviations. They disappear when the associated
Constraints on parameters are found in many conditions (Eq. 81) are satisfied. Alternatively
models used in industrial chemistry. A simple they are weighted according to the magnitude of
example is the reaction rate of a heterogeneously the deviation and added to Φ.
catalyzed reaction according to Equation (53), A more rigorous method for the treatment of
which only makes sense when associated constraints in the form of equations
is based on their geometrical interpretation. In
βi ≥0 (77a)
Figure 13 the sum of squares of the deviations
Equally common are constraints of the type for a two-parameter problem is shown in the pa-
rameter space. A constraint of the form
βi ≥ki , where ki is positive (77b)
β1 +aβ2 =c (82)
0 ≤ βi ≤ 1 (77c)
can be represented as a straight line which inter-
ki∗ ≤ βi ≤ ki (77d) sects the lines of constant Φ. The minimum of
Φ is now searched for along this straight line, so
Explicit constraints of this type can easily be re- that the two-dimensional problem is reduced to a
moved with appropriate transformations. For ex- one-dimensional one. This can be easily demon-
ample, the general transformation rule for Equa- strated for a linear model of the form accord-
tion (77 b) is ing to Equation (5) with the constraint given by
∗ Equation (82) because one parameter is directly
βi = ki +eβi (78a)
eliminated by substitution.
in which the unknown βi∗
is not affected by
any constraints. For Equation (77 d) the general
transformation rule
βi = ki∗ + (ki − ki∗ ) sin2 βi∗ (78b)
can be used, whereas for Equation (77 a)

∗
βi = βi∗2 or βi = eβi (78c,d)
are suitable transformations.

The general constraint
gi (Y , x, β) ≥0, i= 1, ...q (79)
for which transformations are not applicable,

Figure 13. Geometric representation of least squares esti-
can be added as a penalty function to the sum mations with constraints on the parameters
of squares of the deviations:
In problems involving many parameters or or the rates of chemical reactions. For differ-
nonlinear models, reduction of a multidimen- ential equations that are simple to integrate the
sional problem with one or more constraints by parameters can be determined according to the
substitution is either impossible or very difficult. principles presented in Section 3.2, for exam-
In such cases the method of Lagrangian multiple, as with the common first-order differential
pliers is used. Figure 13 illustrates that for the equation
constrained minimum, the slopes ∂β 1 /∂β 2 of
dy (t)
the two curves Φ = const. and β 1 + a β 2 − c = 0 =αy (t) + x (t) , where yt=0 =y0 (88)
dt
are equal. In general these conditions can be ex-
pressed as The general solution of Equation (88) is [45]
∂Φ/∂β1 ∂g/∂β1 t
− =0 (83) y (t) =y0 eαt + x (τ ) eα(t−τ ) dτ (89)
∂Φ/∂β2 ∂g/∂β2
0
or as the gradient ratio
If discrete measured values Y (ti ) are available,
∂Φ/∂β1
=
∂Φ/∂β2
=λ (84)
the condition for the minimum with respect to α
∂g/∂β1 ∂g/∂β2 and y0 is given by
n .
From Equation (84) the system of equations x0 /2
Φ= Y (ti ) − y0 eαti + 1 − e−αti (90)
∂Φ ∂g i=1
α
−λ =0 (85a)
∂β1 ∂β1
This leads to the system of nonlinear equations
and n .
x0 /
Y (ti ) − ŷ0 eα̂ti + 1 − e−α̂ti eα̂ti = 0
∂Φ ∂g α̂
−λ =0 (85b) i=1
∂β2 ∂β2 (91a)
is obtained. Equations (85 a), (85 b), and the con- and
straint given by Equation (82) may be derived n .
from the extended sum of squares
x0 /
Y (ti ) − ŷ0 eα̂ti + 1 − e−α̂ti
i=1
α̂
. x0 α̂ti /
Φ∗ =Φ + λ (β1 +aβ2 −c) (86)
· ti ŷ0 eα̂ti − 2 e (1 − α̂ti ) − 1 = 0 (91b)
α̂
by partial differentiation with respect to the
parameters and the Lagrangian multipliers λ. which can be solved for ŷ0 and α̂ by an appro-
In general, therefore, when the associated con- priate method.
straints are in the form of Equation (81), the min- In the majority of cases, the differential equa-
imum of the extended sum of squares tions of the model are more complex than Equa-
tion (88), so that no analytical solution is avail-

q
!
able; numerical solution of the differential equa-
Φ+ λi gi (Y , x, β) = Φ∗ = Min (87) tions is required to evaluate Yi . New problems
i=1
then arise depending on the type of differen-
must be found by varying the parameters β and tial equation. Especially with systems of cou-
the Lagrange multipliers λi . This can be carried pled partial differential equations used to model
out using the methods discussed previously (see chemical reactors on the basis of transport equa-
Section 3.2.1). tions (see Chap. 5), the solution of the differ-
ential equations is the real problem. In such
cases other methods are often used to determine
3.3.2.2. Models Based on Differential the model parameters. Changing certain process
Equations variables produces a characteristic behavior in
some model solutions which is studied in suit-
Chemical processes often give rise to models in ably designed experiments.
the form of differential equations. Examples are An example is the spread of the concentra-
models of reactors based on transport equations tion profile of a tracer added in the form of a
Dirac function into reactors with axial and/or found at the molecular level in the molecular
radial dispersion. By measurement of the con- velocity resulting from random thermal move-
centration at two points in the reactor, the Péclet ments; the corresponding probability density
number Pe can be derived in a relatively sim- function is the Maxwell – Boltzmann velocity
ple manner. Further examples are discussed in distribution [48]. The use of this concept in ki-
[4], [46]. A feature of these methods is that an netic gas theory and statistical mechanics has
analytical or numerical solution of the differ- been referred to in Section 2.2.
ential equations is often not necessary because Statistical variables can also be found at the
the model parameters are comparatively simple macroscopic level. In the example discussed in
functions of the deterministic moments of the Chapter 3, statistical process variables with pre-
measured variables. Deterministic moments are sumed distribution or probability density func-
defined analogously to the moments of proba- tions were examined and their expected values,
bility density functions of statistical variables variances, and functional relationships to other
(Section 2.2) and are related to the distribution variables were determined.
functions of the deterministic variables. If, for Another example is the jet stirred fluid-phase
example, w (t) is the residence time distribution reactor with turbulent flow presented schemat-
for a chemical reactor, then the first two deter- ically in Figure 14. The surrounding fluid en-
ministic moments m1 and m2 are defined as trains the jet by exchange of momentum. The
intake volume of the jet is greater than the vol-
∞
ume of the surrounding fluid. This leads to re-
m1 = t̄ = t·w (t) dt
circulation of material from further downstream
0
∞ and mixing of the reactor contents. The fluid in
m2 = (t − m1 )2 w (t) dt the jet exhibits turbulent flow. The velocity of
0 the fluid particles is so high that they can no
longer be held in regular streamlines by the vis-
An example is the determination of the Péclet cous forces, and irregular vortices are formed.
number for a chemical reactor with back mixing Vortices of different sizes with different veloc-
on the basis of measurements of the residence-
ities and different macroscopic properties pass
time distribution [46], [47].
a fixed observer. Therefore, the fixed observer
Finally, it should be noted that for processes
measures statistical, time-dependent variations
which can be described in the form of systems of in the physical quantity Φ.
common linear differential equations analogous
to Equation (88), i.e.,
dy
+βy − x (t) , y t=0 = 0 (92)
dt
the parameters can be determined with the
Laplace transforms of the transfer functions. The
transfer functions can be given in the physical
time coordinates as well as in the coordinates
of the Laplace transformation. The methods are
discussed in detail in [4], [9], [13–15].
4. Models Based on Transport

Equations for Probability Density
Functions
Figure 14. Example of a process with statistical variables:
Probability density functions and the probabili- a jet stirred reactor with turbulent flow
ties which can be calculated from them are the In Figure 14 this is shown at two positions in
most adequate way of describing statistical vari- the jet. At the edge of the nozzle (A) either the
ables. Examples of statistical variables can be
properties of the jet or the surroundings are mea- W (Φ≤ 0) =F (0) = 0 and (95a)
sured. Further downstream (B) the macroscopic
properties are balanced due to turbulent mixing. W (Φ≤ 1) =F (1) = 1 (95b)
All physical parameters are thus characterized
by position- and time-dependent distribution or Any event, i.e., any interval E ≡ ϕu ≤ Φ ≤ ϕo in
probability density functions. The objective of the sample space can be obtained by subtraction
models based on transport equations for proba- (see Fig. 15):
bility density functions is the calculation of func-
tions P (Φ1 , . . . , Φn ) in which Φ1 , . . . , Φn is the E= (Φ≤ϕo ) − (Φ≤ϕu ) (96)
vector of the dependent statistical variables. This
has to be specified for each problem. Models Thus
based on transport equations for probability den-
sity functions generally give a differential equa- W (E) =W (ϕu ≤Φ≤ϕo ) =W (Φ ≤ ϕo )
tion for P (Φ1 , . . . , Φn ). − W (Φ≤ϕu ) =F (ϕo ) −F (ϕu ) (97)
4.1. Terminology
4.1.1. One-Dimensional Distribution and

Probability Density Functions
The example shown in Figure 14 will be used

to explain terminology. The temperature of the
fluid is treated as a macroscopic physical quan-
tity. Since the temperature varies between two
limits Tb > T > Ta , it is better to use a normal-
ized variable so that the statistical variable Φ is
defined as
T − Tb
Φ= (93)
Ta − Tb
The sample space for Φ (see Fig. 15) is a line on

which only values between 0 and 1 can be real-
ized. An event is defined as E ≡ ϕu ≤ Φ ≤ ϕo .
The probability of the occurrence of a particu-
lar event is between 0 and 1. When W (E ) = 0,
ϕu ≤ Φ ≤ Φo never occurs and when W (E ) = 1,
ϕu < Φ < ϕo always occurs. Probability defined
in this way does not predict E for the next experi-
ment but instead the fraction of occurrences of E
over a large number of experiments. Since each Figure 15. Representation of the distribution function (A)
event is linked to a defined area of the sample and the probability density function (B) of a statistical vari-
space, the probability of an event is the probabil- able
ity that a random variable lies in this area. The The ϕ axis represents the sample space for the statistical
probability of an event can be defined from the variable Φ. The values ϕo and ϕu confine a finite region
within the sample space.
distribution function of the random variables:
The fundamental characteristics of the distri-
F (Φ) ≡W (Φ≤ϕ) (94) bution function are easily derived by similar rea-
soning. Since in the general case W (Φ ≤ − ∞)
Since the normalized temperatures defined in = F (−∞) = 0 and W (Φ ≤ +∞) = F (+∞) = 1,
Equation (93) can only have values between then
0 ≤ Φ ≤ 1, then
W (E) =F (ϕo ) −F (ϕu ) ≥0 (98) For discontinuous distribution functions with

statistical variables which can only take discrete
and values (see Chap. 3) the above relationships can
be given with additional derivation steps [18],
F (ϕo ) ≥F (ϕu ) for ϕo ≥ϕu (99)
[19], [22]. Continuity of the distribution func-
tion is not a necessary condition for the above
The distribution function F (Φ) is therefore relationships.
a nondecaying function which grows from 0 at The relationships for transformations of dis-
ϕ = −∞ to 1 at ϕ = +∞ (Fig. 15 A). tribution functions and probability density func-
The probability density function of the ran- tions are easy to see from Figure 15 and Equa-
dom variable Φ is the derivative of the distributions (98) – (100). For example if the relation-
tion function with respect to the random variable ship ψ = f (ϕ) holds for a given transformation
(Fig. 15 B). of Φ, then the events Φ ≤ ϕ and Ψ ≤ ψ = f (ϕ) are
identical. From this F (Φ) = F (Ψ ) and according
d
P (Φ) = [F (Φ)] (100) to Equation (100)
dΦ
Using this result then d d dΦ
P (Ψ ) = F (Ψ ) = F (Φ) · =
dΨ dΦ dΨ
ϕo
P (Φ) dΦ = F (ϕo ) − F (ϕu ) dΦ
P (Φ) · (106)
ϕu dΨ
= W (ϕu ≤ Φ ≤ ϕo ) (101) Figure 14 shows that the distribution functions
According to Equation (101) the probability that and probability density functions can be depen-
a random variable falls in a particular area is dent on position and are thus not always homo-
equal to the integral of the probability density geneous. For the area at the edge of the jet close
function over that area. For an infinitely small to the nozzle exit an almost bimodal probability
area dϕ this then becomes density function is produced due to intermitten-
cies of the jet and the surrounding fluid. Further
W (ϕ≤Φ≤ϕ+dϕ) =P (Φ) dΦ (102) downstream in the middle of the turbulent jet
these intermittencies no longer affect the form
(cf. Section 2.2). The fundamental characteris- of the probability density function. Thus proba-
tics of P (Φ) can be derived from Equation (100). bility density functions hold for a given position
Since F (Φ) is a nondecaying function this gives at a given time; they will be written as P (Φ; x,
P (Φ) ≥0 (103)
t) from now on.
For engineering applications the probability
Further density functions themselves are not very illus-
trative. Statistical variables are usually described

+∞
in terms of expected values (see Section 2.2 and
P (Φ) dΦ=1 (104)
Chap. 3). These are easier to handle but have
−∞
a lower information content. The expected val-
since according to Equation (101) the probabil- ues of statistical variables (synonyms are mean
ity of the occurrence of the random variable in values, mathematical expectations, and first mo-
the area from −∞ to +∞ in the sample space ment) are given by
must be 1. The third fundamental characteristic
of the probability density function follows from
+∞
9 :
the monotonic approximation of the distribution Φ (x,t) = ΦP (Φ;x,t) dΦ (107)
function to 0 or 1 when | Φ | → ∞. Thus −∞
d For statistical steady-state processes or for

[F (Φ)]−∞ =P (Φ)−∞
dΦ d Φ/dt dΦ/dt the equivalent form of the av-
=
d
[F (Φ)]+∞ =P (Φ)+∞ = 0 (105)
eraging is
dΦ
continuous form. Therefore all values referred to

t+∆τ
9 : 1 here must be derived from discrete data. This has
Φ (x,t) = Φ (x,t) dt (108)
∆τ been done for the empirical models discussed in
t
Chapter 3 where discrete values of the statistical
For this a continuous function of Φ versus time variables were available.
is necessary as indicated in the plot of Φ against For n independent repetitions of an exper-
time given in Figure 14. iment under constant conditions the ensemble
Functions of statistical variables are them- mean value
selves statistical values, so that the operations
1
n
related to Equation (107) for deriving expected 9 :
Φ n= ϕi (114)
values of functions can be used n i=1
9 :

+∞ gives a good approximation of Φ when n → ∞.
Q (Φ) = Q (Φ) P (Φ;x,t) dΦ (109) In the examples discussed in Chapter 3 the
−∞ number of occurrences is so small that the mean
values from the individual data sets do not repre-
The definitions of Equations (107) and (109) resent the expected values but are statistical values.
spectively are analogously applicable to higher Similarly to Equation (114) the means of func-
moments tions Q (Φ) or higher moments are estimated,

+∞ c.f. Chapter 3 where the sums of squares of the
9 : deviations were used as estimates for the vari-
µn ≡ Φ (x,t)n = Φn P (Φ;x,t) dΦ (110)
−∞
ances. The probability density function is mea-
surable through the number of occurrences of ϕi
For example, the second moment around the in a given area ∆ϕ of the sample space. If this
mean (the variance) is also a characteristic of number is denoted as m (Φ, ∆Φ), the normalized
statistical quantities which is often used in engi- density of occurrences in the sample space pro-
neering applications (see Chap. 3): vides a good estimate for the probability density
9 9 : 2 : function:
Var (Φ) ≡ µ2 ≡ Φ− Φ
m (Φ, ∆Φ)
+∞
9 : 2 Pn (Φ) = ≈ P (Φ;x,t)
= Φ− Φ P (Φ;x,t) dΦ (111) n∆Φ
for n → ∞ (115a)
−∞
All of these quantities can be determined from The discrete form of the probability density
the probability density function. However, the function can also be expressed as
probability density function can only be given
1
n
approximately from a finite number of moments Pn (Φ) = δ (Φ − ϕi ) (115b)
n i=1
which are relatively easy to measure [49].
If a statistical quantity is split up into the ex- Here δ (a − b) is the impulse or Dirac delta func-
pected value and a fluctuating component Φf tion which is defined as the derivative of the
9 : Heaviside or step function:
Φ= Φ +Φf (112)
dH (a − b)
then from Equation (111) δ (a − b) = (116)
da
9 2 : 9 :
Var (Φ) = Φf and Φf = 0 (113a,b) with H (a − b) = 0 for a ≤ b and H (a − b) = 1 for
a > b.
Rules for measuring the statistical moments According to Equation (115 b) the discrete
of statistical steady-state processes are derived form of the probability density function in the
from Equation (108). The continuous function sample space for Φ is the number impulses of
Φ (x, t) is necessary for this. However measure- discrete occurrences normalized with respect to
ments of statistical variables are mostly avail- the total count. The discrete form of the distri-
able in the form of discrete values rather than in bution function
1
n
W (ψ≤Ψ ≤ψ+dψ) =P (Ψ ;x, t) dΨ
Fn (Φ) = H (Φ − ϕi ) (115c)
n i=1
However, this information is not sufficient. More
becomes a stepped curve as shown in Figure 16. information is required about the probability of
the joint events
Eϕ = (ϕ ≤ Φ≤ϕ+dϕ)
and
Eψ = (ψ≤Ψ ≤ψ+dψ)
This information can be derived from the joint

distribution function F (Φ, Ψ ; x, t) which has
characteristics analogous to those of the simple
distribution function:
0 ≤F (Φ, Ψ ) ≤ 1, nondecaying, (118a)
F (−∞, Ψ ) = F (Φ, −∞) = 0, (118b)
F (∞,Ψ ) =F (Ψ ) , and (118c)
F (Φ, ∞) =F (Φ) (118d)
The joint probability density function becomes

∂2
P (Φ, Ψ ;x, t) = [F (Φ, Ψ ; x, t)] (119)
∂Φ∂Ψ
which possesses the same fundamental charac-
teristics as the simple probability density func-
Figure 16. Discrete forms of the distribution function (A) tion:
and the probability density function (B)
The continuous functions are shown as dotted lines. P (Φ, Ψ ;x, t) ≥0 (120a)

P (Φ, Ψ ;x, t) dΨ dΦ = 1 (120b)
4.1.2. Multidimensional Distribution and
The simple probability density function or
Probability Density Functions
marginal distributions (the reduced information)
For the example shown in Figure 14 the normal- can be derived from the joint probability density
ized temperature alone is clearly not sufficient to function:

describe the state at a point x and time t. Other
P (Φ,Ψ ;x,t) dΨ =P (Φ;x,t) (121a)
variables such as the axial velocity U can be used

which is expressed in normalized form as
P (Φ,Ψ ;x,t) dΦ=P (Ψ ;x,t) (121b)
U − Ub
Ψ = (117)
Ua − Ub Conversely the joint probability density func-
tions cannot normally be derived from the
For the statistical variable Ψ the same defini- marginal distributions. Arguments analogous to
tions hold as previously for Φ so that those above may be used for the functions
Q (Φ, Ψ ).
W (ϕ≤Φ≤ϕ+dϕ) = P (Φ;x, t) dΦ
Covariances are another quality of joint prob-
and ability density functions:
9 :
Cov (Φ,Ψ ) = Φf Ψ f F (Ψ |ϕ) = P [(Ψ ≤ ψ) | (Φ = ϕ)]
+∞
+∞ ψ
9 : 9 : P (Ψ, Φ) dΨ
= Φ− Φ Ψ− Ψ = (127)
P (Φ)
−∞ −∞ −∞
·P (Φ,Ψ ;x,t) dΦdΨ (122) The usual definition of probability density func-
They are mostly given in normalized form as tion then gives the following:
correlation coefficients: d P (Ψ ,Φ)
P (Ψ |ϕ) = F (Ψ |ϕ) = (128)
dΨ P (Φ)
Cov (Φ,Ψ )
γ= (123)
[Var (Φ) Var (Ψ )]1/2 It is easy to show that the conditional distri-
bution functions and probability density func-
With the help of Equation (122) it is easy to tions exhibit the same characteristics as uncon-
show that − 1 ≤ γ ≤ 1. If a linear relationship of ditional ones. By using the same operations as
the form ψ = α + β ϕ exists, then | γ | = 1. above, the conditional expected value of a func-
For joint multidimensional probability den- tion Q (Ψ , Φ) can be derived
sity functions, transformation rules are also
valid. Using the same reasoning as with one-
+∞
9 :
dimensional probability density functions and Q (Ψ, Φ) |Φ = ϕ = Q (Ψ, Φ) P (Ψ |ϕ) dΨ (129)
assuming that ξ = ξ (ϕ, ψ) and θ = θ (ϕ, ψ) −∞
From Equation (128) it can be seen that the joint

P (Ξ,Θ) =P (Φ,Ψ ) ·|J|−1 (124) probability density function P (Ψ , Φ) can be ob-
where J is the Jacobi matrix of the system of tained from the conditional probability density
transformation equations. function P (Ψ | ϕ) and the marginal distribution
P (Φ). This important result is used in the de-
termination of expected values and leads to a
4.1.3. Conditional Probability Density further important result:
Functions +∞
+∞
9 :
Q (Ψ, Φ) = Q (Ψ, Φ) P (Ψ, Φ) dΨ dΦ
Conditional probability is a prerequisite for the −∞ −∞
derivation of transport equations for probabiliby  +∞ 

+∞
 
density functions. It denotes the probability of
= P (Φ) Q (Ψ, Φ) P (Ψ |ϕ) dΨ dΦ
an event, for example Ψ ≤ ψ, subject to the con-  
−∞ −∞
dition that the event ϕ ≤ Φ ≤ ϕ + dϕ occurs. It

+∞
is given by the probability for a general event
= P (Φ) <Q (Ψ, Φ) |Φ = ϕ>dΦ (130)
divided by the probability of the condition:
−∞
W [(Ψ ≤ ψ) | (ϕ ≤ Φ ≤ ϕ + dϕ)]
W (Ψ ≤ ψ) (ϕ ≤ Φ ≤ ϕ + dϕ)
= (125)
W (ϕ ≤ Φ ≤ ϕ + dϕ)
4.2. Transport Equations for
Consequently Single-Point Probability Density
Functions
W [(Ψ ≤ ψ) | (ϕ ≤ Φ ≤ ϕ + dϕ)]
ψ
ϕ+dϕ Before going into some examples, the following
P (Φ,Ψ ) dΦdΨ
−∞ ϕ sections will briefly discuss transport equations
= (126) for single-point probability density functions

ϕ+dϕ
P (Φ) dΦ starting from the general conservation equa-
ϕ
tions. Only the important relationships will be
The conditional distribution function is the limit described. A more detailed discussion of the
of the conditional probability for dϕ → 0 so that general conservation equations is given in [48].
The state of a reacting fluid mixture (e.g., The formulation of Equations (132) – (134) im-
the contents of the reactor shown in Fig. 14) plies the continuity equation; is the density; mi
is accurately defined by the velocity U (x, t), is the mass fraction of component i; τij is the vis-
the pressure p (x, t), the mass fraction of the cous stress tensor; gi is the specific mass force
chemical species present in the mixture mi (x, t), in the xi direction (e.g., g1 , where g is the ac-
i = 1, . . . , N, and the specific enthalpy h (x, t). celeration due to gravity); Si is the reaction rate
A complete statistical single-point description and Sh the rate of enthalpy conversion produced
of the mixture is given by the joint prob- by pressure changes, viscosity effects etc.; J m is
ability density function P (U, Φ; x, t) where the mass flux of the chemical species and J h is
U = (U 1 , U 2 , U 3 ) and Φ is a vector of length the enthalpy flux, based on molecular transport
N + 2 which includes the rest of the scalar quan- mechanisms, like τij they are functions of local
tities. Thus the required function is a surface in physical quantities and their gradients.
the (N + 3 + 2)-dimensional Euclidean space. Equations (131) – (134) can be closed by a
The relationship between the instantaneous thermal equation of state
values of the variables stated above is given
by the laws of conservation of total mass, mo- = (mi , h, p) (136)
mentum, and mass of the individual chemical
species, and by the enthalpy. These can be given The expressions for the sources Si and Sh are
in the form [48], [50], [51]: also generally functions of the scalar quantities:
Si =Si (mi , h, p) (137a)

Accumulation + Change due to convective transport =
Change due to molecular transport + Source
∂p
Sh =Sh mi , h, p, (137b)
∂t
This leads to
The assumptions and conditions included in
∂ ∂
+ (Uk ) = 0 (131) this system of equations are discussed fully in
∂t ∂xk
[48], [50–52], see also Chapter 5. The system
for the total mass, of Equations (131) – (137) is deterministic, this
means that a determined solution exists for each
DUi ∂τik ∂p set of determined boundary conditions. The so-
= − + gi , i = 1, 2, 3 (132)
Dt ∂xk ∂xi lution of this system of equations for determin-
for the component of the momentum, istic variables is illustrated with some examples
in Chapter 5. Problems arise for statistical vari-
Dmi ∂Jk i
m ables [52] which can only be solved for simple
=− + Si , i = 1, ...,N − 1 (133) cases [53], [54] or by introducing far-reaching
Dt ∂xk
assumptions (see Chap. 5). The system of con-
for the mass of the individual chemical species, servation equations serves as a starting point for
and finally the derivation of the transport equations for the
probability density functions which are used to
Dh ∂Jkh
= − + Sh (134) overcome the principle problems for solving this
Dt ∂xk
set of equations for statistical variables.
for the enthalpy.
In Equations (132) – (134) the operator D de-
notes the substantial derivative: 4.2.1. General form of the Transport
Equations for Probability Density Functions
D ∂ ∂
= − Uk (135)
Dt ∂t ∂xk Equations (131) – (137) show that the state of
The Einstein summation convention is also used, a chemically reacting system at a position x =
for example: (x 1 , x 2 , x 3 ) and time t is determined by the veloc-
ity vector U = (U 1 ,U 2 ,U 3 ) in the sample space
∂ ∂ ∂ ∂ of velocity (Section 3.1.2.1 and Fig. 7) and the
(Uk ) ≡ (U1 ) + (U2 ) + (U3 )
∂xk x1 x2 x3 vector of scalar quantities Φ = (m1 , . . . , mN , h)
of length σ in the sample space of scalar quan- The characteristics described in Sections 4.1.1,
tities. U and Φ are vectors of random variables, 4.1.2, 4.1.3 apply to these functions. In the ter-
i.e., random vectors. This formulation holds for minology of probabilities these functions predict
low Mach numbers. the fraction of occurrences of discrete values u
The state of the reacting system represents a and ϕ for a large number of occurrences.
measured point in the three-dimensional veloc-
ity space of the vector V and likewise a measured
point in the Euclidean σ-dimensional space of
the vector Φ.
For a homogeneous mixture at rest with con-
stant enthalpy, Equation (133) gives
dmi
= Si (138)
dt
A chemical reaction can be represented in the
composition space as a trajectory between two
measured points. A system with two chemical
species is shown in Figure 17. The reaction rate
is the velocity in the composition space, and the
reaction rates of the individual chemical species
are given by the tangents to the trajectory in
the direction of each species. Since the state of
the system can be described by a vector with Figure 17. Chemical reactions for a system with two chem-
its end point in the plane of the required prob- ical species represented as transport in the sample space of
ability density function, changes of state due to the concentration (Φ1 , Φ2 ) of the species
chemical reactions are therefore trajectories in S 1 and S 2 are the partial derivatives of the trajectory in the
Φ1 and Φ2 direction, the subscripts 0 and e denote initial
this plane. Chemical reactions that constitute the and final states, respectively.
source terms in the conservation equations of the
chemical species (Eq. 133) are contained in the A transport equation for the joint
transport equations for the probability density velocity – composition probability density func-
functions merely as transport in the composition can be derived with help of Equations
tion space. Similarly, forces which are the source (132) – (134) and the terminology described in
terms in the momentum conservation equations Section 4.1. This method is one possibility for
are expressed in the transport equations for prob- deriving the transport equation for probability
ability density functions as transport in the ve- density functions. This will be used in prefer-
locity space. These are the main differences bet- ence to other methods [18], [55–58] because of
ween the simple conservation equations and the its simplicity.
transport equations for the probability density Equations (132) and (133) are rewritten as
functions. The latter do not include forces or Equations (140) and (141), respectively:
chemical reactions as sources.
DUi
Both U and Φ are necessary to complete = Ai (140)
Dt
the information. The complete information at
position x = (x 1 , x 2 , x 3 ) and time t is repre- DΦα
= Θα (141)
sented by a measured point in Euclidean (σ + 3)- Dt
dimensional space. Consequently, the objec- where
tive of the complete description is a (σ + 3)-
dimensional distribution function F (U, Φ; x, t) ∂τik ∂p
Ai (x, t) = − + gi and (142a)
or the corresponding probability density func- ∂xk ∂xi
tion: ∂Jkα
Θα (x, t) = − + Sα (142b)
∂xk
∂ σ+3
[F (U ,Φ;x,t)]
∂U1 ∂U2 ...∂Φn+1 For any function Q (U, Φ) averaging according
= P (U ,Φ;x,t) (139) to Equation (109) gives
9 ∂Q (U , Φ) :
9 DQ (U , Φ) : ∂ Ak
= (Φ) Q (U , Φ) P dU dΦ ∂Uk
Dt ∂t
∂Q (U , Φ) 9 :
∂ = Ak |u, ϕ P dU dΦ (147)
+ (Φ) Uk Q (U , Φ) P dU dΦ ∂Uk
∂xk
(
∂P If Equation (147) is partially integrated, then
= Q (U , Φ) (Φ) + (Φ)
∂t 9 ∂Q (U , Φ) :
Ak =IU −
) ∂Uk
∂P
Uk dU dΦ (143) ∂ 9 :
∂xk Q (U , Φ) Ak |u, ϕ P dU dΦ (148)
∂Uk
In Equation (143) and in the following discus- where
sions, P will be used to represent P (U, Φ; x, t).
In addition, dU will be used to describe the vec- IU =
tor dU 1 , dU 2 , dU 3 and dΦ for dΦ1 , . . . , dΦN +1 .
∂ 9 :
The integral sign in Equation (143) will also (Φ) Q (U , Φ) Ak |u, ϕ P dU dΦ
∂Uk
be interpreted in this way. The continuity equa-
tion (Eq. 131) is used to derive the expression An analogous procedure for the second term on
DQ(U ,Φ) the right-hand side of Equation (145) gives
Dt in Equation (143).
A second independent expression for 9 ∂Q (U , Φ) :
DQ(U ,Φ) Θω = IΦ −
∂Φω
Dt is obtained if Q (U, Φ) is differ-
∂ 9 :
entiated with respect to U and Φ (the Einstein Q (U , Φ) Θω |u, ϕ P dU dΦ (149)
∂Φω
summation convention is used for ω in the same
way as for k in Eqs. 131 – 135). where
DQ (U , Φ) IΦ =
Dt
∂ 9 :
∂Q (U , Φ) DUk ∂Q (U , Φ) DΦω (Φ) Q (U , Φ) Θω |u, ϕ P dU dΦ
= · + · (144) ∂Φω
∂Uk Dt ∂Φω Dt
It can be shown that the integrals IU and
If Equations (140) and (141) are used, the sub- I Φ disappear for a wide class of functions
stantial derivatives can be substituted with the Q (U, Φ). The general condition for this is that
respective right-hand sides. Thus, the functions are bounded and continuous [19].
With this a second independent expression for
9 DQ (U , Φ) : DQ(U ,Φ)
Dt is obtained from Equation (145):
Dt
9 ∂Q (U , Φ) : 9 ∂Q (U , Φ) : 9 DQ (U ,Φ) :
= Ak + Θω (145)
∂Uk ∂Φω Dt

∂ 9 :
The terms on the right-hand side of Equation = − Q (U , Φ) Ak |u,ϕ P dU dΦ
∂Uk
(145) can be rewritten as conditional expected
∂ 9 :
values by using Equation (130). For the first − Q (U , Φ) Θω |u,ϕ P dU dΦ
∂Φω
term of the right-hand side of Equation (145) (150)
this gives
Subtraction of Equation (150) from Equation
9 ∂Q (U , Φ) : (143) gives
Ak (
∂Uk ∂P ∂P
Q (U , Φ) (Φ) + (Φ) Uk +
9 ∂Q (U , Φ) : ∂t ∂xk
= Ak |u, ϕ P dU dΦ (146)
∂Uk
∂ 9 :
Since the differential quotient ∂Q (U, Φ)/∂Uk is ∂Uk
(Φ) Ak |u, ϕ P +
a known function of u and ϕ for a given u and
)
ϕ then from Equation (146) ∂ 9 :
(Φ) Θω |u, ϕ P dU dΦ = 0 (151)
∂Φω
All the terms in the curved brackets are inde- described exactly in the context of the method
pendent of Q (U, Φ). If Q (U, Φ) is the type of of description given here. These processes are
function where the integrals Iu and I Φ disap- transport in physical space (first and second
pear, then a sufficient condition to fulfil Equa- terms), transport in the velocity space due to
tion (151) is that the sums in the curved brackets gravitational forces and average pressure gra-
are zero. With this the transport equation for the dient (third term), and transport in the composi-
joint probability density function P (U, Φ; x, t) is tion space by chemical reactions (fourth term).
All of these processes can be described without
∂P ∂P
(Φ) + (Φ) Uk any model assumptions.
∂t ∂xk The expressions on the right-hand side of
∂ 9 : ∂
= − (Φ) Ak |u,ϕ P − Equation (155) describe transport in the velocity
∂Uk ∂Φω space due to momentum transfer at the molecu-
9 :
· (Φ) Θω |u,ϕ P (152) lar level as well as transport in the composition
For further discussion of this transport equa- space due to molecular diffusion. For a turbulent
tion, Ai and Θα are replaced by their respective flow the decay of turbulent fluctuations is caused
definition functions: by these mechanisms. Viscous forces are respon-
sible for the dissipation of turbulent (statistical)
9 : 9 ∂Jkα : fluctuations in velocity. Molecular diffusion is
(Φ) Θα |u,ϕ = − + (Φ) Sα (Φ) |u, vecϕ
∂xk responsible for the dissipation of turbulent fluc-
9 ∂Jkα : tuations in scalar quantities.
= − |u,ϕ + (Φ) Sα (Φ) (153)
∂xk Before Equation (155) can be solved, these
terms must be defined or approximated using
Using the decomposition p f ≡ p− p gives models. The following sections will describe
9 : with some examples how this can be done.
(Φ) Ai |u,ϕ
9 :
9 ∂τik ∂ p ∂pf :
= − − + gi |u,ϕ
∂xk ∂xi ∂xi 4.2.2. Limitations of Single-Point
9 :
9 ∂τik : ∂ p 9 ∂pf : Probability Density Functions
= |u,ϕ − − |u,ϕ
∂xk ∂xi ∂xi
9 : Solution of Equation (155) gives the joint prob-
+ gi |u,ϕ (154)
ability density function P (U, Φ; x, t) of the ran-
Substitution of these expressions into Equation dom vectors U and Φ at position x = (x1 , x 2 , x 3 )
(152) gives and time t. This result contains the complete sta-
9 :
tistical information at a defined position for a

∂P ∂P ∂ p given time. Even this information includes only
(Φ) + (Φ) Uk + (Φ) gk −
∂t ∂xk ∂xk a partial view of the statistical process being
∂P ∂ considered. The functionals P (U, Φ) described
+ [ (Φ) Sω (Φ) P ] in Section 2.2 or multipoint probability density
∂Uk ∂Φω
functions, such as the two-point probability den-
∂ 9 ∂τlk ∂pf :
=− + |u,ϕ P sity function P (U1 , Φ1 ; x1 , t 1 , U2 , Φ2 ; x2 , t 2 )
∂Uk ∂xl ∂xl
which can be derived from them, provide more
∂ 9 ∂Jkω :
+ |u,ϕ P (155) comprehensive information. The meaning of
∂Φω ∂xk
these multipoint probability density functions
This is the general form of the transport equa- can be illustrated by the example shown in Fig-
tion for the probability density functions in the ure 14. The structure of the vortices in the tur-
combined velocity – composition space (in the bulent flow of the jet stirred reactor is dependent
first term of the right-hand side k and l must on position and time. The “lifetime” and “tracks”
be summed according to the Einstein summa- of the vortices being transported in the flow are
tion convention). Equation (155) can be solved crucial for the chemical reaction. They give an
if the conditional expected values on the right- indication of the degree of mixing and the “seg-
hand side are known. All physical processes re- regation” of the flow. (Segregation denotes the
presented by the terms on the left-hand side are state of a fluid in which individual fluid parcels
maintain their identities when passing through which is evenly distributed between 0 and 1. The
the reactor and do not exchange properties with amplitude of the physical variable is given by
the surrounding fluid [24], [46].) Second-order
1 1
moments (the correlation functions) are used to Φ (x, t) = + sin (2πν t + x1 λ+ζ) (158)
2 2
describe mixing and segregation:
9 9 : If the amplitude is measured sufficiently often
RΦ,Ψ = Φ (x1 ,t1 ) − Φ (x1 ,t1 ) (Ψ (x2 ,t2 ) for a given x, t then the probability density func-
9 : : tion can be obtained from the density of mea-
− Ψ (x2 ,t2 ) sured points in the sample space (Eq. 115 a). The

9 : density of the measured points is given by
= Φ (x1 ,t1 ) − Φ (x1 ,t1 ) (Ψ (x2 , t2 )

9 : ∆Φ ∂Φ 1. /−1/2
≈ = 1 − (2Φ − 1)2
− Ψ (x2 , t2 ) ∆ζ x,t ∂ζ x,t π
·P (U 1 ,Φ1 ; x1 , t1 ,U 2 ,Φ2 ; x2 , t2 ) dΦdΨ
The single-point probability density function is
For Φ = Ψ the autocorrelation functions are ob- thus independent of the frequency ν and the
tained which provide data about the vortex struc- wavelength λ. In addition, information about
ture for a physical property of the fluid e.g., the values such as (∂Φ/∂x)2 cannot be derived
velocity. Time and length scales for the turbulent from the single-point probability density func-
exchange of the considered property can be de- tion. This value is, however, dependent on
rived from the autocorrelation functions [49], the wavelength, (∂Φ/∂x)2 = 1/2(π 2 /λ2 ), com-
[59–61]; these play an important role in the mod- pare Equation (158). The measured single-point
eling of turbulent processes. probability density function gives no informa-
The dimensionality of the transport equations tion about the spatial and time propagation of
for multipoint probability density functions is the disturbances.
proportional to the number of points (Eq. 155). In spite of these limitations, single-point
The problem soon becomes unmanageable, even probability density functions are improvements
with a small number of scalar quantities and over the handling of statistical variables with the
points. moments of probability density functions.
Single-point probability density functions
can be derived from probability density func-
tionals or multipoint probability density func- 4.3. Examples of Calculating
tions: Probability Density Functions
P (Φ1 ; x, t)
For further discussions Equation (155) is rewrit-

+∞
ten as
= P (Φ1 ; x1 , t1 ,Φ2 ; x2 , t2 ) dΦ2 (157)
−∞ ∂P (U , Φ;x,t) ∂P (U ,Φ;x, t)
(Φ) + (Φ) Uk
∂t ∂xk
Single-point probability density functions only
∂ 9 :
give limited information about the field of ran- + (Φ) Ak |u,ϕ P (U ,Φ;x,t)
∂Uk
dom variables. They give complete statistical in-
∂ 9 :
formation at a given site and time but not joint + (Φ) Θω |u,ϕ P (U ,Φ;x,t) =0 (159)
∂Φω
information about two sites and/or two times.
For the example shown in Figure 14 the single- where Ai and Θα are given by Equations (142 a,
point functions therefore contain no information b). Equation (159) is deterministic, i.e., deter-
about the length or time scales of the statistical mined solutions exist for given initial and bound-
(turbulent) fluctuations. ary conditions. The conditional expected val-
This deficiency can be illustrated by a simple ues Ai | u, ϕ and Θα | u, ϕ are not statistical
example. Suppose that a turbulent fluctuation of values. In the general case they are unknown
a physical variable is in the form of a sine wave functions of the variables u and ϕ. For the
of frequency ν and wavelength λ. The statisti- general case (i.e., for fields of statistical vari-
cal character is due to a statistical phase shift ζ ables) model assumptions must be introduced
so that Equation (155) or (159) can be solved. characteristics are transported into the control
For deterministic systems Equations (155) and volume while the characteristics at the down-
(159) can be treated without further assumptions stream boundary surface relate to the internal
because Ai | u, ϕ = Ai (u, ϕ) and Θα | u, ϕ = properties (Fig. 18). Viscosity, pressure, and
Θα (u, ϕ), respectively. gravitational forces and other transport pro-
cesses (with the exception of convection) are
ignored.
4.3.1. Solutions for Deterministic Systems For expediency Equation (159) is integrated
with respect to the volume:
4.3.1.1. Age (Residence Time) Distributions
in Chemical Reactors ∂P ∂P
(Φ) dV + (Φ) u dV
∂t ∂x
V V
The individual types of chemical reactors are
∂
normally treated as deterministic systems al- + [ (Φ) Sω (u, Φ) P ] dV =0 (160)
∂Φω
though under industrial conditions flow is not V
laminar. This simplification is justified if the tur- Using the Gauss – Ostrogradski integrals, Equa-
bulent time scales for the reactions occurring tion (160) can be rewritten as
in the reactor lie several orders of magnitude
0
above that for the turbulent mass or momen- ∂
(Φ) P dV + (Φ) uP dF
tum exchange. The reactor contents have then ∂t
V F
reached the state of molecular mixing, with-
∂
out noticeable chemical conversion having taken + [ (Φ) Sω (u, Φ) P ] dV =0 (161)
∂Φω
place. Distribution functions or probability den- V
sity functions may be given for the residence
time, for example, and can thus indicate the where integration has to be carried out for the
probability for the residence time (the age α) surfaces perpendicular to the direction of the
of a volume element in an interval dα around α; flow.
residence time distribution functions are easily If the age (residence time) distribution is con-
derived from Equation (159). sidered, the variables u, Φ in P (u, Φ) and S (u, Φ)
must be substituted by the age α. Since intervals
in the age space are time intervals, the velocity in
the age space is equal to ∂α/∂t = S (α) = 1. With
this result and for constant density the following
expression can be derived from Equation (161):
∂
P (α) dV + uP (α) dzdy − uP0 (α) dzdy
∂t
∂
+ P (α) dV = 0 (162)
∂α
In the steady state, Equation (162) is easy to
solve since the first term on the left-hand side is
zero:
∂ 1
[P (α)] = [P0 (α) − P (α)] (163a)
Figure 18. Mathematical definition of an ideally mixed re- ∂α τ
actor
The subscripts 0 and e denote inlet and outlet, respectively. where τ = u dz dy/dV is the mean hydrody-
namic residence time. With the boundary
condition P0 (α) = δ (α − 0) and the condition
Ideally Mixed Stirred-Tank Reactor. In
+∞
the mathematical sense an ideally mixed re- P (α) dα = 1 (cf. Eq. 104) then
0
actor is a one-dimensional control volume with 1 α
homogeneous internal properties. The upstream P (α) = exp − (164)
τ τ
δ (α − 0) denotes the impulse function or Dirac Figure 20 shows residence time distribution
delta function (Section 4.1.1). functions and distribution functions for a cas-
cade of n ideally mixed reactors for various val-

+∞
ues of n. It is easy to prove from Equation (166)
αδ (α − b) g (α) dα=ag (b) ; b≥0
that simple relationships exist between the de-
0
terministic moments
is used to integrate Equation (163 a). Equation
(164) is the familiar residence time distribution
+∞
function for ideally mixed reactors (denoted as m1 = tw (t) dt=t̄ and

w (t) in Section 3.3.2.2). If it is transformed to 0
normalized age (θ = α/τ ) then
+∞
α m2 = (t − m1 )2 w (t) dt
∂α 1
P (θ) ≡ w (θ) = P (α) = exp − τ 0
∂θ τ τ
= exp (−θ) (165) (see Section 3.3.2.2) and the number of elements
In Equation (165) the distinction between age α in the cascade. Thus
and time t is no longer maintained. The integral τ2
over the residence time distribution m1 =nτi = τ and m2 =nτi2 = (167a,b)
n

+∞
Given that a reactor can be represented by a cas-
W (t) = w (t) dt or
cade of ideal stirred-tank reactors, the number
0

+∞ of elements required to represent the reactor can
W (θ) = w (θ) dθ easily be determined with Equation (167) from
0
the first two deterministic moments of the mea-
sured residence time distribution, namely from
is denoted as distribution function. Figure 19 the mean residence time and the variance.
shows the residence time distribution and the
distribution function for an ideal stirred-tank re- LIVE GRAPH
Click here to view
actor.
LIVE GRAPH
Click here to view
Figure 20. Residence time distribution for a cascade of n

ideal stirred-tank reactors
Figure 19. Residence time distribution w (t) and distribution For the nonsteady case, Equation (162) be-
function W (t) for the ideal stirred-tank reactor comes:
Alternative boundary conditions lead to al- ∂ ∂
ternative solutions of Equation (163 a). For ex- [P (α;t)] + [P (α;t)] =
∂t ∂α
ample, if n ideally mixed reactors are linked 1
[P0 (α;t) − P (α;t)] (163b)
in a cascade, then Pn−1 (α) = P0n (α) etc. With τ
P01 (α) = δ (α − 0) and τ 1 = τ 2 = · · · τn = τ /n, the
The general solution for Equation (163 b) can
solution of Equation (163 a) then becomes
easily be found by using Laplace or Fourier

1 t(n−1) t
wn (t) = nn exp −n (166)
(n − 1)! τ n τ
transforms and applying the concept of gener- boundary condition P0 (α) = δ (α − 0) is Equa-
alized functions [62], [63]: tion (166) with n → ∞, i.e., an impulse function
at t/n τi = 1.
t Equation (169 b) can also be solved analyti-
P (α;t) = exp − P0 (α − t)
τ cally, the general solution is
1 α
+ exp − [H (α) − H (α − t)] (168)
τ τ 1
P (α;x) = Ω α− x (170)
u
The solution holds for the initial conditions
P (α; t)t=0 = P (α) and the same boundary con- where Ω is any differentiable function [64].
ditions as above; H (α) denotes the Heaviside or Equation (170) clarifies the behavior of ideally
step function (cf. Eq. 116). It can easily be shown nonmixed reactors. A fluid flowing into the re-
that Equation (168) becomes Equation (165) for actor with a given age distribution retains the
t → ∞. form of the age distribution. The age of the in-
dividual fluid elements increases uniformly by
Ideally Nonmixed Reactor (Ideal Tubu- the time necessary to pass the distance x, t = x/u.
lar Reactor). An ideally nonmixed reactor is For example, at the reactor inlet (i.e., x = 0)
a onedimensional flow system with inhomoge-
neous internal properties. Analogously to the Ω (α−0) = δ (α−0)
ideally mixed reactor, in this one-dimensional
model viscosity, pressure, gravitational forces, at the reactor outlet (i.e., x = L)
and other transport processes (excluding con-
L
vection) are neglected. The changes in the in- P (α;x) = δ α− = δ (α−τ )
u
ternal properties occur as a result of physical or
chemical processes. This is identical to Equation (166) for n → ∞.
The age (residence time) distribution of this If an ideally mixed reactor with a mean resi-
model is obtained from Equation (159): dence time τ 1 and an ideally nonmixed reactor
with a mean residence time τ 2 are connected to-
∂
[P (α;x,t)] +u
∂
[P (α;x,t)] gether, then Ω (α − 0) = H (α − 0) exp (− α/τ 1 ),
∂t ∂x and from Equation (170)
∂
+ [P (α;x,t)] =0 (169a)
∂α 1 1
P (α) =H (α − τ2 ) · exp − (α − τ2 )
τ1 τ1
In the steady state, Equation (169 a) becomes
It is seen that the age distribution of the ide-
∂ ∂
u [P (α;x)] + [P (α;x)] = 0 (169b) ally mixed reactor is shifted by the mean resi-
∂x ∂α
dence time τ 2 of the nonmixed reactor. Figure 21
The partial differential Equation (169 b) can be shows the residence time distribution and the
solved in a number of ways. The calculation do- distribution function for this case.
main (the tubular reactor) can be divided into
a number of finite control volumes, for each
of which Equation (169 b) holds. The individ-
ual control volumes have the same characteris-
tics as the ideally mixed reactor. The same op-
erations as discussed above can be carried out
for each of the finite control volumes and an
equation of type (163 b) is obtained for each
control volume. Physically this means that an
ideally nonmixed reactor is represented by a
cascade with an infinite number of elements.
Numerically this means that the partial differ- Figure 21. Residence time distribution w (t) and distribution
ential Equation (169 b) is solved with an up- function W (t) for an ideal stirred-tank reactor connected in
wind difference scheme. The solution for the series with an ideal tubular reactor
Next Page
Reactors with Finite Mixing. Reactors Equation (169 b) is now supplemented by the
∂
with finite mixing can be thought of as the term ∂α [P (α)diff ] so that the transport equa-
transport mechanisms discussed in page 205 tion for the age distribution in the steady-state
combined with another transport mechanism. case takes the form
Usually this is treated in the form of a “diffu-
sion” mechanism in which the relevant diffusion ∂ ∂
[P (α;x)] + u [P (α;x)]
coefficient has the character of a model param- ∂α ∂x
eter (dispersion model). ∂2
Diffusion is expressed in the transport equa- +D [P (α)] = 0 (173)
∂x2
tion for the probability density function as an
additional transport term in the sample space of Equation (173) can be solved analytically for
scalar values (see Eq. 155, last term on the right- simple boundary conditions. For the boundary
hand side and Eq. 159). The basic treatment of condition
these terms is discussed in [19], [65–67], see
∂
also Section 4.3.2.1. Here, a heuristic method [P (α;x)] = 0 for x = 0 and x = L
∂x
will be used to find a transport equation for the
age distribution in reactors where diffusion is this gives
superimposed on convective transport. 1
The problem consists of deriving a term for 1 Pe (1 − α/τ )2 P e
P (α) = exp − (174)
the additional transport in the age space for a 2 πτ α 4α/τ
superimposed diffusion process. In chemical re-
actors with finite mixing, fluid parcels are con- where Pe is the axial Péclet number, Pe = u L/D
vected by turbulent motion, i.e., this process con- (Section 3.3.2.2), it is often called the Boden-
sists of the diffusion of fluid elements which can stein number, Bo.
be handled in the same way as molecular diffu- Figure 22 shows the residence time distribu-
sion. tions (Eq. 174) for different Bodenstein num-
The fluid parcels experience a displacement bers. For large Bodenstein numbers the figure
due to the “diffusion” in addition to the dis- resembles the distributions for the cascade of
placement resulting from convective transport ideally mixed reactors (Fig. 20). This similar-
with velocity u. Analogous to molecular motion, ity is inevitable, because the cascade of ideally
the probability density function for the displace- mixed reactors represents the numerical solu-
ment by diffusion is a normal distribution [68]: tion of the transport Equation (169 b) as n → ∞
and Equation (173) will be identical to this for

1 x2 D → 0. The deterministic moments m1 and m2
P (x)diff = √ exp − (171)
2 πDt 4Dt can be calculated from Equation (174):

where D is the diffusion coefficient. The proba- 2
m1 = 1+ τ and
bility density function for the displacement x of Bo
the fluid elements due to diffusion can be rewrit-
ten as the probability density function for the age 2 8
m2 = + τ2 (175a,b)
with the help of the transformation rule given by Bo Bo2
Equation (106) and α = x/u: For Bo → ∞, the first moment corresponds to the
dx u mean hydrodynamic residence time (Eq. 167 a).
P (α)diff = P (x)diff · = √ If Equation (175 b) is compared with Equation
dα 2 πDα
(167 b) on the basis of the similarity of the solu-
x2
·exp − (172) tions of the age distribution for large Bodenstein
4Dα
numbers, then the relationship
Equation (172) represents the age distribution
1 2 8
for a diffusion process that is analogous to = +
n Bo Bo2
molecular diffusion. The term required for the
transport equation is the differential of this dis- can be derived. For large Bodenstein numbers
tribution in the age space, i.e., ∂α∂
[P (α)diff ]. (i.e., little axial dispersion), n ≈ Bo/2.
Previous Page
function of the crystal size and the concentration

of the substrate c. Often S (L) = S 0 (c)Lb is used
so that Equation (176) becomes
∂ . / 1
S0 (c) Lb P (L) = [P0 (L) − P (L)] (177)
∂L τ
If the feed does not contain solids, P0 (L )
= δ (L − 0). Assuming that the substrate concen-
tration is approximately constant, the solution of
Equation (177) is

L 1−b
Figure 22. Residence time distribution τ w (t) for a reactor P (L) = C1 L −b exp − (178)
with axial mixing S0 (c) τ (1 − b)
Bo = Bodenstein number; n = number of elements of a cas-
cade of ideally mixed reactors to represent the reactor with where C 1 is an integration constant. For b = 0
the corresponding Bodenstein number (McCabe ∆L law) Equation (178) becomes

This discussion shows that the definition or L
P (L) = P (L 0 ) exp − (179)
experimental determination of model parame- S0 (c) τ
ters can be relatively simple even for complex
models. In the above case the formal diffusion where C 1 is substituted by the initial condition
coefficient, the axial mixing coefficient, or the P (L 0 ), i.e., the number density of the nuclei in
Bodenstein number can be simply determined the crystallizer. Equation (179) represents the
from the second deterministic moment of the age number density distribution of crystal sizes for
(residence time) distribution. Furthermore, com- this simple case (b = 0).
plex processes may be built up from a number
of simple elements. In the case described above,
a reactor with finite axial mixing is constructed 4.3.2. Solutions for Statistical Systems
from a cascade of ideally mixed reactors; a sim-
ple relationship exists between the number of The discussion in Section 4.3.1 was confined to
elements and the model parameters of this com- deterministic systems for which either the phys-
plex one-dimensional process. Further examples ical quantities are not subject to turbulent (statis-
for the representation of complex processes by tical) fluctuations or for which the time scales of
simple elements are found in [4], [11], [12], [24], the individual physicochemical processes are of
[46], and text books on chemical reaction engi- vastly different orders of magnitude. In the ide-
neering, see also Chapter 5. ally mixed reactor the time scale for the chemi-
cal reactions is so large in comparison with that
of the turbulent mass exchange that the reactor
4.3.1.2. Size Distribution in Continuously contents can be considered as being mixed at
Operating Crystallizers the molecular level without having reacted. The
point of this discussion was to bring the trans-
The model used for the representation of a port equations for the probability density func-
continuously operating crystallizer is an ideally tions (Eqs. 155, 159) into a simple form which
mixed reactor. The supersaturated solution is fed is closed without any model assumptions and is
into the crystallizer and the substrate grows on also easy to solve analytically in simple cases.
the existing crystals. Using the operations dis- These simplifications do not apply to sta-
cussed in page 205 this gives the transport equa- tistical systems, such as the chemical reac-
tion tions in a turbulent single-phase flow shown
∂ 1 in Figure 14. The transport equations for the
[S (Φ) P (Φ)] = [P0 (Φ) − P (Φ)] (176)
∂Φ τ probability density function in the combined
The property under consideration is the crystal velocity – composition space have advantages
size L. The rate of crystal growth can be de-
scribed empirically by S (L) = S (L, c), i.e., it is a
for describing such processes because, in con- to chemical reactions) are closed and do not re-
trast to the simple equations for turbulent react- quire any model assumptions.
ing flows (see Section 5.1.2), the most important The term (Φ) is a known function
processes (convection and chemical reaction) (e.g., a form of thermal equation of state,
can be handled without model assumptions. As- Eq. 136) and Sα (Φ) is given by Equa-
sumptions must be introduced for the dissipation (137 a). For example, for a bimolecu-
tion of turbulent velocity fluctuations or fluctu- lar reaction A + B → C + D this relationship is
ations of scalar quantities by molecular mixing. S (A) = r A = − k mA mB where the rate coeffi-
These are manifested in the transport equations cient k can often be represented by three pa-
for probability density functions as transport in rameters in the form k = k 0 T α exp (− E a /RT ).
the velocity or composition space. If the equations for the reaction rate and the rate
A method of solving the transport equations coefficients are not considered to be a model,
must also be found. Analytical solutions can then the representation of the reaction rates in
only be obtained for very simple flows, simple Equation (155) is free of models.
models, or deterministic systems under simple No explicit equation for the mean pres-
conditions (Section 4.3.1). In general, Equation sure is contained in the system of Equa-
(155) must be solved numerically with the rel- tions (131) – (137). The momentum conserva-
evant terms on the right-hand side being mod- tion equations (Eq. 132) contain only the pres-
eled. Methods using finite differences (see Sec- sure gradient in each of the directions under
tion 4.3.1.1) can be ruled out for this since consideration. Equations (131) – (137) assume
P (U, Φ; x, t) is a function of (σ + 6) indepen- a known pressure field which is given implic-
dent variables and time. If, for example, a case itly by the conservation equations for the com-
was investigated which required 20 finite vol- ponents of momentum and the continuity equa-
umes in the direction of each of these variables, tion. The mean pressure can be determined from
then the number of grid points for a statisti- a Poisson equation which is derived from the
cal two-dimensional flow with only two chem- conservation equations for the momentum com-
ical species under isothermal conditions would ponents and the continuity equation. Equation
be 207 ≈ 109 . Other methods must therefore be (132) can be rewritten as
used. 9 :
∂Ui ∂ ∂ p
+ (Ui Uk ) = − + Ai (180)
∂t ∂xk ∂xi
4.3.2.1. Closure of the Transport Equation
for Probability Density Functions with
∂τik ∂pf
The equation for the derivation of the joint prob- Ai ≡ − + gi
xk ∂xi
ability density function for a turbulent reacting
flow is given by If Equation (180) is averaged and differentiated
9 :
with respect to xk and the continuity equation
∂P ∂P ∂ p
(Φ) + (Φ) Uk + (Φ) gk − differentiated with respect to t
∂t ∂xk ∂xk
9 :
∂P ∂ ∂ ∂ 9 : ∂2
+ [( (Φ) Sω (Φ) P )] = Uk = − (181)
∂Uk ∂Φω ∂xk ∂t ∂t2

∂ 9 ∂τlk ∂pf :
− + |u, ϕ P is subtracted, then the Poisson equation for the
∂Uk ∂xl ∂xl
mean pressure is obtained which has to be solved
simultaneously to the equation for the probabil-
∂ 9 ∂Jkω :
+ |u, ϕ P (155) ity density function:
∂Φω ∂xk
9 : 9 : 9 : 9 :
All the terms on the right-hand side of the equa- ∂2 p ∂2 ∂ 2 Uk Uk ∂ Ak
= − + (182)
tion (convection in physical space, transport in ∂xk ∂xk ∂t2 ∂xk xk ∂xk
the velocity space due to gravitational forces,
forces due to the gradient of the average pres- In the next step the model assumptions for the
sure, and transport in the composition space due conditional expected values on the right-hand
side of Equation (155) must be discussed, in par- eddies [49] that is rate determining for the dissi-
ticular for pation of the velocity fluctuations at the molec-
ular level. Similarly to the diffusion process ex-
∂ 9 ∂τik ∂pf : amined in page 207, this model gives a normal
+ |u, ϕ P and
∂Uk ∂xk ∂xk distribution for the velocity (a three-dimensional

∂ 9 ∂Jkα : distribution in this case).
|u, ϕ P
∂Φα ∂xk A normal distribution is precisely defined by
Modeling of these expected conditional values the mean value and the variances of the quanti-
is the main problem in developing mathematical ties concerned. Since the normal distribution be-
models for chemically reacting turbulent flows ing discussed is three dimensional, the variances
on the basis of transport equations for proba- and covariances of the velocities are important
bility density functions. The principles used in and, using Equations (112) and (113), can be
these methods will be discussed here, for further expressed as Ufi Ufj (Reynolds stresses). The
details see [18], [19], [70], [71], [79], [80]. problem now is to find models for the Reynolds
The probability density functions in the ve- stresses and their decay over time which will
locity space and the composition space will be guarantee the required normal distribution as the
treated separately. They can be calculated by in- solution for Equation (183).
tegrating Equation (155) over the velocity space A frequently used model for the Reynolds
and composition space or by using the meth- stresses (see also Section 5.1.2.1) which satisfies
ods shown in Section 4.2.1 for the momentum these conditions, is that developed by Lumley
components or the scalar quantities. For further [72] and Launder [73] and modified by Rotta
simplification a turbulent system is considered [49], [74]:
with constant density, homogeneous turbulence, ∂ 9 f f: . 9 f f:
U U = − Ui Uj
and no gradients of the mean velocity. ∂t i j
A uniform fluid flow which flows through a
9 : 2
turbulence-generating grid represents a good ap- −C9 : Uif Ujf − k δij /τ (184)
Uif Ujf 3
proximation to these simplified assumptions. If
the coordinate system moves with the flow at where δij is the Kronecker delta, δij = 1 for i = j,
the mean flow velocity, then no relative convec- δij = 0 for i = j; k is the specific kinetic en-
tion occurs. The probability density function be- ergy of the turbulent velocity fluctuations, k =
comes 1/2 U fk U fk ; and τ is the turbulent time scale,
which has to be defined from model assump-
∂P (U ;t) tions.
∂t The first term on the right-hand side of

∂ 9 ∂ 2 Uk ∂pf : Equation (184) causes exponential decay of the

= − µ − |u P (U ; t) (183)
∂Uk ∂x2k ∂xk Reynolds stresses. The second term is respon-
sible for the isotropy of the “diffusion” of the
Equation (183) represents the time development kinetic energy of the turbulent fluctuations.
of the probability density function ( µ is the dy- The second problem for the solution of Equa-
namic viscosity). The only term to be modeled tion (183) is the modeling of the conditional ex-
is pected values

∂ 9 ∂ 2 Uk ∂pf : 9 ∂pf :
µ 2
− |u P (U ;t) |u
∂Uk ∂xk ∂xk ∂xi
A Poisson equation for the pressure variations
Experimental observations in a turbulent flow
can be derived from the conservation equations
of this type show that the turbulent velocity fluc-
for the momentum components and the conti-
tuations decay with time. Further, if the eddy
nuity equation in a similar manner to the mean
dissipation model outlined in 4 is used, it can be
pressure:
shown that the turbulent momentum exchange
9 :
is an isotropic diffusion process of the turbulent ∂ 2 pf ∂ Uk ∂Ulf ∂ 2 Ukf Ulf
= − 2 · − (185)
∂xk ∂xk ∂xl ∂xk ∂xk ∂xl
Thus the pressure fluctuations have two sources.

The first is the interactions of the turbulent fluc- 9 D ∂2Φ : 1 9 : 1
tuations themselves (second term of the right- |ϕ = − CΦ Φ − Φ (187)
∂x2k 2 τ
hand side) and the interactions of the turbulent
fluctuations with the gradients of the mean ve- in which τ is the turbulent time scale τ /CΦ = τΦ .
locities. The second term is described by the Since diffusion transport is in the composi-
equation for the Reynolds stressses (Eq. 184); tion space, Equation (187) can be interpreted
the first term (“rapid pressure”) must be mod- as transport velocity in the composition space
eled, this can also be carried out with the help of which is proportional to the deviation from the
the Reynolds stresses [19], [66]. mean value. However, model Equation (187)
The third problem is the description of the does not yield a normal distribution from all
conditional expected values initial conditions. Instead, the initial conditions
must contain information about the form of the

∂ 9 ∂Jkα : distribution [19] as in the applications described
|u,ϕ P
∂Φα ∂xk in [57], [76], [77]. A general equation can be de-
rived with a statistical particle interaction model,
These terms can be modeled by using the simpli- for details refer to [19].
fications described above. For the same homoge- The variances of Φ, Φ f2 , according to Equa-
neous system at constant density with isotropic tion (187) are described by an equation similar
turbulence and a moving coordinate system, the to Equation (184):
change in the probability density function over
∂ 9 f2 : 9 :
time for a passive scalar quantity, e.g., the mass Φ = − C9 f2 : Φf2 /τ (188)
∂t Φ
fraction of a nonreacting chemical species is
given by: For the combined velocity – composition space
of the homogeneous system with isotropic turbu-

∂P (Φ;t) ∂ 9 ∂JkΦ : lence the same line of reasoning can be applied.

= |ϕ P (Φ;t) The joint probability density function P (U, Φ; t)
∂t ∂Φ ∂xk

is normally distributed so that it is defined by the
∂ 9 D ∂2Φ : mean values and the second moments U fi U fj ,
= |ϕ P (Φ;t) (186)
∂Φ ∂x2k
Φ fα Φ fβ , and U fi Φ fα . The latter quantities
where D is the diffusion coefficient. Equation (the Reynolds fluxes) are usually defined by a
(186) is obtained for the nonreacting scalar Φ model equation analogous to Equations (188)
from the general transport equation by inte- and (184):
grating over the velocity space or by using the ∂9 f f: 9 :
U Φ = − C9 f f : Uif Φfα /τ (189)
method given in Section 4.2.1. As before with ∂t i α Ui Φα
the dissipation of velocity fluctuations, the eddy which does not change the character of the so-
transport model allows the turbulent exchange of lution for the joint probability density function.
mass to be considered as “eddy diffusion”. This In the combined velocity – composition space,
“diffusion” is rate determining for the dissipa- the diffusion of the Reynolds stresses U f i U fj ,
tion of the turbulent fluctuations of the scalar at the fluctuations of scalar quantities Φ f2α , and
the molecular level. The term the Reynolds fluxes U fi Φ fα are all superim-

posed on one another. The remaining problem is
∂ 9 D ∂2Φ :
|ϕ P (Φ;t) then the modeling of the turbulent time scales for
∂Φ ∂x2k
these “diffusion” processes and the treatment of
must be modeled in such a way that the solu- the “rapid pressure”. Some ideas for modeling
tion of Equation (186) is a normal distribution these are discussed in Sections 5.1 and 5.3.
which decays over time. Thus, the problem con- Under industrial conditions, chemical reac-
sists of modeling the second moment Φ f2 (the tions in turbulent flows occur in nonhomoge-
variance of the scalar quantities). neous systems that usually involve gradients of
A simple deterministic model [75] which sat- the mean velocities and nonisotropic turbulence.
isfies the above requirements is The extension of the simple model described
above to such cases is still being developed [18],
[19]. The general principle is that the main prop- (191 b) symbolize the models used for each of
erties of the model for the second moments are the “diffusion” processes, i.e., the types of mod-
retained. The additional effects are treated as els to describe the conditional expected values
being superimposed on the undisturbed “dif- on the right-hand side of Equation (155). Equa-
fusion”. Often “hybrid” models are also used tion (190) indicates that all three operators influ-
where the expected values of the velocities are ence the probability density function simultane-
computed by other methods (cf. Section 5.1.2.3) ously. However, for a solution the operators are
and only the joint probability density function separated.
for the composition space is evaluated (cf. Sec- A first-order approximation P (1) (t) for P (t)
tion 4.3.2.3). starting from given initial conditions P (t 0 ) is es-
timated by calculating the separate effects of the
three operators in the following way:
4.3.2.2. Solution Methods of the Transport
(1)
Equation for Probability Density Functions P1 (t) = (I +∆tΩ1 ) P (1) (t) (192a)
Equation (155) (Section 4.2.1) P2

(1)
(t) = (I +∆tΩ2 ) P1
(1)
(t) (192b)
9 :
∂P ∂P ∂ p (1)
(Φ) + (Φ) Uk + (Φ) gk − P (1) (t+∆t) = (I +∆tΩ3 ) P2 (t) (192c)
∂t ∂xk ∂xk
∂P ∂ (1) (1)
+ [( (Φ) Sω (Φ) P )] = If the fractional changes P1 (t) and P2 (t) are
∂Uk ∂Φω
eliminated backwards, then P (1) (t + ∆t) can be
∂ 9 ∂τlk ∂pf : expressed by P (1) (t):
− + |u,ϕ P
∂Uk ∂xl ∂xl
P (1) (t+∆t) (193a)
∂ 9 ∂Jkω :
+ |u,ϕ P (155) = (I +∆tΩ3 ) (I +∆tΩ2 ) (I +∆tΩ1 ) P (t) (1)
∂Φω ∂xk
= P (1) (t) +∆t (Ω1 +Ω2 +Ω3 ) P (1) (t) + O ∆t2
is a partial differential equation in (σ + 6) in-
dependent variables and time. Finite difference On the other hand if P (1) (t) is developed as a
methods for solving this equation fail due to the Taylor series, then
large number of variables if drastic simplifica-
tions cannot be applied. Successful methods of ∂P (1) (t)
P (1) (t + ∆t) = P (1) (t) + ∆t
solution have been based on Monte Carlo sim- ∂t
ulations of the discrete form of the probability ∂ 2 P (1) (t) ∆t2
+ + ... = P (1) (t)
density functions in the velocity – composition ∂t2 2!
space [19]. These methods will be described ∂P (1) (t)
+ ∆t+O ∆t2 (193b)
briefly before an example is discussed. ∂t
Equation (155) can be rewritten as
If Equations (193 a) and (193 b) are set equal to
∂P each other and divided by ∆t then
= (Ω1 +Ω2 + Ω3 ) P (190)
∂t
∂P (1) (t)
in which Ω 1 , Ω 2 , and Ω 3 are operators that are = (Ω1 +Ω2 +Ω3 )P (1) (t) + O(∆t2 ) (194)
∂t
obtained by comparison with Equation (155):
Equation (194) is identical to Equation (190)
∂ ∂ ∂Sω
Ω1 ≡ −gk −Sω − I (191a) apart from the development errors of the order
∂Uk ∂Φω ∂Φω
O (∆t 2 ). Thus this procedure of separating the
Ω2 ≡ [...] (191b) operators gives a first-order approximation for
9 : P (t).
∂ 1 ∂ p ∂
Ω3 ≡ Uk + (191c) The Monte Carlo simulation of the develop-
∂xk (Φ) ∂xk ∂Uk
ment of the probability density function uses the
In Equation (190) P denotes P (U, Φ; x, t) discrete form of the probability density function
and in Equation (191 a) I is the identity oper- with n statistical fluid particles:
ator. The terms represented by dots in Equation
discrete form and the remaining task is to cal-

culate the mean values, variances, covariances,
Pn (U , Φ;x,t)
and all values of interest from the discrete prob-
1
n
= δ (U − ui ) δ (Φ − ϕi ) δ (x − xi ) (195) ability density function. This may be achieved
n i=1 by the averaging procedure according to Equa-
tion (114) and the analogous rules for higher mo-
(cf. Eq. 115 b, Section 4.1.1). The discrete form
ments. However, for discrete probability density
of the√ probability density function converges
functions, special interpolation routines are rec-
with n towards P (U, Φ; x, t). The numeri-
ommended for calculating the moments [19].
cal problem is to determine the movement of n
statistical fluid particles in the physical, velocity,
and composition spaces consistent with the op-
4.3.2.3. Example: Combustion of Propane in
erators Ω 1 , Ω 2 , and Ω 3 . Stated in another way:
a Turbulent Diffusion Flame
starting from a given initial distribution Pn (U,
Φ; x, t = 0), n fluid particles with the properties
The solution of Equation (155) for turbulent re-
Ui (t 0 ), Φi (t 0 ), and xi (t 0 ) are chosen at random.
acting flows gives the joint probability density
The fractional changes of Pn are then calcu-
function P (U, Φ; x, t) in discrete form according
lated which lead to Pn (U, Φ; x, t = t + ∆t) with
to the methods outlined in Section 4.3.2.2. All
the particle properties Ui (t = t 0 + ∆t), Φi (t =
the information required for engineering appli-
t 0 + ∆t), and xi (t = t 0 + ∆t). This gives an algo-
cations can be obtained from this complete sta-
rithm for calculating the development of Pn (U,
tistical description.
Φ; x, t) over time by using forward differences
To solve Equation (155) a number of model
with respect to time. The movement equations
parameters must be determined (see Eqs. 184,
consistent with the operators Ω 1 , Ω 2 , and Ω 3
188, or 189 for simple systems) as well as the
are for the third fractional change Ω 3
turbulent time scale τ . Equation (155) contains
9 :
dU 1 ∂ p dΦω
(σ + 6) independent variables so a finite differ-
=− , = 0, and ence method of solution is ruled out. Even if
dt (Φ (t)) ∂xk dt
x(t) the method of solution shown in Section 4.3.2.2
dx overcomes these problems, a reduction in the
= U (t) (196a,b,c)
dt number of variables by a simplification of Equa-
According to Equation (191 a), for the operator tion (155) is worthwhile. In most applications
Ω 1 and thus for the first fractional change: this is achieved by solving Equation (155) for
the composition space only [57], [70], [71], [78–
dU dΦω 80]. The result of this is that, besides the tur-
=gk + [...] , = Sω [Φ (t)] , and
dt dt bulent time scale τ , the expected values of the
dx
=0 (197a,b,c) velocities must also be calculated by other mod-
dt
els (Section 5.1.2).
In Equation (197 a) the contents of the square The combustion of propane with air in a tur-
brackets indicated by dots must be substituted bulent diffusion flame will be described as an
by the model being used for describing the dissi- example. The propane flows from a simple jet
pation of the turbulent velocity fluctuations. The assembly with a Reynolds number of 40 000 re-
second operator only causes a fractional change lated to the nozzle outlet. The gas is mixed with
in the composition space so that the movement the surrounding air and burns in a turbulent dif-
equations for the second fractional change are fusion flame. This example may resemble an in-
dustrial flue gas flare.
dU dΦω dx
=0, = [...] , and =0 (198a,b,c,) The numerical calculation is confined to the
dt dt dt
probability density function in the composition
The movement of the statistical fluid particles in space [70]. Integration of Equation (155) over
the composition space (Eq. 198 b) must again be the velocity space according to Equation (121)
obtained from the model being used. gives
After i time steps, each with three fractional
changes Pn (U, Φ; x, t = t + i ∆t) is obtained in
last three quantities are unknown and must be

∂ [ (Φ) P (Φ;x,t)] ∂ 9 : provided before the solution of Equation (202).
+ (Φ) Uk |ϕ In [70] this occurs together with the calculation
∂t ∂xk
of the expected velocity values using a “second-
∂ order closure model”. In this procedure the con-
·P (Φ;x, t)] + [( (Φ) Sω (Φ) P (Φ;x,t)]] =
∂Φω servation equations are averaged and the corre-

∂ 9 ∂Jk
ω : lations which arise from averaging (the Reynold
|u, ϕ P (Φ;x,t) (199)
∂Φ ∂xk stresses and Reynolds fluxes) are modeled di-
ω
rectly (see also Section 5.1). The remaining
By using density-weighted variables (indicated
problem is the modeling of the dissipation of
by a tilde) [81]
the turbulent fluctuations of the scalar quantities

1 at the molecular level, this is taken care of with
P̃ (Φ;x,t) = 9 : (Φ) P (Φ;x,t) d (200)
information about the form of the distribution
using the method described in Section 4.3.2.1
and decomposing the velocities according to [57], [71], [76], [78].
Equation (112) The combustion of propane with air in a diffu-
9 : 9 : sion flame, comprises ca. 300 elementary reac-
Ui |ϕ = Ũi + Ũif |ϕ (201)
tions between ca. 45 chemical species [82]. The
the following is obtained: composition space is therefore approximately
45-dimensional and numeric simulation using
9 : ∂ P̃ (Φ;x,t) ∂ .9 :9 : the Monte Carlo method is prohibitive due to
+ Ũk
∂t ∂xk the high dimensionality of the problem. The re-
action mechanism for the combustion of propane
∂ .9 : /
·P (Φ;x,t)] + Sω P̃ (Φ;x,t) may be reduced to [70]
∂Φω

∂ 9 1 ∂Jkω :
= |ϕ P̃ (Φ;x,t) C3 H8 + 3/2 O2 → 3 CO + 4 H2 (i)
∂Φω ∂xk
∂ .9 f :9 : / CO + OH CO2 + H (ii)
− Ũk |ϕ P̃ (Φ;x,t) (202)
∂xk and the recombination reactions of the H2 −O2
The problem in using Equation (202) is the un- system
known velocity U and the modeling of the
terms for the dissipation of turbulent fluctua- H + O2 + M HO2 + M (iii)
tions of the scalar quantities at the molecular
level (first term on the right-hand side of Eq. 202) H + H + M H2 + M (iv)
and transport in the physical space by turbulent
velocity fluctuations (second term on the right- H + OH + M H2 O + M (v)
hand side of Eq. 202). For the latter term a gradi-
ent transport approach is used [70] that describes H + O + M OH + M (vi)
the transport of higher moments analogously to
diffusion. The background of such equations is where M denotes a third body collision partner.
briefly treated in Section 5.1. In the special case The chemical system is thus described by four
of propane combustion: scalar variables; the normalized elemental mass
fraction of carbon Φ1 ≡ f , the mixture frac-
9 f :9 :
Ũk |ϕ P̃ (Φ; x, t) tion; the total molar concentration Φ2 ≡ ctot ;
9 : k̃ 9 f f : ∂ the molar concentration of propane Φ3 ≡ cC3 H8 ;
≈ − CS U U P̃ (Φ; x, t) (203) and the molar concentration of carbon monoxide
ε̃ k l ∂xl
Φ4 ≡ cCO . This manipulation reduces the num-
where C s is a model parameter; k̃ is the turbu- ber of variables in Equation (202) to four. The
lence energy (see Section 4.3.2.1); ε̃ = − dk̃/dt reaction rates of these four variables are derived
such that k̃/ε̃ ≡ τ the turbulent time scale; and from the reduced mechanism:
finally U fi U fj are the Reynolds stresses. The
LIVE GRAPH
Click here to view
S (Φ1 ) = 0
1
S (Φ2 ) = 4 r(i) − r(ii) − r(iv) − r(v) − r(vi)
2
S (Φ3 ) = −r(i)
S (Φ4 ) =3r(i) − r(iv)
Figures 23 and 24 show the results of the nu-

meric simulation according to [70]. The results
given in Figure 23 are the joint probability den-
sity function of f at a distance of 10 jet diame-
ters from the fuel nozzle. There is a peak near
the beginning of the coordinates which means
that in the region near the fuel nozzle, the air
from the surrounding fluid entrains the flow. Fig-
ure 24 A gives radial profiles of the mean values LIVE GRAPH
Click here to view
of the propane mole fraction and the mixture
fraction at a distance of 40 mm from the burner
nozzle. These results are important for setting
up an exhaust gas flare and can be derived from
the general probability density function. There
is relatively good correlation between the calcu-
lated and measured values. The correlation bet-
ween the combustion products (CO and CO2 ) is
not as good (Fig. 24 B). This is due to the mod-
els contained in the transport equation for the
joint probability density function and the chem-
ical model which contains drastic assumptions
about the concentrations of radicals formed dur- Figure 24. Simulation of a propane air diffusion flame
ing propane combustion (Eqs. i – vi). 40 mm above the burner nozzle according to [70]
A) Mean values for the normalized elemental mass frac-
tion (mixture fraction) and the mole fraction of propane; B)
Mean values for the mole fraction of carbon monoxide and
carbon dioxide
The open squares and circles denote measured values, the
curves denote calculated values; r = radial distance; D =
nozzle diameter.
5. Models Based on Physicochemical

Principles (Transport Phenomena)
See also → Transport Phenomena and → Fluid
Mechanics.
Models based on physicochemical principles ap-
ply the principles of the transport of momentum,
mass, and energy to chemical engineering pro-
cesses. The representation of processes by this
Figure 23. Joint probability density function for the normal- type of model consists of the formulation of the
ized elemental mass fraction (mixture fraction) and mass conservation equations for the total mass, the
fraction of CO according to [70] for a propane air diffusion mass of the individual chemical species, com-
flame at 10 nozzle diameters above the burner nozzle
f = mixture fraction
ponents of momentum, and the enthalpy for the
system or subsystem under consideration. The
conservation equations can be given in the form in [48], [50], [51]. Except for the pressure gra-
shown in Section 4.2: dients, gravitational forces, density , and the
dynamic viscosity of the material µ, Equation
Accumulation + Change due to convective transport = (204) is closed. In the case of gases, for exam-
Change due to molecular transport + Source ple, µ can be determined from the kinetic the-
ory of gases; other methods of calculating the
The required number, combination, and for- dynamic viscosity are given in [48], [50]. For
mulation of the conservation equations and any systems with constant density (e.g., incompress-
other physicochemical relationships necessary ible fluids) and a known pressure field, Equation
for closing the set of equations depend on the (204) is sufficient for calculating the velocity
kind of process and the physical boundary con- field. This will be demonstrated for the simple
ditions for the system under consideration. example of laminar flow in a tube.
In the following sections, applications of the
principles of conservation of mass, momentum,
and energy will be discussed. Wherever possible 5.1.1. Laminar Tube Flow
the classification according to Figure 4 will be
used. Laminar tube flow is illustrated in Figure 25. The
flow is assumed to be fully developed and steady
state, the accumulation term and the gradients in
5.1. Application of the Principle of the direction of flow therefore disappear. There
Conservation of Momentum are no components of velocity transverse to the
direction of flow. The problem is thus reduced to
(The notation used in this chapter is the same as a one-dimensional problem with one dependent
that employed in Chapter 4.) variable.
The detailed notation for the equation for the
conservation of momentum (Eq. 132) is
∂ui ∂ui ∂τik ∂p
+ uk = − + gi
∂t ∂xk ∂xk ∂xi
i = 1, 2, 3 (204)
Physically this equation represents the change

in momentum flux in a differential control vol-
ume caused by volume-specific forces: viscous
stress (the first term on the right-hand side of
Eq. 204), pressure (the second term on the right-
hand side), and body forces, in this case the grav-
itational forces (the third term on the right-hand
side). The assumptions made in the formulation
of Equation (204) are discussed in [48], [50], Figure 25. Laminar tube flow and parabolic velocity profile
L = length; R = radius; r = radial distance; u = velocity in the
[51]. axial direction
For Newtonian fluids a gradient expression
relates the viscous stresses to the flow velocities. With the definitions specified in Figure 25
In accordance with Newton’s law of friction the and the appropriate formulation in cylindrical
shear stress tensor component τij can be written coordinates, Equation (204) can easily be ar-
as ranged as follows
1 ∂ ∂p
∂ui ∂uj 2 ∂uk 0= (rτrz ) − +gz (206)
τij = µ + − µ δij (205) r ∂r ∂z
∂xj ∂xi 3 ∂xk
If the pressure gradient in Equation (206) is re-
where δij is the Kronecker delta: δij = 1 for i = j placed by the pressure difference over length L,
and δij = 0 for i = j. The assumptions used in which is taken as known, Equation (207) is ob-
the formulation of Equation (205) are discussed tained:
high inertial forces. This leads to the develop-

ment of irregular statistical fluctuations. Tur-
∂ p0 − pL
(rτrz ) = − +g r (207) bulent flows are therefore basically unsteady and
∂r L
three-dimensional. This does not, however, re-
Integration of Equation (207) gives present the principal problem in mathematical
modeling. As indicated in Section 2.2, compli-
p0 − pL r2
rτrz = − + g + C1 (208) ance with physicochemical laws does not lose
L 2
its validity even in statistical processes, such as
where C 1 is an integration constant. If the term turbulent flows. Direct numerical simulation of
from Newton’s law of friction is substituted for such flows in the nonsteady state with threedi-
the laminar viscous shear stress τrz , then Equa- mensionally formulated conservation equations
tion (208) becomes is possible in principle.
However, systematic difficulties arise which
du p0 − pL r C1
= − + g + (209) can only be solved for simple cases [49], [53],
dr L 2µ µr [54]. These problems include the small measure-
Integration of Equation (209) results in ments of characteristic turbulent length scales (
Kolmogorov length) and the extreme sensitivity
p0 − pL r2 C1 of the nonsteady, three-dimensional conserva-
u= − + g + lnr+C2 (210)
L 4µ µ tion equations to changes in the boundary con-
Since for r = 0 the velocity is finite, C 1 must be ditions. Other options for describing statistical
zero. The constant C 2 can be calculated from a processes are the use of probability density func-
further boundary condition, u = 0 for r = R: tions (Sections 4.2 and 4.3.2) or the moments
of probability density functions. Although the

p0 − pL R2 latter do not provide complete statistical infor-
C2 = + g
L 4µ mation, time- or ensemble-averaged values are
often adequate for engineering purposes.
Equation (210) thus takes the form
The most important features of models of sta-
r 2 tistical processes in the form of conservation
p0 − pL R2
u= − + g 1− (211) equations for the moments of probability density
L 4µ R
functions will be outlined below for turbulent
This is the well-known parabolic velocity pro- nonreactive flow. The aim is to derive transport
file for laminar tube flow ( Hagen – Poiseuille equations for the mean values of the velocities
flow). Further integration of Equation (211) starting from the conservation Equation (204)
with the relationship dq = u 2 π r dr provides the for the compounds of momentum which form a
Hagen – Poiseuille relationship for the volumet- system of differential equations for the instanta-
ric flow rate q in laminar tube flow neous values of the velocity components.
The example used is based on a jet stirred
p0 − pL πR4
q= + g (212) reactor, similar to that depicted in Figure 14.
L 8µ
The first step is easily carried out by using
Apart from the assumptions and simplifications the decomposition Equation (112) and is demon-
associated with the momentum balance itself, strated on a convective term in Equation (204).
the example of laminar flow does not contain Equation (204) is first converted into
any troublesome modeling hypotheses. This is
not the case for turbulent flow. ∂ ∂ ∂τik ∂p
(Ui ) + (Uk Ui ) = − + gi
i = 1, 2, 3 (213)
5.1.2. Turbulent, Nonreactive Free Jets
using the continuity Equation (131). From the
convective term in one direction and Equation
Turbulent flows were described in Chapter 4
(112) the following is obtained:
as flows with high kinetic energy so that the
damping viscous forces can no longer hold the
fluid particles on controlled paths due to their
The most commonly used model in engineer-

9 : 9 : 9 : ing is based on the analogy between laminar
Ui Uj = + f Ui + Uif Uj + Ujf
and turbulent transfer of momentum (Chap. 4),
9 :9 :9 : 9 :
= Ui Uj + Ui Ujf established by Boussinesq [87] and expanded
9 : 9 : 9 : by Prandtl [88], [89]. Analogous to the gradi-
+ Uif Uj + Uif Ujf
9 :9 : 9 : ent expression for laminar viscous shear stresses
+ f Ui Uj +f Ui Ujf (Eq. 205) the apparent turbulent viscous stresses
9 :
+ f Uif Uj +f Uif Ujf (214) (Reynolds stresses) are coupled with the gradi-
ents of the mean velocity.
If Equation (214) is averaged, then by taking A tensor for the turbulent shear stresses is
Equation (113 b) into account we get obtained:
9 : 9 :9 :9 : 9 :9 : 9 :
Ui Uj = Ui Uj + Uif Ujf 9 : 9 :
∂ Ui ∂ Uj 2 ∂ Uk
9 :9 : 9 :9 : τtij =µt + − µt δij (217)
+ Ui f Ujf + Uj f Uif ∂xj ∂xi 3 ∂xk
9 f f f:
+ Ui Uj (215)
in which δij is the Kronecker delta and µ t is the
This shows the basic problem in the derivation apparent turbulent viscosity.
of conservation equations for the expected val- The problem is now to determine the appar-
ues: in addition to the expected values, the con- ent turbulent viscosity, which is not (as in the
vective terms contain the covariances of the ve- laminar case) a propensity of the material, but a
locity components and density–velocity covari- characteristic generated by the flow. When deter-
ances. These terms must be modeled or replaced mining this characteristic the analogy between
by assumptions. This is the major difference to molecular and turbulent transfer of momentum
dealing with the problem in terms of probabil- is retained.
ity density functions, where convection is not In the laminar case the viscosity can be given
modeled in the transport equations (cf. Section as
4.2).
1
If Equation (215) is substituted into Equation µ= λ ū (218)
2
(213), taking the average of the other terms and
neglecting fluctuations in density, then from the kinetic gas theory, where ū is the
mean velocity and λ the mean free path of the
∂ 9 :9 : ∂ 9 :9 :9 :
Ui + Uk Ui molecules. For turbulent transfer of momentum
∂t ∂xk
the same argument leads to
∂ 9 : 9 :9 f f :
= τik − Ui Uk
∂xk
9 : L ∗ u∗
µt ∼¯ (219)
∂ p 9 :9 :
− + gi , i=1, 2, 3 (216)
∂xi where L∗ is the analogous term for the mean free
path of the molecules and u∗ the analogue for
Neglection of the density fluctuations in Equa-
the mean velocity of the molecules. This corre-
tion (216) represents an important modeling as-
sponds with Prandtl’s theory of mixing lengths
sumption. Further model formation concerns
[60]. In the turbulent case, not molecules but
the terms U fi U fj which have the units of
turbulent eddies are the elements which trans-
stresses and are thus called Reynolds stresses.
fer momentum. Both of the quantities L∗ and u∗
representing the eddy viscosity hypothesis must
therefore be determined by plausible arguments
5.1.2.1. Models for Reynolds Stresses
[84]. The characteristic velocity for the turbulent
The modeling of Reynolds stresses has already eddies is proportional to the fluctuations of the
been referred to in Section 4.3.2.1. Discussion velocities u∗ ∼ (2/3 U fk U fk )1/2 and the char-
is continued here for the closure of the averaged acteristic length is the distance which the tur-
transport equations for the momentum compo- bulent eddies travel perpendicularly to the di-
nents. More detailed information is given in [49], rection of flow, before they lose their identity
[51], [52], [83–86]. through dissipation at a molecular level.
This can be expressed as L∗ ∼ u∗ τ , where gives half the trace of the tensor for the Reynolds
τ is the turbulent time scale; using the ap- stresses U fl U fl , k = 1/2 U fl U fl , and hence
proximation τ = k/ε (Section 4.3.2.3) gives the equation for turbulence energy
L∗ ∼ U fk U fk 3/2 /ε. The eddy viscosity hy-
∂ 9 :9 : ∂ 9 :9 :9 :
pothesis is thus k + Uk k
∂t ∂xk
9 : 9 :
9 : k 2 ∂ 9 :9 f : 9 :9 : ∂ Ul
µt = C µ 9 : (220) = − Ukk − U fl U fk
ε ∂xk ∂xk
9 f ∂τlk : 9 f ∂p :
where Cµ is a modeling parameter. As a result + Ul − Ul (222)
∂xl ∂xl
of measurements on turbulent boundary layers
its value is given as Cµ = 0.09 [60]. The description of statistical flows using mean
Many of the problems involved in applying values (first moments) additionally requires the
the eddy viscosity hypothesis (e.g., the physical calculation of second moments, in this case those
requirements for gradient transport approaches) of the velocity variances in the form of turbu-
are discussed in the literature [84–86]. A math- lence energy. Transport equations can be simply
ematical model of this simplicity entails a series derived for this (see Eq. 222), but they contain
of other problems which are physically awkward terms with moments of the next higher order so
to deal with. For the model with gradient trans- that this procedure never leads to a closed equa-
port approach and the eddy viscosity hypothesis tion system. The first expression on the right-
(k−ε turbulence model) these problems lie in the hand side of Equation (222), for example, con-
determination of the turbulence energy k and tains moments of the third order. To close the
its dissipation rate ε and require the derivation transport equations at a certain order, model as-
of corresponding transport equations [84]. sumptions have to be introduced for the higher
The description of turbulent flows in terms of order moments. These are often based on the
the mean values of the velocities thus requires same assumptions as the simple gradient trans-
the calculation of second moments, in this case port assumptions and the eddy viscosity hypoth-
of the variances U fi U fj , from which the turbu- esis. The physical basis and the larger number
lence energy and its dissipation rate are derived. of model parameters arising in Reynolds stress
An equation for the turbulence energy may be models are the reasons that further development
derived by multiplying Equation (213) formu- of these [83], [90], [91] is only gradually gaining
lated for the i-direction by U fj and formulated acceptance in engineering.
for the j-direction by U fi . Addition of the two The generally accepted form of the trans-
equations followed by use of Equation (112) for port equation for turbulence energy (Eq. 223)
the components of the velocity, rearrangement of is obtained from Equation (222) by using the
differential quotients, consideration of the con- definition for turbulent shear stresses, gradient
tinuity equation, and averaging finally give transport approaches for third-order moments,
the dissipation hypothesis [49], and other model
∂ 9 :9 f f : ∂ 9 :9 :9 f f :
Ui Uj + Uk Ui Uj assumptions [92]:
∂t ∂xk
∂ 9 :9 f f f : ∂ 9 :9 : ∂ 9 :9 :9 :
= − Uk Ui Uj k + Uk k
∂xk ∂t ∂xk
9 : 9 :
9 :9 : ∂ Uj ∂ µt ∂ k 9 :9 :
− Uif Ukf = + Gk − ε (223)
∂xk ∂xk σkeff ∂xk
9 :
9 :9 f f : ∂ Ui
− Uj Uk with the abbreviation
∂xk
9 f ∂τjk : 9 f ∂τik : 9 : 9 :
+ Ui + Uj ∂ Ul ∂ Uk
∂xj ∂xi Gk = µt +
9 f ∂p : 9 f ∂p : ∂xk ∂xl
− Ui − Uj (221)
∂xj ∂xi 9 :
9 :
2 ∂ Uk 9 :9 : ∂ Uk
gravitational forces being ignored. Summation − + k δik (224)
3 ∂xk ∂xk
over the diagonal elements from Equation (221)
The individual steps in model formation for for the steady-state problem being considered
Equation (123) are described in [48], [51], [86], here. In Equation (226) Jϕ is
[92] and Section 4.3.2.1. For the simplifying ho- 9 :
mogeneous cases described in Section 4.3.2.1, 9 :9 :9 : µt ∂ Φ
Jϕ = Φ Uk − (227)
Equation (223) becomes Equation (184) where σϕeff ∂xk
ε = k/τ . and Sϕ accomodates all other expressions not
For complete definition one more equation included by Equation (227). For the momentum
is needed for the dissipation rate ε = dk/dt equation Sϕ also contains specific terms for
which occurs both in Equation (222) and also the turbulent shear stress tensor from Equation
in the eddy viscosity hypothesis (Eq. 220). The (217) and the right-hand sides of the equation for
derivation takes a similar path to that for the k and ε can be seen from Equations (223) and
equation for turbulence energy and is described (225).
in [49], [92]. The accepted form is The laminar transport of momentum is gener-
∂ 9 :9 : ∂ 9 :9 :9 : ally ignored compared with the turbulent shear
ε + Uk ε stresses. To develop a numerical solution pro-
∂t ∂xk
9 :
cedure, Equation (226) is integrated over a
∂ µt ∂ ε
= control volume (page 205). Using the Gauss–
∂xk σεeff ∂xk
9 : Ostrogradski integration principle this gives
9 :9 : ε 0
+ Cε1 Gk − 2Cε2 ε 9 : (225) 9 :
k divJ ϕ = Jϕk = Sϕ (228)
V F V
In both Equations (223) and (225) σϕ eff is the
turbulent Schmidt number, which compares the The integration has to be carried out over the
mixing length for the velocity fluctuations to the surfaces of the control volume which are per-
mixing length for the Reynolds stresses or the pendicular to the components Jϕi , so that for a
dissipation rate respectively; C ε1 and C ε2 are cartesian system of coordinates the relationship
further model parameters. From the solution of
9 :
Equation (225), the turbulent time scale can be ∆Jϕk dxi dxj,i,j=k = Sϕ
determined; this is a precondition for the closure V
of the models discussed in Sections 4.3.2.1 and 9 : 9 :9 :9 : 9 : 9 :
Φ = U , V , W , k , ε (229)
4.3.2.3.
Describing a nonreactive, isothermal tur- results, in which the operator ∆ denotes the dif-
bulent flow with the model discussed above in ference at two opposite surfaces of the control
terms of the expected velocity values leads to volume. Equation (229) is the basis for setting
the averaged conservation equations of momen- up difference equations which are substituted for
tum (Eq. 216), as well as the equations for turbu- the continuous differential operators in Equa-
lence energy (Eq. 223) and the dissipation rate tions (216), (223), and (225) to allow numerical
(Eq. 225). This system of simultaneous partial integration.
differential equations has to be solved by a suit- The conservation equations for the momen-
able numerical procedure (see Section 5.1.2.2). tum components contain the simple pressure
gradients as sources; a reduction in pressure in
the direction of the ith coordinate thus leads to an
5.1.2.2. Solution Method of the Resulting increase of momentum in this direction. Equa-
System of Partial Differential Equations tions (216), (223), and (225) do not, however,
contain a pressure term so that the pressure p
The partial, simultaneous nonlinear differential or the pressure gradients ∂ p/∂xi cannot be di-
Equations (216), (223), and (225) can be put into rectly calculated from them. The same problem
the form occurs in closing the transport equation for the
9 :
probability density functions (Section 4.3.2.1).
divJ ϕ = Sϕ Solution of these equations assumes a known
9 : 9 :9 :9 :9 :9 :
pressure field, which is implicitly given through
Φ = U , V , W , k , ε (226) the conservation equations for the momentum
components and the continuity equation. If an 8 9 :9 : ;9 :

estimate for the pressure field is assumed for Jϕ1w = − Max + U w , 0 Φ l−1
a numerical solution, then the continuity equa-
8 9 :9 : ;9 :
tion (Eq. 131) is usually not complied with. Con- −Max − U w , 0 Φ l
sequently the numerical solution in an iterative
9 : 9 :
procedure may get further and further away from µt Φ l − Φ l−1
physically meaningful results because the equa- − Fw (232)
σϕeff xl − xl−1
tion system does not contain correction factors
to ensure compliance with the continuity equa- The formulation given in Equation (232)
tion. contains an “up-wind” difference scheme
In the numerical simulation of turbulent [Max {+( U)w , 0} Φl−1 − Max {− (
steady flow or when using the Navier – Stokes · U)w , 0}Φl ] for the convective terms (anal-
equations, this problem is frequently solved by ogous to the cascade of ideally mixed stirred
replacing the primitive variables U and p reactors discussed in Section 4.3.1.1) and a cen-
with stream functions and vorticity [94], [95] tral difference scheme for the diffusive terms.
through the von Mises transformation [93]. The As with the model for ideally mixed reactors,
stream function is defined by the von Mises the up-wind difference scheme is based on the
transformation such that the continuity equation assumption that the upstream value of a physical
is complied with (see also Section 5.2.2.1). In quantity is transported over the control surfaces.
the procedure outlined below another possibil-
ity is suggested, in which the pressure correction
is obtained from the continuity equation and a
simplified form of the momentum balance (the
SIMPLE algorithm) [96], [97].
For the example considered here of a tur-
bulent free jet the formulation in cylinder co-
ordinates is used as in Section 5.1.1. Due to the
rotational symmetry Equation (226) can be ex-
pressed as
9 : 9 :9 :9 :9 :
L (Φ) = Sϕ , Φ= U , V , k , ε (230)
The turbulent transport operator L (Φ) is given
by
9 :9 :9 : 9 :9 :9 :
∂ U Φ 1∂ r V Φ
L (Φ) ≡ +
∂x r ∂r
9 : 9 :
∂ µt ∂ Φ 1 ∂ µt ∂ Φ
− − r
∂x σϕeff ∂x r ∂r σϕeff ∂r
9 : 9 :9 :9 :9 : Figure 26. Diagram illustrating the “up-wind” difference
Φ = U , V , k , ε (231) scheme for elliptical differential equations
l = number of grid point; L = number of grid points in n di-
Since an axially symmetrical system is invariant rection; n = north; e = east; s = south; w = west; ϕ = any vari-
with respect to rotation around the axis of sym- able
metry, then a two-dimensional grid with L nodal
The profiles of the variables brought into dis-
points in the x-direction and M nodal points in
crete form in the x-direction in accordance with
the r-direction is used for replacing the differ-
the “up-wind” difference scheme are also shown
ential operators in Equation (231) by differences
in Figure 26. Problems associated with this dif-
(Fig. 26). The spatial structure of the grid arises
ference scheme (e.g., “numerical diffusion”) and
from rotation about the axis of symmetry, and
measures to limit them are described in [97–
the control volumes are defined by revolving the
101].
grid through the unit angle. The control volume
The grid with L nodal points in the x-direction
is indicated in Figure 26 by a shaded area, the rel-
and M nodal points in the r-direction and the
evant flows, for example Jϕ1w , can be expressed
as
difference scheme can be used to develop the 8 9 :9 : ;

al−L = Max + V s , 0
difference equations from Equation (229); the
fluxes through the remaining surfaces of the con-
µt 1
trol volume are defined analogously to Equation + Fs (236a)
σϕeff xl − xl−L
(232). Summation of the fluxes gives
8 9 :9 : ;9 :
− Max + U w , 0 Φ l−1 8 9 :9 : ;
al−1 = Max + U w , 0
8 9 :9 : ;9 :
−Max − U w , 0 Φ l µt 1
+ Fw (236b)
9 : 9 : σϕeff xl − xl−1
µt Φ l − Φ l−1
− Fw
σϕeff xl − xl−1 8 9 :9 : ;
8 9 :9 : ;9 : al+1 = Max − U e , 0
+ Max + U e , 0 Φ l

8 9 :9 : ;9 : µt 1
−Max − U e , 0 Φ l+1 + Fe (236c)
σϕeff xl+1 − xl
9 : 9 :
µt Φ l+1 − Φ l
− Fe 8 9 :9 : ;
σϕeff xl+1 − xl al+L = Max − V n , 0
8 9 :9 : ;9 :
− Max + V s , 0 Φ l−L
µt 1
+ Fn (236d)
8
9 :9 : ;9 : σϕeff xl+L − xl
− Max − V s , 0 Φ l
9 : 9 :
µt Φ l − Φ l−L bl =al−L +al−1 + al+1 +al+L (236e)
− Fs
σϕeff xl − xl−L Difference equations corresponding to Equation
8 9 :9 : ;9 :
+ Max + V n , 0 Φ l (235) can be formulated for the (L – 2), (M – 2)
8 9 :9 : ;9 :
inner grid points of the calculation domain for all
−Max − V n , 0 Φ l+L variables Φ = U , V , k, ε. Similar rela-
9 : 9 :
tionships are derived for the grid points lying on
µt Φ l+L − Φ l 9 : the boundaries of the calculation domain. The
− Fn = S ϕl (233) resulting system of equations is nonlinear and
σϕeff xl+L − xl
coupled via Sϕl and the coefficients a and b,
In Equation (233) Sϕl represents the source which are not constant but depend on the compo-
terms from Equation (230) integrated over the nents of the velocity and turbulent viscosity. Be-
control volume. If the continuity equation in the cause the numerical procedure for solving Equa-
corresponding discrete form is taken into action (235) is an iterative one these dependencies
count are not resolved.
9 :9 : 9 :9 : 9 :9 :
An analogous equation for pressure correc-
U w Fw − U e Fe + V s Fs tions can be obtained with the procedure sug-
9 :9 : gested in [96], [97]:
− V n Fn = 0 (234)
9 : 9 : 9 :
then Equation (233), after addition of Equation −apl−L ∆ p − apl−1 ∆ p l−1 +bpl ∆ p l
l−L
(234) multiplied by Φl , can be transformed 9 : 9 :
−apl+1 ∆ p l+1 −apl+L ∆ p l+L −Rsl = 0 (237)
into
9 : 9 : 9 :
where ∆ p represents the corrections for the
−al−L Φ l−L − al−1 Φ l−1 +bl Φ l given pressure field, and R sl the “continuity er-
9 : 9 : 9 : ror”, which is obtained from the residuals of the
− al+1 Φ l+1 −al+L Φ l+L − S ϕl = 0 (235)
continuity equation with the calculated velocity
In accordance with Equation (233) the coeffi- field. The coefficients of Equation (237) are ob-
cients for Equation (235) are tained from a simplified form of the momentum
balance [96], [97]. To avoid numerical problems
which originate from the structure of the aver- neighboring lines are calculated with the esti-
aged momentum equations, Equations (235) and mated values from the previous iteration.
(237) are best solved with a “staggered grid” ar- To increase the velocity of convergence, lin-
rangement for the velocities [98]. ear relaxation is used (Section 3.2.1.3) and
Equations (235) and (237) constitute a system the source terms are linearized in the form
of nonlinear equations with 5 (L – 2) (M – 2) un- Sϕ = S linϕ + S propϕ Φ. The latter mea-
knowns for the example considered. The values sure is particularly useful for stiff differential
of the variables at the boundaries of the calcu- equation systems, for which the source terms
lation domain are given by plausible boundary are highly nonlinear and coupled. The mod-
conditions. The system matrix for this system of eling parameters [91] used for calculation are
nonlinear equations has a block pentadiagonal Cµ = 0.09, C ε1 = 1.4, C ε2 = 0.925, σk eff = 1.0,
structure due to the elliptical formulation of the and σε eff = 1.3. Figure 27 shows the predicted
problem (Eq. 231), and the difference scheme values for the mean velocity in the x-direction
used. The system of equations can now be for the turbulent flow of nitrogen at two distances
solved, for example with the Newton – Raphson from the nozzle outlet in comparison with the
procedure outlined in Section 3.2.1.3 or other similarity solutions from [105]. The latter give
methods. the flow velocity as
The model for the Reynolds stresses dis-
9 : 9 : x
cussed in Section 5.1.2.1 as well as the numeri- U m = U 0 / 0.16 − 1.5 (238)
cal procedure given in this section are examples DR
from a rapidly developing field of engineering. and
Other models for the Reynolds stresses repre-
9 : 9 : r 2
sent the phenomena observed in turbulent flows U = U m exp −Cu (239)
better than the k – ε turbulence model [52], [84– x
86], [90–92]. Difference schemes other than the where Cu = 90.
combination of “up-wind” and central differ-
ences are also used for partial elliptical differ-
ential equations and other solution procedures
5.2. Applications of the Principle of
[101–104] are suggested.
Conservation of Enthalpy
5.1.2.3. Example: Turbulent Flow of The conservation equation of enthalpy (Eq. 134)
Nitrogen in Air is written in detail as
∂h ∂h ∂Jkh
In the example discussed here nitrogen is dis- + uk = − + Sh (240a)
∂t ∂xk ∂xk
charged at room temperature from a tube of 10
mm diameter with an exit velocity of 85 m/s into In accordance with Equation (240 a) enthalpy
air which is almost at rest (0.3 m/s) (Fig. 14). transport occurs due to convection and molecu-
The system of nonlinear Equations (235) and lar transport. The term Sh contains all the mech-
(237) is solved for a tensor product grid by an anisms for conversion of enthalpy (e.g., volu-
alternating direction implicit (ADI) procedure metric work due to a change in pressure, work
[101]. In this procedure the block structure is against physical forces or radiation).
first resolved by solving the system of equations Fourier’s simple gradient transport approach
one after the other for the individual variables. can be used to represent molecular transport:
The estimated values from the previous iteration
∂T
are used for the variables contained in the cou- Jih = − λ (241)
∂xi
plings. The system is converted into a quasi-one-
dimensional one by including the elements of the where λ is the thermal conductivity. If a Lewis
two outer diagonals in the right-hand sides. number, Le = Pr/Sc, of one is assumed and other
The system of equations is solved alternately transport effects are neglected, the simple form
along a line of the grid in Figure 26 in the x- of the conservation of energy equation is ob-
or r-direction. The coefficients situated on the tained
Figure 27. Profiles of the expected values for velocities in the x-direction of a turbulent inert flow from a free turbulent jet
The upper diagrams show numerical simulations, the lower diagrams show similarity solutions. The radial profiles at two
distances from the nozzle are given.

∂h ∂h ∂ ∂T 1 d rJrh
+ uk = λ + Sh (240b) − =0 (242)
∂t ∂xk ∂xk ∂xk r dr
Detailed discussion of the assumptions and sim- Integration gives
plifications for this formulation are found in
[48], [50], [51]. −rJrh =C1 (243a)
The conservation equation of enthalpy also
contains the density and the components of the Applying Equation (241) gives
velocity. The enthalpy and momentum equations dT
are thus coupled and have to be solved simulta- rλ = C1 (243b)
dr
neously. To avoid this a simple heat conduction
problem is discussed first. which after integration results in the relationship
C1
T = lnr + C2 (244a)
λ
5.2.1. Heat Conduction
for the temperature profile. For the inner pipe
A simple heat conduction problem is shown in surface, the boundary condition T = T Wi applies
Figure 28. A pipe consisting of two different ma- for r = r Wi . Thus C 2 = T Wi − (C 1 /λi ) ln r Wi and
terials (pipe and insulation) has an internal tem- Equation (244 a) becomes
perature T Wi , the external surface has a temper- C1 r
ature of T Wo . If only molecular conduction is T = TWi − − ln (244b)
λi rWi
considered, Equation (240 a) is reduced to
equation for the temperature can be obtained

from Equation (240 b) by neglecting sources
such as the conversion of mechanical energy or
viscous dissipation and by using the equation
for the definition of enthalpy dh = cp dT and the
usual boundary layer approximations [59], [60]:
∂T ∂T ∂2T
cp u + cp v =λ 2 (245a)
∂x ∂y ∂y
At constant density and specific heat
∂T ∂T ∂2T
u +v =a 2 (245b)
∂x ∂y ∂y
Figure 28. Arrangement and temperature profile for a sim- where a = λ/ cp .
ple heat conduction problem
The subscripts Wi and Wo denote inner wall and outer wall,
respectively.
Correspondingly for the outer pipe surface

the boundary condition is
C1 rWi/o
TWi/o = TWi − ln
λi rWi
Figure 29. Development of a velocity (δu ) and temperature
and (δT ) boundary layer for laminar incompressible flow over
a flat plate
C1 r Pr = 1; u∞ = velocity in the x-direction outside the bound-
T = TWi/o − ln (244c)
λo rWi/o ary layer; T ∞ = temperature outside the boundary layer;
η = similarity coordinate; T W = wall temperature; L = plate
In Equations (244 a – c), C 1 is given by the total length
heat flux (Eq. 243 a).
The differential equation for the temperature
still contains the unknown velocities u and v.
Equations for these variables are obtained from
5.2.2. Heat Transfer
the continuity equation (Eq. 131) and the mo-
mentum equation (Eq. 204) in the x-direction
Layer Problem ∂u ∂v
+ =0 (246)
∂x ∂y
An exact solution for the heat transfer from a ∂u ∂u ∂2u
u +v =ν 2 (247)
fluid to a solid wall is possible for laminar flow ∂x ∂y ∂y
over a flat plate (Fig. 29). A fluid flows over a flat
where ν = µ/ is the kinematic viscosity. For
plate of infinitely small thickness and of length
Pr = ν/a = 1 and hence for ν = a, the enthalpy
L at a velocity u∞ . Due to the viscous stresses
equation is identical with the momentum equa-
at the wall the fluid particles slow down and
tion, so that the solution of the latter produces a
a boundary layer of increasing thickness forms
solution to the enthalpy equation. Furthermore,
along the plate in which the velocity increases
the coupling of the momentum and enthalpy
from zero to u∞ . This gives the boundary con-
equations are removed by these assumptions.
ditions u = 0 for y = 0 and uδu (x) = u∞ . For the
The general expression for temperature is
sake of simplicity, constant pressure is assumed,
pδu (x) = p∞ = const. The flow is steady-state and T u
=A +B
the plate extends infinitely in one direction so T∞ u∞
that the problem can be formulated twodimen- T∞ − TW TW
where A= and B = (248)
sionally. The boundary conditions for tempera- T∞ T∞
ture are T = T W for y = 0 and TδT (x) = T ∞ . An The heat flux to the wall is then
1
∂T T∞ − TW ∂u 1 u∞
h
JW = −λ = −λ (249) Ψy = u∞ fη , Ψx = [ηfη − f (η)] ,
∂y u∞ ∂y 2 νx
W W
1 u∞
Ψyx = − ηfηη ,
Determination of the heat flux to the wall thus 2 x
1
depends on determination of the velocity gradi- u∞
Ψyy = u∞ fηη ,
ent at the wall, which is a function of x and can νx
be obtained from the solution of Equations (246) u∞
Ψyyy = u∞ fηηη (254a,b,c,d,e)
and (247). νx
For the solution, the stream function Ψ is used In Equations (254) fη and the corresponding
to eliminate the velocities u and v [59], [60]: symbols denote the derivatives of f with respect
to η. The ordinary differential equation
∂Ψ ∂Ψ
u= and v = − (250a,b) 1
∂y ∂x fηηη + f ·fηη = 0 (255)
2
The stream function invariably satisfies the con- is thus obtained from Equation (251) which
tinuity equation, as can be seen by suitable dif- has to be solved for the boundary conditions
ferentiation. With this transformation, Equation f (η) = 0, fη = 0 for y = 0 or η = 0 and also for
(247) becomes a partial differental equation of fη = 1 for y → ∞ or η → ∞.
the third order Equation (255) can be solved numerically but
not analytically. The essential quantities
for the
Ψy Ψyx − Ψx Ψyy = ν Ψyyy (251) boundary layer problem, f (η) = (u/u∞ ) dη,
fη = u/u∞ , and fηη = u−1 ∞ (∂u/∂η), can be
in which Ψx and the appropriate symbols for
found in the literature, tabulated as a function of
each of the differential operators are used.
η [60], [106]. According to [106], u/u∞ = 0.99
In the boundary layer formed in laminar flow
for η = 5.0 and fηη = 0.332 for η = 0.
locations√of constant velocity u lie on a parabola
The boundary layer thickness is calculated
η ∼ y/ x (Fig. 29). If the equation system is
from the first of these two values and is defined
therefore transformed to this similarity coordi-
here as the distance δu at which the velocity
nate η, then Equations (247) and (251) can be
reaches 99 % of the flow velocity outside the
reduced to ordinary differential equations. The
boundary layer. It then follows from Equation
exact transformation is
(252) that
1 1
u∞ νx δu 5
η (x, y) = y (252) δu = 5 or = √ (256a,b)
νx u∞ x Rex
in which u∞ /ν represents a scale factor that The essential information provided by Equation
makes η dimensionless. As u is only a function (256) is that the development of the boundary
of η, the general expression u/u∞ = g (η) can be layer thickness for√laminar flow
√ over a flat plate
used for making the stream function dimension- is proportional to x and 1/ u∞ , and inversely
less: proportional to the square root of the Reynolds
number Rex = u∞ x/ν. The solutions of the mo-
Ψ (x, y) = udy=u∞ g (η) dη mentum and enthalpy equations are similar be-
1 cause Pr = 1; as a result δu = δT . A detailed dis-
u∞ cussion of further implications of the solution
= u∞ g (η) dη (253)
ν of the boundary layer equations is given in [59],
[60].
where g (η) dη ≡ f (η) is called the dimen-
Using the value
sionless stream function. Equations (250 a, b),
(252), and (253) provide all the transforma- 1 ∂u 1 ∂u ∂y
0.332 = fηη = =
tions and conversions that are needed to con- u∞ ∂η u∞ ∂y ∂η
vert the partial differential Equation (251) into 1 1 ∂u
= -
an ordinary differential equation of dimension- u∞ u∞ /ν x ∂y
less quantities. the following relation is obtained:
5.2.2.2. General Principles of Modeling Heat

1 Transfer
∂u u∞
=0.332u∞ (257)
∂y W νx
Under industrial conditions the simplifications
Substitution of this term in Equation (249) gives introduced in the previous section become void.
1 The consequence of Pr = 1 and variable den-
h u∞
JW = − 0.332λ (T∞ − TW ) (258) sity is that Equations (245), (213), and (131) are
νx
coupled through the density. Moreover, the so-
If the definition for the heat-transfer coefficient lutions for the momentum balances and the en-
J hW ≡ α ∆T where ∆T = (T W − T ∞ ) is now thalpy balances are no longer identical. The di-
substituted in Equation (258), then mensions of the temperature boundary layer δT
1 and the hydrodynamic boundary layer δu differ.
u∞ 1-
α = 0.332λ = 0.332λ Rex (259) In addition, flow is mostly turbulent sometimes
νx x
with very complicated geometries.
Rearrangement of this equation in dimension-
less groups using Nux = α x/λ yields the solu-
tion for the heat-transfer problem for laminar
flow over a flat plate:
N ux
√ = 0.332 (260)
Rex
The physical background of Equations (259) and
(260) is that the local heat-transfer coefficient,
like the boundary layer thickness, is inversely
proportional to the distance in the x-direction
and the velocity of flow. This is easy to under-
stand because the temperature and velocity gra-
dients level out at the wall with the formation of
the boundary layer.
In technical problems the local heat-transfer
coefficient is often not as important as its mean
value αm from the beginning of the plate to a
distance x or the total length L. Equation (259)
can be written as α = const. x −1/2 :
Figure 30. Representation of a general model for heat trans-
L L fer
1 const. dx δ = film thickness; δT = thickness of temperature boundary
αm = α (x) dx = √ layer; T W = wall temperature; T ∞ = temperature outside the
L L x
0 0 boundary layer.
const. √ L
=2 x = 2αL (261a) As the heat transfer under such conditions can
L 0
still be defined as
The mean heat-transfer coefficient for a plate
with length L is thus double the local heat-trans-
h ∂T
fer coefficient at the distance L. This can also be JW =−λ ≡ α∆T (262)
∂y W
formulated with Equation (260):
-
or from the appropriate mean value over a sur-
N um = 0.664 ReL = 2N uL (261b) face, the problem is thus to determine the tem-
perature gradients at the wall. Heat transfer at
The analysis described here only applies un- the wall is primarily a heat conduction problem.
der the highly simplified assumptions of incom- The temperature profile in the vicinity of the wall
pressible flow and constant density and also
Pr = ν/a = 1. Nevertheless this allows the gen-
eral principles of modeling for heat transfer to
be described.
Next Page
is however determined by simultaneous trans- With the establishment of the mean heat-
fer of momentum, heat, and mass. Analytical transfer coefficients α and the relevant tempera-
or numerical solutions for the system of Equa- ture difference, heat transfer (Eq. 262) is clearly
tions (131), (213), and (245) will only succeed defined. Arrangements such as that shown in
in a few cases with a justifiable amount of effort Figure 28 can be calculated completely with re-
[25], [59], [107], [108], see also the solution of gard to temperature profiles or heat losses. Sum-
the momentum equations for the turbulent inert mation of the temperature differences for the in-
jet of gas in Section 5.1.2.2. dividual “phases” of the arrangement allows heat
In most engineering applications semi- transfer to be related to an “overall resistance”
empirical methods are therefore used which as-
1 1 1 1
sume a linearized temperature profile at the wall. = + +
Figure 30 shows the temperature profile for lam- k αWi λi / (rWo −rWi ) αWo
inar flow over a plate. and to the total temperature difference. The
If the temperature is developed at the wall, equation for heat transfer analogous to Equation
y = 0 in a Taylor series that is truncated after the (262) will then be used depending on the state-
first member, then ment of the question. The calculation procedure
will be shown in an analogous problem of mass
∂T ∂T
T = TW + dy or T∞ = TW + δ transfer in Section 5.3.1.3.
∂y W ∂y W
(263)
If this is substituted into Equation (262) then

5.3. Applications of the Law of
T∞ − TW λ Conservation of Mass
λ = α (T∞ −TW ) or α = (264a,b)
δ δ
Here δ is the film thickness produced by lin- The law of conservation of mass is formulated
earization of the temperature profile as shown in through the continuity equation (Eq. 131) and
Figure 30. This is not identical with the bound- the conservation equations for the mass of the
ary layer thickness δu or δT . As can be seen from individual chemical species, mi
the solutions for the laminar boundary layer
m
- ∂mi ∂mi ∂J i
∂T + uk = − k + Si
= 0.332 (T∞ − TW ) Rex /x ∂t ∂xk ∂xk
∂y W
i = 1, ...,N − 1 (265a,b)
whereas
∗ -
A further equation results from the condition
∂T 1
= (T∞ − TW ) Rex /x
N
∂y W 5 mi = 1. Analogous to the formulations for
1
when the thickness δT of the temperature bound- the conservation of momentum and enthalpy,
ary layer is used for the difference quotients. the transport of chemical species results from
This latter quantity is thus only ca. 60 % of convection and molecular transport. The term
the true temperature gradient. The determina- Si contains sources or sinks based on all pos-
tion of heat transfer thus depends on deter- sible forms of transformation, for example due
mination of the film thickness as in Equation to chemical reactions or due to phase changes
(264). This problem has been solved experi- in multiphase systems. If molecular transport is
mentally in most technical applications, where considered to be adequately described by Fick’s
the mean heat-transfer number depending on law (gradient transport approach)
the various variables is represented in the form
Nu = f (Re, Pr, L/D. . .), see also Equations (260) m
Jj i = − Di
∂mi
(241a)
and (261). ∂xj
These relationships for industrial heat ex-
changers are not treated here. They are described then a simple form of the conservation equations
in [25]. An example of such a relationship for the is obtained that is analogous to Equation (240 b)
transfer of heat for turbulent flow was discussed
in Sections 3.1.1.4 and 3.2.3.
Previous Page
Due to the different boundary condi-

tions for temperature and mass fraction
∂mi ∂mi ∂ ∂mi
+ uk = Di + Si and in analogy with fη = u/u∞ , the term
∂t ∂xk ∂xk ∂xk
i = 1, ...,N − 1 (265b) θ = (T − T W )/(T ∞ − T W ) is used for the tem-
perature and ϕ = (m − mW )/(m∞ − mW ) for the
In Equation (265 b) thermal and pressure dif- mass fraction. With the aid of the relationships
fusion are neglected. Furthermore in general given in Section 5.2.2.1, these transformations
Si = Si (mi , h, p) (Eq. 137 a) is to be set in gen- yield the equation system
eral for the transformation term so that Equa-
tion (265 b) is coupled with the conservation 1
fηηη + f fηη = 0 (255)
equation of momentum through the density and 2
velocities and coupled with the conservation 1
θηη + P rf θη = 0 (267)
equation of enthalpy through the transformation 2
term. The coupled system of equations given in 1
Section 5.2 is thus expanded by one equation. ϕηη + Scf ϕη = 0 where Sc = ν/D (268)
2
5.3.1. Mass Transfer without Chemical that has to be solved simultaneously.

Reaction

Layer Problem
The flat plate in Figure 29 is replaced by a water

surface (Fig. 31) from which the water evapo-
rates into the higher temperature air flow. Un-
der the same assumptions as in Section 5.2.2.1
and with the boundary layer approximations for Figure 31. Development of a velocity (δu ), temperature
(δT ), and concentration (δm ) boundary layer for laminar
Equation (265 b), the following system of equa- incompressible flow over a flat water surface
tions is obtained for this steady-state problem: Pr = Sc = 1
The subscripts ∞ and W indicate values outside the bound-
∂u ∂v ary layer and at the wall, respectively.
+ =0 (246)
∂x ∂y
∂u ∂u ∂2u µ The boundary conditions with the trans-
u +v = ν 2, ν = (247) formed variables are fη = 0, θ = 0, ϕ = 0 and also
∂x ∂y ∂y √
∂T ∂T ∂2T λ (vW /u∞ ) Rex = const. for η = 0 and fη = 1,
u
∂x
+v
∂y
=a 2, a=
∂y cp
(245b) θ = 1, ϕ = 1 for η → ∞.
∂m ∂m ∂2m
The system of Equations (255), (267), (268)
u
∂x
+v
∂y
=D
∂y 2
(266) cannot be solved analytically, but for Le =
Pr/Sc = 1 all profiles are identical and thus re-
where m = mH2 O . The equation system is to sult in identical values for δu , δT , and δm . All
be solved for the boundary conditions u = 0, transport mechanisms exhibit the same devel-
v = vW , T = T W , and also m = mW for y = 0 and opment of the boundary layer. For Pr = Sc = 1
u = u∞ , and m = m∞ for y → ∞. and Pr = Sc √ = 0.7 and also some values of
Since the inclusion of the conservation equa- (vW /u∞ ) Rex , Figure 32 shows the pro-
tion of mass has not altered the nature of the files fη = u/u∞ , θ, and ϕ [59].
equations, it is again logical to transform the √ The curve for
Pr = Sc = 1 and (vW /u∞ ) Rex = 0 corre-
equations into the similarity coordinates sponds to the profile discussed in the previous
1 sections and is called the Blasius profile. The
u∞ y -
η (x, y) =y =
νx x
Rex value of η = 5 for θ = ϕ = u/u∞ ≈ 0.99√ can be
read off from the curve for (vW /u∞ ) Rex =
(see Eq. 252), and to express themin the dimen- 0. Figure 32 shows that, depending on
sionless streams function f (η) = (u/u∞ ) dη.
the magnitude
√ of the “blow out parameter” Further treatment of mass-transfer
(vW /u∞ ) Rex , the profiles of the flat plate coefficients – for example averaging over the
will be either blown off or sucked on. For many length – follows the scheme given in Section
technical applications this is taken advantage of 5.2.2.1 and need not be repeated here.
for stabilization or removal of boundary layers.
LIVE GRAPH
Click here to view
5.3.1.2. General Principles for Modeling
Mass Transfer
As mentioned in Section 5.2.2.2 for heat transfer,

only in very few cases do the Prandtl or Schmidt
numbers have the value one; in addition the ge-
ometric or hydrodynamic assumptions listed in
Section 5.3.1.1 seldom apply. Even if the sys-
tem of Equations (204), (240 b), and (265 b) can
be solved under such conditions, the resulting
solutions deviate from the complete analogy.
For engineering applications mass transfer is
Figure 32. Concentration and temperature distribution therefore also treated by semi-empirical models
with mass transfer for laminar flow over a flat surface
The curves for Pr = Sc = 1 indicated by the dashed lines which assume a linearization of the profile of
also give the velocity profiles. The curves for Pr = Sc = 0.7 the concentrations at the phase boundary. Be-
indicated by the solid lines show temperature and concen- cause of the analogy with heat transfer (Fig. 30)
tration distributions. discussion of this topic can be kept short. If the
θ = (T − T W )/(T ∞ − T W ); ϕ = (m − mW√ )/(m∞ − mW );
η= similarity coordinate = (y/x) Rex Rex ; mass fraction profile is linearized at the phase
v = velocity in y-direction; u = velocity in x-direction; boundary
Rex = Reynolds number defined with u∞ and axial
distance x; the subscripts W and ∞ indicate values at the ∂m
wall and outside the boundary layer, respectively. m = mW + dy
∂y W
or m∞ =mW
In the case of the evaporation
√ example shown
in Figure 31, (vW /u∞ ) Rex can be neglected
∂m
so that the mass transfer, which is to be defined + δ (272)
∂y W
analogously to the heat transfer, is written in the
form the equation defining the mass-transfer coeffi-
cient results in
m ∂m
JW = −D
∂y m∞ − mW D
W
1 D = β (m∞ −mW ) or β = (273a,b)
u∞ ∂ϕ δ δ
= −D (m∞ − mW ) (269)
νx ∂η W where δ again represents the film thickness pro-
If the Blasius solution fηη = ϕη = θη = 0.332 is duced by linearization of the mass fraction pro-
used for Pr = Sc = 1 and, analogous to the file. Determination of the mass-transfer coeffi-
heat-transfer coefficient, a mass-transfer co- cient thus depends on the determination of the
efficient is defined as J m film thickness, which is carried out experimen-
W = β ∆m where
∆m = (mW −m∞ ), it follows that tally for many engineering systems. The results
1
for the mean mass-transfer coefficients in the
u∞ 1- form of the relationships Sh = f (Re, Sc, L/D) are
β = 0.332D =0.332D Rex (270)
νx x described in [25], [59], [109]. For evaluation of
In order to complete the analogy with heat trans- industrial mass transfer equipment there remains
fer the Sherwood number Shx = β x/D should be the problem, analogous to heat transfer, of the
substituted. Thus for Pr = Sc = 1 addition of the “individual resistances” for mass
transfer and reference to the total concentration
Shx difference.
√ = 0.332 (271)
Rex
5.3.1.3. Examples of Simultaneous Mass and and L, respectively) that the latter can likewise be
Heat Transfer: Dynamic Models regarded as nearly constant. The required quan-
tities only change in the x-direction so that the
The system used to illustrate the general princi- problem can be formulated one-dimensionally.
ples of the modeling of simultaneous heat and The heat balance for the gas phase gives the
mass transfer (Sections 5.2.2.2 and 5.3.1.2) is temperature change in the gas based on the heat
based on the boundary layer example shown transfer to the liquid
in Figure 31. Figure 33 shows an evaporation
cooler which is used in an air-conditioning de- dTG sF
= −α (TG −TL ) (274)
vice. A liquid (water) trickles in a thin film over dx GcpG
suitable packings and comes into contact with a
gas (air) flowing in the same direction. The liq- where cp is the specific heat. The mass transfer to
uid evaporates and is thus cooled, so that heat the gas phase gives the change in mass fraction
flow occurs from gas to liquid thus lowering the in the gas phase
gas temperature. dm sF
=β (mPh −m) (275)
dx G
where β is the mass-transfer coefficient and mPh
the mass fraction of liquid in the phase bound-
ary. The temperature change in the liquid phase
is finally obtained from the heat balance for the
liquid phase
dTL sF
=α (TG −TL )
dx L cpL
∆hv sF
−β (mPh −m) (276)
L cpL
where ∆hv is the specific latent heat of vapor-

Figure 33. Example of simultaneous mass and heat transfer
in an evaporation cooler
ization of the liquid.
L = mass flow of liquid; G = mass flow of gas; F = cross sec- Equations (274) – (276) represent a system of
tional area; x = axial distance simultaneous ordinary differential equations for
The subscripts L, G, 0, and e denote liquid, gas, initial, and T G , T L , and m. In order to close these equa-
final, respectively. tions a relationship has to be found for mPh . This
The final steady-state temperature of the gas can be obtained from the Clausius–Clapeyron
must be determined for a given area, S = s F H, equation for vapor pressure ln p = −A /T + B .
where s is the specific transfer area. All terms Since the changes are assumed to be very
are defined in Figure 33. The thickness of the small, a linearized expression can be used in
layer of liquid flowing over the packings is as- the temperature interval being considered, so
sumed to be so small that the temperature in that mPh = A T L + B or dmPh /dx = A (dT L /dx).
the liquid phase is uniform. The mean heat- By substituting the transformations θ = T G − T L
and mass-transfer coefficients for this problem and ϕ = mPh − m, the number of equations can
are known. The temperature changes lie in a be reduced by one:
range which allows the material values to be re- dθ sF
garded as constants. The functions for the Nus- = −α GcpG +L cpL θ
dx GcpG L cpL
selt and Sherwood numbers generally contain
∆hv sF
terms which are functions of the properties of +β ϕ (277a)
L cpL
the material. The assumption of approximately
constant material properties avoids recalculation
of the example with improved Nusselt and Sher-
dϕ AsF A∆hv sF sF
wood numbers. The mass transfer is so small dx
=α
L cpL
θ+ β
L cpL
+β
G
ϕ (277b)
compared with the mass flow of gas and liquid (G
Equations (277 a) and (277 b) can also be abbre- 5.3.1.4. Examples of Simultaneous Mass and
viated as Heat Transfer: Static Models
θx =a1 θ+b1 ϕ (278a) In the examples outlined in Section 5.3.1.3, the

changes in temperature and mass fractions were
ϕx = a2 θ − b2 ϕ (278b) calculated from the rates of transport of enthalpy
and mass between the individual phases. The
where θx and ϕx are the derivatives of θ and concept used in this model is shown in Fig-
ϕ with respect to x. Differentiation of Equation ure 34 A for the mass transfer of a component
(278 a) and elimination of ϕx and ϕ give the or- from the gas phase into a counterflowing liq-
dinary homogeneous second-order differential uid phase. At the phase boundary the mass frac-
equation tion profile shows a jump caused by the relevant
phase equilibrium which may be expressed by
θxx + (a1 +b2 ) θx + (a1 b2 − a2 b1 ) θ= 0 (279) the relationship e.g., mPhG = AmPhL . In contrast
to the cases discussed in Sections 5.3.1.1 and
to which the system of coupled equations is now 5.3.1.3 the component being transferred is dis-
reduced. Since (a1 + b2 )2 > 4 (a1 b2 −a2 b1 ), the solved in the liquid phase. The mass fraction dif-
characteristic equation of differential Equa- ferences between the bulk phases and the phase
tion (279) λ2 + (a1 + b2 ) λ + (a1 b2 −a2 b1 ) = 0 boundary (Fig. 34 A) can be expressed as
has two real roots. The general solution for jm
Equation (279) is thus (mG −mPhG ) = (282a)
G βG sF dx
and
θ = C 1 e λ1 x + C 2 e λ2 x (280a) jm
(mPhL − mL ) = (282b)
L βL sF dx
The integration constants C 1 and C 2 are deter- where j m is the mass flux of the transferred
mined from the boundary conditions, which are component. If Equations (282 a) and (282 b) are
simplified here as T L0 = T G0 , since water and added and the relationship for the phase equi-
air are both assumed to have the same (room) librium is used to eliminate mPhL , then the fol-
temperature. This leads to θ = 0 and θx = b1 ϕ0 lowing equation is obtained for the steady-state
for x = 0. These conditions give C 1 = − C 2 and case, taking into consideration the mass balance
λ1 C 1 + λ2 C 2 = b1 ϕ0 . Thus the solution of Equa- for the gas phase:
tion (279) is
sF
jm = (mG −AmL ) dx
b1 ϕ0 . λ1 x / 1 A
G βG
+ L β L
θ= e − e λ2 x (280b)
λ1 −λ2 = −dmG G (283)
where ϕ0 is to be determined from the known Rearrangement gives
initial temperature of the water and the initial
dmG sF
mass fraction of water in the air; λ1 and λ2 have − = dx (284)
(mG −AmL ) 1
+ Aβ G
to be calculated from the characteristic equation. G βG L L
Equation (280 b) shows that cooling is initiated and after integration
entirely by mass transfer into the gas phase. The
gas temperature can now be determined with the G0
m
dmG
known solution for θ by integration of Equation =
(mG −AmL )
(274): mGe
H
sF
b1 ϕ0 1 λ1 x 1 λ2 x dx (285a)
TG =TG0 −a3 e − e (281) 1
+ Aβ G
(λ1 − λ2 ) λ1 λ2 G βG L L 0
where a3 =αsF/GcpG which can be abbreviated as

H
NTU = (285b)
HTU
where N T U denotes the number of transfer
units and H T U the height of one transfer unit.
The notation and assumptions for the deriva-

tion of Equation (285 b) are the same as those
in Section 5.3.1.3. The same procedure as indi-
cated in Section 5.2.2.2 for the heat transfer leads
to Equation (285 b). A similar relationship is of-
ten used for total heat transfer in heat exchangers
[108].
Equation (285 b) is used to determine the
height of a separation column with a known spe-
cific area and cross-sectional area or conversely
to determine the concentration difference for a
given height of the separation column. The quan-
tity AmL contained in the integral N T U still has
to be expressed in terms of mG and the boundary
conditions mG, 0 and mL, 0 or mL, e . All quanti-
ties in the H T U expression are known.
A completely different model for mass and
heat transfer in mass separation processes is
shown in Figure 34 B. Here the mass transfer
device consists of a series of separation stages,
in which phase equilibrium occurs between the
counterflowing phases. Mass transfer is assumed
to occur infinitely quickly and the separation
stage is homogeneous with regard to the vari-
ables of state. The mass balance in the steady-
state case for the components transferred is then
LmL,n−1 +GmG,n+1 =LmL,n +GmG,n (286)
Since phase equilibrium should exist in the sep-

aration stage, then mG, n can be expressed by
mL, n . Due to the modeling assumptions, the
mass balance does not contain any transport
terms. If the relationship for the phase equil-
brium is expressed in the form mG = A mL + B,
Equation (286) becomes

LmL,n−1 +G AmL,n+1 +B

= LmL,n +G AmL,n +B (287a)
or
LmL,n−1 − (L + AG) mL,n +AGmL,n+1 = 0 (287b)
For a separation column with N separation

stages (Fig. 35) for given mass fractions mG, 0
and mL, 0 , the relevant linear equation system is
− (L + AG) mL,1 +AGmL,2 = − LmL,0 (288,1)

Figure 34. Representation of the dynamic (A) and static (B)
models for mass transfer
L = mass flow of liquid; G = mass flow of gas ..
The subscripts L, G, Ph, and n denote liquid, gas, phase .
boundary, and the number of theoretical plates, respectively.
The superscript eq denotes equilibrium.
LmL,n−1 − (L + AG) mL,n +AGmL,n+1 = 0 line in Figure 36. Working from this point, point
(288,n)
(mL, 1 , mG, 2 ) can be found by inserting mL,1
.. into the mass balance equation (Eq. 290 a); this
. is shown in Figure 36 by the vertical line. In this
LmL,N −1 − (L + AG) mL,N = −G mG,0 −B
way Equation (288) can easily be solved graphi-
(288,N) cally by completing the construction for all sep-
In matrix form this can be written as aration stages step by step. The graphical solu-
tion method is the basis for the McCabe – Thiele
  method and similar procedures for calculating
− (L+AG) AG ...
 L − (L + AG ) AG ...  mass separation equipment (→ Distillation and
 
  Rectification, Chap. 4.1.1.).
 .. .. .. .. 
 . . . . 
... L − (L + AG)
   
mL,1 −LmL,0
.  . 
×
..
 = .
 .



mL,N −G mG,0 −B
or
Bm=c (288b)
The solution of this equation with one of the

methods discussed in Section 3.1.2 is
m=B −1 c (289)
and provides the mass fraction profile in dis-

crete form for the component being transferred
to the liquid phase over the entire length of the
column. Using the appropriate relationships for
phase equilibrium the corresponding profile can Figure 35. Schematic representation of a counterflow sep-
easily be determined for the gas phase. The sys- aration column
For explanation of symbols see Figure 34.
tem of equations could equally well be derived
for the mass fractions in the gas phase.
The above problem can easily be solved in
another way. Transformation of Equation (286)
gives
G
mL,1 − mL,0 = mG,2 − mG,1 or (290a)
L
G
∆mL = ∆mG (290b)
L
for the first separation stage in the column shown
in Figure 35. The geometric interpretation of this
equation is to find the point with coordinates
(mL, 1 , mG, 2 ) on a straight line of slope (L/G)
starting from the point with the coordinates Figure 36. Graphical solution of the equation system (288)
(mL,0 , mG, 1 ). As the first step, a point (mL, 1 , for a counterflow separation column: McCabe – Thiele dia-
mG, 1 ) has to be found that satisfies the phase gram
A and B are coefficients of the relation for thermodynamic
equilibrium relationship mG = AmL + B. This is phase equilibrium mG = f eq (mL ). For explanation of other
done by inserting mG, 1 into the phase equi- symbols see Figure 34.
librium relationship as shown by the horizontal
Static models can also be used for simulta- Ln+1 mL,n+1 +Gn−1 mG,n−1 +FnL mL,n
neous heat and mass transfer in mass separa- + FG
n−1 mG,n−1
tion processes. This will be described briefly G L
= Ln mL,n +Gn mG,n +Sn mG,n + Sn mL,n (292)
for the separation stage of the rectification col-
umn shown in Figure 37. Phase equilibrium is and finally that for the total enthalpy is
assumed in the separation stage and the sepa-
hL,n+1 +hG,n−1 +hL,F L +hG,F G
ration stage is regarded as being homogeneous n n−1
with respect to the variables of state. Phase equi- = hL,n +hG,n +hG,S G +hL,S L
n n
(293)
libria relationships exist both for the mass frac-
For a rectification column of N separation
tions and the enthalpies. With these precondi-
stages, for example, the mass fraction in the liq-
tions, balances for the total mass, the mass of
uid phase, the mass flows of the liquid phase, and
the individual components of the mixture, and
the temperature have to be calculated. To do this
the total enthalpy can be given.
Equations (291) – (293) are simplified by setting
all flows to and from the external surroundings to
zero (see also Fig. 37). This simplification does
not change the character of the resulting equa-
tions.
The expansions of the equations for inputs or
outputs at the individual separation stages, and
likewise the formulations for the condensor at
the top of the column and the reboiler at the bot-
tom of the column, offer no major difficulties.
To reduce Equations (291) – (293) to a system
of equations in L, mL , and T L further relation-
ships are needed to eliminate mG and G. Rela-
tionships for the phase equilibrium are used for
this: mG = f eq (mL ), and Gn /Gn−1 = Rn .
Here f eq is the relation for phase equilib-
rium and Rn is the ratio of the evaporation
Figure 37. Mass flows in a separation stage of a rectification enthalpies Rn = ∆hv, n /∆hv, n−1 . If mixing ef-
column fects are neglected the enthalpies are additive,
so that for example hL = (hA L − hL ) m L + hL .
F = liquid or gaseous feed; S = liquid or gaseous sink B B
The superscripts L and G denote liquid and gas phase, re- Finally, neglecting the mixing effects,
spectively. For explanation of other symbols see Figure 34.
ptot = [ p A (T ) − p B (T )] mL + p B (T ) is used
For the sake of simplicity the mixture is taken to obtain a correlation between the temperature
to be a binary mixture of components A and B. and the composition of the liquid phase. Using
The balances are considered for the steady-state h = h0 + cp (T − T 0 ), the enthalpies can finally
case. (The mass and enthalpy balances can, how- be eliminated. The resulting system of equations
ever, also be formulated without difficulty for a is
multicomponent mixture or for the nonsteady . /
pA (Tn ) − pB (Tn ) mL,n +pB (Tn ) =ptot (294a)
state, for details see [3], [8], [9].) The equa-
1
tion for the total mass is (notation is defined in mL,n − f eq mL,n
Fig. 37) 1+Rn

Rn
Ln+1 +Gn−1 +FnL +F G
n−1 + f eq mL,n−1 L n
1−Rn
G L
= L n + Gn + S n +Sn (291) 1 Rn
+ f eq mL,n − f eq mL,n−1
1+Rn 1−Rn
Analogously, the equation for the mass of a com-
ponent is
−mL,n−1 L n+1 = 0 (294b)

effect of chemical reactions on mass transfer is
Rn
(L n+1 −L n ) now discussed using a simple example (Fig. 38)
1−Rn
6. / based on the simple boundary layer problem
· hAL +∆hv − hL +∆hv
A B B
mL,n−1
given in Sections 5.2.2.1 and 5.3.1.1. The plate is
7 . / replaced by a soluble component A which passes
+ hB L +∆hv
B
−L n hA L −hL mL,n +hL
B B
into the fluid phase where it reacts with a sec-
ond component B. The reaction rate is first order
1
− (L n+1 −L n ) with respect to the individual components, the
1−Rn
6. / reaction rate is thus
· L +∆hv − hL +∆hv
hA A B B
mL,n
dmA
7 = −k (T ) mA mB (295)
+ hB B dt
L +∆hv
. / The component B is assumed to be present in ex-
+L n+1 hA L −hL mL,n+1 +hL = 0
B B
(294c)
cess such that mB ≈ const. If m = mA , then Equa-
In Equations (294) the relationships for mG = tion (295) can be simplified as
f eq (mL ), pi (T ), hiL (T ), and Rn are not explicitly dm
formulated. In this form Equation (294) should = −k (T, mB ) m (296)
dt
be adequate to point to the similarity to Equa-
tion (288). A system of N equations is obtained Using the same assumptions as in Sections
whose system matrix exhibits a distorted tridiag- 5.2.2.1 and 5.3.1.1 (the boundary layer approx-
onal structure. Each element consists of a block imations and negligible reaction enthalpy), the
with 3×3 elements. In contrast to Equation (288) following system of equations is obtained
the sytem is nonlinear and coupled.
∂u ∂v
Consideration of output and input at the in- + =0 (246)
∂x ∂y
dividual separation stages or at the top and bot-
tom of the column does not alter the structure
of this system of equations; further terms are
∂u ∂u ∂2u
simply added to the right-hand side and the di- u +v = ν 2, (247)
∂x ∂y ∂y
mensions of the blocks of the system matrix are
increased on account of consideration of a mul-
ticomponent mixture. Equation (294) is easy to
∂T ∂T ∂2T
solve because of the conditioning of the sys- u +v =a 2 (245b)
∂x ∂y ∂y
tem matrix. Equation (294 a) contains entries
only in the main diagonals, and Equation (294 b) From the addition of a source term S A to Equa-
on two diagonals. In most applications the sys- tion (266) and with SA = dm/dt:
tem is not therefore solved simultaneously, but
is solved successively starting with Equation ∂m ∂m ∂2m
u +v =D −k (T, mB ) m (297)
(294 a) and predefined boundary conditions. Ex- ∂x ∂y ∂y 2
amples of computer programs for the solution of
these problems with multicomponent formula- Due to the simplification used in the formu-
tions and nonsteady-state conditions are found lation of Equation (296), the conservation equa-
in [8], [9]. tions for the chemical species are no longer cou-
pled.
Equation system (246), (247), (245 b), and
5.3.2. Mass Transfer with Chemical (297) cannot be solved analytically. Numerical
Reactions solutions for this problem will not be discussed
here. However, also for Pr = Sc = 1 the similar-
In the dynamic and static models for calculating ity of the equations is lost due to the source
simultaneous mass and heat transfer, chemical term − k (T, mB ) m in Equation (297) originating
reactions have not yet been considered. In many from the chemical reaction. Thus the boundary
industrial mass separation processes, mass trans- layer δm develops differently from δu and δT .
fer is associated with chemical reactions. The
Since the source term in Equation (297) is neg- and λ2 = − Ha and thus the general solution for
ative, a larger gradient of the mass fraction of A Equation (299) is
occurs and this leads to a thinner boundary layer
δm in comparison with δu , δT . From the defi- m = C1 eHaη + C2 e−Haη (300)
nition of the mass-transfer number (see Section
From the above boundary conditions
5.3.1.1) it can be seen that the local mass-transfer
coefficient increases due to the larger gradients. 1 . /
C1 = mL −mPh e−Ha
Mass transfer is accelerated by the chemical re- eHa − e−Ha
action. and
1 . /
C2 = −C1 = mPh e−Ha −mL
eHa − e−Ha
so that the solution becomes
1
m= [mPh sinh (Ha (1−η))
sinhHa
+mL sinh (Haη)] (301)
Mass transfer is defined as usual by the condi-

tion

m dm 1 dm
JW = −D = −D
dy y=0 δm dη η=0
Figure 38. Acceleration of mass transfer by chemical reac-
tions From Equation (301) this condition gives
δ = film thickness; Jm = mass fluxes; D = diffusion coeffi-
cient m D Ha
(JW )react = [mPh coshHa − mL ] (302)
For explanation of other symbols see Figure 34. δm sinhHa
For a more thorough discussion of this ac- If the mass-transfer rates from Equation (302)
celeration effect, the boundary layer problem is are compared with the condition without reac-
further simplified by considering the situation tion (indicated by the subscript inert)
at a large √
distance from the edge of the plate.
D
Since δu ∼ x, the gradients of u, T , and m in the m
(JW )inert = (mPh −mL ) (303)
δm
x-direction become extremely small, and v ap-
proaches zero. Thus for x → ∞ Equation (297) the accelerating effect of the chemical reaction
is simplified to is immediately obvious. The ratio of Equations
(302) and (303) gives the “acceleration factor”
d2 m β r , i.e., the factor by which mass transfer is ac-
D −k (T, mB ) m ≈ 0 (298)
dy 2 celerated as a result of the chemical reaction:
If y is transformed into η = y/δm , then
Ha mPh mL
βr = 1− (304a)
d2 m tanhHa mPh −mL mPh coshHa
D −Ha2 m = 0 (299)
dη 2 For mL = 0
where Ha
1 βr = (304b)
tanhHa
k δm √ 1√
Ha = δm = Dk = Dk
D D β which in turn, for Ha > 3, gives
is the Hatta number. The boundary conditions βr =Ha (304c)
given in Figure 38 are m = mPh for η = 0 and
m = mL for η = 1. The characteristic equation of The acceleration of mass transfer is therefore
the ordinary homogeneous differential Equation proportional to the square root of the rate co-
(299), λ2 − Ha2 = 0 has the solutions λ1 = Ha efficient of the reaction rate. This only applies,
however, if the assumptions made in deriving other is not rate determining. Many heteroge-
the equation for the expression of the reaction neous systems also come within the term “sin-
rate (Eq. 296) are fulfilled. For very fast reac- gle phase”, for example heterogeneous catalytic
tions, i.e., for very high Hatta numbers, this is reactions, which are dealt with as quasi-single
no longer the case. phase. The mathematical treatment of single-
The concentration of component B is then phase reactors differs from the problems dis-
no longer “unlimited”. On the contrary, trans- cussed in the earlier chapters due to the bound-
port of B into the boundary layer becomes rate- ary conditions and the models for the processes
determining. The simultaneous solution for the occurring at and in the phase boundary layers.
conservation equations for A and B produces Definition of the state of the reactive mixture in
a result which is given in Figure 39 [110]. For chemically reactive flows with the fields u (x, t),
Ha >> 3 p (x, t), mi (x, t), i = 1, . . ., N and h (x, t) requires
the solution of the conservation equations for the
νA mBL DB total mass, the components of the momentum,
βr = 1+
νB mAPh DA the mass of the individual chemical species, and
The accelerating effect of the reaction is con- the enthalpy. For closure of the system of equa-
trolled by the limited availability of B. tions other fundamental equations may have to
be incorporated. With the simplifications intro-
duced in the earlier sections for the molecular
LIVE GRAPH
Click here to view transport processes this system of equations can
be given in the form
∂ ∂
+ (uk ) = 0 (131)
∂t ∂xk
for the total mass,

∂ui ∂ui ∂τik ∂p
+ uk = − + gi
i = 1, 2, 3 (204)
Figure 39. Acceleration factor β r as a function of the Hatta for the components of the momentum,
number Ha for various stoichiometric characteristic values
[110] ∂h ∂h ∂ ∂T
ν = stoichiometric coefficient; D = diffusion coefficient + uk = λ + Sh (240b)
The subscripts A and B denote components, L and Ph denote
liquid and phase boundary, respectively.
for the enthalpy, and

Introduction of the acceleration factor β r + uk = Di + Si
means that the effect of the chemical reactions i = 1, ...,N − 1 (265b)
is incorporated into the mass transfer; the chem-
ical reactions are no longer coupled with the for the chemical species. Since the system of
mass transfer. Further aspects of mass transfer Equations (131), (204), (240 b), and (265 b)
with chemical reactions are discussed in Section is coupled, simultaneous solution is necessary.
5.3.3.1. This is usually done numerically.
Before discussing a numerical procedure,
some fundamental characteristics of the mod-
5.3.3. Chemical Reactions in the eling of reactors will be shown by a simplified
Homogeneous Phase version of the system of Equations (131), (204),
(240 b), and (265 b). The first simplification is
Many chemical reactors are single phase. The the assumption of constant density, isothermal
term single phase should be understood here to conditions, chemical reactions that do not in-
mean that mass transfer from one phase to the volve volume changes, and frictionless flow.
5.3.3.1. Isothermal Reactors with Here however the numerical procedure analo-
Frictionless Flow, Constant Density, and gous to Section 5.1.2.2 is discussed in order to
Reactions Without Volume Changes compare various concepts of mathematical mod-
eling.
Under the above conditions it is easy to show
that the equation system

+ u = Di + Si
∂t ∂x ∂x ∂x
i = 1, ...,N − 1 (305)
is adequate for the definition of the problem pro-

vided that pressure effects and physical forces
are neglected and the assumption is made that
v = w = 0 (one-dimensional formulation).
If only two chemical species A and B are
considered which react in a first-order reac-
tion A + B → products, Equation (305) for the
steady-state case and with S A = − k mA is
dm d2 m
u − D +km=0 (306)
dx dx2
Figure 40. “Up-wind” difference scheme for a second-order
In Equation (306) m = mA , and thus also differential equation
For explanation of symbols see Figure 26.
S A = S = − k m. Analytical solutions can be
found for this equation for various boundary To convert the differential operators into dif-
conditions. If the equation is, for example, nor- ferences, Equation (306) is subjected to the same
malized after dividing by the density in the manipulations as Equation (226) and brought
form η = x/L, then into discrete form with an “up-wind” difference
scheme. For a one-dimensional problem a line
d2 m dm
−P e − DaI P em= 0 along the x-direction of the grid in Figure 26 is
dη 2 dη
adequate (Fig. 40). In Figure 40 the profile for m
Here Pe = u L/D, and DaI is the Damköhler num- is also shown. When the operations carried out
ber of the first kind, DaI = k τ , where τ = L/u in Section 5.1.2.2 are applied to Equation (306)
is the mean hydrodynamic residence time. For with the grid given in Figure 40, then the system
DaI < Pe, the characteristic equation of the of equations
above differential equation has two real roots
−al−1 ml−1 +bl ml − al+1 ml+1 −S∆Vl = 0 (307)
!
1 P e2
λ1,2 = P e ± +DaI P e is obtained. The coefficients of this tridiagonal
2 4
system of equations, with the notation from Fig-
The general solution is thus ure 40 are given by

1
m = C 1 e λ1 x + C 2 e λ2 x al−1 = + (u)w +D Fw (308a)
xl − xl−1

where C 1 and C 2 are found from the boundary 1
al+1 = +D Fe (308b)
conditions m = m0 for x = 0 and dm/dx = 0 for xl+1 − xl
x = L as
bl =al−1 +al+1 (308c)
λ2 e λ2 L
C1 = − m 0 and Under the conditions given above
λ1 eλ1 L − λ2 eλ2 L
u > 0. Assuming that (u F ) = ∆Vl /τl where τl
λ2 eλ2 L is the hydrodynamic residence time over a
C2 = m0 − C1 = m0 1 +
λ1 eλ1 L − λ2 eλ2 L distance l, and Pel is a local Péclet number
Pel = u (xl − xl−1 )/D, the coefficients can be Numerically this physical model finds its
converted into equivalent in the discrete form of differential
Equation (306) using an “up-wind” difference
al−1 = ∆Vl + ∆Vl (308d) scheme for the convectively dominated case.
τl τl P el
Equation (310) can easily be solved either by
al+1 = ∆Vl (308e)
τl P el+1 elimination or graphically by plotting both terms
of the equation against ml . The graphical solu-
bl = ∆Vl + ∆Vl + ∆Vl (308f)
τl τl P el τl P el+1 tion is shown in Figure 41 for a nonequidistant
grid, i.e., for ideally mixed reactors with dif-
From Equations (307) and (308 d – f ) the fol- ferent hydrodynamic residence times. It is im-
lowing tridiagonal equation system portant that there is no feedback from elements
further downstream.
1 1 1
1+ ml−1 − 1+ + ml If the flow becomes predominantly diffusive,
τl P el τl P el P el+1
1
then Pe is very small and Equation (309) is writ-
+ ml+1 + S (ml ) = 0 (309) ten as
τl P el+1

is obtained. If the case of convectively domi- 1 1 1
ml−1 − + ml
nated flows is considered where Pe → ∞, Equa- τl P el τl P el P el+1
tion (309) becomes 1
+ ml+1 +S (ml ) = 0 (311)
τl P el+1

(ml−1 − ml ) +S (ml ) = 0 (310)
τl Equation (311) has the same structure as Equa-
This is the mass balance for a cascade of ide- tion (310) but the feed for the ideally mixed reac-
ally mixed reactors. This analysis again shows tor with the number l consists of a flow with the
that reactors with very large Bodenstein or Péclet composition ml−1 and a flow with the composi-
numbers (ideally unmixed reactors) can be re- tion ml+1 (Fig. 42). There is therefore a feedback
presented by a cascade of ideally mixed reactors from the elements further downstream, and the
(see Fig. 41 and Section 4.3.1.1). volumetric mass flows are increased by the fac-
tor 1/Pel etc., as compared with the convective
mass flow m l /τl . Algorithms for the solution
of the tridiagonal Equation (311) on the basis of
LU decomposition of the system matrix can be
found in [29–32].
Figure 42. Cascade of ideally mixed reactors with feedback,

equivalent to a tubular reactor with strong back-mixing
Pe = Péclet number. For explanation of other symbols see
Figure 41.
Figure 41. Cascade of ideally mixed reactors equivalent to

an ideal tubular reactor
The general case where 1/Pel = O (1) has al-
τ = residence time; = density; l = number of reactor. ready been formulated with Equation (309).
Feedback dependent on the local Péclet num- With the definitions given in Figure 44, the
ber exists from the element l + 1 and the volu- mass fraction me at the outlet of the reactor can
metric mass flows are increased as against the be obtained from Equation (310)
convective flows by the factor [1 + (1/Pel )] etc.
1
(Fig. 43). For solution, the modeling parame- me =m0 (312)
(1+kτl )n
ter Pe is required, which contains the molecu-
lar diffusion coefficients or experimentally de- For the sake of simplicity the ideal plug
termined effective mixing coefficients (see page flow reactor in n equidistant sections so that
207). τl = τ = τ tot /n. Thus from Equation (312)
 
 1
me =m0  (313)
(n−1)(n−2)
1+kτtot + n−1
n2!
(kτtot )2 + n2 3!
(kτtot )3 +...
For n 1 and k τ tot 1

 
 1
me ≈m0  =m0 e−kτtot (314)
1+kτtot + 1
2!
(kτtot )2 + 3!
1
(kτtot )3 +...
where m0 and τ tot are unknown and depend on

In the foregoing analysis real reactors were de- the magnitude of the recirculated volume qr .
scribed by numerical solution of differential
Equation (306). This is equivalent to a repre-
sentation by elements of ideally mixed reactors.
Alternative structures of matrices of elements of
ideal reactors can be derived by physical analysis
of complex reactors [4], [11], [12], [24], [111],
[112]. An example which is of some importance Figure 44. Schematic representation of a loop reactor
in chemical engineering will be described here. q = flow rate; m = mass fraction
The subscripts 0, r, and e denote inlet, loop (recirculated),
Example of Combinations of Elements of and final, respectively; the superscript ( ) denotes conditions
after mixing of inlet and backflow.
Ideal Reactors: the Loop Reactor. The layout
of an ideal plug flow reactor with recirculation The term m0 results from the combined mass
(loop reactor) is shown in Figure 44, part of the fractions of the flows entering the plug flow re-
product flow is added to the feed. For analysis the actor and τ tot from the volumes of the flow re-
same assumptions apply as in Section 5.3.3.1. actor and the total volumetric flow. If ϕ = qr /q0
(the recirculation ratio), then
1 ϕ
m0 =m0 + me (315a)
1+ϕ 1+ϕ
and
1
τtot = τ0 (315b)
1+ϕ
where τ 0 is the hydrodynamic residence time
without recirculation. Substitution into Equation
Figure 43. Cascade of ideally mixed reactors with feedback, (314) gives
equivalent to a tubular reactor with back-mixing, general
case e−kτ0 /(1+ϕ)
Pe = Péclet number. For explanation of symbols see Fig- me =m0 (316)
1+ϕ 1 + e−kτ0 /(1+ϕ)
ure 41.
For ϕ → 0 the loop reactor takes on the character This can be regarded as an ideally mixed reac-
of the ideal plug flow reactor and me = m0 e−kτ0 . tor where the essentials of stability analysis can
For k τ 0 = DaI = 0.1, me /m0 ≈ 90 %. For ϕ → ∞, be shown. Three types of chemical reactions will
e−kτ 0 /ϕ = 1 − (k τ 0 /ϕ) and me = m0 /(1 + k τ 0 ). be considered:
The loop reactor is similar to an ideally stirred
1) Normal reactions with declining reaction
reactor with correspondingly lower conversions.
rate
The adjustable recirculation ratio of the loop
A + B → products
reactor is fully exploited in important engi-
where dmA /dt =− k 2 mA mB and
neering applications. When measuring kinetic
mB = mB0 − (mA0 − mA )
data in laboratory reactors the lowest possible
2) Autocatalysis
conversion is required in the reactor so that
A+2B→3B
the measured reaction rates can be assigned to
where dmA /dt = − k 3 mA m2B and
specific temperatures and concentrations. Thus
mB = mB0 + (mA0 − mA )
DaI 1. On the other hand the concentration
3) Self poisoning
differences measured for evaluating the reaction
A→B
rates should be as large as possible to minimize
where dmA /dt =− k 1 mA /(1 + K mA )2
statistical errors. As may be calculated from
(Section 3.2.1.1, Eq. 53).
Equations (314) and (316), for DaI = 0.1 and
ϕ = 10 the conversion in the plug flow reactor Along with the assumptions from Section
is 1 − (me /m 0 ) ≈ 1 %. The measured difference 5.3.3.1, equal molar masses of A and B are also
in the mass fractions is, however, me /m0 ≈ 90 %. assumed. Using the abbreviations α = mA /mA0
For reactions with positive reaction order rel- and β 0 = mB0 /mA0 and Equation (310), the fol-
ative to the reactants, the reaction rate falls off as lowing equations are obtained for the three cases
the concentration decreases. Recirculation of the 1−α
product lowers the concentration in the feed due =α2 + (β0 −1) α (317a)
τ k2 mA0
to dilution. There is however a class of reactions 1−α
in which the reaction rate first increases with de- =α [(β0 +1) −α]2 (317b)
τ k3 m2A0
creasing concentration and then decreases after 1−α 1

passing through a maximum (e.g., in heteroge- =α (317c)
τ k1 1+αmA0 K 2+αmA0 K
neous catalysis, enzymatic catalysis, and auto-
catalysis). Recirculation has a positive effect on where 1 − α is the conversion. The term
conversion in these cases. τ k 2 mA0 , τ k 3 m2A0 , or τ k 1 can be regarded as
the ratio of the hydrodynamic residence time
to a characteristic chemical time and is de-
5.3.3.1.1. Stability of Isothermal Reactors noted as the Damköhler number of the first kind
DaI . Equations (317) can conveniently be solved
Steady-State Cases. The importance of the graphically by plotting both sides against 1 − α.
stability of chemical reactors for safety and eco- Figures 45, 46, 47 show such plots for the three
nomic reasons is obvious. The description of cases above. For the normal case (Fig. 45 A), de-
stability analysis given here refers to the decreasing reaction rate with decreasing reactant
scription of processes in physical space, location concentration, an unambiguous steady-state so-
x = (x 1 , x 2 , x 3 ) and time t. Stability analysis and lution exists for each Damköhler number. With
theories often refer to the description of chemi- increasing Damköhler number (i.e., increasing
cal processes in the form of transfer functions in hydrodynamic residence time), the steady-state
the space of Laplace-transformed variables or solutions give higher conversions. All steady-
to the frequency behavior. Detailed discussion state solutions, which are plotted against the
of these relationships can be found in [3], [9], Damköhler number in Figure 45 B, are stable. If
[113–116]. a small disturbance occurs to the left or right on
To illustrate stability analysis in isothermal, the conversion axis in the steady-state solution,
steady-state reactors one element of the ideal opposing changes are produced in the right-hand
plug flow reactor will be used (Fig. 40). side (RHS) or left-hand side (LHS) respectively
of Equation (317 a).
for stability (Eq. 318). For Equation (317 b)

d(1−α) [RHS] = [β0 + (1−α)] [2 − 3 (1−α)
d
−β0 ], so that the stability criterion is not met

for small values of (1 − α).
Figure 45. Mono-steady-state conversion points for “nor-

mal” chemical reactions (A) and bifurcation diagram (B)
for isothermal conditions in a well-stirred reactor
LHS = left-hand side (Eq. 317 a); RHS = right-hand side
(Eq. 317 a); 1 − α = conversion; DaI = Damköhler number
of first kind; β 0 = mB0 /mA0
The “convective term” on the LHS decreases

(increases), whilst the “reaction term” on the
RHS increases (decreases). A lesser (greater)
availability of A due to convection therefore Figure 46. Multiple steady-state conversion points for au-
counterbalances a greater (lesser) consumption tocatalytic chemical reactions (A) and bifurcation diagram
of A due to reaction, so that the conversion is (B) for isothermal conditions in a well-stirred reactor
shifted to the right or to the left. The general LHS = left-hand side (Eq. 317 b); RHS = right-hand side
(Eq. 317 b)
condition for stability can be given in the termi- For explanation of other symbols see Figure 45.
nology of Equation (317) as
d d
In this range a small disturbance of (1 − α)
d (1−α)
[LHS] >
d (1−α)
[RHS] to the right leads to a larger increase in the “re-
at LHS = RHS (318a)
action term” than in the availability due to con-
d
vection; conversion therefore increases. The re-
For Equation (317 a), [LHS] = 1/DaI
d(1−α) action system thus always heads for the nearest
and d(1−α) [RHS] =2 (1−α) −β − 1; this sat-
d adjacent stable operating point. In the bifurca-
isfies the condition for stability for all possible tion diagrams shown in Figures 46 B and 47 B,
values of 1 − α based on the inlet condition β 0 . these unstable steady-state solutions lie on an S-
A completely different picture results for shaped branch. With a continuous increase in the
autocatalysis (Fig. 46 A) or self poisoning Damköhler number (residence time) however
(Fig. 47 A). In these cases multiple steady- the system cannot pass through this S-shaped
state solutions occur for a particular range branch, but jumps from a condition with low
of Damköhler numbers. Some of the so- conversion to one with high conversion. The bi-
lutions do not comply with the conditions furcation diagrams show that in both cases with
multiple steady-state solutions the Damköhler concentration of the catalyst β 0 , the S-shaped
number for “igniting” the reaction is higher than curve unfolds. Increasing the concentration of
that for “extinguishing” it. Thus hysteresis oc- the catalyst at the reactor inlet results in stable
curs. The jumping points are given by the con- reactor behavior, shown by the disappearance of
dition for the coalescence of an unstable with a multiple steady-state solutions.
stable steady-state solution: An analogous picture results for self poison-
d d ing. The appropriate conditions can easily be
[LHS] = [RHS] calculated from Equation (317 c) and the stabil-
d (1−α) d (1−α)
at LHS = RHS (318b) ity condition. Here the parameter controlling the
nonambiguity of the solutions is K mA0 which
In the case of autocatalysis this condition occurs can be regarded as a measure of the poisoning.
for A decrease in this quantity (lower pressure or
8 - lower inlet concentration of A in heterogeneous
= 1 + 20β0 −8β02 ± (1 − 4β0 ) (1 − 8β0 )
DaI catalytic reactions) leads to a range of conver-
sions that exhibits unambiguous, stable, steady-
state solutions (compare Figs. 45 B, 46 B, 47 B).
Nonsteady-State Cases. The stability anal-

ysis of steady-state, isothermal, ideally mixed
reactors has shown that the phenomenon of mul-
tiple steady states with hysteresis always occurs
when there is feedback. A feedback system will
now be considered for the stability analysis of
nonsteady-state reactions. The chemical reac-
tion is formulated as
where the step A → B is a noncatalytic first-

order reaction and a cubic (third-order) reaction
catalyzed with B. The feedback mechanism in
this reaction is clear: the more B is formed, the
faster A is consumed. Since the supply of A
from P remains limited, at high concentrations
of catalyst B the reaction A → B breaks down
until adequate A is again supplied.
Analysis will be performed on a batch reac-
tor so that the system of Equations (305) can be
written in the form
dmP
= −k0 mP (319a)
dt
Figure 47. Multiple steady-state conversion points for
chemical reactions with self poisoning (A) and bifurcation dmA
= k0 mP −k1 mA m2B −ku mA (319b)
diagram (B) for isothermal conditions in a well-stirred re- dt
actor
dmB
K = adsorption coefficient; mA0 = inlet mass fraction = k1 mA m2B +ku mA −k2 mB (319c)
of component A; LHS = left-hand side (Eq. 317 c), dt
RHS = right-hand side (Eq. 317 c)
For explanation of other symbols see Figure 45. A condition for mC results from the mass bal-
ance of the system. The quantity (k 2 /k 1 )1/2 is
The positions of the two jumping points move
closer together and, with an increase in the inlet
used to normalize the mass fraction, and the nor- For the stability analysis α and β are regarded
malization of the time is achieved through (1/k 2 ). as being subject to small disturbances ∆α and
The system of equations can then be written as ∆β, respectively. The time evolution of these
disturbances are then considered. The perturbed
dπ
= −επ (320a) quantities thus become
dτ
∂f (α,β)
where π = mP (k 2 /k 1 ) 1/2
, ε = (k 0 /k 2 ), and α = α0 +∆α, f (α,β) =f (α,β)0 + ∆α
∂α 0
τ = t/k 2
∂f (α,β)
+ ∆β+... (325a)
dα ∂β 0
= επ − αβ 2 − κα (320b)
dτ and
1/2 1/2
where α = mA (k 2 /k 1 ) , β = mB (k 2 k 1 ) , and ∂g (α,β)
β = β0 +∆β,g (α,β) =g (α,β)0 + ∆α
κ = (k u /k 2 ), and finally ∂α 0

∂g (α, β)
dβ + ∆β+... (325b)
= αβ 2 + κα − β (320c) ∂β 0
dτ
The functions f (α, β) and g (α, β) in Equations
The initial conditions are π = π 0 , α = β = 0 (325) are developed in Taylor series at α0 and
for τ = 0. Thus Equation (320 a) can easily be β 0 that are truncated after the first term. This
solved. The result is a reasonable approximation for small dis-
turbances. If Equation (325) is substituted into
π = π0 e−ετ (321)
Equation (322), the time evolution of the distur-
is used in the system of Equations (320) which bances can be expressed as
thus become a system of coupled first-order dif-
∂α0 ∂∆α ∂f (α, β)
ferential equations + = f (α, β)0 + ∆α
∂τ ∂τ ∂α 0

dα ∂f (α, β)
= µ − αβ 2 −κα=f (α, β) (322a) + ∆β (326a)
dτ ∂β 0
dβ and
= αβ 2 +κα − β = g (α, β) (322b)
dτ
∂β0 ∂∆β ∂g (α, β)
+ = g (α, β)0 + ∆α
where the abbreviation µ denotes ∂τ ∂τ ∂α 0

µ = ε π 0 e−ετ = µ0 e−ετ . For k 0 k 1 , k u , k 2 ∂g (α, β)
+ ∆β (326b)
the principle of quasi-steady state is applicable ∂β 0
for the mass fractions α and β. Thus Equations
If the quasi-steady-state solutions are consid-
(322 a, b) are solved without integration; ap-
ered, then Equation (326) becomes the system
proximate solutions for α and β can be obtained
of coupled ordinary differential equations
from the conditions
d∆α
∆α
dα dβ dτ
d∆β − J qs =0 (327a)
= =0 dτ
∆β
dτ dτ
From where Jqs is the Jacobi matrix of Equation (323)
∂f (α,β) ∂f (α,β)

µ − αβ 2 −κα= 0 (323a) J qs = ∂α
∂g(α,β)
∂β
∂g(α,β) (327b)
∂α ∂β qs
and
Equation (327) can easily be solved analytically
αβ +κα − β= 0
2
(323b) after being transformed into a second-order dif-
ferential equation (see Section 5.3.1.3). The gen-
the quasi-steady-state mass fractions αqs , β qs eral solution is
are given by
∆α (τ ) =C1 eλ1 τ + C2 eλ2 τ (328a)
2

αqs =µ/ µ +κ and βqs =µ (324a,b)
The different domains of the solutions of Equa-

∆β (τ ) = C3 eλ1 τ +C4 eλ2 τ (328b) tions (327) are shown in Figure 48 in a stability
where the eigenvalues λ1 and λ2 are determined diagram.
from the characteristic equation To demonstrate some of the possible cases the
simplifying assumption is made that the first-
λ2 −Tr (J qs ) λ+Det (J qs ) = 0 (329) order noncatalytic reaction (A → B) proceeds
very slowly, i.e., κ 1. Equations (323) and
This expression has already been used in Sec- (324) can then be further simplified
tions 5.3.1.3, 5.3.2, and 5.3.3.1. The trace of the
Jacobi matrix is the sum of the diagonal elements Tr (J qs ) = 1−µ2 (331a)

∂f (α, β) ∂g (α, β) Det (J qs ) =µ2 (331b)
Tr (J qs ) = +
∂α qs ∂β qs
Tr (J qs )2 −4Det (J qs ) =µ4 −6µ2 +1 (331c)

and its determinant is
As µ is a function of time, it is to be expected that
∂f (α, β) ∂g (α, β)
Det (J qs ) = during the course of the reaction with the deple-
∂α qs ∂β qs
tion of the reservoir P, the discriminants, Equa-
∂g (α, β) ∂f (α, β)
− tion (331 c), as well as Tr (Jqs ) and Det (Jqs ) will
∂α ∂β
qs qs change their values and signs, so that λ1, 2 take
so that the solution of the characteristic equation all possible combinations
is √
1) Initial condition, µ>1+ 2
1. 6 Initially only P is present so µ is very large.
λ1,2 = Tr (J qs ) ± Tr (J qs )2
2 Then Tr (Jqs ) is negative, Det (Jqs ) is pos-
/ itive, and the discriminant is also positive.
−4Det (J qs )}1/2 (330) Thus λ1, 2 become both real and negative.
Small disturbances ∆α and ∆β decay mono-
tonically, and the quasi-steady-state mass
fractions represent a stable node of the sys-
tem. The terms node (and focus) are derived
from the phase diagrams of ∆α and ∆β, see
[114]. In Figure 49 this range is shown in the
plot of αqs and β qs against µ. √
2) Progressive reaction, 1<µ<1+ 2
In this range of conversion of P, Tr (Jqs ) is
negative and Det (Jqs ) positive. The discrim-
inant has now changed its sign however. Due
to this λ1, 2 become conjugate complex with
a negative real part. In this case the distur-
bances ∆α and ∆β behave as damped oscil-
lations and the quasi-steady-state solutions
represent a stable focus of the system.√
3) Further progress of the reaction, 2 −
1<µ<1
In this concentration range of P, Tr (Jqs ) is
Figure 48. Stability diagram and nature of the steady-state positive and the discriminant negative. Here
solutions for the example in Section 5.3.3.1 too λ1, 2 are conjugate complex but with a
λ1, 2 = eigenvalues of Equations (328).
positive real part. The disturbances ∆α and
The time evolution of the disturbances ∆α and ∆β increase in the form of divergent oscil-
∆β is affected by the eigenvalues of λ1, 2 , which lations. The quasi-steady-state solutions are
depend on the values of Tr (Jqs ) and Det (Jqs ). an unstable focus of the system.
Next Page

√
4) Depletion of P, 0<µ< 2−1 3
µ1Bf = 1− κ+... and
Towards the end of the reaction the trace of 2
the Jacobi matrix is always positive; the dis- µ2Bf =κ1/2 (1 + 2κ) +...
criminant has changed its sign and is also
positive again. Now λ1, 2 are both real and Since Det (Jqs ) is always positive, then with con-
positive so that the disturbances grow expo- sumption of P the system passes through two
nentially. The state of the system is described Hopf bifurcation points between which solu-
as an unstable node. tions for λ1, 2 occur with a predominantly imag-
inary part. In this range instabilities can develop
in the form of stable oscillations, the amplitude
and frequency of which alter with the decreasing
concentration of P [113].
In chemical engineering practice instabilities
can only be avoided in systems with the proper-
ties quoted above for the range µ > 1. Details
of the Hopf bifurcation analysis and the de-
tailed calculation of the oscillation properties
(frequency, amplitude, and stability) are given in
[113–116], see also → Mathematics in Chemi-
cal Engineering, Chap. 6.7.
Figure 49. Quasi-steady-state solutions (a) αqs ( µ) and
(b) β qs ( µ) for an isothermal nonsteady-state system with
cubic autocatalysis 5.3.3.1.2. Sensitivity Analysis
For further explanation of symbols see text.
In Section 3.1.1.3 sensitivity analysis was de-
scribed as the change in the dependent variables
Between the conditions (2) and (3), a state of a model with a change of its modeling param-
exists at which µ = 1. At this point Tr (Jqs ) = 0 eters. If the dependent variables Φ are developed
and Det (Jqs ) > 0 so that λ1, 2 become imagi- as a Taylor series at a specific solution Φ0 , the
nary. Here the disturbances ∆α and ∆β behave change is given by
as undamped sinusoidal oscillations and the sys-
tem forms stable oscillations around the quasi-
∂Φ ∂2Φ ∆β 2
steady-state solutions. This point is designated Φ=Φ0 + ∆β+ + ... (332)
∂β 0 ∂β 2 0 2!
the Hopf bifurcation point.
For the simplified system without the non- where β is the vector of the parameters.
catalytic reaction, the trace of the Jacobi matrix The simplest measure of the system’s sensi-
is given by Equation (331 a). Thus the condi- tivity are the gradients (∂Φ/∂β) with which the
tion for the change of sign, i.e., Tr (Jqs ) = 0 and change in the dependent variables is calculated
dTr (Jqs )/dµ = 0, only occurs when µ = 1. If the with the aid of a Taylor series truncated after the
noncatalytic reaction is also considered, then first term. The gradients (∂Φ/∂β) are denoted
as a first-order sensitivity coefficients, the curve
µ4 − (1 − 2κ) µ2 +κ (1+κ) and the higher derivatives of Equation (332) as
Tr (J qs ) =
µ2 +κ sensitivity coefficients of the second and corre-
spondingly higher orders.
If the solution Φ is available in explicit form
(see also Eq. 323). Two Hopf bifurcation points
(e.g., Eq. 323), calculation of the sensitivity co-
are then obtained from
efficients is simple. For very many models of
2 1. / chemical engineering processes the differential
µ1,2Bf = (1 − 2κ) ± (1 − 8κ)1/2
2 equations which constitute the model cannot,
however, be solved analytically or with the help
For κ 1 the upper equation may be expanded
of simple assumptions. The sensitivity coeffi-
into a series and the two bifurcation points are
cients must then be determined from the differ-
ential equations or from the numerical solutions
Previous Page
[117], [118]. The latter method will now be de- For the calculation and discussion of the sen-
scribed. sitivity coefficients of higher order, reference
Numerical solutions provide the dependent should be made to the literature [117], [118].
variables not in the form of continuous functions An example of calculating first-order sensitiv-
but in discrete form (discrete values), calcula- ity coefficients for a complex model follows in
tion of the gradients is therefore not trivial. The Section 5.3.3.2.
numerical solution of a differential equation is
(e.g., for the example in Section 5.3.3.1) given
implicitly through Equation (309) in the form of 5.3.3.2. Nonisothermal Reactors
a system of equations.
In nonisothermal reactors the density does not
F (Φ) = 0 (333)
remain constant. The couplings in the system
The first-order sensitivity coefficients are ob- of Equations (131), (204), (240 b), and (265 b)
tained from Equation (333) by the differentia- therefore cannot be resolved and the equations
tion rule must be solved simultaneously.
∂F (Φ) ∂ (Φ) ∂F (Φ)
+ =0 (334)
∂ (Φ) ∂β ∂β
Thus the gradients are given by 5.3.3.2.1. Heterogeneous Catalytic Reactions
∂ (Φ) ∂F (Φ)
= −J −1 (335) Example: Heterogeneous Catalytic De-
∂β ∂β
hydration of Ethylbenzene to Styrene. The
In the example from Section 5.3.3.1 the corre- heterogeneous catalytic dehydration of ethyl-
sponding relations are easily verified: the Ja- benzene to styrene is outlined in Fig-
cobi matrix is given by the coefficients al−1 , ure 50. Ethylbenzene is preheated and mixed
− [bl − (∂S (ml )/∂ml )], and al+1 and is iden- with superheated steam. The mixture is passed
tical to the coefficient matrix for the equa- through a cylindrical reactor packed with an iron
tion system (Eq. 309). For β = k the deriva- oxide catalyst. Dehydration is endothermic. The
tives with respect to the parameters are sim- steam, used as a heat carrier, causes some sec-
ply (∂S (ml )/∂k). For a first-order reaction ondary reactions. A suitable reaction scheme is
(∂S (ml )/∂k) =− ml . If we simplify in Equa- [11], [119], [120]:
tion (309) Pel = Pel+1 = Pe then
∂F
=− (ml−1 − 2ml + ml+1 )
∂P e τl P e2
so for the sensitivity coefficients the equation
system (336) has to be solved. Equation system
(336) for the gradients ∂(Φ)/∂β has the same
structure as the original equation system (Eq.
309) and can consequently be solved by similar
methods.
 ∂m ∂m1 
1
∂k ∂P e
. .. 
. =
. . 
∂mn ∂mn
∂k ∂P e
 −1
− (b1 +k) a2
 a1 − (b2 +k) a3 
 
−
 ..


 . 
an−1 − (bn +k)
 
−m1 − τ P e2 (m0 −2m1 +m2 )
1
. .. 

· ..  (336)
. 

−mn −τ 2 (mn−1 −2mn )
nPe
0 ∂∗ 0 u0 ∗ ∂
+ (u∗ )
τ ∂t∗ L ∂x∗
0 u0 ∗ 1 ∂
+ ∗ ∗ (r ∗ v ∗ ) = 0 (337b)
R r ∂r
This can be transformed into

∂∗ ∂ 1 ∂ R
+ ∗ ∗ (u∗ ) + ∗ ∗ ∗ r∗ v∗ =0
∂t∗ ∂x r ∂r L
(337c)
∗ ∗ ∗
Since u , x , and r are all of the order of magni-
tude O (1), then v ∗ (L/R) = O (1) or v ∗ ≈ (R/L ),
and thus for (R/L ) 1 the third term in Equation
(337 c) can be neglected. In dimensional quanti-
ties the continuity equation for the steady-state
case thus has the form
Figure 50. Schematic of a pilot plant for catalytic dehydra-
tion of ethylbenzene du
a) Superheater; b) Catalytic reactor; c) Heat exchanger; =0 (337d)
dx
d) Separator.
The balance of momentum (Eq. 204) with the
C6 H5 −C2 H5 (1) → C6 H5 −C2 H3 (2) + H2 (3) (i) above result in cylindrical coordinates is

∂u ∂u ∂τxx 1 ∂ (rτrx )
C6 H5 −C2 H5 → C6 H6 (4) + C2 H4 (7) (ii) + u = +
∂t ∂x ∂x r ∂r
C6 H5 −C2 H5 + H2 → C6 H5 −CH3 (5) + CH4 (6) (iii)

1 ∂τθx ∂p
+ − (338a)
r ∂θ ∂x
1/2C2 H4 + H2 O (10) → CO (8) + 2 H2 (iv)
For flows through packed catalyst beds the vis-
CH4 + H2 O → CO + 3 H2 (v) cous stress term can be expressed by the perme-
ability κ according to Darcy’s Law [8], [121].
CO + H2 O → CO2 (9) + H2 (vi)
The term in the square brackets in Equation
(338 a) then becomes
The formulation of this set of reactions is nec-
∂τxx 1 ∂ (rτrx ) 1 ∂τθx µu
essary because they all have an appreciable re- + + =
∂x r ∂r r ∂θ κ
action enthalpy so that conversion into the vari-
ous byproducts also affects the temperature pro- If the same normalized variables are used as
file. Furthermore the reaction rate of reaction (i) in Equation (337) together with the normalized
is given by r (i) = k 1 (m1 − m2 m3 /K ) [8], [108] pressure p∗ = p/p0 , Equation (338 a) becomes
which indicates poisoning due to the products
R ∂u∗ R ∂u∗
styrene and hydrogen, and thus the mass frac- + u∗ ∗
tion m1 is coupled with m2 , m3 . τ u0 ∂t∗ L ∂x
µR u∗ Rp0 1 ∂p∗
The appropriate formulation of Equations =− − (338b)
κu0 0 ∗ L 0 u20 ∗ ∂x∗
(131), (204), (240 b), and (265 b) is in cylin-
drical coordinates for this axially symmetrical Estimates of the orders of magnitude of the fac-
problem. The continuity equation in this form is tors in front of the differential quotients in Equa-
∂ ∂ 1 ∂
tion (338 b) under pilot plant conditions (τ ≈ 1 s,
∂t
+
∂x
(u) +
r ∂r
(rv) = 0 (337a) u0 ≈ 0.2 m/s, R/L ≈ 5×10−2 , 0 ≈ 0.5 kg/m3 ,
p0 ≈ 1.5×105 Pa, µ ≈ 10−5 kg m−1 s−1 , and fi-
If we use the normalized variables u∗ = u/u0 , nally κ ≈ 1.5×10−8 m2 ) leads to
v ∗ = v/u0 , ∗ = /0 , t ∗ = t/τ , x ∗ = x/L , and
r ∗ = r/R, then from Equation (337 a) it follows R
<
R
<1<
µR

Rp0
that L τ u0 κu0 0 L 0 u20
Thus, for the given conditions, the pressure term ≈ 4×10−5 kJ m−1 K−1 s−1 , α ≈ 4×10−2 kW ·
predominates in the steady-state balance of mo- m−2 K−1 , ε ≈ 0.36, and s ≈ 1.5×103 m−1 ) re-
mentum which in dimensional quantities simpli- sults in
fies to
λ0 L λ0 L L αs
< ≈1
dp R2 0 cp0 u0 L 0 cp0 u0 τ u0 ε0 cp0 u0
≈ 0 or p ≈ const. (338c)
dx
The fundamental mechanisms for energy
Consequently the continuity equation and the
transport are therefore expressed in the one-
momentum equation are no longer coupled with
dimensional form of the temperature equation,
the other transport equations and pressure p and
which in steady-state formulation with dimen-
velocity u are simple to estimate.
sional quantities becomes
Using the definition equation for enthalpy,
the conservation equation for the enthalpy dT αs
cp u = (TCat −T ) + ri ( − ∆hri ) (339c)
(Eq. 240 b) can be transformed into a differential dx ε
equation for temperature (see Section 5.2.2.1).
For a multicomponent system the conservation The heat-transfer term in Equation (339 c) cou-
equations for the mass of the chemical species ples the temperature of the gas phase T with
must be used for this. The result, also in cylin- the catalyst temperature T Cat . This coupling re-
drical coordinates, is quires an equation for determining the catalyst
temperature, which is derived from the heat bal-
2
∂T ∂T ∂ T 1 ∂ ∂T ance for the catalyst bed:
cp +cp u +λ 2
+ r
∂t ∂x ∂x r ∂r ∂r
∂TCat ∂ 2 TCat λeff ∂ ∂TCat
= ri (−∆hri ) +SC (339a) Cat cpCat = λeff + r
∂t ∂x2 r ∂r ∂r

Equation (339 a) contains the assumptions in- 1
− αs (TCat −T ) (340a)
troduced in Section 5.2. In addition since 1−ε
p ≈ const., S C only includes a term for heat Normalizing the equation in similar fashion to
transfer from the gas phase to the catalyst. Due to Equations (337), (338), or (339) results in
the transformation of the conservation equation
of enthalpy into a differential equation for tem-

T0 ∂T ∗Cat λeff TCat0 ∂ 2 T ∗Cat
perature, the term ri (− ∆hri ) occurs which Cat cpCat =
τ ∂t∗ L2 ∂x∗2
describes the release of heat due to chemical re- ∗
TCat0 1 ∂ ∂T
actions. As in Equations (337) and (338), all +λeff r∗ Cat
R2 r ∗ ∂r∗ ∂r∗
quantities are normalized to the conditions at
1 ∗
the inlet of the reactor. For Equation (339 a) this − αsTCat0 (TCat −T ∗ ) (340b)
1−ε
results in
Estimation of the orders of magnitude of the fac-
L ∗ ∗ ∂T ∗ ∂T ∗
cp ∗ +∗ c∗p u∗ tors preceding the differential quotients gives
τ u0 ∂t ∂x∗
λ0 ∂ T2 ∗ λeff TCat0 TCat0
= λ∗ λeff
L 0 cp0 u0 ∂x∗2 L2 R2
∗ ∗
λ0 L λ ∂ ∗ ∂T and thus the fundamental mechanism for the
+ 2 r
R 0 cp0 u0 r∗ ∂r∗ ∂r∗ transport of enthalpy in the catalyst bed in the
L αs steady state is represented by an equation which
+ (T ∗Cat −T ∗ )
ε0 cp0 u0 is one-dimensional in the radial direction
L
+ ri (−∆hri ) (339b)
u0 T0 0 cp0 λeff d dTCat 1
0= r −
r dr dr 1−ε
where α is the heat-transfer coefficient, s the
specific surface area, ε the intergranular volume, αs (TCat −T ) (340c)
and T Cat the catalyst temperature. Estimation of
the factors preceding the differential quotients
in Equation (339 b) (cp0 ≈ 2.5 kJ kg−1 K−1 , λ0
LIVE GRAPH and for the pilot plant conditions assumed

Click here to view
here, obviously convective transport in the ax-
ial direction is dominant. The following one-
dimensional equation results for the steady-state
case
dmi
u = Si = ri , i = 1, ..., 8 (341c)
dx
The above estimates have resulted in a reduction
of the model for the fixed bed catalyst reactor:
convective transport of mass in the axial direc-
tion is the main transport mechanism for the gas
phase, whilst for the catalyst phase conductive
transport of heat in the radial direction along
with heat transfer predominates. Consequently
the couplings in Equations (131), (204), (240 b),
and (265 b) are largely reduced.
To solve the system of Equations (339 c),
(340 c), and (341 c), Equation (340 c) for the cat-
alyst temperature is transformed into normalized
variables with the transformations
r TCat −T
r∗ = , θ=
R TW −t
Figure 51. Calculated temperature, conversion, and selec-
tivity profiles for the catalytic dehydration of ethylbenzene (T W is the wall temperature) and
[119]
R2 αs
β2 =
The remaining problem is the expression of the λeff (1−ε)
conservation equations for the chemical species
by means of similar estimates of orders of mag- This gives
nitudes. The conservation equation for the chem- d2 θ 1 dθ
ical species with the simplified continuity equa- + − β2θ = 0 (342)
dr ∗2 r ∗ dr ∗
tion (Eq. 337 d)
with the boundary condition (dθ/dr ∗ ) = 0 at
+ u = Di r ∗ = 0. This is the modified Bessel differential
∂t ∂x ∂x ∂x
equation with variable coefficients, the general
1 ∂ ∂mi
+ rDi +Si solution of which is given by [122]:
r ∂r ∂r
i = 1, ..., 8 (341a) θ = C1 I0 (βr ∗ ) +C2 K0 (βr ∗ ) (343)
is first formulated with the variables normalized
to the state at the reactor inlet. where
0 mi0 ∗ ∂m∗i 0 mi0 u0 ∗ ∗ ∂m∗i ∞

βr ∗ 2n+p 1
∗
+ u Ip (βr ∗ ) = and
τ ∂t L ∂x∗ 2 n! (n+p) !
∗ n=0
0 Di0 mi0 ∗ ∗ ∂ mi 2

= Di d (βr∗ )
L2 ∂x∗2 Kp (βr ∗ ) =Ip (βr ∗ )
βr ∗ Ip2 (βr ∗ )
0 Di0 mi0 1 ∂ ∂m∗i
+ 2 ∗ ∗
r ∗ ∗ Di∗ ∗
R r ∂r ∂r From the above boundary condition and the
+0 ∗ Si , i = 1, ..., 8 (341b) properties of the Bessel functions dI 0 /d ( β r∗ )
With Di0 ≈ 10−3 m2 s−1 = I −1 ( β r∗ ) and dK 0 /d ( β r ∗ ) = K −1 ( β r ∗ ),
0 Di0 mi0 0 Di0 mi0 0 mi0 u0

L2 R2 L
then C 2 is zero. With a further boundary condi- and radial dispersion) can be reduced to a one-
tion θ = 1 for r ∗ = 1, it follows that C 1 = 1/I 0 ( β), dimensional problem and of how the system of
so the general solution changes to model differential equations is decoupled. Nev-
ertheless the model successfully reproduces ex-
I0 (βr ∗ ) I0 (βr ∗ )
θ= or (TC −T ) = (TW −T ) perimental temperature and concentration pro-
I0 (β) I0 (β)
files measured in a pilot plant [11]. Another spe-
(344)
cial feature of the above model is the treatment
Equations (339 c) and (341 c) can only be solved of the heterogeneous catalytic reactions. Mass
numerically. Equation (339 c) has to be trans- transport processes in the catalyst phase were
formed into a difference equation in the axial assumed to have no effect on the reaction rates.
direction. With the solution of Equation (344) The heterogeneous system is thereby regarded
for the catalyst temperature the cross-section- as being quasi-homogeneous and all couplings
averaged heat flow to the catalyst bed can be cal- between mass fractions in the gas phase and cat-
culated for each control volume. For this Equa- alyst phase are neglected. This assumption is not
tion (339 c) with solution Equation (344) is in- always true. The effect of transport processes on
tegrated over the cross section of the reactor: the reaction rates and the repercussion on mod-
els for reactors with heterogeneous catalysis are
1 discussed below.
dT ∗
0=− ε2πr ∗ cp u dr
dx
0 Some Particulars of Heterogeneous Cat-
1 alytic Reactions. The effect of transport pro-
αs
+ ε2πr ∗ (TC −T ) dr ∗ cesses on reaction rates in heterogeneous catal-
ε
0 ysis can be treated analogously to the acceler-
1 ation of mass transport by chemical reactions
+ 2πr∗ ri (−∆hri ) dr∗ (345) described in Section 5.3.2 (Fig. 38). The core
0 of the liquid phase is replaced by a porous cat-
1 alyst sphere that is one-dimensional in spheri-
The solution of the integral (TC −T ) r∗ dr∗ cal coordinates (Fig. 52). Furthermore if a sim-
0 ple reaction A → products is considered, the
also results from the general properties of the heterogeneous reaction rate of which is as-
Bessel functions sumed to follow a formal first-order rate law
1 r = − k mA = − k m, where k is a rate coeffi-
R3/2 I1 (β) cient related to the surface area of the catalyst.
(TC −T ) r∗ dr ∗ = √ (TW −T ) (346)
β I0 (β)
0
This expression can be inserted into Equation

(339 c) which is then solved numerically and si-
multaneously with Equation (341 c).
Numerical solutions for pilot plant conditions
with integration routines from [28] are taken
from [119] and shown in Figure 51. Kinetic data
for reactions (i) – (vi) (see above) are given in
[8], [11], [119]. A drop in temperature of ca.
75 K and a continuous increase in conversion
occur over the length of the reactor. At higher
conversions the reactions forming the byprod-
ucts gain greater importance. Figure 52. The effect of mass transport in heterogeneous
The estimates used to obtain the model in the catalytic reactions
m = mass fraction; r = radial distance; Rcat = radius of cat-
form of Equations (339 c), (340 c), and (341 c) alyst sphere
are undoubtedly drastic. They should there- The subscripts G and S denote gas phase and surface of
fore be regarded as an example of how a two- catalyst, respectively.
dimensional problem (a reactor model with axial
The steady-state mass flux to the surface of The heat transferred to the surroundings is re-
the catalyst (see also Section 5.3.1) is given by leased by chemical reactions occurring at the
catalyst. Thus from the steady-state condition
j m = βs (mG −mS ) (347) j h = r S (− ∆ hr )
This flow is compensated for by the consumption
−1
TG (−∆hr ) mG ηext k (TG )
of component A by the chemical reaction. If an = 1+ λ
(353)
TS LeTG βs
“effective” reaction rate r S = − k s m S with the D eff
mass fraction at the surface of the catalyst is for- To derive Equation (353) full analogy for heat
mulated, then the mass fraction m S for steady- and mass transfer, i.e., Pr = Le · Sc, is assumed.
state conditions is given by Using the abbreviations γ = E a /R T G (Arrhenius
mG number), and
mS = (348)
k
1+ βs (−∆hr ) mG
βH = λ
(Prater number)
LeTG
where k = k s. In Equation (347) m S can now Deff
be eliminated so that Equations (351) and (353) are combined to give

k −1 ηext
j m = βsmG 1− 1+ (349) . /
βs exp −γ (1+βH ηext DaII )−1
6 . /7−1
Equation (349) also gives the effective reaction = 1+DaII exp −γ (1+βH ηext DaII )−1 (354)
rate for steady-state conditions. As in Section
5.3.2, Equation (349) illustrates the accelera- η ext can also take values greater than 1 in the
tion of mass transport with an increasing ratio nonisothermal case if β H > 0. In this case the re-
Da I I = k/β s, i.e., with increasing reaction rate action at the surface of the catalyst occurs at a
where Da I I is the Damköhler number of the sec- higher temperature than the gas-phase tempera-
ond kind. The degree of external utilization (i.e., ture T G . Since all quantities in Equation (354)
effectiveness) of the catalyst η ext is defined as are related to T G , then values of η ext > 1 are also
the ratio of the surface reaction rate r S to the consistent with the definition of η ext .
reaction rate for Da I I → 0, i.e., m S → m G . It Conditions inside the catalyst can be illus-
thus follows that (cf. Eq. 348) trated in a similar fashion. For spherical geom-
etry (Fig. 52) diffusive mass flux inside the cat-
kmG 1
ηext = = (350) alyst is given by
k
kmG 1+ βs 1+DaII
dm
j m = −Deff 4πr2 (355)
For nonisothermal conditions the temperature dr
dependence of the reaction rate must be consid-
Changes in the diffusive mass flux are caused by
ered. If Da I I is defined with the conditions in
chemical reactions at the internal surface of the
the gas phase and constant density is assumed,
catalyst, so that under steady-state conditions the
it follows from Equation (350) that
mass balance is
−1
k (TS ) k (TS ) dj m
ηext = 1+ DaII (351) = k 4πr2 m (356)
k (TG ) k (TG ) dr
Given the temperature dependence of the rate Using Equation (355)
coefficient in the form of an Arrhenius equation
k = k 0 e−E a /RT , the temperature at the surface d2 ϕ 2 dϕ
+ − Φ2K ϕ = 0 (357)
T S must be eliminated from Equation (351) to dη 2 η dη
calculate η ext . The temperature at the surface T S
is obtained where the normalized quantities
may be calculated in a similar way as m S . In the
ϕ = m/m S
and η = r/RCat and the abbreviation
steady-state case
ΦK =RCat k s/Deff are used (RCat is the ra-
j h = αs (TS −TG ) (352) dius of the catalyst sphere). The solution of
Equation (357) with the boundary conditions Subtracting Equation (363) from Equation (360)
ϕ = 1 for η = 1 and dϕ/dη = 0 for η = 0 is gives
sinh (ΦK η) λeff
ϕ= (358) d2 m 2 dm Deff d2 T 2 dT
ηsinh (ΦK ) + − + = 0 (364)
dr 2 r dr (−∆hr ) dr 2 r dr
Completely analogous to the external mass
transfer, a degree of internal utilization of the which, after integrating twice with the boundary
catalyst η int (internal effectiveness factor) can conditions m = m S and T = T S for r = R Cat , and
be defined as the ratio of the mean reaction rate dm/dr = 0, and dT /dr = 0 for r = 0, leads to the
in the catalyst, result
Cat
R
T − TS =
Deff (−∆hr )
(mS −m) (365)
reff = k sm4πr 2 dr λeff
0
With this the temperature can now be eliminated
and reaction rate for m → m S . Integration of from Equation (360). If the Prater number, Ar-
Equation (358) gives rhenius number, and Thiele modulus ΦK are de-
−1 fined with the conditions at the outer surface of
3 1
ηint = tanhΦK − (359) the catalyst, i.e.,
ΦK ΦK
For ΦK > 3, η int ≈ 3/ΦK , for ΦK < 0.3, βH =
(−∆hr ) mS
, γ=
Ea
, and
η int ≈ 1. The result is similar to the acceler-
λ RT
Deff
T S S
ation of mass transfer by chemical reactions,

k0 s Ea
cf. Section 3.3.2. The calculation of η int for Φ2K =RCat
2
exp −
Deff RTS
other catalyst geometries including more realis-
tic pore structures and other classes of reaction Equation (364) becomes
are described in [24], [123].
d2 ϕ 2 dϕ
For nonisothermal conditions the tempera- +
dη 2 η dη
ture dependence of the reaction rate must once
(1−ϕ)
again be taken into consideration. If the sim- − Φ2K ϕexp γβH =0 (366)
1+βH (1−ϕ)
ple Arrhenius expression is substituted for k in
Equation (356), then assuming constant density Equation (366) cannot be solved analytically,
and neglecting the temperature dependence of numerical solutions are given in [124]. If the in-
the effective diffusion coefficient, the result is ternal effectiveness factor η int is calculated from
the numerical solutions [124] the results shown
d2 m 2 dm k0 Ea
+ = sexp − m (360) in Figure 53 are obtained. For γ = 20, multiple
dr 2 r dr Deff RT
solutions exist for η int at high values of β H and
Inside the catalyst heat is transported by con- low values of the Thiele modulus. The middle
duction. The conductive heat flow is given by solutions are unstable so that ignition and extinc-
dT tion of the exothermic chemical reaction in the
j h = −λ4πr 2 (361) catalyst can occur for certain values of Thiele
dr
moduli. As all parameters are related to the state
Changes in heat flow are caused by heat release
at the outer surface of the catalyst, values of
due to chemical reactions. Under steady-state
η int > 1 are consistent with the definition of the
conditions
internal effectiveness factor. Due to the exother-
dj h mic reaction the temperature inside the catalyst
= k s4πr2 m (−∆hr ) (362)
dr can be higher than temperature on the outer sur-
From Equations (361) and (362) a differential face.
equation for the temperature is obtained By introducing an effective reaction rate
r eff = η eff r G , the rate of heterogeneous catalytic
d2 T 2 dT (−∆hr ) k0 sexp − RT
Ea reaction is related to the conditions in the gas
+ = m (363)
dr 2 r dr Deff λeff Deff
phase and is thus no longer coupled with the pression is of the first order with respect to the
internal transport in the catalyst. This permits mass fraction of A. Inhibition by mass transport
the description of reactors with heterogeneous shifts the order of reaction in the direction of
catalysis as quasi-single-phase systems. The ef- first order. Selectivity in parallel or secondary
fectiveness factors η int or η ext can be calculated reactions will be similarly affected.
from the variables of state at the surface of the The temperature dependence of the re-
catalyst or in the gas phase, respectively. For the action rate is also influenced by inhibi-
isothermal case and spherical geometry tion by mass transport. If the expression
−1 r eff = − η eff k m G = − k∗ m G is used for a first-
1 Φ2K order reaction, and the temperature dependence
ηeff = + ∗
ηint 3Bi is given as usual by k∗ = k ∗0 e−E a /RT , then
where the Biot number Bi = β R Cat /Deff . Ea∗
lnk∗ = lnk0∗ − (367)
Nonisothermal conditions and other geome- RT
tries are discussed in [24], [123], [124]. For η eff = 1 there is chemical control, k ∗0 = k 0
and E ∗a = E a . If diffusion in the catalyst pores
LIVE GRAPH
Click here to view is rate controlling, η ≈ 3/ΦK . Then ln k ∗ =
− ln ΦK − E a /R T . Substitution of
ln k 0 + ln 3
ΦK =RCat k/Deff gives
1 1 1 Ea
lnk∗ = lnk0 +ln3+ lnDeff −
2 2 2 RT
√
thus k0∗ = 3 k0 Deff and Ea∗ = 12 Ea . If the
temperature dependence of the effective diffu-
sion coefficients is neglected, the activation en-
ergy for pore diffusion-controlled reaction is
about half that for chemical control. If control
is exclusively due to mass transfer, then r eff ≈
− β s m G and k ∗ = β s ∼ Deff . Taking into ac-
count the temperature dependence of Deff , then
lnk ∗ = lnk0∗ + 32 lnT which leads to an acti-
vation energy E ∗a of ca. 5 kJ/mol for this case.
Thus the experimental determination of the ef-
fective formal activation energy for a heteroge-
neous catalytic reaction clarifies the extent of
control by different transport processes. For fur-
ther discussion of these relationships see [24],
[123], [124].
Figure 53. Effectiveness factor of a catalyst as a function of
the Thiele modulus ΦK and the Prater number β H for spher- In addition to the formulation of conservation
ical catalyst geometry (Arrhenius number γ = 20) [124] equations for reactor models for heterogeneous
γ = Arrhenius number; η int = internal effectiveness factor. catalytic reactions, combinations of simple re-
actor elements are frequently used for model-
The discussion in this section was based on
ing these systems. For further information, see
first-order reactions with no changes in the mole
[12], [125]. Other complicated reactors (e.g., flu-
number. Very few reactions in heterogeneous
idized bed reactors) for heterogeneous catalytic
catalysis can be described with these expres-
reactions can be similarly dealt with [24], [123].
sions, higher order reactions are much more fre-
quent. Furthermore the catalysts may be “poi-
soned” by adsorption of the reactants or prod- 5.3.3.2.2. Stability Analysis of
ucts (see page 249) yielding nonintegral orders Nonisothermal Reactors
of reaction. Inhibition by mass transport influ-
ences the order of the catalytic reaction. In the Steady-State Cases. The stability analysis
extreme case r eff = β s (m G − m S ). This rate ex- of isothermal reactors discussed in Section
5.3.3.1 demonstrated the close connection of the cp cp k0

phenomenon of multiple steady states in steady- τN = =
αstchem αs
state systems and the instability of nonsteady-
state systems to a feedback mechanism. For the can be defined from the heat transfer. A recipro-
isothermal cases a chemical feedback mecha- cal Arrhenius number γ r = RT A /E a is also intro-
nism was discussed in the form of autocatalysis duced. With these abbreviations Equations (368)
and self-poisoning. Another feedback mecha- and (369) become
nism is the heat release from a chemical reaction.
1−α θ
This will be discussed for a simple first-order −αexp =0 (370a)
DaI 1+γr θ
reaction, A → B + heat, the temperature depen-
θ 1 1 θC
dence of the rate coefficient is of the Arrhenius θad αexp − + θ+ =0
form, k = k0 e−Ea /RT . With increasing conver- 1+γr θ DaI τN τN
(370b)
sion of A heat is released. The released heat in-
creases the temperature of the reaction mixture Equations (370 a, b) contain the variables α and
and the reaction rate. This in turn increases the θ as a function of six parameters. To reduce the
rate of heat release. The reaction rate is an ex- number of parameters, the case of very high ac-
ponential function of the temperature. Therefore tivation energy, γ r 1, T A = T 0 , and θC = 0 is
the feedback mechanism is nonlinear in temper- considered. With these assumptions the follow-
ature. ing simplified equations are obtained
Stability analysis for nonisothermal steady-
state reactors will again be carried out for a well- 1−α
−αeθ = 0 (371a)
stirred reactor (one element of a reactor cascade DaI

of ideally mixed reactors which is used to repre- 1 1
θad αeθ − + θ=0 (371b)
sent a flow reactor with convectively dominated DaI τN
flow). In analogy with Equation (310), the mass
balance for A gives In order to remain as close as possible to the
notation used in Section 5.3.3.2, θ in Equation
(371 a) is replaced by Equation (371 b) so that
(m0 −m) −mk0 e−Ea /RT =0 (368)
τ
 
From the enthalpy balance and transformation 1−α
=αexp 
(1−α) θ ad  (372a)
of Equation (240 b) into an equation for temper- DaI 1+ DaI τN
ature, the following equation is obtained:
The temperature increase can easily be attributed
cp
(T0 −T ) + (−∆hr ) mk0 e−Ea /RT to α from Equations (371 a, b):
τ
− αs (T − TA ) =0 (369)  
 (1−α) θ ad 
θ= (372b)
where the specific surface area s is the effective 1+ Da
τ
I
N
surface for heat transfer to the surroundings di-
vided by the total volume of the ideally mixed re- Equation (372 a) can be solved graphically by
actor. The source term in Equation (240 b) is thus plotting both sides against the progress of the
represented by a heat-transfer term. As in Sec- reaction 1 − α (conversion). In order to further
tion 5.3.3.1, Equations (368) and (369) are trans- reduce the number of parameters, ideal adiabatic
formed into normalized variables: α = mA /mA0 , conditions are assumed, i.e., τ N → ∞. Thus
θ = (T − T 0 ) E a /RT 20 , θC = (T A − T 0 ) E a /RT 20 , the left-hand side (LHS) of Equation (372 a) is
and DaI = τ k 0 . The Damköhler number (the ra- only dependent on DaI , whilst the right-hand
tio of the mean residence time to a charac- side (RHS) is only dependent on the adiabatic
teristic chemical time, the time required un- temperature increase. The solutions for the case
til m/m0 = e−1 ) is defined with the inlet con- discussed here (Fig. 54) are qualitatively simi-
ditions. If the adiabatic temperature differ- lar to the solutions for the isothermal case with
ence ∆T ad = (− ∆hr ) m0 /cp is also defined with self poisoning (see page 243). Here too for a
E a /RT 20 , then θad = (− ∆hr ) m0 E a /cp RT 20 . Fi- given residence time (Damköhler number) mul-
nally a “cooling time” tiple steady states occur for particular areas of
the adiabatic temperature increase θad . Using F (x, y;p, q, r, s, ...) = 0 (374b)
the same argumentation as in Section 5.3.3.2,
where x is the variable for describing the steady
the stability condition Equation (318 a)
state, y the bifurcation parameter which controls
d d the multiple steady state, and p, q, r, s, . . . are
(LHS) > (RHS)
d (1−α) d (1−α) additional parameters which produce folding or
at LHS = RHS (318a) unfolding of the surface of x in space y and p, q,
r, s, . . .
is not complied with for the middle one of the LIVE GRAPH
Click here to view
multiple solutions. In this state a small perturba-
tion of the conversion causes an increase or de-
crease in the “convective term” (LHS). The “re-
action term” (RHS) however reacts in the same
way so that a greater (smaller) availability of
A due to convection is followed by a greater
(smaller) consumption due to reaction. The sys-
tem therefore tends towards one of the exter-
nal stable steady-state solutions. As can be seen
from Figure 54 A, the shape of the curve de-
pends on the adiabatic temperature increase θad .
Figure 54 B shows that as θad becomes smaller
the S-shaped profile vanishes and the surface
of solutions unfolds. Figure 54 B also demon-
strates that the unstable branch of the solutions
is not passed. The system jumps from low con-
version to high conversion with increasing res-
idence time DaI . On igniting and extinguishing
the reaction, hysteresis occurs and the jumping
points can be calculated from Equation (318 b)
d d
(LHS) = (RHS)
d (1−α) d (1−α)
at LHS = RHS (318b)
For the example discussed here the jumping

points are given by
Figure 54. Multiple steady-state conversion points for “nor-
!
mal” exothermic chemical reactions (A) and bifurcation di-
1 4 agram (B) for nonisothermal conditions in a well-stirred
(1−α) = 1± 1− (373)
2 θad reactor
θad = adiabatic temperature increase; for explanation of
Since θad is always positive for exothermic reac- other symbols see Figure 45.
tions, then for the point at which the discriminant One or more steady-state solutions exist for
in Equation (373) disappears, θad = 4. If θad > 4, the condition given by Equation (374 b). The
multiple steady states are observed. steady-state solution is stable for
If the simplification γ r → 0 is discarded, the
following equation is obtained for the steady- F (x, y; p, q, r, s, ...) = 0 and Fx >0 (374c)
state solutions For the unfolding of the hysteresis loop the fol-
lowing applies
1−α (1−α) θad
=αexp (374a)
DaI 1+γr θad (1−α) F (x, y;p, q, r, s, ...) = 0, Fx >0,
and Fxx = 0 (374d)
The right-hand side of Equation (374 a) now de-
pends on two parameters. In general it can be and “islands” finally occur in the bifurcation di-
written in the form agram which grow into “mushrooms” when
F (x, y;p, q, r, s, ...) = 0, Fx = 0, Fy = 0, mP =m0P e−k0 t or π = π0 e−ετ (377)

Fxy = 0, Fxx = 0, and Fyy = 0 (374e)
Using this Equations (376 a) and (377 b) give
Depending on the process under considera-
tion these conditions apply for various pa- dα θ
= επ0 e−ετ − καexp
rameter combinations. For Equation (374 a) dτ (1+γr θ)

the condition for unfolding occurs when θ
=µ − καexp (378a)
θad (4 γ r − 1) + 4 = 0. In the system of Equations (1+γr θ)
(374), Fx , Fy , etc. denote the derivatives accord-
ing to the variable in the index.
dθ θ
=αexp −θ (378b)
Nonsteady-State Cases. As in the stability dτ (1+γr θ)
analysis of isothermal reactors, the stability of
where µ = ε π 0 e−ετ = µ0 e−ετ . For the sake of
nonsteady-state nonisothermal reactors is inves-
simplicity the case of high activation energy
tigated for a consecutive reaction P → A → B
(i.e., γ r 1) will be investigated. Equations
where A is produced from a large reservoir of
(378 a, b) are thus again simplified into
P. The second reaction A → B is exothermic and
its rate coefficient k1 is temperature dependent. dα
= µ − καeθ (379a)
For the reaction sequence P → A → B where dτ
k1 = k01 e−E a /RT , the mass and enthalpy bal- dθ
ances for a batchwise operating ideally mixed = αeθ − θ (379b)
dτ
reactor are given by
For very small values of ε (i.e., for a very much
dmP quicker time scale for the changes in α and θ
= −k0 mP (375)
dt than for the consumption of P) the principle of
dmA quasi-steady-state can again be used, and hence
= k0 mP −k1 mA (376a)
dt Equations (379 a, b) do not have to be integrated.
dT The quasi-steady-state solutions for α and θ re-
cp = (−∆hr ) k1 mA −αs (T − TA ) (376b)
dt sult from dα/ dτ = 0 and dθ/ dτ = 0, hence
(see page 245). The feedback in this sys-
tem results from the temperature depen- µ − καeθ = 0 (380a)
dence of the second reaction rate which
increases the reaction rate with increasing αeθ − θ= 0 (380b)
conversion. As previously, normalized vari-
ables are used: α = mA /mref , π = mP /mref , giving
θ = (T − T A ) E a /RT 2A and γ r = RT A /E a . For the µ
θqs = (381a)
temperature-dependent reaction rate coefficient κ
it thus follows that µ
αqs = e−µ/κ (381b)
κ
−Ea /RTA
k1 =k01 e exp [θ/ (1+γr θ)]
The approximate solutions αqs and θqs are a
The cooling time is not related to a character- function of the ratio µ/κ, and also of time since µ
istic chemical time τ N = cp /α s, so that a nor- is a function of time. With these operations and
malized time can be given as τ = t/τ N . Thus the simplifications the quasi-steady-state solutions
rate coefficients k 0 and k 1 are normalized so αqs and θqs in Equation (381) have the same
that ε = k 0 τ N and κ = τ N k 01 e−E a /RT A . Finally form as for the isothermal case (Eq. 324). The
mref is established from stability analysis which now follows is carried
2
out in the same way as for the isothermal case
αsRTA
mref = (Section 5.3.3.1).
Ea (−∆hr ) k01 e−Ea /RTA The development of Equation (380 a) into a
There is no feedback to reservoir P thus Equation Taylor series around the quasi-steady-state solu-
(375) can be integrated separately: tions provides a system of coupled differential
equations for the disturbances ∆α and ∆θ, the - 2

general solution of which is given by κ1,2 = θqs ±1 e−θqs (386a)
∆α (τ ) =C1 eλ1 τ + C2 eλ2 τ (382a) which satisfy the above condition for the dis-
criminant to be zero. The appropriate values for
∆θ (τ ) =C3 eλ1 τ + C4 eλ2 τ (382b) µ are
The eigenvalues λ1 , λ2 once again determine the µ1,2 =κ1,2 θqs (386b)
characteristics of the time evolution of the dis-
turbances. They are given by the solutions to the The stability diagram is best displayed in the
characteristic Equation (329) form given in Figure 55 with the two parameters
µ and κ. Two closed loops are obtained, the outer
λ2 −Tr (J qs ) λ+Det (J qs ) = 0 (329) of which corresponds to the larger root from
i.e., Equation (386 a) and the inner to the smaller.
The area outside the outer curve represents sta-
1. 6 ble nodes, stable or unstable foci lie between the
λ1,2 = Tr (J qs ) ± Tr (J qs )2
2 two curves, and the area within the inner curve
/ gives unstable nodes.
−4Det (J qs )}1/2 (330) The second case is the loss of stability of the
system given by the condition Tr (Jqs ) = 0. This
In this case the Jacobi matrix takes the form is also a condition for Hopf bifurcation. If µ in
Equation (384 a) is replaced by Equation (381 a),
∂f (α,θ) ∂f (α,θ)
J qs = ∂α
∂g(α,θ)
∂θ
∂g(α,θ) (383) this condition is given as
∂α ∂θ qs
κ= (θqs −1) e−θqs and µ=κθqs (387a,b)
The three quantities which decide the nature of
the solutions are the discriminant of the char- The pertinent curve in the stability diagram is
acteristic equation Tr (Jqs )2 − 4 Det (Jqs ), the a closed loop which lies between the two loops
trace of the Jacobi matrix for the transition from nodes to foci. The region
µ within this curve denotes unstable foci, see the
Tr (J qs ) = −1−κeµ/κ (384a) enlarged section of Figure 55 in the area of the
κ
origin. The maximum of this curve is at e−2 .
and also their determinant Stability analysis for nonisothermal
nonsteady-state batchwise operating models ex-
Det (J qs ) =κeµ/κ (384b)
hibits the following important results: for each
As µ/κ is always positive, not all the combina- combination of the experimental conditions µ
tions of λ1 , λ2 given in the stability diagram and κ there is an unambiguous solution for the
(Fig. 48) will be passed through with increasing quasi-steady-state concentration of the inter-
conversion of P. mediate αqs and the normalized temperature
Two states will now be discussed that are of increase θqs . If the normalized reaction rate co-
practical importance. The first case is the tran- efficient is κ > e−2 , then the quasi-steady-state
sition of the solutions from a node of the sys- solutions are always stable. For κ ≈ 1.78 transi-
tem into a focus. The condition for this is that tion from stable nodes to stable foci occurs. For
λ1 , λ2 become conjugate complex, the discrim- κ < e−2 the quasi-steady-state solutions are un-
inant thus passes through zero. If µ in Equations stable. At the location of the Hopf bifurcations
(384 a, b) is replaced by Equation (381 a), the two solutions occur (Fig. 55). Between the two
result is the following equation for the discrim- bifurcation points for αqs and θqs as functions
inant of the conversion (i.e., as functions of µ), os-
cillations of varying frequency and amplitude
κ2 e2θqs − 2κ (1+θqs ) eθqs + (θqs − 1)2 = 0 (385) occur.
For each positive value of θqs , there are thus two
values of κ
is given in Section 5.1.2.1. The averaged equa-

tions then take the form
∂ 9 :9 : ∂ 9 :9 :9 :
Ui + Uk Ui
∂t ∂xk
LIVE GRAPH 9 :
Click here to view ∂ 9 : ∂ p 9 :9 :
= τtik − + gi ,
∂xk ∂xi
i = 1, 2, 3 (388)
which is a transport equation for the first mo-

ment of the velocities. The accompanying prob-
lem of describing the turbulent viscosity was
solved using the eddy viscosity hypothesis,
µt = Cµ (k2 /ε) .
As well as the solution of Equation (388),
LIVE GRAPH the model requires the solution of the equations
Click here to view
for the turbulence energy, k (Eq. 222), and its
dissipation rate, ε (Eq. 225), thereby defining
a turbulent time scale according to τ = k/ε .
A numerical solution that takes into account
Figure 55. Stability diagram for exothermic consecutive the special nature of the averaged conservation
reactions for quasi-steady-state nonisothermal conditions equations of momentum is demonstrated in Sec-
[113] tion 5.1.2.2.
For explanation of symbols see Figure 49 and text.
For nonisothermal reacting systems this con-
For engineering purposes it is important that, cept has to be expanded to the equations for the
for the simplified case discussed here, stabil- conservation of enthalpy (Eq. 134 or 240 a) and
ity can be controlled through the parameter κ. for the conservation of mass of the chemical
For κ > e−2 the system remains stable. If the species (Eq. 133 or 265 a). Averaging Equations
properties of the chemical reaction are given by (240 a) and (265 a) using the same assumptions
k 1 = k 01 e−E a /RT , stability can only be achieved as in Section 5.1.2.1 results in the equations
by altering the cooling time by means of in- ∂ 9 :9 : ∂ 9 :9 :9 :
creased heat transfer to the surroundings. De- ∂t
h +
∂xk
Uk h
tailed discussions on the stability of nonisother- ∂ 9 h : 9 :9 f f : 9 :
mal reactors can be found in [113], [114]. = − J + h Uk + Sh (389)
∂xk
and
5.3.3.2.3. Use on Statistical Processes
∂ 9 :9 : ∂ 9 :9 :9 :
mi + Uk mi
∂t ∂xk
The description of statistical processes by av- 9 m : 9 :9 f f : 9 :
∂
eraging the conservation equations of momen- =− J i + mi Uk + Si
∂xk
tum is discussed in Section 5.1.2 for isother-
i=1, ...,N − 1 (390)
mal inert systems. The averaged equations how-
ever contain terms with higher moments which The problem now lies in modeling the Reynolds
must be modeled; in Equation (216) these are fluxes hf U fj and mfi U fj , and also the
the Reynolds stresses U fi U fj . expected values of the source term Si and
A model for the Reynolds stresses which Sh .
shows them in analogy to the laminar viscous
stresses as an isotropic tensor of turbulent vis- Modeling the Reynolds Fluxes. The prob-
cous stresses lem of modeling the Reynolds fluxes
9 : 9 : 9 : hf U f j and mf i U f j can be solved
∂ Ui ∂ Uj 2 ∂ Uk
τtij =µt + − µt ∂ij analogously to the modeling of the Reynolds
∂xj ∂xi 3 ∂xk stresses. As with the transport equations for
the Reynolds stresses (see Section 5.1.2.1, Modeling of the Mean Reaction Rates.
Eq. 221), the analogous transport equation for The discussion of models for the mean reaction
the Reynolds fluxes is not closed however. The rates in turbulent (statistical) flows is of simi-
same reasons as were discussed in Section lar importance in engineering to the modeling
5.1.2.1 for the Reynolds stresses, lie behind of Reynolds stresses and Reynolds fluxes. Re-
the fact that transport equations for Reynolds views are given in [126–128].
fluxes are usually not solved in engineering but The reaction rates are generally a function of
are modeled directly. mass fractions and temperature (Eq. 137 a). The
The direct modeling of Reynolds fluxes is expected values Si are obtained from Equa-
based on the Boussinesq hypothesis and assumes tion (109) since the averaging rule (Eq. 107) is
that there is a similarity between the turbulent applicable to functions. If changes in density are
transport of momentum, and enthalpy, and mass. neglected, then Equation (137 a) gives
This principle has already been used in Sections
5.2.2.1 and 5.3.1.1 for deterministic systems. T0 1 1
9 :
The turbulent flux of a scalar quantity is thus Si = ... P (ml , ...,mo , T )
related to the gradients of the expected values Tu 0 0
of the scalar. The proportionality number is a ·Si (ml , ...,mo ,T ) dml ...dmo dT (394)
turbulent transport coefficient which is obtained
from the turbulent viscosity: In Equation (394) P (ml , . . ., mo , T ) is a joint
9 : probability density function of temperature and
9 :9 : µt ∂ Φ the mass fractions of the chemical species that
− Φf Ukf = (391)
σϕ ∂xk are contained in the expression for the reaction
This expression has already been used in the rates. Si (ml , . . ., mo , T ) are usually known func-
equation for turbulence energy (Eq. 223); σϕ is a tions and hence to determine Si , the joint prob-
turbulent Prandtl or Schmidt number, which re- ability density functions have to be established.
lates the turbulent transfer of the scalar in ques- The example shown in Figure 14 demonstrates
tion and the turbulent transfer of momentum. that a priori determinations for this are diffi-
With the help of the eddy viscosity hypothesis, cult; there are intermittencies in the region at the
σϕ can be interpreted as the ratio of the mixing jet boundary so that P (ml , . . ., mo , T ) becomes
length of the velocity fluctuations to the mixing “bimodal”. The bimodal structure is not domi-
length of the fluctuations in the scalar. nant further downstream and within the turbulent
With this hypothesis and neglecting the pro- jet. An acceptable assumption for the form of
portion of laminar flux to turbulent flux, Equa- P (ml , . . ., mo , T ) is a multidimensional normal
tions (389) and (390) become distribution, which must be suitably clipped due
to the restricted domain of definition of tempera-
∂ 9 :9 : ∂ 9 :9 :9 : ture and mass fractions. Although this form does
h + Uk h
∂t ∂xk not cover the intermittencies at the boundary of
9 :
∂ µt ∂ h 9 : the turbulent jet, it is a good approximation for
= + Sh (392)
∂xk σh ∂xk the inside of the turbulent jet and further down-
and stream. For many applications the deficiencies
in representation by a multidimensional normal
∂ 9 :9 : ∂ 9 :9 :9 :
mi + Uk mi distribution is of no consequence because the
∂t ∂xk
9 : mean reaction rates in the areas with strong in-
∂ µt ∂ mi 9 :
= + Si termittencies are mostly small compared with
∂xk σm ∂xk those inside the turbulent jet. If the approxima-
i = 1, ...,N − 1 (393) tion of P (ml , . . ., mo , T ) by means of a multidi-
The remaining problem is now the modeling mensional normal distribution is adequate, the
of the terms Sh and Si . If the change in form of P (ml , . . ., mo , T ) must be established
enthalpy due to mechanical work and radiation quantitatively. As in the one-dimensional case,
are neglected in Equation (392), then the term this is achieved through the expected values
Sh vanishes. A modeling expression then
only needs to be found for Si .
and the second moments. Consequently in or- (Eq. 393), no other equations originate from this
der to determine P (ml , . . ., mo , T ) calculation part of the model. Modeling of the mean chemi-
of ml , . . . , mo , T , mfi mfj , i, j = l, o, and cal reaction rates through the simple expression
mfi T f , i = l, o is necessary. (Eq. 394) with presumed shape joint probability
Equation (394) can be presented in the form density functions requires the solution of equa-
tions for the variances and covariances mfi mfj ,
9 : 9 : 9 : 9 :
Si =Si ml , ..., mo , T i, j = 1, . . . , N, and mfi T f , i = 1, . . . , N. In ad-
9 :9 :
·F mfi mfj , mfi T f ,i, j=l,o (395) dition the density has to be calculated from the
averaged form of the thermal equation of state
in which F (mfi mfi , mfi T f , i, j = l, o) are cor- 9 : N
rection functions for reproducing the effect of 9 : p mi
= 9 :9 : 9 : (396)
turbulent fluctuations in temperature and mass R i=1 T mi + mfi T f
fractions in the averaging procedure of weight-
ing with the joint probability density functions. which also contains the second moments
These correction functions can be given as mfi T f , i = 1, . . . , N. Equation (396) can easily
polynomials of the second moments mfi mfj , be derived from the ideal gas equation. The tem-
perature must be determined from the expected
mfi T f (or more precisely of the turbulence in- value of the enthalpy of the mixture through the
tensities and correlation coefficients) and of the definition of the enthalpy:
activation energies for the reactions in question
[129], [130]. The coefficients of these polyno- 9 : N
9 :
mials can be obtained by applying the averaging h = mi hi =
procedure (Eq. 394) for a number of predefined i=1

values of mfi mfj mfi T f and E a ; Si is then
N
9 :
mi h0i + cpi dT (397)
represented as a function of these quantities by i=1
an empirical polynomial expression [129]. Thus
integration of Equation (394) is unnecessary for Equation (397) is not solved here for the tem-
the numerical solution of the resulting system of perature, for further details see [129–131].
equations.
Calculation of the expected values Si of Example: Combustion of Hydrogen in a
the reaction rates from Equation (395) assumes Turbulent Diffusion Flame. The simulation of
knowledge of the second moments mfi mfj , a turbulent nonisothermal reacting flow by the
i, j = 1, . . . , N and mfi T f , i = 1, . . . , N. In this system of equations outlined above will be
case too closure of the equation system at the demonstrated briefly on an example. A circu-
level of the expected values necessitates calcula- lar jet of hydrogen with a Reynolds number of
tion of the second moments. The relevant trans- 12 000 relative to the nozzle outlet is injected
port equations can be derived by similar con- into virtually stationary air and is burned in a
siderations and modeling assumptions used for horizontal combustion chamber. In the experi-
deriving the equation for other second moments, ments described in [132–134], velocities, tem-
see Section 5.1.2.1 [52], [126–128], [130]. peratures, and concentrations of stable chemical
The numerical work involved in calculating species and of OH radicals are measured down-
a statistical reacting nonisothermal flow is con- stream of the burner nozzle. The system is axi-
siderable, despite the relatively simple struc- ally symmetrical.
ture of the modeling components. In addition The numerical solution contains the solu-
to the solution of the balances of momentum, tions of Equations (223), (225), (388), (392),
direct modeling of Reynolds stresses requires (393) and also of the equations for the vari-
the solution of two further equations for turbu- ances and covariances mfi mfj , i, j = 1, . . . , N
lence energy and the turbulent time scale. The and mf i T f , i = 1, . . . , N in axially symmetri-
Reynolds fluxes are modeled on the same ba- cal formulation. The numerical procedure is the
sis as the Reynolds stresses, so that apart from same as that outlined for the isothermal case
the enthalpy balance (Eq. 392) and the transport in Section 5.1.2.3. The chemical reactions are
equations for the mass of the chemical species described by 44 elementary reactions between
eleven chemical species: H2 , O2 , H2 O, N2 , H, lates them to the gradients of the mean velocities,
O, OH, HO2 , H2 O2 and also N and NO [135]. large sensitivities inevitably result in response to
The reaction rates of each of these components changes in the apparent turbulent viscosity in ar-
consists of the summation of reaction rates of all eas with high velocity gradients.
the elementary reactions j in which the compo-

R
nent in question i occurs, i.e., ri = rij . The
j=1
rate coefficients of the reactions are expressed
in the form kj = k0j T αj e−E a /RT and are thus
not freely selectable modeling parameters. For
details of the reaction rate coefficients of the
H2 –O2 system see [130], [135]. The modeling
parameters used are the coefficients Cµ = 0.09,
C ε1 = 1.4, C ε2 = 0.925, σ k eff = 1.0, σ ε eff = 1.3;
the turbulent Prandtl numbers in Equations (392)
and (393); and also the equations for the second
moments which are defined as σϕ = 0.7 [91].
Figure 56 shows the result of the simulations
from the model compared with the measured re-
sults given in [132–134]. The correspondence
between the measured results and the model is
satisfactory. In particular the penetration of oxy-
gen to the axis of the turbulent jet close to the
nozzle is well predicted. Along with the cal-
culation of the OH radical concentrations, this
is a particular potential of the model that is
based on an elementary reaction scheme for de-
scribing the chemical reactions for the H2 – O2 –
N2 system.
Another aspect of the model presented here
can be shown with the results of sensitivity anal-
ysis. The first-order sensitivity coefficients are
calculated as described in Section 5.3.3.1.2. Due
to the elliptical form of the conservation equa-
tions and the difference form which follows from
this (see Section 5.1.2.2, Equation 232), the re-
sulting system of equations has a block pentadi-
agonal structure and is solved by an ADI proce-
dure.
Figure 57 A shows the results in the form of
the gradients of the axial velocity U with re-
spect to the model parameter Cµ , which con-
trols the turbulent viscosity. The sensitivity co-
efficients are given in relative form (∂U/U)/
(∂Cµ /Cµ ) as in Equations (29) and (30). The
sensitivity with respect to a change in the param-
Figure 57. Relative sensitivity coefficient for a H2 –O2 dif-
eter Cµ is particularly large in areas with high fusion flame
velocity gradients. The sensitivity analysis thus A) Coefficients for the axial velocity U with respect to the
reflects the physical background and the limi- modeling parameter Cµ ; B) Coefficients for the mole frac-
tations of the model used: since the turbulent tion of oxygen X O2 with respect to the rate coefficient
k 01 x = axial distance; r = radial distance.
stresses are described by an approach which re-
LIVE GRAPH
Click here to view LIVE GRAPH
Click here to view
LIVE GRAPH LIVE GRAPH

Click here to view Click here to view
Figure 56. Measured (upper section) and calculated (lower section) profiles for temperature, mole fraction of oxygen and
water, and mass fraction of OH radicals for a turbulent hydrogen – air diffusion flame [130], [131]
x = axial distance; y = radial distance; D = nozzle diameter
Figure 57 B shows the gradients of the mo- The result of averaging the reaction rates with
lar fractions for oxygen with respect to the rate Equations (394) and (395) can be interpreted as
coefficient for the reaction O2 + H → OH + O, the change in the rate coefficients due to the
this is one of the most important oxygen- correction functions. The unsatisfactory repre-
consuming reactions. Here to, the sensitiv- sentation of the joint probability density function
ity coefficients are given in relative form P (ml , . . . , mo , T ) by a multidimensional normal
(∂X O2 /X O2 )/(∂k 01 / k 01 ). Sensitivity is only distribution used to calculate these correction
obvious in the main reaction zones of the tur- functions is therefore no longer of importance
bulent hydrogen flame. Thus, the molar fraction at the edge of the jet for the prediction of the
of oxygen only reacts sensitively to the change in oxygen molar fraction. This is due to the low
these rate coefficients in the main reaction zone reaction rates for the consumption of oxygen in
of the flame. this region.
For further discussion of sensitivity analysis, 18. E. E. O’Brien in P. A. Libby, F. A. Williams

especially for discussion of the possibility of re- (eds.): Turbulent Reacting Flows, Springer
duction of the chemical models, see [131]. Verlag, Berlin-Heidelberg 1980, p. 191.
19. S. B. Pope, Prog. Energy Combust. Sci. 11
(1985) 119.
20. G. Emig, U. Hoffmann, H. Hofmann:
6. References DECHEMA-Kurs: Planung und Auswertung
von Versuchen zur Erstellung mathematischer
1. G. Klaus: Wörterbuch der Kybernetik, Fischer Modelle, parts I and II, DECHEMA,
Verlag, Frankfurt 1969. Frankfurt-Main 1974.
2. A. I. Bojarinow, W. W. Kafarow: 21. E. Kreyszig: Statistische Methoden und ihre
Optimierungsmethoden in der chemischen Anwendung, Verlag Vandenhoeck und
Technologie, Verlag Chemie, Weinheim 1972. Ruprecht, Göttingen 1972.
3. D. M. Himmelblau, K. B. Bischoff: Process 22. M. Fisz: Wahrscheinlichkeitsrechnung und
Analysis and Simulation: Deterministic mathematische Statistik, VEB Deutscher
Systems, J. Wiley and Sons, New York 1968. Verlag der Wissenschaften, Berlin 1980.
4. D. M. Himmelblau: Process Analysis by 23. A. Lindner: Statistische Methoden,
Statistical Methods, J. Wiley and Sons, New Birkhäuser, Stuttgart 1964.
York 1970. 24. M. Baerns, H. Hofmann, A. Renken:
5. U. Hoffmann, H. Hofmann: Einführung in die Chemische Reaktionstechnik, Lehrbuch der
Optimierung mit Beispielen aus dem Technischen Chemie 1, Thieme Verlag,
Chemie-Ingenieur-Wesen, Verlag Chemie, Stuttgart 1987.
Weinheim 1971. 25. VDI-Gesellschaft Verfahrenstechnik und
6. D. M. Himmelblau in A. Bisio, R. Kabel Chemieingenieurwesen: “Berechnungsblätter
(eds.): Scaleup of Chemical Processes, J. für den Wärmeübergang,” VDI-Wärmeatlas,
Wiley and Sons, New York 1985. VDI-Verlag, Düsseldorf 1984.
7. T. E. Edgar, D. M. Himmelblau: Optimization 26. IBM – Scientific Subroutine Package – System
of Chemical Processes, McGraw-Hill, New 360, IBM Corporation, White Plains 1972.
York 1988. 27. NAG Fortran Library-Mark 8, Numerical
8. F. W. Ramirez: Computational Methods for Algorithms Group Inc., Downers Grove 1981.
Process Simulation, Butterworth Publishers, 28. IMSL Library Reference Manual, IMSL Inc.,
Stoneham 1989. Houston 1980.
9. W. F. Luyben: Process Modeling, Simulation 29. W. H. Press, B. B. Flannery, S. A. Teukolsky,
and Control for Chemical Engineers, W. T. Vetterling: Numerical Recipes. The Art
McGraw-Hill, New York 1990. of Scientific Computing (Fortran Version),
10. Ullmann, 4th ed., 4, 451. Cambridge University Press, Cambridge 1989
11. G. Emig, Ber. Bunsenges. Phys. Chem. 90 (also available in Pascal and C).
(1986) 986. 30. W. H. Press, B. B. Flannery, S. A. Teukolsky,
12. H. Hofmann: “Future Trends in Chemical W. T. Vetterling: Numerical Recipes. Example
Engineering Modelling,” Proceedings of the Book (Fortran), Cambridge University Press,
18th EFCE Congress, Apr. 26 – 30, 1987, Cambridge 1985 (also available in Pascal and
p. 579. C).
13. W. W. Kafarow: Kybernetische Methoden in 31. G. Engeln-Müllges, F. Reutter: Numerische
der Chemie und chemischen Technologie, Mathematik für Ingenieure, B.-I.
Verlag Chemie, Weinheim 1971. Wissenschaftsverlag, Mannheim 1987.
14. L. A. Gould: Chemical Process Control: 32. G. Engeln-Müllges, F. Reutter:
Theory and Applications, Addison-Wesley Formelsammlung zur Numerischen
Publishing Company, Reading 1969. Mathematik mit Standard-Fortran
15. P. S. Buckley: Techniques of Process Control, 77-Programmen, B.-I. Wissenschaftsverlag,
Robert E. Krieger Publishing Company, Mannheim 1988.
Huntington 1979. 33. J. Hildenrath et al.: “OMNITAB, A Computer
16. P. V. Danckwerts, Chem. Eng. Sci. 2 (1953) 1. Program for Statistical and Numerical
17. A. D. Randolph, Can. J. Chem. Eng. 42 Analysis,” Handbook 101, Nat. Bur. of
(1964) 280. Standards, U.S. Government Printing Office,
Washington, D.C., 1968.
34. R. Hooke, T. A. Jeeves, J. Assoc. Compt. 57. J. Janicka, W. Kolbe, W. Kollmann in C. T.

Mach. 8 (1961) 212. Crowe, W. L. Grosshandler (eds.): Proc. of the
35. N. Spendley, G. R. Hext, F. R. Himsworth, 1978 Heat Transf. Fluid Mech. Inst.,
Technometrics 4 (1962) 441. Standford University Press, Stanford 1978,
36. J. A. Nelder, R. Mead, Comput. J. 7 (1965) p. 296.
308. 58. S. B. Pope, Philos. Trans. R. Soc. Lond. Ser. A
37. H. H. Rosenbrock, C. Storey: Computational 291 (1979) 529.
Techniques for Chemical Engineers, 59. M. Jischa: Konvektiver Impuls-, Wärme- und
Pergamon Press, Oxford 1966. Stoffaustausch, Vieweg und Sohn,
38. C. S. Beightler, D. T. Phillips, D. G. Wilde: Braunschweig 1982.
Foundations of Optimization, Prentice Hall, 60. H. Schlichting: Grenzschichttheorie, Verlag
Englewood Cliffs, N.Y. 1979. G. Braun, Karlsruhe 1982.
39. P. E. Gill, W. Murray, M. H. Wright: Practical 61. N. Peters in E. S. Oran, J. P. Boris (eds.):
Optimization, Academic Press, New York Approaches to Combustion Modeling,
1981. 62. M. J. Lighthill: Introduction to Fourier
40. D. W. Marquardt, J. Soc. Ind. Appl. Math. 11 Analysis and Generalized Functions,
(1963) 431. Cambridge University Press, Cambridge 1958.
41. H. O. Hartley, A. Booker, Ann. Math. Stat. 36 63. H. M. Hulburt, S. Katz, Chem. Eng. Sci. 19
(1965) 638. (1964) 555.
42. E. J. Williams, J. Royal Stat. Soc. B 24 (1962) 64. E. Kamke: Differentialgleichungen,
125. Lösungsmethoden und Lösungen II, B. G.
43. J. J. More in G. A. Watson (ed.): Numerical Teubner Verlag, Stuttgart 1979.
Analysis, Lecture Notes in Mathematics, 65. P. Langevin, C. R. Acad. Sci. Paris 146 (1908)
vol. 630, Springer Verlag, Berlin 1977, p. 105. 530.
44. Z. E. Beisinger, S. Bell: H2 SAND MIN, 66. S. B. Pope, Phys. Fluids 24 (1981) 588.
Sandia Corporation. 67. L. Arnold: Stochastic Differential Equations:
45. I. N. Bronstein, K. H. Semendjajew: Theory and Applications, J. Wiley and Sons,
Taschenbuch der Mathematik, Verlag Harry New York 1974.
Deutsch, Thun 1983. 68. W. Jost: Diffusion in Solids, Liquids and
46. O. Levenspiel: Chemical Reaction Gases, Academic Press, New York 1952.
Engineering, J. Wiley and Sons, New York 69. O. Levenspiel, K. B. Bischoff: Adv. Chem.
1972. Eng. 4 (1963) 95.
47. O. Levenspiel, W. K. Smith, Chem. Eng. Sci. 6 70. J.-Y. Chen, W. Kollmann: Twenty-Second
(1975) 227. Symposium (International) on Combustion,
48. J. O. Hirschfelder, C. F. Curtiss, R. B. Bird: The Combustion Institute, Pittsburgh 1989,
Molecular Theory of Gases and Liquids, J. p. 645.
Wiley and Sons, New York 1954. 71. J.-Y. Chen, W. Kollmann, Combust. Flame 79
49. J. C. Rotta: Turbulente Strömungen, B. G. (1990) 75.
Teubner, Stuttgart 1972. 72. J. L. Lumley, Adv. Appl. Mech. 18 (1978) 123.
50. R. B. Bird, W. E. Stewart, E. N. Lightfoot:
73. B. E. Launder, C. J. Reece, W. Rodi, J. Fluid.
Transport Phenomena, J. Wiley and Sons,
Mech. 68 (1975) 573.
New York 1960.
74. J. C. Rotta, Z. Phys. 129 (1951) 547.
51. F. A. Williams: Combustion Theory, The
75. C. Dopazo, Phys. Fluids 18 (1975) 397.
Benjamin/Cummings Publishing Company,
76. J. Janicka, W. Kolbe, W. Kollman, J.
Menlo Park, Calif. 1985.
Non-Equilib. Thermodyn. 4 (1978) 47.
52. P. A. Libby, F. A. Wiliams in P. A. Libby, F. A.
77. C. Dopazo, Phys. Fluids 22 (1979) 20.
Williams (eds.): Turbulent Reacting Flows,
78. J. Janicka, W. Kollman in L. J. S. Bradbury et
Springer Verlag, Berlin – Heidelberg 1980,
al. (eds.): Turbulent Shear Flows 4, Selected
p. 1.
Papers from the Fourth International
53. P. Givi, Prog. Energy Combust. Sci. 15 (1989)
Symposium on Turbulent Shear Flows,
121.
Springer Verlag, Berlin – Heidelberg 1985,
54. M. Lesieur: Turbulence in Fluids, Martinus
p. 73.
Nijhoff Publishers, Dordrecht 1987.
55. T. S. Lundgreen, Phys. Fluids 12 (1969) 485. 79. S. B. Pope, Combust. Sci. Technol. 25 (1981)
56. S. B. Pope, Combust. Flame 27 (1976) 294. 159.
80. T. V. Nguyen, S. B. Pope, Combust. Sci. 100. P. J. Roach: Computational Fluid Dynamics,
Technol. 42 (1984) 13. Hermosa Publishers, Albuquerque 1976.
81. A. Favre in Society for Industrial and Applied 101. E. S. Oran, J. P. Boris: Numerical Simulation of
Mathematics (ed.): Problems of Reactive Flow, Elsevier Science Publishing
Hydrodynamics and Continuous Mechanics, Company, New York 1987.
Philadelphia 1969, p. 231. 102. C. Hirsch: Numerical Computation of Internal
82. G. Stahl, J. Warnatz, B. Rogg in AIAA (ed.): and External Flows, vol. 1, J. Wiley and Sons,
Progr. Aeronaut. Astronaut., vol. 113, New York 1988.
Washington 1988, p. 195. 103. C. Hirsch: Numerical Computation of Internal
83. P. Bradshaw in P. Bradshaw (ed.): Turbulence, and External Flows, vol. 2, J. Wiley and Sons,
Springer Verlag, Berlin – Heidelberg 1978, New York 1990.
p. 1. 104. A. J. Baker: Finite Element Computational
84. B. E. Launder, D. B. Spalding: Lectures in Fluid Mechanics, McGraw-Hill, New York
Mathematical Models of Turbulence, 1985.
Academic Press, London – New York 1972. 105. J. M. Beer, N. A. Chigier: Combustion
85. K. K. Kuo: Principles of Combustion, J. Wiley Aerodynamics, Applied Science Publishers
and Sons, New York 1986. Ltd., London 1972.
86. J. O. Hinze: Turbulence, McGraw-Hill, New 106. L. Horvarth, Proc. R. Soc. London Ser. A 164
York 1975. (1938) 547.
87. J. Boussinesq, Mém. prés. Acad. Sci. XXIII, 107. E. R. G. Eckert, R. M. Drake: Analysis of Heat
46, Paris1877. and Mass Transfer, McGraw-Hill, New York
88. L. Prandtl, Z. Angew. Math. Mech. 22 (1942) 1972.
241. 108. M. N. Özisik: Basic Heat Transfer,
89. L. Prandtl, Nachr. Akad. Wiss. Göttingen, McGraw-Hill, New York 1985.
Math. Phys. Kl. 2 (1945) 6 – 19. 109. H. Brauer: Stoffaustausch einschließlich
90. J. Janicka: Twenty-First Symposium chemischer Reaktionen, Verlag Sauerländer,
(International) on Combustion, The Aarau 1971.
Combustion Institute, Pittsburgh 1988, p. 1409. 110. P. Trambouze in A. E. Rodriguez, J. M. Calo,
91. S. M. Correa, W. Shyy, Prog. Energy Combust. N. H. S. Sweed (eds.): Multiphase Chemical
Sci. 13 (1987) 249. Reactors, Fundamentals (vol. I), Sijthoff and
92. H. Tennekes, J. L. Lumley: A First Course in Noordhoff, Alphen 1981.
Turbulence, MIT-Press, Boston 1972. 111. J. A. van der Vusse, Chem. Eng. Sci. 17 (1962)
93. W. F. Ames: Nonlinear Partial Differential 507.
Equations in Engineering, Academic Press, 112. L. Cloutier, Can. J. Chem. Eng. 37 (1959) 105.
New York – London 1965. 113. P. Gray, S. K. Scott: Chemical Oscillations and
94. A. D. Gosman et al.: Heat and Mass Transfer Instabilities: Nonlinear Chemical Kinetics,
in Recirculating Flows, Academic Press, Clarendon Press, Oxford 1990.
London 1969. 114. G. Iooss, D. D. Joseph: Elementary Stability
95. M. D. Smooke, A. A. Turnbull, R. E. Mitchell, and Bifurcation Theory, Springer Verlag, New
D. E. Keyes in C.-M. Brauner, C. York 1980.
Schmidt-Lainé (eds.): Mathematical Modeling 115. J. H. Merkin, D. J. Needham, S. K. Scott, Proc.
in Combustion and Related Topics, Martinus R. Soc. London Ser. A 406 (1986) 299.
Nijhoff Publishers, Dordrecht 1988, p. 261. 116. B. F. Gray, M. J. Roberts, Proc. R. Soc.
96. D. B. Spalding: Basic Equations of Fluid London Ser. A 416 (1988) 391.
Mechanics and Heat and Mass Transfer, 117. P. M. Frank: Introduction to System Sensitivity
Imperial College London, Mechanical Theory, Academic Press, New York 1978.
Engineering Department, Report HTS/76/6, 118. T. P. Coffee, J. M. Heimerl, Combust. Flame
London 1976. 50 (1983) 323.
97. S. V. Patankar: Numerical Heat Transfer and 119. D. E. Clough, W. F. Ramirez, AIChE J. 22
Fluid Flow, McGraw-Hill, New York 1980. (1976) no. 4, 1097.
98. F. H. Harlow, J. E. Welch, Phys. Fluids 8 120. J. C. P. Sheel, C. M. Crowe, Can. J. Chem.
(1965) 2182. Eng. 47 (1969) 183.
99. A. O. Demurren, Comput. Fluids 13 (1985) 121. R. A. Greenkorn: Flow Phenomena in Porous
411. Media, Marcel Dekker, New York 1983.
122. E. Kreyszig: Advanced Engineering 129. H. Bockhorn in C.-M. Brauner, C.

Mathematics, J. Wiley and Sons, New York Schmidt-Lainé (eds.): Mathematical Modeling
1988. in Combustion and Related Topics, Martinus
123. G. F. Fromment, K. B. Bishoff: Chemical Nijhoff Publishers, Dordrecht 1988, p. 411.
Reactor Analysis and Design, J. Wiley and 130. H. Bockhorn: Twenty-Second Symposium
Sons, New York 1990. (International ) on Combustion, The
124. P. B. Weisz, J. S. Hicks, Chem. Eng. Sci. 17 Combustion Institute, Pittsburgh 1988, p. 665.
(1962) 265. 131. H. Bockhorn: Twenty-Third Symposium
125. J. Ganoulis, F. Durst: “Finite Elements in (International ) on Combustion, The
Water Resources,” Proceedings VI Int. Conf., Combustion Institute, Pittsburgh.
Lisbon 1986, p. 655. 132. M. C. Drake et al.: Twentieth Symposium
126. S. N. B. Murthy (ed.): Turbulent Mixing in (International ) on Combustion, The
Nonreactive and Reactive Flows, Plenum Combustion Institute, Pittsburgh 1984, p. 327.
Press, New York – London 1975. 133. M. C. Drake, R. W. Pitz, M. Lapp: AIAA Pap.
127. R. W. Bilger in P. A. Libby, F. A. Williams 84-0544 (1984).
(eds.): Turbulent Reacting Flows, Springer 134. G. M. Faeth, G. S. Samuelson, Prog. Energy
Verlag, Berlin – Heidelberg 1980, p. 65. Combust. Sci. 12 (1986) 305.
128. R. Borghi, Prog. Energy Combust. Sci. 14 135. J. Warnatz in W. C. Gardiner, Jr. (ed.):
(1988) 245. Combustion Chemistry, Springer Verlag, New
York 1984, p. 196.
Transport Phenomena 271
Transport Phenomena
See also → Mathematics in Chemical Engineering and Fluid Mechanics
Raymond W. Flumerfelt, Department of Chemical Engineering, Texas A & M University, College Station,
Texas 77843, United States
Charles J. Glover, Department of Chemical Engineering, Texas A & M University, College Station, Texas
77843, United States
1. Foundations . . . . . . . . . . . . . . . 278 2.1.3. Steady, One-Dimensional Conduc-

1.1. Mathematical Preliminaries . . . . 279 tion . . . . . . . . . . . . . . . . . . . . . 296
1.1.1. Coordinate Systems . . . . . . . . . . 279 2.1.4. Convective Boundary Conditions . . 297
1.1.2. Vector and Tensor Operations . . . . 279 2.1.5. Composite Systems . . . . . . . . . . 298
1.1.3. The Jacobian . . . . . . . . . . . . . . . 280 2.1.6. Steady Conduction with Heat Gener-
1.1.4. Calculus of Vectors and Tensors . . . 281 ation and in Multidimensions . . . . 298
1.1.5. Divergence Theorem . . . . . . . . . . 282 2.1.7. Transient Heat Conduction – Lumped
1.1.6. Kinematic Relations . . . . . . . . . . 282 Capacity Systems . . . . . . . . . . . . 299
1.1.7. Partial and Total Derivatives . . . . . 283 2.1.8. Transient Heat Conduction – More
1.1.8. Relation Between Different Time General Solutions . . . . . . . . . . . . 299
Derivatives . . . . . . . . . . . . . . . . 283 2.2. Steady, One-Dimensional Flows . . 302
1.2. Basic Equations for Composition- 2.2.1. Generalized Couette Flow . . . . . . 303
ally Homogeneous Systems . . . . . 283 2.2.2. One-Dimensional Poiseuille Flows . 304
1.2.1. The Reynolds Transport Theorem . . 283 2.2.3. Flow in Channels of Arbitrary Cross
1.2.2. Conservation of Total Mass . . . . . . 284 Section . . . . . . . . . . . . . . . . . . 305
1.2.3. Conservation of Linear Momentum . 284
2.2.4. Poiseuille Flow of Non-Newtonian
1.2.4. Condition of Local Stress Equilib- Fluids . . . . . . . . . . . . . . . . . . . 306
rium . . . . . . . . . . . . . . . . . . . . 285
2.2.5. Two-Phase Concentric Flow
1.2.5. Stress Tensor . . . . . . . . . . . . . . . 285
in a Tube – Segregated Flow . . . . . 308
1.2.6. Equation of Motion . . . . . . . . . . . 285
2.3. Multidimensional Momentum
1.2.7. Conservation of Angular Momentum 285
Transfer . . . . . . . . . . . . . . . . . 309
1.2.8. Mechanical Energy Accounting
2.3.1. Two-Dimensional Flows
Equation . . . . . . . . . . . . . . . . . 286
– Stream Function Equations . . . . . 309
1.2.9. Conservation of Total Energy . . . . 286
2.3.2. Creeping Flow Around a Sphere and
1.2.10. Thermal Energy Accounting Equa-
Other Bodies of Revolution . . . . . . 310
tion . . . . . . . . . . . . . . . . . . . . . 286
1.2.11. Forms of the Governing Equations . 287 2.3.3. Flow in Channels with Varying Cross
1.2.12. Entropy Inequality . . . . . . . . . . . 287 Sections – Lubrication Analysis . . . 313
1.2.13. Linear Transport Fluxes and Rela- 2.4. Coupled Momentum and Energy
tions . . . . . . . . . . . . . . . . . . . . 287 Transfer . . . . . . . . . . . . . . . . . 316
1.2.14. Transport Properties from Molecular 2.4.1. Heat Transfer in Laminar Tube Flow 317
Theories . . . . . . . . . . . . . . . . . . 288 2.4.2. Momentum and Heat Transfer in
1.2.15. Non-Newtonian Fluids . . . . . . . . 289 Laminar Boundary Layers . . . . . . 319
1.3. Summary of Basic Equations . . . 290 2.4.3. Free Convection on a Vertical Plate . 323
1.4. Boundary Conditions . . . . . . . . 291 2.5. Turbulent Momentum and Energy
1.5. Solution Philosophy . . . . . . . . . . 292 Transfer . . . . . . . . . . . . . . . . . 324
1.6. Dimensionless Equations 2.5.1. Physical Characteristics . . . . . . . . 324
of Change . . . . . . . . . . . . . . . . 292 2.5.2. Time-Smoothed Momentum and En-
2. Transport in Compositionally ergy Balances for Turbulent Flow . . 327
Homogeneous Systems . . . . . . . . 294 2.5.3. Mixing Length Theories . . . . . . . . 328
2.1. Heat Conduction in Solids . . . . . 294 2.5.4. Turbulent Heat Transfer in
2.1.1. Heat Conduction Equations . . . . . 294 Tubes – Reynolds, Prandtl, and
2.1.2. Initial and Boundary Conditions . . . 295 von Karman Analogies . . . . . . . . 329
272 Transport Phenomena
2.5.5. Turbulent Momentum and Heat 3.3.2. Functional Forms of Mass-Transfer

Transferon a Flat Plate . . . . . . . . . 331 Coefficient Relations . . . . . . . . . . 352
2.6. Summary of Heat-Transfer 3.3.3. Relations for Low Mass-Transfer
Relations . . . . . . . . . . . . . . . . . 332 Rates . . . . . . . . . . . . . . . . . . . . 353
3. Transport in Multicomponent 3.3.4. Relations for High Mass-Transfer
Systems . . . . . . . . . . . . . . . . . . 332 Rates . . . . . . . . . . . . . . . . . . . . 354
3.1. Diffusive Mass Transfer in Binary 4. Macroscopic Systems . . . . . . . . . 356
Systems . . . . . . . . . . . . . . . . . . 332 4.1. Conservation of Total Mass . . . . 356
3.1.1. Species Mass Balances . . . . . . . . 332 4.2. Conservation of Linear
3.1.2. Species Diffusion Fluxes . . . . . . . 336 Momentum . . . . . . . . . . . . . . . 357
3.1.3. Fick’s First Law of Diffusion . . . . 336 4.3. Conservation of Angular
3.1.4. Special Cases of Diffusion . . . . . . 337 Momentum . . . . . . . . . . . . . . . 358
3.1.5. Diffusivities of Gases and Liquids . 338 4.4. An Accounting of Mechanical
3.1.6. Theoretical Foundations of Steady- Energy . . . . . . . . . . . . . . . . . . 358
State Measurement of Diffusion . . . 339 4.5. Conservation of Total Energy . . . 359
3.1.7. Diffusion with Homogeneous Chem- 4.6. An Accounting of Thermal Energy 360
ical Reaction . . . . . . . . . . . . . . . 342 4.7. The Second Law
3.1.8. Diffusion with Heterogeneous Reac- of Thermodynamics . . . . . . . . . 360
tion . . . . . . . . . . . . . . . . . . . . . 343 4.8. Tabular Summary of the
3.1.9. Perspective . . . . . . . . . . . . . . . . 345 Macroscopic Equations . . . . . . . 362
3.2. Convective Mass Transport . . . . 345 4.9. Some Examples . . . . . . . . . . . . 362
3.2.1. Gas Absorption in a Falling Film with 4.9.1. Pressure Drops and Temperature
Reaction . . . . . . . . . . . . . . . . . 345 Changes for Closed Channel Flow . 362
3.2.2. Mass Transfer in Laminar and Tur- 4.9.2. Compressible Flow in a Tube . . . . 363
bulent Boundary Layers . . . . . . . . 348 4.9.3. Heterogeneous Reaction in a
3.3. Mass Transfer Across Interfaces . 349 Fluidized-Bed Reactor . . . . . . . . . 364
3.3.1. Mass-Transfer Coefficients . . . . . . 350 5. References . . . . . . . . . . . . . . . . 366
Symbols Br Brinkman number, Equation (1.118a)

a, b major and minor axes of spheroids c molar concentration, moles per vol-
a acceleration ume
a, b, c arbitrary vectors cp constant pressure heat capacity per
A area unit mass
A area vector (magnitude and direction) cv constant volume heat capacity per unit
A, B arbitrary second-order tensors mass
Ac cross-sectional area cA , cB , ci moles of A, B, i in a mixture per unit
An numerical parameters defined by volume of mixture
Equation (2.174) c∗A dimensionless molar concentration of
Aw wall surface area species A
Aξ area perpendicular to ξ-direction c̄A time-averaged value of cA
cA0 molar concentration at interface
Â Helmholtz free energy per unit mass cA∞ molar concentration of A in free
ATSB A through stagnant B diffusion situa- stream, or in bulk fluid in contact with
tion surface
b flow geometry height C constant
b∗ dimensionless flow channel height, CD drag coefficient defined by Equation
defined below Equation (2.174) (2.155)
b 0 , bL flow channel vertical dimensions at C Dx local drag coefficient defined in Equa-
x = 0 and x = L, Figure 13 tion (2.235)
B applied load, Figure 13 C DL overall drag coefficient defined by
Bi Biot number; Equation (2.19) and def- Equation (2.236)
inition below Equation (2.27)
Ck coefficients in Equation (2.49) g i , g j , g k i, j, k base vectors in a curvilinear co-

C 1 , C 2 , Ĉ 1 , Ĉ 2 integrating constants ordinate system
d diameter gx , gy , gz components of gravitational force
d/dt time derivative seen by an observer per unit mass, in x, y, z directions
moving at arbitrary velocity; the total G scalar function in Equation (2.125)
time derivative of a function Grx local Grashoff number, Equation
D/Dt time derivative seen by observer (2.273)
maintaining constant material coordi- GrL Grashoff number associated with sur-
nates (following the motion of an el- face of length L
ement, Eq. 1.50) Ĝ Gibbs free energy per unit mass
DAB diffusivity of species A in B h heat-transfer coefficient, Equation
D◦AB diffusivity of infinitely dilute A in sol- (2.6)
vent B hk heat-transfer coefficient associated
Daδ Damköhler number based on film with surface at position xk
thickness, Equation (3.100) hlm log mean heat-transfer coefficient,
DaL Damköhler number based on film Equation (2.206)
length hx,lam local heat-transfer coefficient, lam-
e height of wall roughness (protuber- inar boundary layer
ances) hx, turb local heat-transfer coefficient, tur-
eijk permutation symbol, Equation (1.12) bulent boundary layer
E2 differential operator, Equation hL overall heat-transfer coefficient over
(2.137) surface of length L, Equation (2.254)
E (k) complete elliptic integral with argu- h̄ average heat-transfer coefficient over
ment k surface A
ECD equimolar counter diffusion situation Ĥ enthalpy per unit mass
f in Section 2.4.1, function of r de- ii , ij , ik base vectors in a rectangular cartesian
fined by Equation (2.197); in Section coordinate system
2.3.2, function of r defined by Equa- ix , iy , iz unit base vectors in x, y, z directions
tions (2.133) and (2.134); in Section ir , iθ , iz unit base vectors in cylindrical coor-
2.3.3, a function defined below Equa- dinates
tion (2.162); friction factor defined by ir , iθ , iφ unit base vectors in spherical coordi-
Equation (2.79) nates
F a function of time (1.56) I identity tensor
F force, a vector I∆ , II∆ , III∆ first, second, and third scalar in-
FB buoyancy force variants of second-order tensor ∆, de-
FD drag force fined by Equations (1.107) – (1.109)
Fext external force Iu intensity of turbulence, Equation
F in , F out volumetric flow rate entering and (2.280)
leaving a system Iφ a measure of the fluctuating part of φ
Fx , Fy , Fz force components in a turbulent flow, Equation (2.279)
F∗x , F∗y , F∗z dimensionless force components jA mass diffusion flux of species A rela-
F in Chapter 1, an arbitrary scalar, vective to u, Equation (3.16)
tor, or tensor function of time and j̃A mass diffusion flux of species A rela-
position; in Section 2.5.2, any linear tive to ũ, Equation (3.19)
time or spatial derivative operator J Jacobian relating differential volume
Fr Froude number, Equation (1.114) elements in two coordinate systems
F̂ conversion of mechanical energy to and defined by Equations (1.23) and
thermal energy by viscous dissipa- (1.24)
tion, per unit mass (fluid friction Jn ( ) Bessel functions of the first kind with
losses) argument ( ) and n = 0, 1, . . .
g body force per unit mass or gravita- JA molar diffusion flux of species A, rel-
tional acceleration ative to u, Equation (3.18)
J̃A molar diffusion flux of species A, rel- n outwardly directed unit normal on
ative to ũ, Equation (3.14) surface enclosing volume V
k arbitrary constant, Equation (1.4); in NA molar flux (vector) of species A
Section 2.2.3, defined below Equation N Ay mole flux of A in y-direction
(2.94); in Section 2.5.3, proportional- N̄ Ay time-averaged value of N Ay
ity constant in Equation (2.299); re- NuAB mass-transfer Nusselt number,
action rate constant, Equation (4.29) NuAB = kx d/c DAB
k reaction rate constant, Equation Nud Nusselt number based on diameter,
(3.98) Equation (2.202)
k y drift factor-corrected gas-phase mass- Nud, lm log mean Nusselt number, Equations
transfer coefficient (2.205) and (2.206)
kc single-phase mass-transfer coeffi- NuL overall Nusselt number associated
cient based on molar concentrations with surface of length L, Equation
k cL average mass-transfer coefficient de- (2.255)
fined by Equation (3.112) Nux local heat-transfer Nusselt number,
kG gas-phase mass-transfer coefficient Equation (2.251)
based on gas-phase partial pressures, O() order of magnitude of ( )
Equation (3.132) p linear momentum
kx liquid-phase mass-transfer coefficient p pressure, the isotropic stress
based on liquid-phase mole fractions p0 reference pressure
ky gas-phase mass-transfer coefficient pA , pB partial pressure of species A, B
based on gas-phase mole fractions pH hydrostatic pressure, Equation (2.63)
k1 first-order reaction rate constant p̄ time-averaged pressure
K pressure gradient defined by Equation P dynamic pressure, Equation (2.62)
(2.68); overall reaction rate constant, P0 reference dynamic pressure
Equation (4.31) ∆P pressure drop across flow channel in
K∗ dimensionless pressure gradient, de- direction of flow
fined by Equation (2.73) Pe Péclet number, Equation (1.117)
Kc overall two-phase mass-transfer co- PeL mass-transfer Péclet number based on
efficient based on liquid-phase molar film length
concentrations Peδ mass-transfer Péclet number based on
KG overall two-phase mass-transfer co- film thickness, Equation (3.83)
efficient based on gas-phase partial Pr Prandtl number ( ≡ ν/α)
pressures, Equation (3.134) PÊ potential energy per unit mass
Kx overall two-phase mass-transfer co- q a dimensionless parameter defined by
efficient based on liquid-phase mole Equation (3.103)
fractions q heat flux vector (heat flow rate per unit
Ky overall two-phase mass-transfer coef- area)
ficient based on gas-phase mole frac- q̄ time-averaged heat flux
tions qn heat flux component normal to sur-
ˆ
KE kinetic energy per unit mass face, Equation (2.6)
l characteristic length, Equation (2.82); qr , qθ , qz heat flux components in cylindrical
in Section 2.5.3, the Prandtl mixing coordinates
length qw wall heat flux
L angular momentum qx , qy , qz heat flux components in x-, y-, and
L characteristic length for a process or z-directions
flow, Chapter 1; length of body, sur- (t)
qy turbulent heat flux component in y-
face, or flow channel direction, Equation (2.301)
m, n material parameters for power-law qξ heat flux in ξ-direction
non-Newtonian fluid, Equation (2.97) Q energy transferred as heat, Chapter 4;
n coordinate in direction normal to sur- volumetric flow rate, Chapter 2
face, Equation (2.6)
Q, Q̂ volumetric flow rates in inner and Sh Sherwood number ( ≡ kx d/cDAB )

outer regions, respectively, Section ShL Sherwood number based on length L,
2.2.5 Equation (3.95)
Q∗ defined by Equation (2.110) Shx local Sherwood number defined be-
Q̂ heat transfer per unit mass low Equation (3.110)
Q̇ heat transfer rate St Stanton number, Equation (2.311)
r molecular separation, Lennard – Jones Ŝ entropy per unit mass
function Ṡgen entropy generation rate
r position vector Ṡin rate of entropy addition
r∗ dimensionless radial position t time
r A , r B , ri mass rate of production of species A, t exp diffusion penetration theory exposure
B, i per unit volume due to reaction time, Equations (3.136) and (3.137)
(r A > 0 for generation of A; r A < 0 t(n) traction vector acting on surface A,
for consumption of A) Equation (1.67)
rc radial position of interface between t0 in Section 2.5.1, time over which
inner and outer phases quantities are averaged; elsewhere, a
r ∗c dimensionless radial position, defined reference time
below Equation (2.107) t∗ dimensionless time, defined below
rH hydraulic radius defined below Equa- Equation (2.27)
tion (2.96) tr trace operation of a second-order ten-
rY radial position of yield surface sor, Equation (1.8)
r0, r1 radii associated with cylinder or T absolute temperature
spherical surfaces T total stress tensor, a symmetric
R ideal gas constant; in Section 2.3.3, second-order tensor
the flow channel radius T∗ dimensionless temperature, Equation
RA , RB , Ri molar rate of production of species (2.34)
A, B, i per unit volume of mixture due Tb bulk average temperature, Equation
to reaction (RA > 0 for production of (2.195)
A; RA < 0 for consumption of A) Tf film temperature [≡ (T w + T ∞ )/2] in
Rcond conductive resistance, Equation Section 2.5.5 and Table 7; bulk fluid
(2.14) temperature
Rconv,i convective heat-transfer resistance, Tfk temperature of bulk fluid next to sur-
Equation (2.24) face at xk
Re Reynolds number, Equations (1.113) Ti initial temperature
and (2.81) Tk temperature at position xk
Recr critical Reynolds number for laminar T0 characteristic reference temperature
to turbulent transition for a process
Red Reynolds number based on diameter Tw wall temperature
d, defined below Equation (2.127) T w0 , T wL wall temperatures at positions z = 0
ReL Reynolds number based on length L and z = L
Rex local Reynolds number, Equation Tx , Ty , Tz , Tr solutions defined below
(2.231) Equations(2.54) – (2.56)
Reδ Reynolds number based on length Tξ time-averaged temperature at y = ξ
scale δ T∞ temperature in free stream
r, θ, z coordinates in cylindrical coordinate T 0 , T 1 , T 2 temperatures at positions x 0 , x 1 , and
system x2
r, θ, φ coordinates in spherical coordinate ∆T ratio of momentum and ther-
system mal boundary layer thicknesses
s defined below Equation (2.98) ( ≡ δ m /δ T )
s displacement vector ∆T lm log mean temperature difference,
S control volume surface Equation (2.207)
Sc Schmidt number ( ≡ v/DAB )
T̄ average spatial temperature in a re- WA rate of mass transfer, moles/time

gion, Section 2.1.7; time-averaged Ẇ work rate (power)
temperature, Section 2.5.2 Ŵes work done on the fluid at the entrance
u, u velocity vector (momentum per unit and exit points by extra stress, per unit
mass) of magnitude u; in a mixture: a mass
mass average velocity, Equation (3.8) Ẇ np nonpressure work rate, Section 4.5
u fluctuating part of velocity in tur- Ŵ s shaft work per unit mass
bulent field x, xi , xj , xk i, j, k components of a position vec-
ux , uy , uz fluctuating velocity components tor x in a curvilinear coordinate sys-
uavg average velocity tem
uc characteristic velocity, Equation xA mole fraction of species A in a mix-
(2.268) ture: x A = cA /c
ui velocity of species i in a mixture x Ae mole fraction of species A in the liq-
uinterface fluid velocity at a gas–liquid interface uid phase required for equilibrium
umax maximum velocity with a given bulk gas-phase mole frac-
ux , uy , uz components of velocity in rectangu- tion, Figure 29
lar cartesian system x Ai , x Ab mole fraction of species A at the in-
u0 characteristic velocity, Equation terface in the liquid phase and in the
(2.159) bulk liquid phase, Figure 29
u∞ free stream velocity; see Figures 10, x cr position on surface where boundary
11, 14, 15, 16 layer becomes turbulent, Figure 14
u∗ friction velocity, Equation (2.286) x∗ dimensionless coordinate position
u∗ dimensionless velocity x 0 , y0 principal axes of elliptic cross section;
u+ dimensionless velocity, Equation defined above Equation (2.92)
(2.284) x 0 , y0 , z0 linear half-thickness associated with
ũ mixture molar average velocity, rectangular parallelepiped or rectan-
Equation (3.12) gular bar, Section 2.1.8; reference po-
ũ time-averaged velocity in turbulent sition, Section 2.2
field defined by Equation (2.277) ∆xk thickness of kth slab (xk − xk−1 )
ūx , ūy , ūz time-averaged velocity components Xi , Xj , Xk material coordinates (yi , yj , yk at a
uz , ûz velocity components in inner and reference time) of an element of mass
outer regions, respectively, Section yA mole fraction of species A in a gas
2.2.5 mixture
ūξ time-averaged velocity at y = ξ yAe mole fraction of species A in the gas
U characteristic velocity for a process phase required for equilibrium with a
or flow; velocity of moving surface, given bulk liquid-phase mole fraction,
Figure 5; velocity of lower plate, Fig- Figure 29
ure 13 yAi , yAb mole fraction of species A at the inter-
Û internal energy per unit mass face in the gas phase and in the bulk
V volume gas phase, Figure 29
VA molar volume of species A, volume yi , yj , yk i, j, k components of a vector y or po-
per mole sition vector in a rectangular cartesian
V0 material volume in the reference co- coordinate system
ordinates y y coordinate measured from chan-
V̂ volume per unit mass ( ≡ 1/) nel centerline, defined above Equa-
w arbitrary velocity of an observer, tion (2.76)
Equation (1.55) y∗ dimensionless y coordinate
w flow geometry width y+ dimensionless distance from wall,
wA mass fraction of species A in a mix- Equation (2.285)
ture: wA = A / ze thermal entry length defined above
W film width (in x direction), Figure 25; Equation (2.204)
work, Equation (4.8)
z1 , z2 elevation at points 1 and 2 in a flow εs surface shear viscosity

conduit ξ dependent variable, Equation (2.35)
z∗ dimensionless z coordinate η viscosity; catalyst effectiveness fac-
tor, Equation (4.28)
η, η̂ in Section 2.2.5, viscosities of core
Greek Symbols fluid and outer fluid, respectively; in
α thermal diffusivity (≡ λ/ cp ) Section 2.3.1, viscosities of continu-
αKE factor representing deviation from a ous and drop phases, respectively
flat velocity profile, Equation (4.6) ηB viscosity of solvent B, Equation
αmom factor representing deviation from a (3.29)
flat velocity profile, Equation (4.4) ηp plastic viscosity in Bingham plastic
β dimensionless quantity defined by model
Equation (2.43); isobaric coeffi- η ∞ , η w viscosities evaluated at bulk and wall
cient of thermal expansion, Equation temperatures, respectively
(2.185) θ angle subtended by two vectors,
βn eigenvalues given by Equations Equation (1.5)
(2.48), (2.51), or (2.53) with n = 1, κ heat capacity ratio, cp /cv ; equal to
2,... bL /b0 in Section 2.3.3
β∞ coefficient of thermal expansion at Λ interference parameter associated
T∞ with hindered settling (see Eq. 2.157)
γ defined below Equation (3.69) λ thermal conductivity
γ̇ shear rate, Equation (1.110c) λ̄ average thermal conductivity similar
∆ rate of deformation tensor, Equation to Equation (2.10) with T replacing
(1.105) T1
δ film thickness λ̄1 average thermal conductivity, Equa-
δ, δij Kronecker delta defined by Equations tion (2.10)
(1.10) and (1.11) λ̄k average thermal conductivity, Equa-
δc boundary layer thickness for mass tion (2.10) with Tk replacing T 1
transfer analogous to Equations ν kinematic viscosity (≡ µ/)
(2.211) and (2.237) ξ coordinate direction; dummy integra-
δm momentum boundary layer thickness, tion variable; y position associated
Equation (2.211) with edge of sublayer in turbulent flow
δT thermal boundary layer thickness, density, mass per unit volume
Equation (2.237) A , B , i mass per unit volume of A, B, i in a
ε fractional penetration of a gas into mixture
a film, used for nondimension- s density of sphere
alizing the penetration, Equation ∞ density at T ∞
(3.81a); smallness parameter, Equa- σ hard-sphere diameter, Equation
tion (2.158); in Section 2.5.3, the eddy (1.99); Lennard–Jones potential func-
diffusivity; in Section 3.2.1, a small- tion separation parameter, Equation
ness parameter defined by Equation (1.100)
(3.84); Lennard–Jones potential func- σ A , σ B , σ AB Lennard–Jones hard-sphere di-
tion energy parameter, Chapter 1 ameters for species A and B and for
εA , εB , εAB Lennard–Jones potential function the mixture, σ AB = (σ A + σ B )/2
energy parameters for species A and B τ extra stress second-order tensor,
and for the mixture, εAB = (εA εB )1/2 Equation (1.84)
εc , εm , εT eddy mass, momentum, and ther- τij stress components
mal diffusivities, Equations (3.113), τrz , τ̂rz stress components in inner and outer
(2.296), and (2.297) regions, respectively, Section 2.2.5
εM eddy diffusivity associated with trans- τw magnitude of wall shear stress
fer of quantity M by turbulent fluctu- τY yield stress in Bingham plastic model
ations
(t)
τ yx turbulent stress component, Equation phenomena that occur in continua as a result
(2.300) of driving forces in momentum, mass, and heat
τ0 shear stress at y = 0 transfer. The descriptions can be concerned with
Φ arbitrary flux vector or tensor, Equa- continua on either differential or macroscopic
tion (1.39); in Equations (2.289) and scales; the results can be used for process anal-
(2.290), represents a scalar, vector, or ysis or for design to improve the efficiency of
tensor function; rate of heat produc- existing processes and to develop new processes.
tion and rate of radiation energy ab- The analysis of transport processes relies on
sorption, per unit volume a small set of fundamental laws. These laws, to-
Φv rate of conversion of mechanical en- gether with specific information and data about
ergy to thermal energy by viscous dis- the properties and behavior of the process ma-
sipation, per unit mass (Eq. 1.97) for a terials and about the constitutive relations bet-
constant-density Newtonian material ween driving forces and their resulting fluxes,
Φ0 , Φ1 , Φ2 coefficients for the general viscous are used to provide a mathematical description of
fluid, Equation (1.106) the behavior of the process or phenomenon. This
φ function described by Equations mathematical description, together with process
(2.90) and (2.91); association fac- constraints such as geometry and boundary con-
tor, Equation (3.29); fractional flow, ditions, defines the mathematical problem. Its
Equation (2.109) solution, then, is approached by using a variety
φ ( y ∗, z∗) in Section 3.2.1, the cA solution from of mathematical and engineering strategies for
Equation (3.91) solutions to algebraic, ordinary, and partial dif-
χ ratio of concentric cylinder inner and ferential equations.
outer radii The governing laws that establish the behav-
ψ stream function defined by Equation ior of continua are the conservation laws for
(2.125); in Section 2.4.1, function de- mass, energy, and linear and angular momen-
fined by Equation (2.210); in Equa- tum (and their subset accounting equations for
tions (2.289) and (2.290), represents species mass, mechanical energy, and thermal
a scalar, vector, or tensor function energy) plus the second law of thermodynamics.
ΩD collision integral correction factor for These laws require a knowledge of the properties
intermolecular interactions, Equation and behavior of materials in the form of (1) vol-
(3.28) umetric (pressure – volume – temperature) prop-
Ωv collision integral correction factor erty relations and data; (2) thermodynamic prop-
for intermolecular interactions, Equa- erty relations and data (such as internal energy,
tions (1.101) and (1.102) enthalpy, and entropy); and (3) transport flux re-
∂/∂t time derivative seen by an observer lations and data (for heat, mass, and momentum
maintaining constant spatial coordi- fluxes in terms of their driving forces: tempera-
nates (position) ture gradient, mole fraction gradient, and veloc-
ity gradient).
The foundations establish conventions and
Others
identities that are used throughout this article:
∇ Del operator for spatial differentiation, (1) kinematic relationships used in describing
defined by Equation (1.29) for rectangu- the motion of continua, (2) development of the
lar cartesian coordinate systems conservation laws and their corollary equations
∇2 Laplacian operator, ∇2 = ∇ · ∇, Equation related to mechanical and thermal energy bal-
(1.38) ances, (3) linear transport relations for heat and
∼
order of magnitude estimate momentum fluxes, and (4) discussion of how
this material is combined in a methodology es-
tablishing quantitative models for describing the
1. Foundations behavior of continua. Additionally, the molecu-
lar foundations for transport properties of ma-
The objective of this article is to provide the terials are discussed. Theories for these proper-
foundations for understanding and analyzing ties, used to quantify the relations between the
transport fluxes and their driving forces, work held constant). A coordinate system is referred
reasonably well for gases to calculate proper- to as curvilinear if it is not rectangular.
ties such as thermal conductivity, viscosity, and
diffusivity. However, for more dense phases in
which intermolecular interactions play a signif- 1.1.2. Vector and Tensor Operations
icant role the theories serve primarily as a guid-
ing framework for empirical relations. Finally, Useful references for vector and tensor notation,
a brief discussion of non-Newtonian fluids and and their operation are given in [1] and [2]. The
their constitutive relations is presented. relations presented below summarize operations
After development of the basic equations, for rectangular cartesian systems for the pur-
boundary conditions and a solution philosophy pose of setting notation and conventions.
for attacking problems are discussed briefly. Accordingly, any vector a may be written as
Also, the equations of change in dimensionless a linear combination of its components and base
form are presented as the basis for dimension- vectors in the following way:
less group correlations and analogies between
3
different modes of transport.
Chapter 2 is limited to compositionally ho- a = a i ii ≡ a i ii (1.1)
i=1
mogeneous systems, whereas transport in mul-
ticomponent systems is discussed in Chapter 3. A second-order tensor A is written in terms of
its base vectors and components in the following
way:
1.1. Mathematical Preliminaries
A = Aij ii ij (1.2)
1.1.1. Coordinate Systems
Here summation occurs over both indices i and
The study of transport processes is concerned j. The addition of two vectors is a vector that is
with scalars, which are represented by a single obtained by adding corresponding components:
number (their magnitude), and with vectors and
3
tensors, which have directions in space as well
a+b= (ai + bi ) ii (1.3)
as magnitude associated with them. i=1
To describe vectors and tensors a coordinate
system is defined for representing positions in Multiplication of a vector or tensor by a scalar
three-dimensional space (direction and magni- k is performed by multiplying each component
tude). A variety of systems are possible and by that scalar:
can be used. Each coordinate system has de-
fined base vectors, and all other vectors can be ka = k (ai ii ) = (k ai ) ii (1.4)
described as linear combinations of these base
vectors. Any three noncoplanar vectors can be The dot product of two vectors (which is a scalar)
used as base vectors. However, orthogonal vec- by definition (→ Mathematics in Chemical En-
tors (mutually perpendicular) that form a right- gineering) is the product of their magnitudes and
handed system are normally used. Base vectors the cosine of their subtended angle, which im-
are cartesian if they are of unit length. If they plies a sum of the products of the corresponding
are both orthogonal and cartesian, then they are components (for an orthonormal system):
orthonormal. Base vectors are rectangular, carte-
sian if they are orthonormal and everywhere the a ·b = |a| |b|cos θ = ai bi (1.5)
same (in both magnitude and direction). In gen- The dot product of a vector and tensor is cal-
eral, the base vectors for a coordinate system culated by a similar sum over adjacent indices
are not independent of position. For example, according to
the base vectors for a cylindrical or spherical
system vary with position (in a cylindrical sys- a ·B = ai Bij ij
tem, the radius vector changes direction as the
B ·a = Bij aj ii (1.6)
angular coordinate varies and the z coordinate is
The components thus obtained are analogous to and

the elements of a vector obtained from the matrix
multiplication of a vector and a square matrix. A eijk emjk = 2 δ im (1.16)
different result is obtained for pre-versus post-
multiplication. The dot product of two second- The dyadic or tensor product of two vectors is
order tensors is a second-order tensor given by a second-order tensor whose dot product with a
vector is given by
A ·B = Aij Bjk ii ik (1.7)
(a b) ·c = a (b ·c) (1.17)
The trace of a second-order tensor is a scalar
In terms of index notation the tensor product a b
given by the sum of its diagonal terms
is written
tr (A) = Aii (1.8)
a b = ai bj ii j j (1.18)
and the trace of the dot product of two second-
The transpose AT of a second-order tensor is
order tensors is a double sum performed in the
defined so that the i j component of A is the j i
following way:
component of the second-order tensor AT . Ac-
cordingly,
tr (A ·B) = Aij Bji (1.9)
The identity second-order tensor is defined such AT = Aij ij ii (1.19)

that
δ = δij ii ij (1.10)
where δij is the Kronecker delta defined by 1.1.3. The Jacobian

1 for i = j The Jacobian is the ratio of differential volume
δij = (1.11) elements represented in two coordinate systems.
0 fori = j
It has special value when one of the coordinate
This identity tensor, either pre- or post-dotted systems involves material coordinates and the
with a vector, returns the original vector. Like- other involves the spatial coordinate system dis-
wise, when it is dotted with a second-order ten- cussed below in kinematics. In rectangular carte-
sor, the original second-order tensor is obtained. sian coordinates, the differential volume element
The permutation symbol eijk is defined such can be written as
that
 dV = dy1 dy2 dy3 (1.20)

1 for an even permutation of 123
eijk = 0 when any two indices are repeated (1.12) which can be expressed equivalently in terms of

−1 the triple scalar product:
for an odd permutation of 123
The cross product of two vectors is then defined dV = dy1 i1 · (dy2 i2 ×dy3 i3 )
by
A position vector in space can be represented in
a × b = ai bj eijk ik (1.13) terms of a rectangular coordinate system or in
terms of an alternate system according to
and the cross product of a vector and a second-
order tensor is similarly given by r = y i ii = x i g i (1.21)
a × B = ai Bjm eijk ik im (1.14) where xi are the components of the position vec-
tor in the alternate system with base vectors g i .
Two convenient identities between the permuta- Each of the cartesian coordinates can be ex-
tion symbol and the Kronecker delta are pressed as a function of the other system coor-
dinates, yi = yi (x 1 , x 2 , x 3 ). Then, the differential
eijk emnk = (δim δjn − δin δjm ) (1.15) volume element can be expressed in terms of the
triple scalar product of three vectors written in Derivatives with Respect to Position. The del
terms of the derivatives with respect to each of operator ∇ is defined to differentiate quanti-
the new coordinate system’s three coordinates: ties that are functions of position. In rectangular
cartesian coordinate systems the del operator is
∂y ∂y ∂y
dV = dx1 · dx2 × dx3 (1.22)
∂x1 ∂x2 ∂x3 ∂
∇ ≡ii (1.29)
∂yi
or
The del operator can operate in dyadic, dot, or
dy1 dy2 dy3 = Jdx1 dx2 dx3 (1.23) cross product forms on scalars, vectors, or ten-
sors. As a dyadic operation, grad (ϕ) is
and the Jacobian is the determinant of the par-
tial derivatives relating changes in coordinates ∂ϕ
∇ϕ = ii (1.30)
between the two systems: ∂yi
∂y1 ∂y3
∂y2 and grad (a)
∂x1 ∂x1 ∂x1

∂y1 ∂y2 ∂y3
J ≡ ∂x ∂x2 (1.24) ∂aj
2 ∂x2 ∇a = ii ij (1.31)
∂y ∂y3 ∂yi
1 ∂y2
∂x3 ∂x3 ∂x3
For grad (a), note the order of the index cor-
The Jacobian only exists if there is a unique responding to the del operator with respect to
transformation between the two coordinate sys- that corresponding to the vector. The opposite
tems. order is sometimes used in the literature, and
care must be taken to follow a consistent con-
vention throughout a given work.
1.1.4. Calculus of Vectors and Tensors The dot product of the del operator with a
vector a or tensor A is given by
In transport phenomena generally, two kinds of
vector and tensor derivatives exist with respect ∂ai
∇ ·a = (1.32)
to time and with respect to position. ∂yi
Derivatives with Respect to Time. The ∂Aij
derivative of a vector that is a function of time ∇ ·A = ij (1.33)
∂xi
is a vector; a derivative of a second-order tensor
with respect to time is a second-order tensor. and is called the divergence of the vector or ten-
Derivatives are obtained straightforwardly by sor. Again, note the order of the indices corre-
differentiating each of their components with sponding to the del operator and the second-
respect to time: order tensor. The divergence of a vector is a
scalar, so the order is immaterial. The del oper-
da dai ator can also be crossed with a vector or tensor,
= ii (1.25)
dt dt and these operations are given by
dA dAij
= ii ij (1.26) ∂aj
dt dt ∇×a = eijk ik (1.34)
∂yi
Differentiating products of vectors is similar to ∂
differentiating products of scalars: ∇×A = Ajm eijk ik im (1.35)
∂yi
d da db and called the curl of the vector or tensor. Here,
(a ·b) = ·b + a · (1.27)
dt dt dt only one definition with respect to the order of
the indices seems to exist in the literature.
Because of its dual vector – operator role, the
d da db
(a×b) = ×b+ a× (1.28) del operator may be dotted with one entity and
dt dt dt
operate on (differentiate) another. For example,
in the thermal energy equation in Section 1.2
(Eq. 1.96), the term
1.1.6. Kinematic Relations

u ·∇F (1.36)
appears, in which the del operator is pre-dotted A fundamental concept of kinematics, the de-
with the velocity vector u but operates (by differ- scription of motion without reference to its
entiation) on the temperature (see also Eq. 1.53): cause, is that of material coordinates. Given a
fluid or material undergoing motion (translation,
∂T rotation, deformation), each particle of that ma-
u ·∇T = ui (1.37)
∂yi terial has a current position y
The Laplacian is another operator, a scalar oper-
y = y i ii (1.41)
ator, defined by ∇ · ∇. For rectangular cartesian
systems it is given by Also, each element of the material can be iden-
tified with the position it had at some reference
∂2ϕ
∇2 ϕ = ∇ · ∇ϕ = (1.38) time (t = 0, for example):
∂yi ∂yi
X = Xi ii (1.42)
The spatial coordinates yi are used to identify a

1.1.5. Divergence Theorem position in space, and the material coordinates
Xi are used to identify elements of the material.
The divergence theorem is extremely important Furthermore, the position in space can be de-
in deriving and understanding the basic trans- fined in terms of the element of the material that
port relations. This theorem equates an integral resides there (identified by its position at time
over the entire volume of a region of space en- t = 0, its reference position) at time t:
closed by a closed surface to an integral over that
surface: y = y (X, t) (1.43)

Inversely, the material coordinates X can be de-
∇ ·ΦdV = n ·Φ dA (1.39)
fined in terms of the spatial coordinates and time
V A
t; each element of mass can be defined in terms
In this equation, Φ can be a vector or a second- of its location at time t
order tensor. If it is an isotropic second-order
tensor ( p I, for example), then a form involving X = X (y, t) (1.44)
a scalar function is obtained: This inversion depends on 0 < J < ∞ where J is
the Jacobian.
∇pdV = pn dA (1.40) Every quantity expressed in terms of spa-
V A tial coordinates and time can just as well be
In transport phenomena, Φ represents the flux expressed in terms of material coordinates and
of an extensive property and the surface integral time. For example, for a flowing fluid the den-
represents the rate at which the property (as writ- sity, velocity, etc., vary with position
ten here using the outward normal vector n) is
= (y, t) (1.45)
leaving the volume element across the surface.
With the del operator defined as above, the sur-
u = u (y, t) (1.46)
face integral must be written with the surface
outward normal vector pre-dotting the quantity or, equivalently, vary from material element to
Φ. material element:
= (X, t) (1.47)
u = u (X, t) (1.48)

1.1.7. Partial and Total Derivatives dF ∂F dx
= + ·∇F (1.54)
dt ∂t x dt
The partial derivative with respect to time [of a
function F (x, t)], if position is held constant, is or
written as
dF ∂F
= + w ·∇F (1.55)
∂F(x, t) ∂F dt ∂t x
≡ (1.49)
∂t ∂t x A physical interpretation of the three deriva-
and represents changes in the variable of interest tives follows [3]. An observer interested in de-
with time at a fixed point in space. termining the changes in the concentration of
The partial derivative with respect to time fish in a river cf can do so while staying at a
[of a function F (X, t)], if the material coordi- fixed position in the river ∂cf /∂t, while drifting
nates are kept constant, is called the material in a canoe at the velocity of the river D cf /D t,
derivative or substantial derivative, and repre- or while moving around in a motorboat with ve-
sents changes observed while following the mo- locity w (dcf /dt).
tion of the material:

D F(X, t) ∂F
≡ (1.50) 1.2. Basic Equations for
Dt ∂t X
Compositionally Homogeneous Systems
Note that if F is the spatial coordinate of an
[3–7]
element of fluid, then D F/D t = D x/D t is the
change in position with time of a material el-
1.2.1. The Reynolds Transport Theorem
ement, i.e., the fluid velocity:

∂x Dx In deriving the conservation equations of mass,
u ≡ = (1.51)
∂t X Dt energy, and momentum for a continuum, a vol-
ume (system) that always encloses the same el-
The total derivative represents changes that
ements of mass should be defined. This vol-
would be observed while moving around at an
ume must then move and deform with the fluid,
arbitrary velocity w; it is represented by dF/dt.
which is convenient because no convected input
This velocity w then represents the total deriva-
or output term need be considered. This con-
tive of the position vector:
cept, and the substantial derivative and Jacobian
w = dx/dt from kinematics, are very useful in deriving the
desired conservation equations.
If F (x, t) is a function of position and
time (scalar, vector, or tensor), representing the
amount of the desired property per unit volume,
1.1.8. Relation Between Different Time and V (t) is the closed volume moving with the
Derivatives fluid, then

A property F written in terms of x and t has the
F (t) ≡ F(x, t) dV (1.56)
total differential
V

∂F ∂F
dF = dt + dxi (1.52) represents the total amount of the desired prop-
∂t x ∂xi t
erty contained within the system V (t). For the
from which the relation between the substantial conservation equation, then, the accumulation
and partial derivatives and u may be determined: rate of the property within the system is required
D F (t)/D t. Here the substantial derivative must
∂F DF ∂F
= = + u ·∇F (1.53) be used because it is the derivative “following
∂t X Dt ∂t x
the motion.” Then
In an analogous way, the total derivative is re-
lated to the partial and substantial derivatives and
to w by
or leaves the system, so the mass conservation
DF D
= F(x, t) dV (1.57) equation is
Dt Dt
V
D
dV = 0 (1.62)
However, the derivative cannot be taken across Dt
the integral in this form because the volume is a V
function of time. This difficulty is circumvented By the Reynolds transport theorem then,
by transforming the system to the reference co-
D
ordinates, differentiating, and then transforming + ∇ ·u dV = 0 (1.63)
Dt
back. In the reference coordinates, the volume V
element is a constant. Now,
The volume chosen as the system is completely
arbitrary, so this result implies
dV = JdV0 (1.58)
D
So = − ∇ ·u (1.64)
Dt
or, in terms of the partial derivative,
DF D
= F[x (X, t) , t] J dV0
Dt Dt ∂
V0 = − ∇ ·u (1.65)
∂t
DF DJ
= J +F dV0 (1.59)
Dt Dt This equation (in either form) is called the con-
V0
tinuity equation (see also, → Fluid Mechanics,
Chap. 2.1.). Note that if F in Equation (1.61) is
DJ proportional to (i.e., F = G), then by conti-
= J∇·u so nuity
Dt

D DG
G dV = dV (1.66)
Dt Dt
DF DF V V
= +F∇ ·u J dV0 (1.60)
Dt Dt
V0
Finally, converting back to spatial coordinates 1.2.3. Conservation of Linear Momentum

gives
An equation for the conservation of momentum
DF DF or energy for a continuum must be able to ex-
= +F∇ ·u dV (1.61)
Dt Dt press the forces that are exerted on an element in
V
the continuum. These forces are of two kinds:
which is known as the Reynolds transport theo-
rem (RTT). 1) Body forces act upon the entire volume
(reach inside the volume and act upon each
element) and may be gravitational, electro-
1.2.2. Conservation of Total Mass magnetic, etc.
2) Contact (or internal) forces act at the surface
In the absence of nuclear conversions, total mass of the element of the continuum.
is conserved; no generation or consumption oc- Cauchy’s stress principle states that if t(n )
curs. (The term balance is commonly used to is the force per unit area (stress vector or trac-
apply to both conservation and accounting equation) at a point on the surface of a system volume
tions. In this section, and in Chapter 4 on macro- (surface orientation indicated by n), then t(n ) is
scopic systems, the term “accounting” is used for a function of x, t, and the orientation of the sur-
properties that may be generated or consumed face. The stress vector at a point x at a particular
and the term “conservation” for properties that time is not sufficient; the surface upon which the
may not be generated or consumed.) Now, for stress vector acts must also be defined.
the volume that moves and deforms with the Note that t(n ) is a vector force per area (the
flowing fluid, as described above, no mass enters stress vector or traction vector) and that t(n ) dA
is the force acting from outside the surface. For 1.2.6. Equation of Motion
a volume (with a surface) the total force acting
on this volume due to these contact forces is the Now,
integral over the entire surface A:
D
u dV = g dV + n ·T dA (1.71)
t(n) dA (1.67) Dt
V V A
A
Body forces can be summed by a volume inte- or, by the divergence theorem and Reynolds
gral (g is force per unit mass) transport theorem,

Du
g dV (1.68) dV = g dV + ∇ ·T dV (1.72)
Dt
V V V V
and the conservation of linear momentum (for so (again, V is arbitrary)

a system that moves with the material) can be
expressed as Du
= g +∇ ·T (1.73)
Dt
D
Dt
u dV = g dV + t(n) dA (1.69) or
V V A
This is known as Euler’s first law. a = g+∇ ·T (1.74)
where a = D u/D t, the acceleration. This is

1.2.4. Condition of Local Stress Equilibrium known as Cauchy’s first law, the conservation
of linear momentum, or simply the equation of
As a direct consequence of the conservation of motion for a continuum. For further details, see
linear momentum, the stress vector (traction) → Fluid Mechanics, Chap. 2.2.
acting at a point on a surface is matched by
an opposite and equal reaction force on the sur-
roundings. That is, if momentum is conserved, 1.2.7. Conservation of Angular Momentum
the transfer of momentum between the system
and its surroundings due to forces is mutual (con- If angular momentum is conserved locally in a
dition of local stress equilibrium). continuum (the usual situation),

D
(u × x) dV = (g × x) dV +
1.2.5. Stress Tensor Dt
V V

The condition of local stress equilibrium leads to t(n) × x dA (1.75)
an important decoupling of stress from the sur- A
face orientation. Consideration of the stresses
acting on the surfaces of a tetrahedron shows which is Euler’s second law. By writing t(n )
that in terms of T (Eq. 1.70) and using the diver-
gence theorem, Reynold’s transport theorem,
t(n) =n ·T (1.70) and vector – tensor identities, this statement of
the conservation of angular momentum reduces
where T is the second-order stress tensor to the result that the stress tensor is symmetric.
(→ Fluid Mechanics, Chap. 3.1.), which may be That is, a necessary and sufficient condition for
a function of position and time but not of surface satisfying the conservation of angular momen-
orientation. tum is:
The state of stress in a continuum at a point
is the totality of all possible pairs of traction T = TT (1.76)
vectors t(n ) and surface orientations n (i.e., an
infinite number). However, the nine-component
stress tensor can be used to obtain t(n ) if n is
given.
However, this is restricted to fluids that have no 1.2.9. Conservation of Total Energy
couple stresses (i.e., torques on the fluid are the
result only of forces) [5], [6]. If Û is the internal energy per unit mass, then a
Also, if T is a symmetric second-order ten- total energy balance is
sor (nondiagonal, in general), a rotated coordi-
D 1 2
nate system exists in which T is diagonal. In this u + Û dV = g ·u dV +
Dt 2
system, the coordinate axes are called the prin-
V

V

cipal axes of stress and the three normal stresses t(n) ·u dA − n ·q dA + Φ dV (1.81)
(eigenvalues) are called the principal stresses. A A V
In mechanics, analysis of the principal axes of
stress provides the basis for Mohr’s stress circle where q is the heat flux at the system boundary.
technique [6], [7]. The left side of this equation represents changes
in kinetic and internal energy, and the terms on
the right side have the following meaning:

1.2.8. Mechanical Energy Accounting g ·udV rate at which work is done by body forces,
Equation
V
t(n) ·udA rate at which work is done due to traction,
A
− n ·qdA rate of energy transfer due to q, and
Now, because of the conservation of linear mo- A
mentum (Eq. 1.74), ΦdV rate of radiant energy absorption.
V
(a − g − ∇ ·T ) ·u = 0 (1.77)
This last term may also be used to represent
or heat generation (conversion of energy from other
forms to thermal energy) by mechanisms such
D 1 as electrical heating and chemical or nuclear re-
u ·u − g ·u − (∇ ·T ) ·u = 0
Dt 2 actions instead of accounting for these conver-

D (u·u) Du Du sions through changes in, e.g., changes in inter-
= ·u + u · =
Dt Dt Dt nal energy from one form to another within the
material volume. From Equation (1.81) the con-
a ·u+u ·a= 2a ·u (1.78) tinuum statement of total energy conservation
is
Now, as an identity, for T symmetric
D 1 2
u + Û
Dt 2
∇ · (T ·u) = (∇ ·T ) ·u+ tr (T ·∇u) (1.79) = g ·u+∇ · (T ·u) − ∇ ·q + Φ (1.82)
so that

D 1
u ·u = g ·u+∇ · (T ·u) − tr (T ·∇u)(1.80)
Dt 2 1.2.10. Thermal Energy Accounting
Equation
This scalar equation is a rate accounting equa-
tion of mechanical energy in the form of kinetic Subtracting the mechanical energy accounting
energy (the left-hand side), work done by body equation from the total energy conservation
forces ( g · u), work done by traction forces equation gives an accounting of thermal energy:
[∇ · (T · u)], and the conversion of mechanical
energy to thermal energy due to traction through
D Û
= − ∇ ·q+tr (T ·∇u) +Φ (1.83)
both fluid compression and viscous dissipation Dt
[tr (T · ∇ u)], all per unit volume. Obviously, this In this result, tr (T · ∇u) represents the conver-
result is not independent of the equation of mo- sion of mechanical energy to thermal energy.
tion and, in fact, as a scalar equation must con- Equation (1.83) is not an independent equation
tain less information than the vector equation of but has the advantage of not involving mechan-
motion. ical energy terms. It can be used in place of the
total energy equation.
1.2.11. Forms of the Governing Equations Now, from experience, q is known to

be in the opposite direction of ∇T , so
Many possible forms of the continuity, motion, − q · ∇T ≥ 0. Furthermore, and also from ex-
and energy equations exist, depending, for experience, − tr (τ · ∇u) ≥ 0. Consequently, an
ample, on whether partial or substantial deriva- inequality results that must hold for all contin-
tives are used and whether heat capacities (cp or uum processes:
cv ) are used instead of internal energy. A con-
venient table for compositionally homogeneous q
DŜ Φ
continua summarizing these forms appears in +∇ · − ≥0 (1.90)
Dt T T
[3]. Further summary of the governing equations
is given in Section 1.4. Alternatively, − q · ∇T ≥ 0 and − tr (τ · ∇v) ≥ 0
In these forms, the stress tensor is commonly may be viewed as constraints on allowable con-
separated into isotropic stress p I and extra stress stitutive equations for q and T.
τ (→ Fluid Mechanics, Chap. 3.1.). Following
the convention of Bird,
1.2.13. Linear Transport Fluxes and
T = − τ − pI (1.84) Relations
where p ≡ − tr (T )/3. As a result ∇ · T be- The above transport equations describe the con-
comes − ∇ · τ − ∇p and tr (T · ∇u) becomes servation of mass, linear momentum, and total
− tr (τ · ∇u) − p∇ · u. energy, and include terms representing heat and
momentum fluxes. The flux relations that are
normally adopted follow the observation that the
1.2.12. Entropy Inequality flux is proportional to a gradient driving force;
i.e., the heat flux is proportional to the temper-
If T = − τ − pI for a compressible fluid, then the ature gradient and the momentum flux is pro-
thermal energy equation is portional to the velocity gradient (actually, the
symmetric part of the velocity gradient tensor).
DÛ
= − ∇ ·q − p∇ ·u − tr (τ ·∇u) + Φ (1.85) Fourier‘s Law. For heat conduction,
Dt
Now if Û = Û (Ŝ, V̂ ), where Ŝ is the entropy per

q = − λ∇T (1.91)
unit mass and V̂ the volume per unit mass, then
dÛ = T dŜ − pdV̂ (1.86) where λ is the thermal conductivity and, in gen-
or by the equation of continuity eral, may be a function of location in the material
and temperature. (To be more general, the heat
DÛ DŜ DV̂ DŜ flux can be written in terms of an anisotropic
= T − p = T − p∇ ·u (1.87) thermal conductivity tensor to allow for direc-
Dt Dt Dt Dt
tionality in the thermal conductivity.) In rectan-
This gives for the thermal energy equation gular cartesian coordinates the components of
the heat flux are
D Ŝ
T = − ∇ ·q − tr (τ ·∇u) + Φ (1.88)
Dt
or ∂T
qx = − λ
∂x y,z
DŜ q ∇T
= − ∇· − q· 2
Dt T T ∂T
qy = − λ
∂y x,z
1 Φ
− tr (τ ·∇u) + (1.89)
T T ∂T
qz = − λ (1.92)
∂z x,y
Momentum Flux Relations. For viscous ma- non-Newtonian stress relations are given in the
terials the most common momentum flux rela- following paragraphs.
tion is Newton’s law of viscosity, which for an
incompressible material is written in terms of
the rate of deformation tensor ∆ as 1.2.14. Transport Properties from
Molecular Theories
τ = − η∆ (1.93)
where η is the viscosity. For Newtonian mate- The calculation of transport properties by using
rials the viscosity is constant at constant tem- molecular transport theories with parameters es-
perature (i.e., it is independent of shear rate), timated from experimental data is quite reliable
resulting in this linear flux relation. For one- for dilute (low-density) gases. This is a direct
dimensional shear flow with only one velocity result of the fact that at low densities, intermo-
gradient component, this result becomes lecular collisions and forces are minimized. De-
dux
tails of the theories are available in the original
τyx = − η (1.94) references or in summaries such as [8]. In this
dy
section, theories for viscosity and thermal con-
These linear relations can be used together ductivity are considered. Section 3.1.5 discusses
with the conservation equations to model the theories for diffusivities.
behavior of continua. For a Newtonian fluid Viscosity. Based on two-body, hard-sphere
of constant viscosity and density (or for iso- collisions the viscosity of a gas (in micropascal
choric flow for which ∇ · u = 0), the equation seconds, i.e., 10−6 Pa · s) theoretically is given
of motion becomes the Navier – Stokes equa- by
tion (for further details, see → Fluid Mechanics,
Chap. 3.2., → Fluid Mechanics, Chap. 3.3.) √
5
16
(π Mr R T )1/2 Mr T
η = = 26.69 (1.99)
∂u π σ2 σ2
+ u ·∇u = g − ∇p + η∇2 u (1.95)
∂t where T is in kelvin and the hard-sphere diam-
Also, for a Newtonian fluid of constant density, eter σ is in ångströms (i.e., 10−10 m); M r is the
thermal conductivity, and viscosity, the thermal molecular mass of the gas.
energy equation becomes To adjust for non-hard-sphere interactions,
Chapman and Enskog introduced the use of
∂T
cp + u ·∇T = λ∇2 T + Φv (1.96) spherically symmetric molecular potential func-
∂t
tions [9], [10]. The most commonly used func-
where the distinction between constant pressure tion is the Lennard – Jones 12 – 6 potential
and constant volume heat capacities vanishes for
σ 6
true incompressibility. In this result, Φv accounts σ 12
ψ (r) = 4 ε − (1.100)
for the conversion of mechanical energy to ther- r r
mal energy through viscous dissipation and is
given by from which can be calculated the interaction
6 . /7 forces between molecules as a result of their sep-
Φv = η tr [∇u ·∇u] +tr (∇u)T · ∇u (1.97) aration r and model parameters σ and ε. These
forces are then used to adjust the viscosity cal-
Further simplifications are often appropriate,
culations through the dimensionless collision in-
such as for a solid material whose velocity terms
tegral Ωv , which is a function of k T/ε where k
in the thermal energy equation become insignif-
is the Boltzmann constant. Tabulations of this
icant, giving

quantity are readily found in the literature, and
∂T a convenient and accurate computational form
cp = λ∇2 T (1.98)
∂t for Ωv is given by Neufeld et al. [8], [11]. The
Understanding material behavior with respect value of Ωv is unity for the ideal hard sphere;
to thermal conductivity and viscosity is an im- thus, deviations are a measure of the departure
portant factor in understanding transport phe- from this ideal model. The Chapman – Enskog
nomena. Theoretical foundations for calculat- relation for viscosity, then, is
ing these properties for low-density gases and
√ using the viscosity relation (Eq. 1.101), the ther-
5
16
(π Mr R T )1/2 Mr T
η = = 26.69 (1.101) mal conductivity can be expressed in terms of
(π σ 2 ) Ωv σ 2 Ωv
the viscosity and constant volume heat capacity
where again η is in 1 micropascal seconds, T in as
kelvin, and σ in ångströms.
Other potential functions have been used. The λ Mr
= 2.5 (1.103)
Stockmayer potential adjusts for polarity and η cv
should be used instead of the Lennard – Jones This result works quite well for monatomic
potential for polar molecules. Calculation of the gases. For polyatomic gases it must be adjusted
Stockmayer potential by using the analytical to account for the additional degrees of freedom.
correction to the Lennard – Jones potential pro- The Eucken equation
vided by Brokaw is recommended [8], [12].
These potential energy functions rely on mo- λ Mr
= cv + 1.872 × 104 (1.104)
lecular parameters that must be determined from η
data. In practice, tabulations of these parame-
is a simple, yet reasonably accurate method for
ters, which are available for individual materi-
this correction. Other methods are available and
als, are derived from experimental data for vis-
are discussed and evaluated by Reid et al. [8].
cosity by using the appropriate potential func-
tion with the Chapman – Enskog theory. Using
the parameters, then, along with the potential
1.2.15. Non-Newtonian Fluids (see also
function (collision integral) to calculate viscos-
→ Fluid Mechanics, Chap. 4.)
ity, amounts to adjusting the measured values
to the desired temperature by using the square-
In the momentum and energy balances, q and
root temperature dependence of the molecular
τ represent heat and momentum fluxes. Before
theory. As long as the form of the theory is cor-
problems can be solved, constitutive relations
rect, the calculations should be very good. In
must be selected for these fluxes in terms of ap-
fact, when tabulated potential function parame-
propriate driving forces (e.g., ∇T or ∇u).
ters are used for a dilute gas, calculated viscos-
The specific relation for τ that is appropriate
ity values are correct to within ca. 1 %. Methods
for a particular material is the subject of rheol-
also exist for estimating the parameters; these
ogy. Specific rules dictate the form of constitu-
too give quite reasonable viscosity values, with
tive equations or set constraints on them. Useful
errors from 1 to 3 % [8].
references on non-Newtonian rheology are [13–
Thermal Conductivity. The molecular theory
15].
for thermal conductivity is complicated by the
The rheological constitutive equation that
fact that internal energy is stored in molecules
is applicable in a given circumstance can be
in internal vibrational and rotational modes as
viewed as depending on either the type of ma-
well as in the translational mode, unlike vis-
terial or on the specific flow situation. That is,
cosity (momentum) which is manifest only in
the material may behave in a certain way be-
translation. Consequently, although the basic
cause it behaves according to that model in all
molecular theory parallels that for viscosity,
circumstances (i.e., it is that kind of material) or
an additional term for these internal energy
because all materials behave in that way for a
modes is necessary for polyatomic molecules.
particular flow situation.
For monatomic gases (which do not have the
From a materials viewpoint, behavior is nor-
internal modes) the Chapman – Enskog thermal
mally classified as viscous, elastic, or viscoelas-
conductivity relation is
tic. Complicating this classification by material
- type is the presence of history or memory effects
25
32
(π Mr R T )1/2 cv T /Mr
λ = = 0.0833 (1.102) (→ Fluid Mechanics, Chap. 4.1.4.).
Mr (π σ 2 ) Ωv σ 2 Ωv
One very common type of constant stretch
where T is expressed in K, σ in Å, and λ history flow is viscometric flow. The importance
in J m−1 s−1 K−1 . In this relation a value of of viscometric flows with respect to the char-
cv = 3 k/2 (monatomic ideal gas) was used. By acterization of materials is that all materials,
whether they are viscous, elastic, or viscoelas- 1. /

II∆ = (tr (∆))2 − tr ∆2 (1.108)
tic, can be characterized by the same set of vis- 2
cometric functions. The functions are referred III∆ = det∆ (1.109)
to as the shear stress (or, equivalently, the vis-
cosity) and the first and second normal stress Note that I∆ = tr (∆) = 2 ∇ · u, which is zero for
differences (for further details, see → Fluid Me- an incompressible fluid or for isochoric flow. For
chanics, Chap. 4.3.1.). incompressible flow then, the general viscous
Other kinds of flows are elongational, slow, equation reduces to
and small deformation oscillatory flows. The last
are periodic and yield a set of dynamic viscoelas- T = − pI + Φ1 ∆ + Φ2 ∆2 (1.110)
tic functions such as the dynamic elasticity and
which is called the Reiner – Rivlin equation. In
the dynamic viscosity (also referred to as the
this case, Φ1 and Φ2 are functions only of II∆
storage and loss moduli, respectively).
and III∆ because I∆ = 0. Apparently, actual flu-
A Newtonian fluid has a constant viscosity
ids of this type have not been documented (i.e.,
independent of shear rate (at constant temper-
fluids with a nonzero second-order term and
ature). Other materials may show a decrease
which are purely viscous have not been ob-
(pseudoplastic) or an increase (dilatant) in vis-
served). Nevertheless, it may be a useful model
cosity with increasing shear rate or exhibit a
because the second-order term provides a mech-
yield stress (e.g., the Bingham plastic). Compli-
anism for generating normal stress differences
cating this picture is the fact that time-dependent
in steady shear flow. However, because nor-
behavior may also be observed and such fluids
mal stress differences are not generally observed
are referred to as thixotropic (decrease in viscos-
with viscous fluids, the second-order term is usu-
ity with time at fixed shear stress) or rheopectic
ally dropped (Φ2 = 0), and the model then reduces
(increase).
to the form generally used for incompressible
In addition to shear stress, normal stresses
Newtonian and non-Newtonian (non-constant-
may be generated by steady shear flow. These
viscosity) fluids:
are stresses that are normal to the flow direc-
tion and are additional to the isotropic stress T = − pI − η∆ (1.110a)
(pressure). The generation of normal stresses
can have some rather dramatic effects on the or, in terms of the extra stress τ ,
flow of fluids and may have to be considered
in process design. Experimentally, the only ma- τ = − η∆ (1.110b)
terials that have been observed to exhibit normal
where η = η (II∆ , III∆ ) is the non-Newtonian
stresses are viscoelastic, such as polymer melts
viscosity. For shear flows, [u1 = u1 (x 2 )], III∆ is
and polymer solutions.
zero so that η is only a function of the second
More quantitatively, a viscous fluid is one
invariant which can be related to the shear rate
whose stress tensor is a function only of the rate
γ̇ by
of deformation tensor ∆ (a function of strain
rate and not of strain), where 1/2
1
γ̇ ≡ |du1 /dx2 | = |II∆ | (1.110c)
2
∆ ≡ ∇u + (∇u)T (1.105)
Equation (1.110 b) is commonly used with
A completely general form for a purely viscous η = η (γ̇) for other kinds of flow (nonshear), even
fluid is though to do so is not well-founded theoretically.
T = Φ0 I + Φ1 ∆ + Φ2 ∆2 (1.106)
where the coefficients Φ0 , Φ1 , and Φ2 are func- 1.3. Summary of Basic Equations
tions of the three scalar invariants of ∆ (I∆ ,
II∆ , and III∆ ) and are defined in the following A handful of conservation laws govern physi-
way: cal behavior and, as such, provide the basics of
transport phenomena: total mass, linear momen-
I∆ = tr (∆) (1.107) tum, angular momentum, and total energy. In
Table 1. Summary of the basic transport relations
Equation name Conservation law Equation Equation number
D
Continuity total mass Dt = − ∇ ·u (1.64)
∂
total mass ∂t = −∇ · (u) (1.65)
Motion linear
momentum a= g+∇ ·T (1.74)

linear momentum ∂u∂t + u ·∇u = g+∇ ·T
∂u
linear momentum ∂t + u ·∇u = g − ∇ ·τ − ∇p
angular momentum T=T T (1.76)

2 u + Û = g ·u+∇ · (T ·u) − ∇ ·q + Φ
D 1 2
total energy Dt (1.82)
Dt = − ∇ ·q+tr (T · ∇u) + Φ
D û
Thermal energy (1.83)
accounting

∂p
Dt = − ∇ ·q + T
cv DT ∂T (∇ ·u) − tr (τ ·∇u) + Φ

Dp
cp Dt = − ∇ ·q + ∂lnT
DT ∂lnV̂
Dt − tr (τ ·∇u) + Φ
p
q Φ
Entropy inequality Dt +∇ · T
DŜ
− T ≥0 (1.90)
addition, subsets of energy give useful account- 1) A dependent variable is known throughout
ing relations, and the entropy inequality (second the region of space of interest at time zero;
law of thermodynamics) provides constraints on values at subsequent times result from the
the conservation laws. These relations are sum- behavior of the system as destined through
marized in Table 1 along with some forms not transport principles. For example, the tem-
presented in the text. perature of a fluid over a region of space may
be initially set to a prescribed value or func-
tion of position. Likewise, the velocity of the
1.4. Boundary Conditions fluid may be known initially over the region
of interest (e.g., if the fluid initially is stag-
The transport conservation relations (mass, nant, then u = 0 at t = 0).
total energy – or an accounting of thermal 2) The dependent variable at a boundary of the
energy – and linear and angular momentum), region of space of interest is known; it may
along with the second law of thermodynamics be fixed at a constant value over time or it
and relations that describe material behavior, are may be a known variable as a function of
not completely adequate for describing transport time. For example, in fluid mechanics a fluid
processes. With the addition of appropriate ini- in contact with a solid usually meets the no-
tial and boundary conditions the transport partial slip condition: the velocity of the fluid at this
differential equations can be solved to obtain fu- solid boundary is equal to the velocity of the
ture behavior of the process over the required re- solid surface. Similarly, the temperature at a
gion of space. Specific examples appear in later boundary could be a known value or function
sections. The principal types of conditions that of time.
are encountered and applied are outlined briefly 3) The transport flux at a boundary of the re-
in this section. gion of interest is known as a function of
The conditions apply to the dependent vari- time. This is not a condition on a dependent
ables of the transport equations (such as tem- variable directly; however, it is an indirect
perature or velocity), their derivatives, or other condition. For example, in Fourier’s law the
aspects of their behavior. The following are the heat flux is proportional to the temperature
types of conditions encountered: gradient; thus, specifying the heat flux at the
boundary places a condition on the behav-
ior of the temperature at the boundary. If the law. The above equations have six independent
component of the heat flux normal to the sur- variables: , ux , uy , uz (or x, y, and z), p, and T .
face is known, a condition on n · q is estab- [The stress T and heat flux q are expressed in
lished. For momentum transport, a known terms of position derivatives and temperature
traction (stress vector) at the boundary is gradients, respectively. Furthermore, the ther-
stated in terms of n · τ . As an example, at modynamic properties (Û, Ĥ, and Ŝ) are ex-
gas – liquid interfaces the stresses supported pressed as functions of T and pressure (or )
by the gas phase are very low (low viscos- through heat capacity and p – – T data or equa-
ity), the momentum flux (traction) due to the tion of state.] The five equations plus one volu-
extra stress at the interface is therefore zero: metric equation of state [p = p (, T )] along with
n · τ = 0. appropriate boundary or initial conditions dic-
4) The continuity of properties across the sur- tate the subsequent behavior of the system.
face can also serve as a boundary condition. If temperature is constant, the number of vari-
For example, at a surface (boundary) veloc- ables is reduced by one, as is the number of
ity, temperature, traction, and heat flux are equations (energy conservation reduces to the
normally continuous. The continuity of heat mechanical energy accounting equation, which
transfer across the interface holds as long as is not an independent equation).
no thermal energy accumulates at the sur- If density is constant, the number of variables
face of interest. This, however, does not im- and equations (volumetric equation of state)
ply that temperature gradients are continu- both decrease by one.
ous; thermal conductivities may change at a
boundary. Likewise, the continuity of trac-
tion is necessitated by the condition of local 1.6. Dimensionless Equations of Change
stress equilibrium (i.e., by the conservation (→ Scale-Up in Chemical Engineering)
of linear momentum).
5) The stress in fluids is finite, that is, fluids can- As discussed above, for a given flow situation
not sustain stresses without deforming so as involving momentum and heat transfer, a scalar
to reduce those stresses. This condition is ap- equation of continuity, a vector equation of mo-
plicable, for example, in pipe flow problems tion, and a scalar equation of energy (either total
where, if such a condition is not imposed a energy or a thermal energy accounting equation)
priori, solutions to the equation of motion are available. These laws govern the behavior of
could yield an infinite stress at the center of the process at hand. In these equations, each term
the pipe. has a specific physical meaning or origin impor-
tant to the current situation. Consequently, each
term carries with it dimensional characteristics
that result from those physical meanings.
1.5. Solution Philosophy Frequently, from both computational and
conceptual perspectives, equations are usefully
We now have a total of five equations and one in-
recast into a dimensionless form by means of
equality. The equations are (1) continuity (mass
dimensions or parameters that are characteristic
conservation), (2) linear momentum conserva-
of the process. These dimensionless forms have
tion (three equations, one for each spatial direc-
several advantages. First, grouping the charac-
tion), and (3) total energy conservation. Addi-
teristic parameters or dimensions into a reduced
tionally, the conservation of angular momentum
number of parameters allows parametric calcu-
constrains T to be symmetric, and the entropy
lations for a reduced number of cases. Second,
inequality places further constraints on q and
the dimensionless equations allow comparison
T. Also, linear momentum conservation can be
of processes of different size, which otherwise
used to obtain an accounting of mechanical en-
are the same; the dimensionless equations clarify
ergy (not an independent equation), which can
the adjustments that must be made between the
be employed with total energy conservation to
two processes to have them behave the same dy-
give an accounting of thermal energy that can
namically. In this way, a small-scale process can
be used in place of the total energy conservation
give an accurate prediction of a large-scale pro- The selection of specific constants for the
cess for design purposes. Third, correlations of nondimensionalizing process is not necessarily
experimental data can be made very efficiently unique. In comparing two processes of geomet-
by using dimensionless groups and correlations. rical similarity and comparable boundary con-
Correlations developed for one transport phe- ditions, however, the same physical dimension
nomenon can even be used for another one when must be selected for the two processes (e.g., the
the situations (process, apparatus, and bound- diameter of a process tank for both situations).
ary conditions) are analogous (e.g., heat-trans- Also, for order-of-magnitude scaling, the char-
fer results can be used to predict mass-transfer acteristic dimensions chosen must represent the
behavior). This is the very important Reynolds physical phenomena in a quantitatively mean-
analogy, which rests upon the similarity of con- ingful way.
servation laws (momentum, mass, and energy) Nondimensionalizing the equation of mo-
and flux relations (Fourier’s law, Newton’s law tion for an incompressible, Newtonian mate-
of viscosity, and Fick’s first law of diffusion) for rial provides a basis for comparing the rela-
certain situations. Finally, dimensionless forms tive importance of viscous forces, inertial forces,
of the transport laws have considerable value body forces, etc. The Navier – Stokes equation
in understanding the relative importance of the (Eq. 1.95),
various contributions to process behavior (e.g.,
convective versus conductive heat transfer). This ∂u
+ u ·∇u = g − ∇p + η∇2 u (1.111)
order-of-magnitude scaling is discussed further ∂t
in Chapter 2. can be nondimensionalized by the three charac-
The objective of dimensional analysis using teristic dimensions L, U, and (time is nondi-
the governing equations, then, is to convert the mensionalized by L/U) to give
equation to a dimensionless form, thereby ex-
tracting dimensionless groups. First, the vari- ∂u∗
+ u∗ ·∇u∗
ables of the equations are expressed in terms of ∂t∗
∗
dimensionless quantities (herein denoted by ∗) =
Lg g
− ∇∗ p∗ +
η
∇∗2 u∗
2
by dividing each of them by a characteristic pa- U g LU
rameter of the same dimensions. For example, (1.112)
a temperature-dependent variable would be di-
vided by a reference characteristic temperature where in Equation (1.111) the u · ∇ u term re-
or, as is more frequently used, a temperature dif- presents inertial forces and the viscosity term
ference (T 1 − T 0 ); velocity, by a velocity U that represents viscous forces. Body forces such as
is characteristic of the process; variables involv- gravity are accounted for by g. In obtaining the
ing distance, such as a derivative with respect to dimensionless form (Eq. 1.112) the coefficient
a distance coordinate, by a characteristic length of the inertial term has been set to unity by divi-
L; time, either by a characteristic process time sion so that the remaining coefficients represent
(e.g., t c , a relaxation time) or by the ratio of the a ratio to the inertial forces. For example, the co-
characteristic distance to the characteristic ve- efficient of the viscous term in Equation (1.112)
locity L/U; mass, by a characteristic mass or, is a dimensionless group representing the ratio
if the material density is constant, by the den- of the viscous force to the inertial force charac-
sity (M/L 3 ); and pressure, by U 2 . Then, when teristic quantities. The inverse of this group is
all the variables have been nondimensionalized the Reynolds number
by appropriate constants, the resulting coeffi- LU
cients of the various terms can be grouped into a Re = (1.113)
η
smaller number of coefficients. When this is car-
ried out, some terms in a given equation will con- The coefficient of the body force term represents
sist solely of the nondimensional variables of the the ratio of the body forces to the inertial forces
problem, and other terms will consist of quan- and is the inverse of the Froude number:
tities involving nondimensional variables multi-
U2
plied by nondimensional groups of the constants Fr = (1.114)
gL
and characteristic parameters of the equation.
These dimensionless groups represent the rela- coefficient of the viscous dissipation term repre-
tive importance of these terms in the equation of sents the relative importance of viscous dissipa-
motion. A large Reynolds number signifies large tion to convection and is normally expressed as
inertial forces compared to viscous forces, and the ratio of the Brinkman to the Péclet number,
a large Froude number signifies a greater impor- where the Brinkman number is
tance of inertial forces relative to the body forces
η U2
(e.g., forced convection versus natural convec- Br = (1.118a)
λ T0
tion).
The equation of energy can be nondimen- and T 0 is a reference temperature or temperature
sionalized in a similar way to obtain analogous difference.
dimensionless groups. In dimensional form the Use of dimensionless forms of the governing
equation of thermal energy for an incompress- equations provides an excellent basis for com-
ible Newtonian fluid with Fourier’s law of heat paring the same process at different scales. If
conduction is two processes are the same, that is, if they ac-
complish the same task in geometrically simi-
∂T lar apparatuses and with comparable boundary
cp + u ·∇T = λ∇2 T + Φv (1.115)
∂t conditions, then they are mathematically iden-
where Φv is the viscous dissipation defined by tical with respect to these governing equations.
Equation (1.97). This energy equation can be For further details, see → Scale-Up in Chemical
nondimensionalized to give Engineering.
∂T ∗ 1 ∗2 ∗ Br ∗
+ u∗ ·∇∗ T ∗ = ∇ T + Φ (1.116)
∂t∗ Pe Pe v 2. Transport in Compositionally
In Equation (1.115) the u · ∇T term is the trans- Homogeneous Systems
fer of heat as a result of fluid convection, λ ∇2 T
represents heat transfer by conduction, and Φv is 2.1. Heat Conduction in Solids
the irreversible conversion of mechanical energy
to thermal energy by viscous dissipation. When Heat transfer by conduction arises from spatial
these terms are nondimensionalized and the co- variations of temperature in a body. If the body
efficient of the convection heat-transfer term is is a stationary, opaque solid, conduction is the
made equal to unity, the inverse of the coeffi- only mechanism for heat transfer. In this sec-
cient of the conduction term represents the relation the basic equations for heat conduction are
tive importance of convention to conduction and summarized and specific results are presented
is termed the Péclet number: that illustrate the effects of geometry, thermal
properties, initial state, and boundary condi-
L U cp
Pe = (1.117) tions. Good general references for this material
λ
are [16, Chaps. 2 – 4], [17, Chaps. 9 – 11], [18,
It may also be viewed as the product of the Chaps. 1 – 5], and [19].
Reynolds number and another dimensionless
group termed the Prandtl number, given by
cp η
2.1.1. Heat Conduction Equations
Pr = (1.118)
λ
The general energy balance was given in Equa-
Evidently, the Prandtl number may be thought tion (1.83). For heat conduction in solids it is
of as a conversion factor relating momentum simplified in several ways: In the case of sta-
transport (the ratio of transport by convection tionary materials where u = 0, only the accumu-
to that by molecular processes, i.e., stresses) to lation, conduction, and generation terms are re-
heat transport (the ratio of transport by convec- tained. Also, the continuity equation (Eq. 1.65)
tion to that by molecular processes, i.e., con- implies that the density is time-invariant. Fur-
duction) and expressed alternatively as the ratio ther, local equilibrium is assumed, and the spe-
of momentum diffusivity (kinematic viscosity) cific internal energy Û is represented in terms of
ν (= µ/) to thermal diffusivity, α (= λ/ cp ). The the density and temperature. Then,
Next Page
∂
Û (, T ) = cv
∂T
(2.1)
The quantity α ≡ λ/ cp is the thermal diffusiv-
∂t ∂t ity, which plays the same role in heat transfer
For solids, the specific heat capacity at constant that mass diffusivity plays in mass transfer; it
volume cv ≡ (∂ Û/∂T ) is approximately equal also has the same units (m2 /s).
to the specific heat capacity at constant pres- Typical values of the thermal properties
sure cp = (∂ Ĥ/∂T )p . The latter quantity is usu- of various solid materials are given in Ta-
ally measured and found in data tables. ble 2. Properties can vary widely depending on
With these simplifications, the energy bal- the material, composition, and structural form.
ance (Eq. 1.83) reduces to Table 2. Thermal properties of various solid materials∗ at θ = 20 ◦ C
∂T
cp = − ∇ ·q + Φ (2.2) Material λ, cp , , α×106 ,
∂t W m−1 K−1 J kg−1 K−1 kg/m3 m2 /s
This equation is the differential form of the heat Aluminum 237 905 2 707 96.7
conduction equation. The term on the left is the Copper 398 384 8 954 115.7
accumulation term, and the terms on the right Cast iron (4 % 52 420 7 272 17.0
C)
are the conductive flux and thermal energy gen- Stainless steel 13.8 400 8 000 4.0
eration and radiation terms, respectively. (304)
To use the above equations to determine tem- Lead 35 130 11 373 23.4
Silver 427 236 10 524 171.9
perature fields and heat-transfer rates, the heat Common red 0.69 840 1 600 0.51
flux vector q must be related to the temperature brick
gradient through Fourier’s law, i.e., Concrete 1 800 2 100 0.6
Glass 0.76 800 2 690 0.35
Plaster 0.48 800 1 400 0.43
q = − λ∇T (2.3)
Wood, pine 0.1 2 500 600 0.07
Asbestos 0.2 580
which is written here for isotropic materials. In Glass wool 0.038 24
general, the thermal conductivity λ depends on Corkboard 0.043 160
temperature, pressure, and composition. For ho-
∗ Adapted from [16, p. 543] and [21, p. 592]. The values for
mogeneous stationary solids, only the tempera- construction materials can vary significantly depending on the
ture dependence is important. specific composition and packing of the material.
Substituting Fourier’s law into the heat con-
duction equation gives
∂T
cp = ∇ · (λ∇T ) + Φ (2.4) 2.1.2. Initial and Boundary Conditions
∂t
which, with the specifications of λ (T ), cp (T ), The initial condition required in the solution of
and Φ, as well as the necessary boundary and the conduction equation involves the specifica-
initial conditions, can be used to determine the tion of temperature as a function of position at
temperature field. Once the temperature field is some initial time, say t = 0.
known, the directional heat-transfer rates can be The boundary conditions can take several
determined from Fourier’s law. forms:
When a temperature-dependent thermal con-
ductivity is used, the conduction equation is 1) The temperature on the bounding surface of
nonlinear and advanced analytical or numeri- the solid can be specified as a function of
cal methods are generally required for solution position and time. Although this is the most
[19, pp. 10 – 12]. For many materials, the depen- convenient boundary condition from a so-
dence of λ on T is weak and λ can be taken lution standpoint, surface temperatures are
as constant. Under these conditions, the heat very difficult to measure. More commonly,
conduction equation reduces to the nonhomo- the temperature of the fluid in contact with
geneous form of the classical heat conduction the surface is known (see condition 3 below).
(or diffusion) equation: 2) The heat flux normal to the bounding sur-
face is specified as a function of position and
∂T Φ
= α∇2 T + (2.5) time. A special case arises with a perfectly
∂t cp
Previous Page
insulated surface where the normal heat flux

component is zero.
3) For a fluid – solid boundary, the normal com-
ponent of the conductive heat flux on the
solid side is equated to the “convective” flux
away from the surface on the fluid side. This
is expressed as
∂T
On A : qn = − λ = h (T − Tf ) (2.6)
∂n
where the conductive flux has been repre-
sented by Fourier’s law and the “convective”
flux by Newton’s law of cooling. The lat-
ter relation represents the “convective” flux
in terms of the temperature difference bet-
ween the surface and the fluid (T f ) and the
quantity h, which is called the heat-trans-
fer coefficient. Actually, the flux on the fluid
side arises from complex, coupled, conduc-
tion, and convection mechanisms that de-
pend on the flow field in the neighborhood
of the surface. Such effects are not repre-
sented explicitly in this relation but are em-
bedded in the heat-transfer coefficient h,
which is an effective thermal conductance
that depends on fluid properties, geometry,
and fluid motion. Large values of h are as-
sociated with efficient fluid mixing and ef-
ficient convective – conductive heat transfer
in the neighborhood of the surface (e.g.,
turbulent transport in high-conductivity liq-
uids). Small values of h are associated with
nearly stagnant fluids of low conductivity.
Typical values of h for various physical sit-
uations are given in Table 3.
Table 3. Order of magnitude of heat-transfer coefficients
Physical situation h, W m−2 K−1
Free convection, air 4 – 50

Forced convection, air 10 – 300
Forced convection, oil 60 – 1800
Forced convection, water 250 – 15 000
Boiling water 300 – 100 000
Condensing steam 4000 – 160 000
2.1.3. Steady, One-Dimensional Conduction Figure 1. Steady one-dimensional heat conduction in vari-
ous geometries
In many problems, the temperature field is time- A) Conduction in a plane wall; B) Radial conduction in a
invariant and depends on only one spatial vari- cylindrical shell; C) Radial conduction in a spherical shell
able. Consider first the plane slab case illustrated Conductive resistance Rcond obtained from Equation
(2.14); heat-transfer rate Q̇ from Equation (2.13).
in Figure 1 A where no heat is generated, con- with the conductive resistance Rcond given by
duction is in the x direction, and the temperature
dependence is T (x). In this case, Equation (2.2) ξ1
1 dξ
reduces to Rcond = (2.14)
λ1 Aξ
ξ0
dqx
= 0 (2.7)
dx Here Aξ is the cross-sectional area perpendic-
or ular to the ξ direction. For radial conduction in
cylindrical shells (see Fig. 1 B), ξ corresponds to
qx =
Q̇
= constant (2.8)
r and Aξ is 2 π rL; for radial conduction in spher-
A ical shells (see Fig. 1 C), ξ corresponds to r and
where Q̇ is the heat-transfer rate in joules per Aξ is 4 π r 2 . The temperature profile is obtained
second across the slab face of area A. If the tem- in the same way as for the plane slab:
peratures T 0 and T 1 are specified at x 0 and x 1 , ξ
and Fourier’s law is used for the heat flux, the T = T0 −
Q̇ dξ
(2.15)
heat-transfer rate Q̇ can be obtained by direct λ (T ) Aξ
ξ0
integration:
If the dependence of thermal conductivity
λ1 A (T0 − T1 )
Q̇ = (2.9) on temperature is sufficiently weak, where
∆x1
λ (T ) ≈ λ (T 1 ), using Equations 2.13 and 2.14
where ∆x 1 ≡ x 1 − x 0 and λ̄1 is the average ther- gives
mal conductivity defined by
ξ
(T0 − T1 ) dξ
T1 T = T0 − (2.16)
1 1
ξ Aξ
λ1 ≡ λdT (2.10) dξ
ξ0
(T1 − T0 ) ξ0
Aξ
T0
For the cylindrical and spherical geometries il-

The temperature field is obtained similarly lustrated in Figure 1, the conductive resistances
except that the range of integration is from x 0 to and the heat-transfer rates are given by:
any position x:
ln (r1 , r0 )
Q̇ (Cylindrical) Rcond = (2.16a)
T = T0 − (x − x0 ) (2.11) 2π L λ1
λA
2π λ1 (T0 −T1 )
where λ̄ = λ (T ) is the average conductivity in Q̇ = (2.16b)
ln (r1 /r0 )
the range from T 0 to T and is defined by an equa-
(r1 −r0 )
tion similar to Equation (2.10) except that T 1 is (Spherical) Rcond = (2.16c)
4π r0 r1 λ1
replaced everywhere by T . If Equation (2.9) is
substituted into Equation (2.11), then 4π r0 r1 λ1 (T0 −T1 )
Q̇ = (2.16d)
(r1 −r0 )
λ1 (T0 − T1 )
T = T0 − (x − x0 ) (2.12)
λ∆x1
If the dependence of λ on T is sufficiently weak
and λ̄ ≈ λ̄1 , a linear temperature profile results. 2.1.4. Convective Boundary Conditions
If λ is a stronger function of temperature, non-
linear profiles develop. As noted previously, the temperature of the fluid
These results can be extended to more general in contact with a surface is more commonly
geometries with a few modifications. If ξ is the known than the surface temperature. Consider
direction of the nonzero heat flux component, again the plane slab case in Figure 1 A, but now
the heat-transfer rate can be expressed as assume that the left face is in contact with a fluid
of temperature T f0 , then from Newton’s law of
(T0 − T1 )
Q̇ = qξ Aξ = (2.13) cooling,
Rcond
qx Q̇
Tf0 − T0 = = (2.17)
h0 h0 A
Eliminating T 0 between Equations (2.9) and

(2.17) gives
(Tf0 − T1 )
Q̇ = (2.18)
1 ∆x1
h0 A
+
λ1 A
where ∆x 1 = x 1 − x 0 . This equation gives the to-

tal heat-transfer rate in terms of the temperature
driving force T f0 − T 1 and the series of convec-
tive and conductive resistances. The ratio of the
conductive (∆x 1 /λ̄1 A) and the convective resis-
tances (1/h0 A) is the dimensionless Biot number:
h0 ∆x1
Bi ≡ (2.19) Figure 2. Conduction through a composite two-layer slab
λ1
Left face is exposed to a fluid at temperature T f0 ; right face
When the Biot number is large, conduction is exposed to a fluid of temperature T f2 . The overall driving
is the controlling heat-transfer mechanism and force for the heat transfer and the conductive resistances are
shown in the equivalent electronic circuit.
T 0 ≈ T f0 . When the Biot number is small, con-
vection is controlling and T 0 ≈ T 1 .
Similar expressions can be written for com-
2.1.5. Composite Systems posite systems in other geometries (cylinders,
spheres, etc.). In these cases, the heat-transfer
The results of Sections 2.1.1, 2.1.2, 2.1.3, and rate is given by Equation (2.22), with the Rcond,i
2.1.4 can be extended to composite or multi- contributions for each layer obtained from Equa-
layered systems by simply applying equations tion (2.14) and the Rconv, i contributions from
similar to Equation (2.9) across each solid layer 1
and Newton’s law of cooling at each fluid – solid Rconv,i = (2.24)
hi Ai
boundary. For the two-layer slab shown in Fig-
ure 2 where hi is the heat-transfer coefficient at the
“ith” fluid – solid surface and Ai the correspond-
λ1 (T0 − T1 ) λ2 (T1 − T2 ) ing surface area.
Q̇ = =
∆x1 ∆x2
= α0 (Tf0 − T0 ) = α2 (T2 − Tf2 ) (2.20)
2.1.6. Steady Conduction with Heat
where ∆xk = xk − xk−1 . Using these equations Generation and in Multidimensions
to eliminate T 0 , T 1 , and T 2 yields
(Tf0 − Tf2 ) Heat is commonly generated in solids by elec-
Q̇ = (2.21) trical heating as well as by chemical and nu-
1 ∆x1 ∆x2 1
+ + +
α0 A λA λ2 A α2 A clear reactions. If heat generation is uniform and
or conduction is one-dimensional, the temperature
field can be determined by direct integration. For
(Tf0 − Tf2 ) more complex problems involving multidimen-
Q̇ = (2.22)
Rconv + Rcond sional conduction and nonuniform generation,
Generalizing to N layers gives advanced mathematical methods are required.
These are outside the scope of this article but
(Tf0 − TfN ) are discussed in [19].
Q̇ =
(2.23)
N

1 ∆xi 1
α0 A
+ + αN A
λi A
i=1
2.1.7. Transient Heat Conduction – Lumped 2.1.8. Transient Heat Conduction – More
Capacity Systems General Solutions
When a solid body with an initial temperature T i At higher Biot numbers, the spatial variations of
is exposed to a fluid of temperature T f , the tem- temperature cannot be neglected and the prob-
perature field in the body changes with time to lem is mathematically more complex than that
decrease the magnitude of the temperature dif- given in the previous section. In this section, so-
ference. Under the conditions of small Biot num- lutions for the semi-infinite body, the plane slab,
bers, the determination of the resulting transient the infinite cylinder, and the sphere are summa-
temperature change can be analyzed by using rized. Mathematical details are presented in [19,
a lumped parameter approach. In particular, if pp. 50 – 73 (semi-infinite solid), pp. 119 – 127
Newton’s law of cooling describes the condi- (plane slab), pp. 201 – 203 (infinite cylinder),
tions at the fluid – solid boundary, an order-of- and pp. 237 – 238 (sphere)].
magnitude estimate (symbolized by “∼”) gives Consider first the transient heating (or cool-
ing) of a body bounded by the plane x = 0 and
hl extending to infinity in the positive x direction.
∆T ∼ (T0 − Tf ) (2.25)
λ The body is initially at temperature T i and its
where l is the characteristic length scale of the face at x = 0 is held at temperature T f . If constant
body and ∆T is the approximate temperature properties are assumed, the governing equations
change occurring over this length scale. Clearly, for T (x, t) are
when Bi ≡ (h l/λ) 1, the spatial temperature
∂T ∂2T
change ∆T in the body is much smaller than = α (2.29)
∂t ∂x2
the temperature changes T 0 − T f across the fluid
layer adjacent to the bounding face. Under such
conditions, the surface temperature of the body
T (x, 0) = Ti , x ≥ 0 (2.30)
(T 0 ) can be assumed to be approximately equal
to the average body temperature (T̄ ). The energy
balance then becomes T (0, t) = Tf , t > 0 (2.31)
dT̄ T (∞, t) = Ti , t≥0 (2.32)

cp V = − h̄ A T̄ − Tf (2.26)
dt
These equations suggest a solution of the form
where h̄ and T̄ represent average values over the
surface and volume V of the body, respectively. T − Tf = f (x, t, α, Ti − Tf ) (2.33)
If the material properties are taken to be con-
stant, this equation can be integrated to give If dimensional analysis is used, the dimension-
less temperature can be expressed in terms of a
T̄ = Tf + (Ti − Tf ) exp {−Bi t∗ } (2.27) single independent variable, i.e.,
where, in this case, the characteristic length is T − Tf

T∗ ≡ = T ∗ (ζ) (2.34)
l ≡ V/A, the Biot number is Bi ≡ l h/λ, and the di- Ti − Tf
mensionless time is t∗ ≡ α t/l 2 . The correspond- where
ing rate of heat transfer to the fluid is given by
x
ζ = √ (2.35)
Q̇ = h̄ A (Ti − Tf ) exp {−Bi t∗ } (2.28) 4αt
The significance of these results for Bi 1 is When Equation (2.34) is substituted into Equa-
that the rate of heat transfer given by Equation tions (2.29) – (2.32), the problem is reduced to
(2.28) represents an upper bound; i.e., the cool- the solution of an ordinary differential equation
ing or heating rates found at higher Biot numbers d2 T ∗ dT ∗
will be slower and the characteristic time for + 2ζ = 0 (2.36)
dζ 2 dζ
temperature accommodation of the body with
the fluid will be longer. subject to the boundary conditions
T ∗ (0) = 0 (2.37) the solution takes the form

1
T ∗ (∞) = 1 (2.38) T ∗ = erf (ζ) + exp ζ β + β 2 ·
4

Integrating Equation (2.36) first for dT ∗/dζ and 1
erfc ζ + β (2.42)
then again for T ∗ (ζ) and using the boundary 2
conditions to determine the two integrating con- where
stants give
√
2 αth
ζ β ≡ (2.43)
2 2 λ
T∗ = √ e−ξ dξ ≡ erf (ζ) (2.39)
π
0
and erfc ( y) = 1 − erf ( y) is the complementary
error function.
The middle term is called the error function Although these results have been developed
[erf (ζ)]. Tabulated values can be found in var- in the context of a semi-infinite body, they are
ious sources [19, pp. 485 – 487]. Of particular also valid for a body of finite thickness (e.g., a
interest here is the fact that the error function slab of thickness 2 l ) for all times when δ T ≤ l.
(as well as T ∗) takes on a value of approxi- For times longer than this, the boundary layer
mately 0.99 when its argument ζ takes on a value exceeds the half thickness and a semi-infinite
of 1.8. Physically, this implies that the tempera- solution is no longer valid. Then solutions for
ture change (T − T f ) reaches 99 % of the maxi- finite bodies must be used. Solutions of the lat-
mum change (T i − T f ) within a thermal bound- ter type are now presented for the plane slab, the
ary layer defined by infinite cylinder, and the sphere.
√ √ Consider one-dimensional heat conduction in
δT = 1.8 4α t = 3.6 αt (2.40) a plane slab bounded by the surfaces at x = ± l.
For constant thermal properties the governing
This is illustrated in Figure 3 where the time evo-
energy equation is Equation (2.29); the initial
lution of the temperature profile is plotted for the
and boundary conditions take the form
transient heating of a semi-infinite body.
T (x, 0) = Ti , −l ≤ x ≤ l (2.44)
∂T
(0, t) = 0, all t (2.45)
∂x
∂T
−λ (l, t) = h [T (l, t) − Tf ] , t > 0 (2.46)
∂x
The second equation arises from the fact that the
midplane (x = 0) is a plane of symmetry and the
flux across it is zero.
The solution to this problem in terms of the
dimensionless position x∗ ≡ x/l and the dimen-
sionless time t∗ ≡ α t/l 2 is obtained as a Fourier
series:
Figure 3. Time evolution of the temperature profile during
heating of a semi-infinite slab (x > 0) T − Tf
The x position where T = T f − 0.99 (T f − T i ) defines the T∗ ≡
thermal boundary layer δT which according to Equation Ti − Tf
√ ∞
(2.40) increases in proportion to α t α t. sin βn cos (βn x∗ ) 8 2 ∗;
= 2 exp −βn t (2.47)
If the temperature boundary condition at x = 0 n=1
βn + sin βn cos βn
(Eq. 2.31) is replaced by a convective flux con-
dition, i.e., where the eigenvalues βn are obtained from
∂T βn tanβn = Bi (2.48)
λ (0, t) = h [T (0, t) − Tf ] (2.41)
∂x
For short times the convergence of Equation As before, for t∗ > 0.25, only the first term of
(2.47) is slow and many terms must be taken be- Equation (2.50) is important. Also, the first root
fore an accurate solution can be obtained. How- of Equation (2.51) can be obtained from Equa-
ever, for t∗ > 0.25, only the first term of this tion (2.49) with the coefficients Ck given in the
equation is needed to obtain results with errors second column of Table 4.
less than 1 %. Even in these cases the solution is For a sphere, the solution is
not convenient because β 1 must be determined
from an implicit relation (Eq. 2.48). Fortunately, T∗ =
∞
the roots of the latter equation can be accurately 2 Bi sin βn sin (βn r ∗ ) 8 2 ∗;
fitted to an expression of the form exp −βn t (2.52)
r ∗ n=1 βn [βn − sin βn cos βn ]
5
with the eigenvalues given by
β1 = Ck (logBi)k−1 for 0.02 ≤ Bi ≤ 8 (2.49)
k=1
βn cotβn = 1 − Bi (2.53)
For the plane slab case, the coefficients Ck are
given in the first column of Table 4. When this The one-term solution is again valid for
equation is used with the first term of Equation t∗ > 0.25, and the first eigenvalue can be ob-
(2.47), temperatures can be predicted to within tained from Equation (2.49) by using the coeffi-
5 % and, in most cases, depending on the Biot cients in the third column of Table 4.
number, to within 1 %. When Bi > 8, tabulated The solutions of these one-dimensional
values of βn can be used [19, p. 491]. Such ap- unsteady-state problems can be used in simple
proaches are preferred to the time – temperature ways to obtain solutions to multidimensional,
charts used by many investigators [22–25] be- unsteady-state problems. These are now summa-
cause these charts are often difficult to read and rized for several cases. Consider first the case of
to interpolate accurately. an infinite rectangular bar bounded by the sur-
faces at x = ± x 0 and y = ± y0 . The solution at
Table 4. Coefficients for Equation (2.49)
any position (x, y) at time t is given by
Coefficient Plane slab Cylinder Sphere
T (x, y, t) = Tx (x, t) Ty (y, t) (2.54)
C1 0.859777 1.256701 1.573305
C2 0.702996 1.112492 1.450377
C3 0.050636 0.148517 0.251563 Here Tx (x, t) is obtained from Equation (2.47)
C4 −0.144345 −0.260841 −0.306763 with x 0 replacing l as the length scale. Similarly,
C5 −0.044631 −0.111339 −0.139485 Ty ( y, t) is obtained from Equation (2.47) with y
replacing x in that equation and y0 replacing l.
Similar types of solutions are available for For a rectangular parallelepiped with bound-
the infinite cylinder (radius r 0 ) and the sphere ing surfaces at x = ± x 0 , y = ± y0 , and z = ± z0 ,
(also radius r 0 ). Here again, the body is assumed the solution is given by
to be at an initial temperature T i and at t = 0 is
immersed in a fluid at temperature T f . For the T (x, y, z, t) = Tx (x, t) Ty ( y, t) Tz (z, t) (2.55)
cylinder, the solution in terms of the first- and The Tx and Ty solutions are obtained in the man-
second-order Bessel functions of the first kind ner just described for the infinite rectangular bar.
is The Tz solution is obtained from Equation (2.47)
T∗ = with z replacing x in that equation and z0 replac-
∞

ing l.
J1 (βn ) J0 (βn r∗ ) 8 2 ∗;
2 exp −βn t (2.50) Finally, for a finite cylinder bounded by the
βn J02 (βn ) + J12 (βn )
n=1 surfaces r = r 0 and z = ± l, the solution is
where T ∗ is defined as in Equation (2.47),
r∗ ≡ r/r 0 and t∗ ≡ α t/r 20 . The eigenvalues βn are T (r, z, t) = Tr (r, t) Tz (z, t) (2.56)
obtained from Here Tr is obtained from Equation (2.50) and Tz
J1 (βn ) from Equation (2.47) (z replaces x).
βn = Bi (2.51)
J0 (βn )
Examples of the use of Equations flows commonly arise with internal flows in
(2.54) – (2.56) are given in many texts [26, straight channels where the cross-sectional area
pp. 307 – 310], [27, pp. 174 – 177]. The ap- is invariant in the flow direction. Under such
proach suggested here is different in that the one- conditions, the velocity uz does not vary in the
dimensional solutions are obtained from one- z-direction and the most general form of the
term analytical solutions instead of time – tem- velocity field is u = [0, 0, uz (x, y)]. The latter
perature charts. two-dimensional problem arises with systems
of arbitrary cross section. For simpler systems
such as flow between parallel plates or flow
2.2. Steady, One-Dimensional Flows in cylindrical tubes, the problem becomes one-
(→ Fluid Mechanics, Chap. 3.3.1.) dimensional and uz is dependent on only one
spatial variable.
As in the sections above where heat transfer The driving force for unidirectional flows can
arose from the existence of temperature gra- be pressure gradients, gravity, or moving bound-
dients, momentum transfer arises from fluid- aries. The pressure gradient and gravity effects
deforming velocity gradients. In particular, for appear directly in the equation of motion and can
the one-dimensional unidirectional flow be combined into an overall driving force term
∇P:
u ≡ (ux , uy , uz ) = [0, 0, uz ( y)] (2.57)
∇P = ∇p − g (2.59)
the resulting momentum transfer involves z-
momentum being transferred in the y-direction. To achieve a unidirectional flow without moving
This is illustrated in Figure 4 where faster mov- boundaries, ∇P must be nonzero and the flow
ing fluid layers transfer momentum to adjacent direction must be coincident with the directions
slower moving layers. The nonzero stress com- of ∇P. For flow in the z-direction where P (z),
ponents associated with this velocity field can be the only nonzero component of Equation (2.59)
interpreted as momentum fluxes [17, Chap. 2], is
and if the fluid is Newtonian, these components
dp dP
can be expressed as = − gz (2.60)
dz dz
duz
τyz = τzy = − η (2.58) where gz is the component of gravity in the z-
dy direction. Integration of this equation along the
which is analogous to Fourier’s law for one- flow channel from z = z0 to any point z gives
dimensional heat conduction in the y-direction.
P − P0 = p − p0 − gz (z − z0 ) (2.61)
That is, the driving force for flow arises from

variations of pressure and potential energy along
the flow direction. The quantity P is sometimes
referred to as the dynamic pressure because it
can be written as the difference between the pres-
sure existing during flow and that arising under
no flow or hydrostatic conditions:
P = p − pH (2.62)
Figure 4. Flow resulting from the movement of a surface Here, pH is the hydrostatic pressure which is
In this case, z-momentum is being transferred from layer to obtained from
layer in the y-direction. The stress component τyz can be
interpreted as a momentum flux (z momentum transferred
in the y direction). ∇pH − g=0 (2.63)
The flow above is a special case of the gen- In Equation (2.61) the hydrostatic pressure part
eral class of unidirectional flows. Unidirectional is p0 + gz (z − z0 ).
Another characteristic of steady unidirec-

tional flows is that these are noninertial flows.
Specifically, a fluid element in this flow does
not accelerate along its path, and the nonlinear
inertial term u · ∇u in the equation of motion is
zero. The z-component of the equation of motion
then takes the form
dP
(∇ ·τ ) ·iz + = 0 (2.64)
dz
where iz is the unit base vector in the z direc- Figure 5. Generalized Couette flow between parallel sur-
tion. If the fluid is an incompressible Newtonian faces
fluid, this equation can be expressed as The upper surface moves with velocity U; the lower surface
is stationary. The nature of the flow depends on the magni-
dP tude and sign of the applied pressure gradient dP/dz. In the
η ∇ 2 uz − = 0 (2.65) case above, DP/Dz > 0.
dz
With respect to Newton’s laws of motion, this The nonzero stress components for this flow
equation can be interpreted as a balance of forces are τyz and τzy , and Equation (2.64) reduces to
per unit volume on any fluid element in the
dτyz dP
flow; specifically, the driving force for the flow + = 0 (2.66)
dy dz
is (− dP/dz) and the viscous resisting force is
η ∇ 2 uz . Since the first term on the left-hand side is at
The only material parameter that arises in most a function of y and the second term at most
the treatment of steady, unidirectional flows is a function of z, this equation is satisfied only if
the viscosity η. In more general flows, the den- both terms are equal to a constant. Integration
sity also arises. In Table 5, typical values of then gives
density and viscosity for a number of fluids are
presented. Values for the heat capacity cp , the τyz = K y + τ0 (2.67)
thermal conductivity λ, and the Prandtl number
(P0 − PL )
Pr ≡ ν/α are also provided. All of these quanti- K ≡ (2.68)
ties arise later in the treatment of convective heat L
transfer. where τ 0 is the shear stress at y = 0. At this point,
the quantity τ 0 is unknown. It is determined by
using the velocity boundary conditions.
2.2.1. Generalized Couette Flow If the fluid is an incompressible Newtonian
fluid, Equation (2.58) can be combined with
A flow pattern arising in many different appli- Equation (2.67) and integrated to give the ve-
cations (polymer extrusion, screw pumping and locity profile
expression, journal-bearing lubrication, etc.) is
the unidirectional plane parallel flow illustrated b2 ∆P y y y
uz = 1− +U (2.69)
in Figure 5. The flow is driven by both the move- 2η L b b b
ment of the upper plate at velocity U and the where the quantity τ 0 and the additional constant
application of a pressure gradient (P0 − PL )/L that arises from the integration are evaluated by
in the direction of flow. The flow geometry is using the boundary conditions
assumed to be of thickness b in the y-direction,
width w in the x-direction, and length L in the uz (0) = 0 (2.70)
z-direction. The thickness-to-width ratio (b/w)
and the thickness-to-length ratio (b/L) are as- uz (b) = U (2.71)
sumed to be sufficiently small that edge effects
and entrance or exit effects can be neglected, In dimensionless form, the velocity is
and the velocity field can be represented by uz y y y
u = (ux , uy , uz ) = [0, 0, uz (y)]. = K∗ 1− + (2.72)
U b b b
Table 5. Thermophysical properties of various gases and liquids∗
Fluid θ, ◦ C , kg/m3 η, Pa s λ, W m−1 K−1 cp , J kg−1 K−1 Pr
Gases (101.3 kPa)

Air 27 1.183 1.853×10−5 0.02614 1.003×103 0.711
Carbon dioxide 27 1 .7973 1.4958×10−5 0.016572 0.871×103 0.770
Helium −18 0.1906 1.817×10−5 0.1357 5.200×103 0.70
Hydrogen 27 0.08185 0.8963×10−5 0.182 14.314×103 0.706
Nitrogen 27 1.1233 1.784×10−5 0.0259 1.0408×103 0.715
Oxygen 27 1.3007 2.063×10−5 0.02676 0.09203×103 0.709
Liquids (saturated)
Dichlorodifluoromethane 27 1305 0.2545×10−3 0.0690 980 3.62
Glycerol 20 1261 1412×10−3 0.285 2350 11 630
Mercury 27 13 611 1.633×10−3 8.34 139.1 0.027
Light machine oil 16 907 145.1×10−3
Water 27 996.6 0.8232×10−3 0.6084 4177 5.65
∗ Adapted from [21, pp. 595 – 601].
where When K ∗ = − 3, the volumetric flow rate asso-

ciated with the moving boundary is balanced by
b2 ∆P the flow rate arising from the adverse pressure
K∗ = (2.73)
2η U L gradient and Q = 0.
is the dimensionless pressure gradient.
Depending on the magnitude and sign of K ∗,
the velocity profile can take various forms (see
Fig. 6). When K ∗ = 0, the profile is linear and
corresponds to simple Couette flow:
y
uz = U (2.74)
b
When K ∗ > 0, the pressure gradient and the
moving upper boundary both contribute to flow
in the positive z direction, and if K ∗ is suffi-
ciently large a maximum occurs in the velocity
profile (see the K ∗ ≥ 2 cases in Fig. 6). When
K ∗ < 0, the pressure gradient causes a reverse
flow. If the magnitude of this adverse gradient is Figure 6. Dimensionless velocity profiles for generalized
sufficiently large, the fluid moves in the positive Couette flow
z-direction in the upper part of the flow channel If the fluid is non-Newtonian, significantly
(due to motion of the upper boundary) and in more complex flow equations are obtained for
the negative z-direction in the lower part of the generalized Couette flow. For the case of power-
channel (see the K ∗ = − 4 case in Fig. 6). law, viscous non-Newtonian behavior, see [28],
The volumetric flow rate Q and the average [29] (see also → Fluid Mechanics, Chap. 4.1.2.).
velocity uavg associated with this flow are given
by
b 2.2.2. One-Dimensional Poiseuille Flows
b3 w∆P 1
Q = uavg b w = uz wdy = + bwU (→ Fluid Mechanics)
12 η L 2
0
(2.75) When U = 0, the flow illustrated in Figure 5 be-
comes a pressure-driven Poiseuille flow. Un-
The first term on the right represents the flow der such conditions, the velocity profile be-
contribution arising from the pressure gradient comes parabolic with a plane of symmetry at
and the second that from the moving boundary. y = b/2. Specifically, in terms of a y coordi-
nate measured from the channel centerline, i.e., f Re = C = 24 (2.83)

y = y − b/2, Equation (2.69) takes the form
2
where Re ≡ 2 uavg b/η.
b2 ∆P y Another flow that arises in many industrial
uz = 1−4 (2.76)
8η L b applications is Poiseuille flow in a tube. If the
and the volumetric flow rate reduces to a tube has radius r 1 and length L, the stress and ve-
Hagen – Poiseuille relation where Q is propor- locity fields for incompressible Newtonian fluids
tional to (P0 − PL )/L, i.e., are

∆P1
b3 w∆P τrz = τzr = r (2.84)
Q = uavg b w = (2.77) L 2
12 η L
2
In the case of one-dimensional Poiseuille flows r 2 ∆P r

uz = 1 1− (2.85)
in channels with circular and concentric an- 4η L r1
nulus cross-sectional geometries, analogous re-
where r is the radial coordinate. The volumetric
sults can be obtained . In all cases the volu-
flow rate is then
metric flow rate is proportional to the pressure
drop (for further details, see → Fluid Mechanics, r1
π r14 ∆P
Chap. 3.3.1.). Q = uavg π r12 = 2 π uz rdr = (2.86)
8η L
An alternate representation of flow 0
rate – pressure drop results for unidirectional
flows is in terms of the friction factor re- If the latter result is used in Equation (2.80), then
lation. In particular, the wall shear stress
τ w ≡ − η | duz /dy |w is assumed to be propor- f Re = 16 (2.87)
tional to the kinetic energy per unit volume where the characteristic length l is 2 r 1 ,
expressed in terms of the average velocity uavg : and the Reynolds number is defined by
Re ≡ 2 uavg r 1 /η.
1
τw = f u2avg (2.78) Similar results can be obtained for axial flow
2
in the annular region between concentric cylin-
Here, the constant of proportionality is the fric- ders of radii r 0 and r 1 where r 1 > r 0 . In this case,
tion factor f . Since the pressure force must be the characteristic length is l = 2 (r 1 − r 0 ), and the
balanced by the drag force on the walls value of C in Equation (2.80) varies with the ratio
χ ≡ r 0 /r 1 . In the limit of small values of r 0 /r 1 , C
1
∆P Ac = τw Aw = f Aw u2avg (2.79) takes on the value of 16; it approaches an upper
2
limit of 24 as r 0 /r 1 approaches 1.
Here Ac is the cross-sectional area and Aw is the
wall surface area. The friction factor can then be
expressed as 2.2.3. Flow in Channels of Arbitrary Cross
l2 (∆P/L )
Section
f Re = C ≡ (2.80)
2 η uavg
For flows in channels with more complex cross
where the Reynolds number Re and the charac- sections (e.g., flow in rectangular, elliptic, or ec-
teristic length l are defined by centric annular channels) or flow in channels
with irregular cross sections, the velocity uz is a
uavg l
Re = (2.81) function of two spatial variables, i.e.,
η
and uz = uz (x, y) (2.88)
4 Ac L For incompressible Newtonian fluids, Equation

l = (2.82)
Aw (2.65) is applicable, and the solution to this equa-
For plane Poiseuille flow where l = 2 b, Equation tion is given by
(2.77) can be used in Equation (2.80) to obtain

1 2 dP a hydraulic radius approach where an effec-
uz = x + y2 + ϕ (x, y) (2.89)
4η dz tive radius is defined for the channel, i.e.,
r H ≡ l/2 = 2 Ac L/Aw , and C in Equation (2.80)
where the function ϕ (x, y) is a solution of
is taken to be 16, the value corresponding to
Laplace’s equation
Poiseuille flow in a tube. However, this approach
∂2ϕ ∂2ϕ is approximate and can lead to sizable errors
2
+ = 0 (2.90) if the actual C for the geometry differs signif-
∂x ∂y 2
icantly from 16. For flow in channels with ellip-
If a no-slip velocity condition is assumed (i.e., tic cross sections, the maximum error would be
uz ,S = 0), then ca. 19 %; for square channels, the error would
be 12 %.
1 2 dP
ϕ = ϕS = − x + y2 (2.91) All of these results are for laminar flow.
4η dz S
When the Reynolds number reaches suffi-
on the bounding surfaces. ciently high values, the flow becomes unsta-
For a channel with an elliptic cross section ble and turbulent flow arises. For flow in circu-
defined by (x/x 0 )2 + (y/y0 )2 = 1, the velocity is lar tubes, turbulent flow is generally observed
given by [30, p. 38] when Re ≡ 2 uavg r 1 /η > 2100. For other ge-
2 2
ometries, the transition values are different and
x2 y 2 ∆P x y must be determined in each individual case.
uz = 02 0 2 1− −
2 η x0 + y 0 L x0 y0
(2.92)
2.2.4. Poiseuille Flow of Non-Newtonian
and the volumetric flow rate by
Fluids (→ Fluid Mechanics, Chap. 4.2.)
π x30 y03 ∆P
Q = uavg π x0 y0 = (2.93) The flow characteristics of non-Newtonian flu-
4 η x20 + y02 L
ids in tubes and planar channels can be quite dif-
In terms of the friction factor, this result can be ferent from those observed with Newtonian flu-
written ids. This is illustrated by considering the steady
2
flow of a power-law, non-Newtonian fluid in a
2 π2 y0
f Re = 1+ = tube of radius r 0 . As in the Newtonian case, the
[E (k)]2 x0 only nonzero stress components are τrz = τzr ,
( )
function of
y0
(2.94)
and these are described by Equation (2.84). Be-
x0 cause duz /dr < 0 for this flow, the shear stress
where E (k) is the complete elliptic integral with can be written as
argument k = [1 − (y0 /x 0 )2 ] [31, p. 509]. When n
duz
y0 /x 0 → 0, f Re → 19.74, and when y0 /x 0 = 1, τrz = m − (2.97)
dr
f Re = 16 (the cylindrical tube result).
For flow in channels with square and Combining this equation with Equation (2.84),
equilateral-triangle cross sections with sides a, integrating, and using the no-slip boundary con-
the flow rate – pressure drop relations are given dition uz = 0 at the tube wall give
by s+1
τ s r1 r
w
uz = 1− (2.98)
Square : f Re = 14.2 (2.95) m s+1 r1
Triangular : f Re = 13.3 (2.96) where s ≡ 1/n, and τ w is the wall shear stress
given by

Results for other cross sections (rectangu- 1 ∆P
τw ≡ |τrz |r=r1 = r1 (2.99)
lar and eccentric annuli) are given in [30, 2 L
pp. 33 – 39]. For even more complex and less
Because the maximum velocity occurs at r = 0,
regular cross-sectional geometries, estimates
Equation (2.98) can also be written as
(sometimes crude) can be obtained by using
s+1
r the yield surface, i.e., the position r = r Y where

uz = umax 1 − (2.100) | τrz | = τ Y . From Equation (2.84)
r1
τY r1 2 τY
with umax given by rY = = (2.103)
τw (∆P/L )
τ s r1
w
umax = (2.101) At radial positions outside the yield surface
m (s + 1)
(r > r Y ), the magnitude of the shear stress
For s = 1 (or n = 1), the behavior is Newtonian exceeds the yield stress and a shear flow
and the profile is parabolic. For pseudoplastic [uz = uz (r)] results. At radial positions inside
fluids where s > 1 (or n < 1), the profile becomes the yield surface (r < r Y ), the magnitude of the
more blunted and pluglike as s takes on larger shear stress is less than τ Y and a uniform plug
and larger values (see Fig. 7). For dilatant flu- flow occurs with velocity uz (r Y ). As (∆ P/L)
ids where s < 1 (or n > 1), the velocity profile decreases, the radial position of the yield sur-
becomes more and more pointed as s decreases. face moves closer and closer to the tube wall. At
a value of (∆ P/L) = 2 τ Y /r 1 , the position of the
yield surface coincides with the wall and flow
ceases. Hence, application of a finite pressure
gradient does not ensure flow in the case of ma-
terials with plastic behavior.
Flow rate results for Newtonian fluids,
power-law fluids, and Bingham plastics may be
summarized as follows:
Flow geometry: Circular tube radius r 1 ,
length L
Newtonian fluid (viscosity η)
Figure 7. Velocity profiles for the flow of a power-law fluid π r14 ∆P
in a tube Q =
The parameter s is the reciprocal of the power-law slope 8η L
parameter n. When s = 1, Newtonian behavior is observed.
When s > 0, the behavior is dilatant. Power-law fluid (parameters m, n)
s
Comparison of the average velocity with the π r13 ∆P r1 1
Q = , s ≡
maximum velocity gives (s + 3) 2L m n
uavg s+1 Bingham plastic (parameters τ Y , η p )

= (2.102)
umax s+3 4
π r13 τw 4 τy 1 τy
For Newtonian fluids (s = 1), this reduces Q = 1− + ,
4 ηp 3 τw 3 τw
to uavg /umax = 1/2. For pseudoplastic fluids
when τw >τy
(s > 1), this ratio increases with s and ap-
proaches the limit of 1 ( plug flow) as s gets where
very large (n → 0). For dilatant fluids, uavg /umax
ranges from 1/2 to 1/3 as s decreases (or n in- ∆P r1
τw ≡
creases). These results are illustrated in Figure 7. 2L
The flow rate – pressure drop expression for Q = 0, when τw ≤τy
this flow is obtained directly from Q = π r 21 uavg . Expressions for other types of non-Newtonian
For values of s different from 1, this relation is fluids can be found in various sources. These
nonlinear, with d (∆ P/L)/dQ increasing with Q developments are described and the results sum-
for dilatant fluids and d (∆ P/L)/dQ decreasing marized for various non-Newtonian fluid models
with Q for pseudoplastic fluids. [32, Chap. 5], [33–35]. Further details are given
In the case of a Bingham plastic with a yield in → Fluid Mechanics, Chap. 4.2.1.
stress τ Y and a plastic viscosity η p , the nature
of the flow depends on the radial position of
2.2.5. Two-Phase Concentric Flow in a The integrating constants can be evaluated by

Tube – Segregated Flow using the conditions (1) that the stress τrz is fi-
nite at r = 0, (2) that the velocity uz is zero at the
An interesting example of viscous, one- tube wall, and (3) that the stress and velocity are
dimensional laminar flow in a tube takes place continuous at the boundary r = r c between the
when two immiscible fluids are injected into a phases [τrz (r c ) = τ̂rz (r c ) and uz (r c ) = ûz (r c )].
tube of radius r 1 such that one fluid occupies the Integrating the respective velocity profiles over
core region r < r c and the other fluid the outer the inner and outer fluid regions according to
region r > r c (see Fig. 8). The core fluid has vis- Equation (2.86) gives the corresponding volu-
cosity η and the outer fluid viscosity η̂. metric flow rates

π ∆P η̂ ∗4
Q = r14 r + 2 1 − rc∗2 rc∗2
8 η̂ L η c
(2.106)

π ∆P 2
Q̂ = r14 1 − rc∗2 (2.107)
8 η̂ L
Here, r c ∗ ≡ r c /r 1 is the dimensionless radial po-

sition of the boundary between the inner and
outer fluid regions.
Eliminating ∆ P/L between these equations
gives an implicit expression for r c ∗:

2 η̂ ∗2
(1 − ϕ) 1 − rc∗2 − ϕrc∗2 rc + 2 1 − rc∗2 = 0
η
(2.108)
Figure 8. Segregated two-phase flow in a tube
where
Such problems are often encountered in
Q̂
pipelines where the flow of a viscous fluid is ϕ = (2.109)
facilitated by the injection of a second low- Q̂ + Q
viscosity immiscible phase. The interest here is is the fractional flow of the outer fluid. Spec-
in the flow rate enhancement that results from ification of ϕ and the viscosity ratio η̂/η then
the injection of this second fluid. allows the determination of r c ∗ by using simple
The analysis of flow in the separate fluid re- numerical root finding methods. The flow rate
gions is similar to that for Poiseuille flow in enhancement for the inner fluid is
cylindrical tubes and annuli. In particular, for

Newtonian fluids, Equations (2.64) and (2.65) Q η
Q∗ ≡ = rc∗4 + 2 1 − rc∗2 rc∗2
can be integrated to give the stress and velocity (Q)r∗ =1
c
η̂
fields for the inner fluid region as (2.110)

1 ∆P C1
τrz = r+ (2.104) Here (Q)r ∗c =1 is the volumetric flow rate when
2 L r
the inner fluid occupies the entire flow region
(no outer fluid present).
1 ∆P C1 For a specified viscosity ratio η̂/η, Equations
uz = − r2 − lnr + C2 (2.105)
4η L η (2.108) – (2.110) can be used to determine the
where C 1 and C 2 are the integrating constants. flow rate enhancement in terms of the fractional
Identical expressions are obtained for the outer flow of the outer fluid and the viscosity ratio. The
fluid region except that τrz , uz , η, C 1 , and C 2 numerical results for several values of viscosity
are replaced by τ̂rz , ûz , η̂, Ĉ 1 , and Ĉ 2 . It writ- ratio are given in Figure 9. In particular, for the
ing these expressions, the axial pressure distribu- case in which the outer fluid is 100 times less
tions in the two phases are assumed to be equal. viscous than the inner fluid (η̂/η = 0.01) and the
fractional flow is 10 %, the flow rate of the more vides the velocity field. Physically, lines of con-
viscous inner fluid is enhanced by a factor of stant ψ represent streamlines of the flow.
30. For higher fractional flows and lower viscos- To illustrate this more explicitly, consider the
ity ratios, even greater enhancement factors are flow
obtained. Clearly, when such segregated flows
are possible, significant increases in through- ux = ux (x, y, t) , uy = uy (x, y, t) , uz = 0 (2.111)
put can be achieved per unit of applied pres-
sure drop. In practice, the application of such where the governing equations of continuity and
approaches is limited only by the ability to cre- motion are
ate and maintain a stable outer concentric region ∂ux ∂uy
of the lower viscosity fluid. + = 0 (2.112)
∂x ∂y
and

∂ux ∂ux ∂ux
+ ux + uy
∂t ∂x ∂y
2
∂P ∂ ux ∂ 2 ux
=− +η 2
+ 2
(2.113)
∂x ∂x ∂y

∂uy ∂uy ∂uy
+ ux + uy
∂t ∂x ∂y
2 2
∂P ∂ uy ∂ uy
=− +η + (2.114)
∂y ∂x2 ∂y 2
Figure 9. Flow rate enhancement associated with the in- If the stream function ψ is defined in terms of
jection of an immiscible low-viscosity fluid into a transport the velocity components by
line
∂ψ
ux = − (2.115)
∂y
∂ψ
2.3. Multidimensional Momentum uy = (2.116)
∂x
Transfer
the continuity equation (Eq. 2.112) is satisfied
2.3.1. Two-Dimensional Flows – Stream identically. To obtain the desired stream function
Function Equations equation, the motion equations are combined in
the following way. First operate on Equation
The flow examples considered to this point have (2.113) by ∂/∂y and Equation (2.114) by ∂/∂x;
involved only one nonvanishing velocity com- then subtract the resulting equations to eliminate
ponent. More complex flows are now consid- the pressure terms; finally, replace ux and uy
ered, particularly two-dimensional incompress- with Equations (2.115) and (2.116). After sim-
ible flows of Newtonian fluids having two non- plification, the resulting equation is
vanishing velocity components that depend on
∂ ∇2 ψ ∂ ψ, ∇2 ψ
two spatial variables and time. The govern- + = ν∇4 ψ (2.117)
∂t ∂ (x, y)
ing equations are the continuity equation and
the two nonvanishing components of the equa- where ν ≡ η/ and
tion of motion. Rather than solving these equa-
tions directly, the equations are more conve- ∂2 ∂2
∇2 ≡ 2
+ , ∇ 4 ≡ ∇ 2 ∇2 (2.118)
niently transformed into a single equation in ∂x ∂y 2
terms of a stream function ψ (→ Fluid Mechan- Also,
ics, Chap. 2.1.). Because the stream function is
∂f
∂ ( f , g) ∂x
defined in terms of the nonvanishing velocity ∂f
∂y
components, solution of this equation then pro- ≡ ∂g ∂g (2.119)
∂ (x, y) ∂x ∂y

where a determinant operation is implied by the Similar relations for other flows are given in
straight brackets. [17, p. 131], [36, pp. 114 – 115]. Specification of
Solution of Equation (2.117) gives the the velocity in terms of the stream function ψ is
stream function ψ (x, y, t). The velocity compo- given by
nents are then obtained from Equations (2.115)
and (2.116), and the pressure P is obtained u = ∇ψ × ∇G (2.125)
from these velocity components and Equations
(2.113) and (2.114). where G is a scalar function. This form satisfies
A similar approach can be used in other the continuity equation (∇ · u = 0) for incom-
two-dimensional flows, but the velocity – stream pressible flow [20, pp. 227 – 228]. For axisym-
function relations and the stream function equa- metric flow, the scalar function G is simply the
tion may take different forms depending on flow coordinate ξ corresponding to the azimuthal an-
characteristics. For example, for axisymmetric gle about the axis of symmetry. For axisymmet-
flow around a sphere (see Fig. 10) where ric flow around a sphere, G = ϕ and the resulting
components of Equation (2.125) are the same
ur = ur (r, θ, t) , uθ = uθ (r, θ, t) , uϕ = 0 (2.120) as those of Equations (2.121) and (2.122). For
two-dimensional axisymmetric flow in a cylin-
the velocity – stream function relations are drical geometry with uθ = 0, G = θ is used, and
1 ∂ψ the velocity – stream function relations take the
ur = (2.121)
r2 sin θ ∂θ forms
1 ∂ψ
uθ = − (2.122) 1 ∂ψ 1 ∂ψ
r sin θ ∂r ur = − , uz = (2.126)
r ∂z r ∂r
and the stream function equation is
If Equation (2.123) is put in dimensionless form
∂ E2ψ 1 ∂ ψ, E 2 ψ 2 E2 ψ by scaling t, r, and ψ using d/u∞ , d, and u∞ d 2 ,
− 2 + 2 2
∂t r sin θ ∂ (r, θ) r sin θ respectively, where d is the sphere diameter and

∂ψ 1 ∂ψ u∞ the free stream velocity, then
· cos θ − sin θ = ν E E 2 ψ
2
(2.123)
∂r r ∂θ
Red {left − hand side terms} = E ∗4 ψ ∗ (2.127)
where E2 is an operator defined by
∂2 sin θ ∂

1 ∂
where Red ≡ u∞ d/η is the Reynolds number.
E2 ≡ + 2 (2.124) Since all terms except Red are scaled to order 1
∂r2 r ∂θ sin θ ∂θ
by the selections of d and u∞ , when Red 1
the left-hand side can be set to zero and a creep-
ing flow solution can be obtained. The latter is
generally associated with small spheres, viscous
fluids, and low velocities. When Red 1, the
right-hand side can be set to zero and a nonvis-
cous flow solution can be obtained.
2.3.2. Creeping Flow Around a Sphere and

Other Bodies of Revolution
Consider the steady, axisymmetrical flow of an

incompressible Newtonian fluid past a sphere as
illustrated in Figure 10. If the coordinate system
is attached to the sphere, this representation is
valid either for flow past a stationary sphere as
illustrated or for the steady fall of a sphere (at
terminal velocity u∞ ) in a fluid at rest. The ve-
Figure 10. Axisymmetric flow past a sphere locity and pressure fields under creeping flow
conditions (Red 1) are of particular interest, P

(r,θ) r
∂P
along with the drag force associated with viscous P = dP = dr +
∂r
and pressure effects. 0 ∞
θ=π/2
Under creeping flow conditions, Equation θ

(2.123) reduces to ∂P
dθ (2.137)
∂θ r
π/2
E4 ψ = 0 (2.128)
If (∂P/∂r) and (∂P/∂θ) are obtained from the
with boundary conditions r and θ components of the equation of motion
(creeping flow conditions) by using Equations
1 ∂ψ
at r = r1 , ur = =0 (2.129) (2.135) and (2.136), then
r 2 sin θ ∂θ
3 η u∞ r1 2
P = − cos θ (2.138)
2 r1 r
1 ∂ψ
at r = r1 , uθ = − = 0 (2.130) Also, the hydrostatic pressure is
rsin θ ∂r
pH = p0 − g z (2.139)
as r → ∞, uz =
ur
= −
uθ
→ u∞ (2.131) where p0 is the pressure at r → ∞ and
cos θ sin θ θ = π/2. Combining the dynamic and hydrostatic
By using Equations (2.121) and (2.122), the lat- results (Eq. 2.62) gives the pressure field
ter condition can be written as 3 η u∞ r1 2
p = p0 − g z − cos θ (2.140)
1 2 r1 r
r → ∞, ψ → u∞ r 2 sin2 θ (2.132)
2 The drag force of the fluid on the sphere is then
Because Equation (2.132) is valid at all θ, the obtained from

θ dependence at smaller r values might be ex-
F = n · (−pI − τ ) dS (2.141)
pected to be the same. This suggests a solution
S
to Equation (2.128) of the form
where n = ir is the outwardly directed unit nor-
ψ = f (r) sin2 θ (2.133) mal to the sphere surface. Expanding Equation
(2.141) and finding the component in the z-
Substituting this expression into Equation direction give
(2.128) and using Equations (2.129), (2.130),
and (2.132) give 2ππ
Fz = − [( p + τrr ) cos θ −

1 r13
f = − u∞ + 3 r1 r − 2 r 2 (2.134) 0 0
4 r
τrθ sin θ]r1 r12 sin2 θ dθdϕ (2.142)
Then, from Equations (2.133), (2.121), and
(2.122), Then, by using Equations (2.135) and (2.136),
the stress components and the pressure are eval-
3 r1 1 r1 3 uated at r 1 with the results
ur = − u ∞ 1− + cos θ (2.135)
2 r 2 r
∂ur

τrr = − 2η = 0 (2.143)
r1 ∂r r1

3 r1 1 r 1 3 ∂ ur 1 ∂ur
uθ = − u ∞ 1− − sin θ (2.136) τrθ = −η r +
4 r 4 r r1 ∂r r r ∂θ r1
3 η u∞
The dynamic pressure P is obtained from a = sin θ (2.144)
r1
line integration between the position r → ∞ and
θ = π/2 (where P = 0) and any position r, θ [where and
P = P (r, θ)], i.e.,
3 η u∞
p = p0 − g r1 cos θ − cos θ (2.145)
r1 2r1
Thus, If surface-active agents are present that give

rise to a surface shear viscosity εs , the drag force
Fz = 4/3 πr 31
g+ 2 π η r 1 u∞ + 4 π η r 1 u∞ (2.146)
Buoyancy Form drag Viscous drag
for a fluid sphere is [30, pp. 129]:
from pH from P from τrθ
(εs /r1 ) + 3 η̂ + 2 η
F D = 6 π η r 1 u∞ (2.152)
(εs /r1 ) + 3 η̂ + 3 η
The first term arises from hydrostatic pres-
The important point here is that if r 1 is suffi-
sure effects around the sphere (pressure is higher
ciently small, surface viscosity effects dominate
as θ → π causing a net upward force); the second
to give rigid sphere results, even when η̂ is small
term, from dynamic pressure effects (again from
(gas bubble case). Small bubbles often behave
higher pressure on the sphere bottom); and the
as rigid spheres when contaminant amounts of
third, from viscous effects associated with τrθ on
surface-active agents are present.
the sphere surface. If this result is represented in
terms of a buoyancy force F B (static effect) and
a drag force F D (dynamic effect), i.e.,
Fz = F B + F D (2.147)
then F B is just the first term of Equation (2.146)

and F D the sum of the other two terms, i.e.,
F D = 6 π η r1 u ∞ (2.148)
This equation is known as Stokes law and indi-

cates that the drag force on a solid sphere in-
creases in direct proportion to viscosity, radius,
and terminal (or free stream) velocity.
If a sphere of density s settles under its
own weight in a fluid, the terminal velocity
can be determined by equating the sum of F B Figure 11. Drag force for creeping flow around oblate and
prolate spheroids
and F D to the gravitational force on the sphere A) Oblate spheroid, drag force F D = 6 π ηa u∞ K; B)
(4/3 π r 31 s g). The result is Prolate spheroid, drag force F D = 6 π η b u∞ K
2 (s − ) r12 g
u∞ = (2.149) b/a K (oblate) K (prolate)
9η 0.0 0.8488 ∞
0.1 0.8525 2.6471
This result indicates that for particle settling in 0.5 0.9053 1.2039
viscous fluids, the terminal velocity is most sen- 1.0 1.0000 1.0000
sitive to variations in particle size.
Finally, the drag force results for several vari-
ations of this problem are noted. In particular, for
creeping flow past a fluid sphere (or droplet) of For nonspherical solid bodies, somewhat dif-
viscosity η̂ [30, pp. 127 – 129] ferent drag force results are obtained. For oblate
and prolate spheroids, the results are summa-

3 η̂ + 2 η rized in Figure 11. Note that the drag force for
F D = 6 π η r1 u ∞ (2.150)
3 η̂ + 3 η the prolate spheroid is particularly sensitive to
the ratio of the minor and major axes. In the
For a very viscous droplet or solid sphere where limit as b/a goes to zero, the oblate spheroid re-
η̂ η, this result reduces to Stokes law. For gas duces to a circular flat disk with the drag force
bubbles where η̂ η given by
F D = 4 π η r1 u ∞ (2.151) FD = 5.093 π η a u∞ (2.153)
In this case, the drag is two-thirds that of a rigid where a is the radius of the flat disk. In the limit
sphere. as b/a goes to zero for the prolate spheroid, the
results for an elongated rod of radius b and length 2.3.3. Flow in Channels with Varying Cross
2 a are Sections – Lubrication Analysis
4 π η a u∞ In many problems the flow geometry is suffi-
FD = (2.154)
ln (a/b) + 0.1932 ciently complex that exact solutions of the mo-
Additional drag force results for creeping flow tion equations are not possible, and approximate
around bodies are given in [30]. or numerical methods are required to obtain the
An alternate way of representing drag force solutions desired. In this section an approximate
results around bodies is in terms of a drag coef- analysis is described, called lubrication theory.
ficient C D (→ Fluid Mechanics, Chap. 3.3.3.): (The name lubrication theory arose from early
applications of this approximate analysis to thin-
FD = CD (Characteristic area of body) ·
film lubrication problems). This method is appli-
cable when the change in flow channel geometry
(Characteristic kinetic energy of fluid
in the direction of flow is weak.
per unit volume) (2.155)
Consider steady two-dimensional flow
u = [ux (x, y), uy (x, y), 0] in a channel with a
For flow past a sphere slowly changing cross-sectional area as shown
in Figure 12. The flow channel gap b varies with
π 1 2
FD = C D d2 u∞ (2.156)
x, but the magnitude of this change at any x is
4 2 small, i.e.,
24 db
CD = (2.156a) ε≡ 1 (2.158)
Red dx
For the settling of multiple bodies, interaction The equation of continuity and the x and y com-
effects can be quite important, even over fairly ponents of the equation of motion are the same
large separation distances. In the case of two as Equations (2.112) – (2.114), but without the
identical spheres of diameter d settling either time derivative terms. To scale these equations
parallel or perpendicular to their line of centers, and determine the most dominant terms, the ve-
the drag coefficient on each sphere is locity component ux must first be scaled to the
characteristic average velocity u0 in the channel:
24 Λ
CD = (2.157) Q Q
Red ux ∼ uavg (x) = ∼ ≡ u0 (2.159)
b (x) w b0 w
where Λ is an interference parameter which is a
function of the ratio l/d of the distance between Here Q is the volumetric flow rate, w the channel
the particles and the particle diameter. When width, b0 the channel gap at x = 0, and the sym-
l/d → ∞, Λ → 1. For two spheres settling side bol ∼ indicates an order-of-magnitude estimate.
by side, Λ is found to be < 1 for finite values From this result,
of l/d. As a result, two interfering spheres fall ∂ux Q db u0
faster than isolated spheres. ∼ 2 ∼ ε (2.160)
∂x b w dx b0
Even though two spheres may fall faster than
and from the equation of continuity,
an isolated sphere, a suspension of many spheres
usually experiences a higher drag than the iso- ∂uy ∂ux u0
= − ∼ ε (2.161)
lated sphere case. As a result, when a suspen- ∂y ∂x b0
sion settles in a beaker, a sharp line is observed or
separating the clear fluid from the particle-laden
fluid. This hindered settling phenomenon arises ∂f ε ∂f 1
uy ∼ u0 ε, ∼ f, ∼ f (2.162)
because particles in the low-concentration re- ∂x b0 ∂y b0
gions near the top of the settling suspension tend where f may be ux or uy , or higher derivatives
to overtake the more slowly settling particles in of these variables.
the underlying high-concentration regions. Based upon these scalings, the magnitudes
of the various terms in the x component of the
equation of motion can now be compared:
The solution of Equation (2.166) with the

boundary conditions
at y = 0, ux = U (2.169)
at y = h (x) , ux = 0 (2.170)
The inertial term will be negligible compared to is

the y derivative viscous term if y 2
y b2 dP y
ux = U 1− − −
u20 η u0 b 2 η dx b b
ε 2 (2.164)
b0 b0 (2.171)
u0 b0
ε 1 (2.164a) with the volumetric flow rate being
η
Similarly, the x-derivative viscous term will be b
1 b3 w dP
negligible compared to the y-derivative viscous Q = ux wdy = U bw − (2.172)
2 12 η dx
term if 0
η u0 2 η u 0 If this equation is solved for (dP/dx) and then

ε 2 (2.165)
b20 b0 integrated, the pressure drop between x = 0 and
or x = L is
ε2 1 (2.165a) 12 A3 η Q L 6 A2 η U L
∆P ≡ − (2.173)
w h30 h20
Equation (2.163) then reduces to
Here A2 and A3 are numerical parameters that
∂P ∂ 2 ux depend on the geometry of the flow channel
0 = − +η (2.166)
∂x ∂y 2 [h (x)]; they are given by
In a similar way, the y-component of the equa-
1
tion of motion can be simplified to dx∗
An = , n = 2, 3 (2.174)
h∗n
∂P ∂ 2 uy 0
0 = − +η (2.167)
∂y ∂y 2
where x∗ ≡ x/L and b∗ ≡ b/b0 . Equation (2.173)
From these equations, is the pressure drop – flow rate relation for flow
∂P η u0 ∂P
in a two-dimensional channel with a weakly
∼ 2 ε ∼ ε (2.168) varying cross section.
∂y b0 ∂x
Similar relations can be obtained for axisym-
which indicates that when ε 1, pressure metric flows where the cross section varies along
changes in the y-direction are negligible com- the axis of flow [39]. This includes flows in sinu-
pared to those in the x-direction. Hence, changes soidal tubes, and converging or diverging ducts.
of P in the y-direction can be neglected and the Lubrication theory is applicable in such prob-
assumption made that P = P (x). lems as long as ε ≡ dR/dz is sufficiently small,
where R (Z) is the local channel radius. Good
engineering approximations are often possible
even for values of ε as high as 0.2.
To conclude this section an application of lu-
brication theory is presented which involves the
analysis of slipper block performance. Consider
the slipper block shown in Figure 13, which
Figure 12. Flow in a two-dimensional channel with varying
cross section
could represent a wiping block or ring on a
Flow can arise from an applied pressure gradient or from moving piston. In some applications, the surface
moving wall(s). moves and the block is stationary (see Fig. 13);
in others, the block moves and the surface is sta- If the gap geometry is described by the linear
tionary. The thickness of the film gap between relation
the block and the moving surface, as well as the x
drag force on the block, depends on the applied b = b0 + (bL − b0 ) (2.178)
L
load B, the speed U, the viscosity of the film
fluid η, the width w, the length L, and the vari- the dimensionless pressure distribution can be
ation of the gap thickness with x. Lubrication obtained from Equations (2.175) and (2.177)
theory is used to develop the appropriate rela- with the result
tions between these variables.
(P − P0 ) L (b∗ − 1) (b∗ − κ)
P∗ ≡ = (2.179)
6η U (b0 /L )2 (κ2 − 1)
where κ ≡ bL /b0 . As depicted in Figure 13, the

pressure is positive in the gap and exhibits a max-
imum toward the narrow gap end. The magni-
tude of the pressure increases with U and η, and
decreases with (b0 /L). The pressure also causes
a vertical force Fy on the block, which is ob-
tained by integrating P over the block length.
The result is
Fy 1
Fy∗ ≡ =
LIVE GRAPH 6η U w (b0 /L )2 (κ − 1)2
Click here to view
2 (κ − 1)
− ln κ (2.180)
κ+1
For a given b0 /L, the maximum vertical

force is obtained for a block geometry where
κ = 2.19. Also, because the vertical pressure
force must be equal to the load B, the resulting
thickness b∗0 is
( )1/2
b0 6η U w 2 (κ − 1)
b∗0 ≡ = 2
− ln κ
Figure 13. Lubrication flow between block and moving sur- L B (κ − 1) κ+1
face
(2.181)
A) Geometry; B) Pressure distribution
Begin by using Equation (2.172): Here, for a given κ, the gap thickness increases
with increasing U and η, and decreases with in-

dP 12 η Ub Q creasing load B, and each case has a square-root
= 3 − (2.175)
dx b 2 w dependence.
In this problem, Q is not known and must be The drag force Fx on the moving plate is ob-
determined from known pressure conditions. tained by integrating τyx over this surface:
In particular, at x = 0 and x = L the pressure is Fx 1
assumed to be zero. Integration of Equation Fx∗ ≡ =
6η wU (b0 /L ) (κ − 1)
(2.175) between these points then yields
(κ − 1) 2
− lnκ (2.182)
L κ+1 3
12 η L 1 A3 Q
dP = 0 = A2 U − (2.176) Finally, if Equation (2.181) is used to eliminate
h20 2 h0 w
0 b0 /L,
where the An are defined by Equation (2.174).  
1/2  3 κ − 1 − 2 lnκ 
The volumetric flow rate is then 2

κ+1

Fx = ηU wB
3  2 κ − 1 − lnκ 
A2 w b0 U κ+1
Q = (2.177)
2 A3 (2.183)
which shows that the drag force is proportional Consider now the case of steady flow of a
to the square root of the applied load. This half- Newtonian fluid in a heated tube where the tem-
power dependence when a lubricating film is perature of the fluid varies in the radial and ax-
present is in contrast to the first-power depen- ial directions because of heat exchange with the
dence generally assumed between sliding solid walls, viscous heat generation, and reversible
surfaces with no lubricant. Also, the effective work effects. If free convection, generation, and
coefficient of friction for lubricated surfaces is radiation effects are neglected, and the velocity
orders of magnitude smaller than that associated field is assumed to be u = [0, 0, uz (r)], Equation
with direct – contact solid surfaces. (2.184) takes the form
∂T dp
cp uz = ∇ · (λ∇T ) + T β uz +
∂z dz
2.4. Coupled Momentum and Energy
2
Transfer duz
2η (2.186)
dr
This discussion has been concerned with ex-
amples that involve only heat or momentum The contribution of viscous dissipation to the
transfer, but not both. In this section, exam- temperature gradient in the z-direction can be
ples are considered in which heat and momen- estimated from
tum are transferred simultaneously and, specifi-
∂T 2 η (duz /dr)2
cally, heat is being transferred in a flowing fluid. = ∼
∂z viscous dissipation cp uz
When such heat transfer results directly from
fluid movement, the transfer is termed heat con- ν2
O Red (2.187)
vection. If the flow arises from applied pressure cp d3
gradients or moving boundaries, the heat transfer where Red ≡ (uavg d/ν) is the Reynolds num-
is called forced convection. When the flow arises ber; ν ≡ η/, the momentum diffusivity, d the
from buoyancy effects associated with density tube diameter; and uavg the average velocity in
variations in nonisothermal fluids, it is called the tube. For air at room temperature (ν ≈ 2×
free or natural convection. 10−5 m2 /s, cp ≈ 103 J kg−1 K−1 ) flowing in a
In analyzing heat transfer with flow, the 0.025-m tube at a Reynolds number Red = 103 ,
energy balance is expressed in the form [16, the temperature gradient due to viscous effects
pp. 215 – 216]: is on the order of 3×10−5 K/m. For water under
∂T
the same conditions (ν ≈ 8×10−7 m2 /s, cp ≈ 4
cp
∂t
+ u ·∇T = ∇ · (λ∇T ) ×103 J kg−1 K−1 ), the gradient is on the or-

∂p
der of 1×10−8 K/m; for an oil with proper-
+ Tβ
∂t
+ u ·∇p + tr (τ ·∇u) + Φ (2.184) ties ν ≈ 9×10−4 m2 /s, cp ∼ 2×103 J kg−1 K−1 ,
the gradient is ca. 3×10−2 K/m. In most heat-
which is equivalent to Equation (1.85) with exchange applications, such effects are negli-
Fourier’s law (Eq. 1.91) used for the conductive gible compared to the conduction contributions
heat flux q; β is the coefficient of thermal ex- (first term on right-hand side, Eq. 2.186) which
pansion defined by can be on the order of several kelvin per meter.
Therefore, viscous dissipation effects are gen-
1 ∂
β ≡ − (2.185) erally neglected in most heat-exchange applica-
∂T p tions. However, viscous dissipation can be im-
In Equation (2.184) the second term on the portant in lubrication problems where viscous
left, which involves velocity, accounts for con- oils are being sheared at high rates between mov-
vective heat transfer, and the terms on the ing surfaces.
right are the conductive, reversible work (fluid If a similar order-of-magnitude analysis is
expansion – contraction), viscous dissipation, carried out for the contribution of the reversible
and thermal generation terms, respectively. work term to the axial temperature gradient:

∂T T β (dp/dz) 2.4.1. Heat Transfer in Laminar Tube Flow
= ∼
∂z rev. work cp
Consider the heat exchange that occurs when a
T β ν2
O 32 Red (2.188) fluid is passed through a heated or cooled tube
cp d3
under steady laminar flow conditions. If a New-
Here, the pressure gradient is related to ve- tonian fluid, constant physical properties, negli-
locity through the Hagen – Poiseuille equation gible axial conduction, and fully developed ve-
(Eq. 2.86). Comparing Equations (2.187) and locity and temperature profiles are assumed, the
(2.188) gives energy balance can be written as

∂T ∂T ∂T 1∂ ∂T
∼ ± 32 T β uz = α r (2.192)
∂z rev. work ∂z viscous dissipation ∂z r ∂r ∂r
(2.189)
where
where the sign depends on whether dp/dz in 2
Equation (2.188) is positive or negative. When 1 r

uz = uavg 1 − (2.193)
dp/dz < 0, the reversible work results in a de- 2 r1
crease in temperature in the direction of flow;
with r 1 being the tube radius and uavg the aver-
in contrast, the viscous dissipation causes an in-
age velocity. Depending on the boundary condi-
crease in temperature. For air at room tempera-
tions, various solutions are possible. When the
ture where β = − 1/T (ideal gas), the temperature
heat flux at the wall qw is constant, a particu-
gradient contribution associated with reversible
larly simple solution is possible. In particular,
work effects is on the order of 30 times that asso-
if Equation (2.192) is multiplied by r and inte-
ciated with viscous dissipation effects. For liq-
grated with respect to r, then
uids where β ∼ 10−3 K−1 , the reversible work
contribution to the temperature gradient is on the
∂T
2α
order of 10 times that arising from viscous dissi- dTb
=
∂r r1
=
2 α qw
(2.194)
pation. Still, in most applications, these effects dz r1 uavg r1 uavg λ
are small compared to conduction or convection
effects and can be neglected. where T b is the bulk average temperature de-
The other effect that is not commonly consid- fined by
ered in convection analyses is the temperature r1
dependence of thermal conductivity. For most 1
Tb = uz T 2 π rdr (2.195)
fluids, the magnitude of (1/λ) (∂λ/∂T ) is on the π r12 uavg
0
order of 10−3 K−1 and

The bulk average temperature is simply the
∇ · (λ∇T ) = λ ∇ T +
1 2 ∂λ
|∇T | 2 “cup-mixing temperature” that would be mea-
λ ∂T sured if the tube were chopped off at z and the
fluid issuing forth were collected and thoroughly
∼ λ∇2 T (2.190) mixed in a container.
Equation (2.194) implies that T b varies lin-
Hence, if viscous dissipation and reversible
early with z. The achievement of a fully devel-
work effects are neglected, the heat generation
oped temperature profile requires that
term is zero, and the conductivity is assumed to
be temperature-independent, the energy balance
∂ Tw − T
(Eq. 2.184) reduces to =0 (2.196)
∂z Tw − Tb
∂T or
+u ·∇T = a∇2 T (2.191)
∂t
Tw − T
= f (r) (2.197)
where α ≡ λ/ cp is the thermal diffusivity. This Tw − Tb
is the equation used in the forced convection ex-
amples considered here. From Newton’s law of cooling,
Next Page

λ ∂T long and fully developed thermal profiles are sel-
∂r r1 ∂ Tw − T dom achieved. In the latter cases, more complete
h = − = λ
(Tw − Tb ) ∂r Tw − Tb r1 solutions must be used to describe heat transfer
= λ f (r1 ) = const. (2.198) in the developing regions, and these are con-
siderably more complicated than the fully de-
or veloped solutions presented above [38–42]. The
qw classical Graetz solution [38], which involves
Tw − Tb = = const. (2.199)
h the solution of Equation (2.192) for parabolic
By using this equation with Equations (2.194) and flat velocity profiles and constant wall tem-
and (2.197), peratures are the best known among these solu-
tions.
dTw dTb ∂T dT 2 qw α A useful empirical expression is given by
= = = = (2.200)
dz dz ∂z dz r1 uavg λ Sieder and Tate [43]; it is an empirical modifi-
cation of the Graetz solution, ( parabolic veloc-
Substituting this result into Equation (2.192) and
ity) i.e.,
integrating over r give
hlm d
11 qw r1 11 qw d N ud,lm ≡ =
Tw − Tb = = (2.201) λ
24 λ 48 λ
P r1/3 (L /d)−1/3 (ηbm /ηw )0.14
1/3
1.86 Red (2.205)
The latter result indicates that when the fluid is
heated (or cooled) under constant wall heat flux Here, the physical properties of the fluid are
conditions, the temperature difference between evaluated at the mean bulk fluid temperature,
the wall and the bulk fluid is constant. T bm ≡ (T b0 + T bL )/2, where T b0 and T bL are
If Equations (2.201) and (2.199) are com- the entering and exit bulk temperatures for a tube
bined, section of length L. The viscosity ratio (η bm /η w )
is the ratio of the viscosities evaluated at the
hd
N ud ≡ = 4.364 (qw = const., large z) (2.202) mean bulk temperature and at the mean wall tem-
λ
perature; the quantity hlm is the log-mean film
where Nud is the dimensionless Nusselt number heat-transfer coefficient defined by
based upon the tube diameter d. This result pro-
vides a simple expression for estimating h under L
(qr )r1 dz
constant wall heat flux conditions and in zones hlm =
Q̇
= −
0
(2.206)
(large z) where the profiles are fully developed. λ L d∆Tlm L∆Tlm
For the case of constant wall temperature, the
where
solution is somewhat more involved [38]; how-
ever, Nud is still constant but equal to a different  
(T − T ) − (T − T )
∆Tlm ≡  
wL bL w0 b0
value (2.207)
− TbL
ln TTwL − T
w0 b0
N ud = 3.658 (Tw = const., large z) (2.203)
is the log-mean temperature difference. The
Use of this result is limited to z values greater heat-transfer rate Q̇ across the wall can be ex-
than the thermal entry length ze which is the pressed in terms of the difference between the
position from the tube entrance where Equa- convected energy input and output to the heated
tion (2.196) is approximately satisfied, say (or cooled) section by
∂ (T w − T )/∂z ∼ 0.01. For laminar flow, this en-
try length can be estimated from π d2
Q̇ = uavg ( cp T )L − ( cp T )0 (2.208)
4
ze
≈ 0.05 Red P r (2.204)
d For large values of L/d, Equation (2.205) pre-
In particular, for water at room temperature dicts that the log-mean Nusselt number goes
(Pr ≡ ν/α ∼ 10) flowing at a Reynolds number to zero, which is not consistent with results
of 103 , the entry length would be 500 diameters; for the fully developed regions. Whitaker [16,
for oils with Pr ∼ 104 , the entry lengths are very
Previous Page
pp. 324 – 325] suggests the use of the follow- fluid-deforming velocity gradients) are negligi-
ing expression, which is based on the work of ble. When applicable, such an approach simpli-
Hausen [42]: fies the solution considerably, and approximate
analytical solutions are possible in many cases.
0.0745 ψ 3
N ud,lm = 3.66 + (2.209)
1 + 0.04 ψ 2 Momentum Transfer in a Laminar Bound-
where ary Layer. To illustrate this approach, consider
first the momentum transfer associated with
ψ ≡ (Re P r)1/3 (L /d)−1/3 (ηbm /ηw )0.14 (2.210) flow past the surface shown in Figure 14. In
this case, the flow is two dimensional where
This result is accurate to ca. ± 10 % for situa- u = [ux (x, y), uy (x, y), 0], with the x-coordinate
tions in which the wall temperature is constant or measured along the surface and the y-coordinate
nearly constant. In the case of constant wall heat measured normal to the surface. As the fluid
flux, variations of T w can be large; however, the moves over the surface with velocity u, a bound-
local Nusselt numbers are only ca. 20 % higher ary layer is formed that encompasses most of the
than those for constant-temperature cases. As velocity changes resulting from interactions of
a result, Equation (2.209) is used even for the the fluid with the surface. Although many differ-
case of constant heat flux and surface tempera- ent ways of defining the boundary layer thick-
ture variations are ignored. ness exist [44], in this article thickness is defined
When the entering fluid temperature and the as the y-position at which the velocity is 99 % of
wall temperature are known, the exit tempera- the mainstream velocity u∞ , i.e.,
ture TL and the overall heat transfer rate Q̇ can be
calculated by using Equations (2.206) – (2.210). δm (x) ≡ {The y−position at each x
Since the evaluation of the properties requires a
knowledge of TL , an iterative procedure is re- where ux = 0.99 u∞ } (2.211)
quired in which TL is assumed and hlm is calcu- The subscript m indicates the boundary layer
lated from Equation (2.209). Then this value of thickness for momentum transfer; boundary
the heat-transfer coefficient is used with Equa- layer thicknesses for heat- and mass-transfer
tions (2.207) and (2.208) to determine TL and Q̇. processes are defined later and denoted by δT
The new value of TL is then employed to update and δc , respectively.
the value of hlm , and the procedure is repeated
until convergence is obtained.
2.4.2. Momentum and Heat Transfer in

Laminar Boundary Layers
A characteristic of real fluids moving around

solid bodies is the adherence of the fluid to Figure 14. Momentum boundary layer on a surface
the solid surface. This no-slip condition causes a) Fluid; b) Solid body; c) Laminar boundary layer; d) Tur-
fluid-deforming velocity gradients that tend to bulent boundary layer; e) Laminar sublayer
be large in the neighborhood of the body and As illustrated in Figure 14, the boundary layer
to diminish far away from it. If the Reynolds thickness increases with distance x along the sur-
number based on the characteristic length of the face. For a certain distance x < x cr , flow in the
body is sufficiently high, the resulting velocity boundary layer is laminar. At the position x cr ,
gradient is restricted largely to a thin region in which can be estimated from
the neighborhood of the boundary. Under such
conditions, a boundary layer approach is pos- u∞ xcr
Recr ≡ ≈ 2 × 105 (2.212)
sible where the flow field is divided into two ν
regions: (1) a thin boundary layer in which both inertial effects become sufficiently large com-
viscous and inertial effects are important, and (2) pared to viscous effects to destabilize the flow
an external region in which viscous effects (and and except for a very thin laminar sublayer next
to the surface of the body, the flow exhibits In principle, if u∞ is known (obtained from the
sporadic vortex-like instabilities that eventually solution of the nonviscous equations for the flow
grow into fully developed turbulence. Physi- geometry [45]), Equations (2.215) and (2.220)
cally, this is observed in flow visualization when can be solved for the velocity components ux
the boundary layer thickness increases rather and uy . Although these equations can be solved
abruptly as shown in Figure 14 (in graphically numerically [44], [46], here the focus is on the
depicting a boundary layer as in Fig. 14, the use of approximate integral methods.
thickness is exaggerated and not to scale). Gen-
erally, x cr may be on the order of meters and δ m
on the order of millimeters.
The velocity field in the laminar portion of the
boundary layer, and the associated drag force on
the surface are now determined. If the radius of
curvature of the surface is sufficiently large com-
pared to the boundary layer thickness, the flow
can be represented as that along a flat plate as Figure 15. Laminar momentum and thermal boundary lay-
shown in Figure 15. If the scalings ers on a flat plate
In particular, note that

ux ∼ u ∞ (2.213)
∂ux ∂ ∂uy
∂ux u∞ uy = (uy ux ) − ux (2.221)
∼ (2.214) ∂y ∂y ∂y
∂x L
are used, the equation of continuity If (∂uy /∂y) is replaced with − (∂ux /∂x) by using
the equation of continuity, Equation (2.220) can
∂ux
+
∂uy
= 0 (2.215)
then be written as
∂x ∂y
∂ 2 ∂ 1 d 2 ∂ 2 ux
yields u + (uy ux ) = u +ν
∂x x ∂y 2 dx ∞ ∂y 2
∂uy u∞ (2.222)
∼ (2.216)
∂y L
When this equation is integrated over y from
uy ∼ u ∞
δm
(2.217) y = 0 to y = ∞, and the conditions
L
By using these scalings, the x- and y-components ux = 0, uy = 0 at y = 0 (2.223)
of the equation of motion can be simplified. In
particular, if δ m /L 1, the x component takes ux = u ∞ ,
∂ux
= 0 at y ≥ δm (2.224)
the form [44, p. 131] ∂y
∂ux ∂ux 1 dp ∂ 2 ux
along with (from Eq. 2.215)
ux + uy = − +ν + gx (2.218)
∂x ∂y dx ∂y 2 δm
∂ux
The y-component simply reduces to ∂p/∂y = 0, uy (x, ∞) = − dy (2.225)
∂x
which indicates that the pressure is independent 0
of y and hence is simply the pressure p (x) out- are used, the result is
side the boundary layer. If the external flow is
assumed to be nonviscous the pressure field can δm
be determined from: d
ux (u∞ − ux ) dy +
dx
0
1
p = − u2∞ − gx x + constant (2.219) δm
2 du∞ τw
(u∞ − ux ) dy = (2.226)
using this equation in Equation (2.218) gives dx
0

∂ux ∂ux du∞ ∂ 2 ux where τ w is the wall shear stress given by

ux + uy = u∞ +ν (2.220)
∂x ∂y dx ∂y 2

∂ux L
τw = η (2.227) 1 1.292
∂y y=0 CDL ≡ CDx dx = 1/2
(2.234)
L ReL
0
Equation (2.226) is the von Karman momen-
tum integral equation. For a given external flow and ReL ≡ u∞ L/ν.
u∞ (x), its solution requires a knowledge of the The exact solution for a laminar boundary
velocity ux as a function of y. Even with crude layer on a flat plate with a uniform free stream
approximations for ux (y), reasonably accurate velocity was obtained by Blasius [44]. The cor-
estimates of the drag force can be obtained. responding local and overall drag coefficient re-
As an example, consider the case of a flat sults are
plate in a free stream flow where u∞ = constant.
0.664
If a cubic relation is assumed for ux (y), i.e., CDx = 1/2
(2.235)
Rex
ux = a + b y + c y 2 + d y 3 (2.228) 1.328
CDL = 1/2
(2.236)
ReL
and the boundary conditions of Equations
(2.223) and (2.224) are used, along with The approximate results of Equations (2.232)
(∂ 2 ux /∂y2 ) = 0 at y = δ m to evaluate the con- and (2.234) compare favorably with the exact
stants, then results. This demonstrates the utility of the inte-
gral method. Even more accurate results could
3
3 y 1 y have been obtained if higher order approxima-

ux = u ∞ − (2.229)
2 δm 2 δm tions (beyond the cubic) were used for the veloc-
ity profile. In general, such integral approaches
If this assumed profile is substituted in the mo- are valuable tools in engineering analysis and
mentum integral balance (Eq. 2.226) and the provide excellent approximations with compa-
necessary integrations are performed, the fol- rable ease relative to the numerical methods re-
lowing differential equation for boundary layer quired to obtain exact results.
thickness is obtained:
dδm 140 ν 1
Heat Transfer in a Laminar Boundary
= (2.230) Layer. Just as the momentum boundary layer
dx 13 u∞ δm
thickness was defined as the region in which
Integration with the condition δ m = 0 at y = 0 most of the fluid-deforming velocity gradients
gives the boundary layer thickness occur, a thermal boundary layer thickness δT
can be defined as that region next to a heated
δm 4.64
= 1/2
(2.231) (or cooled) surface in which most of the tem-
x Rex perature gradients occur. Specifically, for heat
where Rex ≡ u∞ x/ν is the local Reynolds num- transfer from a flat plate at temperature T w to a
ber. The corresponding drag coefficient is given flowing fluid with free stream temperature T ∞ ,
by the thermal boundary layer is defined as
τw 2 3 η u∞ 0.646 δt ≡ {The y−position where T − Tw =

CDx ≡ 1
= 2 = 1/2
(2.232)
u 2 u 2 δm
2 ∞ ∞ Rex
0.99 (T∞ − Tw )} (2.237)
where the subscript x on C D indicates the co-
efficient is a local value that varies with x. The In general, as shown in Figure 15, the thermal
drag force per unit width is then boundary layer thickness is not equal to the mo-
mentum boundary layer thickness. However, the

L
relation between the thermal and momentum
FD 1 2
= τw dx = CDL L u (2.233) boundary layers in laminar flow can be approx-
w 2 ∞
0 imated by [47]
where the overall film coefficient C DL is given δm
≡ ∆T = const. (2.238)
by δT
Equation (2.238) implies that the dependence of where ∆T ≡ δ m /δT has been assumed to be con-
δT on x is the same as that of δ m on x. stant. By integrating this equation with the con-
For heat transfer in a laminar boundary layer dition δT = 0 at y = 0, the thermal boundary layer
on a flat plate where δT /L 1, the energy bal- thickness is found to be
ance (Eq. 2.191) can be simplified to 1/2
3/2
δT 4.47 ∆T 14
∂T ∂T ∂2T = (2.248)
ux + uy = α (2.239) x 1/2
Rex P r1/2 14 ∆2T − 1
∂x ∂y ∂y 2
By integrating over y from 0 to ∞ and using the where Pr = ν/α is the Prandtl number, the ra-
equation of continuity to replace uy (the steps in- tio of the momentum and thermal diffusivi-
volved are analogous to Eqs. 2.221 – 2.226), the ties. Then, from Equations (2.231), (2.238), and
energy balance can be put into the integral form (2.248),

1/3
δT δm 14 1
d qw ∆T ≡ 1− P r1/3
ux (T − T∞ ) dy = (2.240) δT 13 14 ∆2T
dx cp
0
where qw is the wall heat flux given by ≈ P r1/3 (2.249)
∂T and
qw = − λ (2.241)
∂y y=0
δT −1/2
= 4.47 Rex P r1/3 (2.250)
Equation (2.240) is analogous to the momen- x
tum integral equation (Eq. 2.226). To obtain a where it has been assumed
solution to this integral energy balance, a tem-
perature profile must be assumed that satisfies 14 ∆2T 1
the conditions
Based upon these results, the momentum bound-
at y = 0, T = Tw (2.242) ary layer thickness increases relative to the ther-
mal boundary layer as the momentum diffusivity
at y = δT , T = T∞ (2.243) ν increases relative to the thermal diffusivity a
∂nT
(or Pr increases). For gases, the Prandtl number
at y = δT ,
∂y n
= 0 for n = 1, 2, . . . (2.244) is on the order of 1 and the boundary layer thick-
ness δ m and δT have similar magnitudes. For
If a cubic power relation is assumed for the tem- liquids, the Prandtl number can be much higher
perature profile than 1 and δ m can be larger than δT . For liq-
uid metals, Pr 1 and the momentum boundary
T = a + b y + c y2 + d y3 (2.245) layer thickness is much smaller than the thermal
boundary layer thickness.
the boundary conditions of Equations
Thus, from Equations (2.241), (2.246), and
(2.242) – (2.244) can be used to determine the
Newton’s law of cooling,
coefficients, with the result
3
hx χ 1/2
3 y 1 y N ux ≡ = 0.36 Rex P r1/3 (2.251)
T = Tw + (T∞ − Tw ) − λ
2 δT 2 δT
(2.246)
where Nux is the dimensionless local Nusselt
number. This result is ca. 8 % higher than the
When this profile is substituted into the integral exact result from numerical solutions, which is
form of the energy balance, Equation (2.229) is given by
used for ux , and Equation (2.238) is used for δ m ,
1/2
then N ux = 0.332 Rex P r1/3 (2.252)

dδT 10 α 14 ∆3T Heat transfer from the plate can then be deter-
δT = (2.247) mined from
dx u∞ 14 ∆2T − 1
L the behavior of these variables. Outside the

Q̇ = h (Tw − T∞ ) wdx = hL w L (Tw − T∞ ) boundary layer, the pressure gradient is simply
0
the hydrostatic gradient
(2.253)
dp
= − ∞ g (2.258)
where dx
L
where ∞ is the density of the fluid at T ∞ . In-
1 side the thermal boundary layer, the density can
hL ≡ hdx (2.254)
L be related to the temperature by
0

Using Equation (2.252) yields ∂
= ∞ + (T − T∞ )
∂T T∞
hL L 1/2
N uL ≡ = 0.664 ReL P r1/3 (2.255) = ∞ [1 − β∞ (T − T∞ )] (2.259)
λ
where ReL ≡ (u∞ L/ν). Hence, if the properties Substituting Equations (2.258) and (2.259) into
are determined from the average film tempera- Equation (2.218) gives the momentum equation
ture, 1/2 (T w + T ∞ ), the total heat-transfer rate for free convection, i.e.,
from the plate can be determined from Equa-
∂ux ∂ux ∂ 2 ux
tion (2.253), with hL estimated from Equation ux + uy = ν + g β∞ (T − T∞ )
∂x ∂y ∂y 2
(2.255).
(2.260)
For the case of constant heat flux at the plate
surface, the local Nusselt number is given by In integral form, this equation becomes
1/2
N ux = 0.453 Rex P r1/3 (2.256) δm
d ∂ux
u2x dy = − ν +
In this case, wall temperature varies with posi- dx ∂y y=0
0
tion x on the plate according to
δT
qw g β∞ (T − T∞ ) dy (2.261)
Tw = T∞ + (2.257)
hx 0
Although the above relations have been derived The integral form of the energy balance is the
for flat surfaces, they are also useful as approxi- same as Equation (2.240).
mations for curved surfaces if the characteristic In selecting appropriate velocity and temper-
radius of curvature for the surface is much larger ature expressions to use in these equations, the
than the boundary layer thickness. following boundary conditions are applicable:
at y = 0, ux = 0 (2.262)
2.4.3. Free Convection on a Vertical Plate
T = Tw (2.263)
When a stagnant fluid is in contact with a heated
surface, the fluid layers near the surface are at
at y = δm , ux = 0 (2.264)
higher temperatures than the fluid layers fur-
ther removed from the surface. Because of their ∂ n ux
higher temperatures, the layers near the surface = 0, n = 1, 2, . . . (2.265)
∂y n
have lower densities and will rise relative to the
stagnant bulk fluid. Such free convection pro- at y = δT , T = T∞ (2.266)
cesses can be analyzed in much the same way as
∂nT
forced convection on a flat plate was analyzed = 0, n = 1, 2, . . . (2.267)
∂y n
by using boundary layer methods.
The velocity and temperature field inside the In particular, if a cubic expression is used for
momentum and thermal boundary layers are il- ux ( y) and a quadratic expression for T ( y), the
lustrated in Figure 16. The boundary layer equa- resulting profiles that are consistent with the
tions, Equations (2.218) and (2.239), describe boundary conditions are
hL L
N uL ≡
λ
1/4
Pr
= 0.678 (P r GrL )1/4 (2.272)
0.952 + P r
Here Grx is the local Grashof number given by

g β∞ (Tw − T∞ ) x3
Grx = (2.273)
ν
and Pr Grx is the Rayleigh number given by
g β (Tw − T∞ ) x3
Rax ≡ P r Grx = (2.273a)
να
The assumption of δ m = δT would seem to limit
the results to Prandtl numbers on the order of 1;
however, because the effect of the velocity pro-
file on the temperature profile is small as Pr in-
creases, the result is also useful at higher Prandtl
numbers.
Empirically, Churchill and Chu [47] have
found that free convection data on vertical sur-
faces correlate quite accurately with
N uL = 0.68 + 0.67 (P r GrL )1/4

−4/9
0.492 9/16
· 1+ (2.274)
Pr
Figure 16. Free convection from a vertical heated plate,
development of momentum, and thermal boundary layers
In using this correlation, the thermal properties
should be evaluated at the mean boundary layer
temperature, except for β ∞ which should be
y y 2
ux = uc (x) 1− (2.268) evaluated at T ∞ if the fluid is a gas. Equation
δm δm
(2.272) is quite accurate at Pr ≈ 1 or greater;
y 2 however, it is not valid at low Prandtl numbers
T = T∞ + (Tw − T∞ ) 1 − (2.269)
δT (liquid metals), and Equation (2.274) must be
where uc is a characteristic velocity that varies used instead.
with x. If uc = A xm and δ m = δT = B x n , and these
relations are substituted into Equations (2.261)
and (2.240), the boundary layer thickness δ m and 2.5. Turbulent Momentum and Energy
the local and overall heat-transfer coefficients Transfer
can be determined [21, pp. 371 – 376]. The re-
sults are 2.5.1. Physical Characteristics
1/4 Much flow of industrial importance is turbulent
δ 0.952 + P r 1
= 3.936 (2.270) flow. Momentum and energy transport in tur-
x P r2 1/4
Grx
bulent flow are characterized by time-varying
velocity and temperature fields. In particular,
hx x for turbulent flow in a tube under constant flow
N ux ≡
λ rate conditions, the axial velocity component at
1/4
Pr a specific position in the flow appears as in Fig-
= 0.508 (P r Grx )1/4 (2.271)
0.952 + P r ure 17 A with the velocity fluctuating around a
time-averaged value. The same fluctuating be-
and havior is also observed for the other velocity
components. Also, if heat is convected between average is taken is long compared to the recipro-
the wall and the fluid, the temperature at each cal frequency of the fluctuations, but short com-
spatial position in the flow also fluctuates. pared to the time of macroscopic changes in
pressure drop, wall temperature, and other ex-
ternally controlled variables.
Although turbulence is inherently unsteady,
steady conditions in turbulent flow can be con-
sidered if
∂ ϕ̄
= 0 (2.278)
∂t
In Figure 17 A, steady turbulent flow is illus-
trated; in Figure 17 B, unsteady turbulent flow.
The latter might arise in a flow field if the applied
pressure drop decreases with time.
To obtain a measure of the relative magni-
tude of the fluctuating part of a turbulent flow
variable, the quantity
2
(ϕ )2
Iϕ ≡ (2.279)
ϕ̄
can be defined. In particular, for a shear flow
[ūx = ūx (y)] the intensity of turbulence is defined
by
2 2
(ux )2 + uy + (uz )2
Iu ≡ (2.280)
ū
Figure 17. Illustration of velocity fluctuations in turbulent
LIVE GRAPH
flow Click here to view
The velocity consists of a time-average part (ūz) and a fluc-
tuating part (u z).
A) Steady turbulent flow, ūz constant with time; B) Un-
steady turbulent flow, ūz varying with time
In describing this behavior, the velocity and

temperature variables are conveniently sepa-
rated into time-averaged values plus fluctuating
parts, i.e.,
u = ū + u (2.275)
and
T = T̄ + T (2.276)
Figure 18. Distribution of intensities of the different
where ū and T̄ are the time-averaged values and velocity components in a turbulent boundary layer
u and T are the fluctuating parts. The time-
2 2
averaged value at time t of a variable ϕ is defined ux (ux )2 + uy +(uz )2
by a = u∞
,

0
t+t
uz
2
(ux )2 + uy
2
+(uz )
2
1 b=
ϕ̄ ≡ ϕdt (2.277) u∞
,
t0
t 2 2
uy (ux )2 + uy +(uz )
2
where ϕ can correspond to u, T, p, or any other c= u∞
dependent variable. The time t 0 over which the
In Figure 18, the intensities of individual veloc- LIVE GRAPH

Click here to view
ity components are shown for a turbulent bound-
ary layer on a flat plate as observed by Kle-
banoff [16, p. 275], [49]. As can be seen, the
largest component intensity is that associated
with the contribution in the direction of flow
(ux ), with a maximum value of 0.11 which oc-
(t)
curs very close to the wall ( y/δ m ≈ 0.007).
The smallest component intensity is that asso-
ciated with uy , the velocity component normal
to the wall, where a value of 0.04 is observed
(t)
at y/δ m = 0.15. Although the fluctuating inten-
sities may appear small, these quantities are im-
portant in the heat- and mass-transfer rates ob-
served in turbulent flow.
In Figure 19, the normalized velocity profile Figure 19. Dimensionless laminar and turbulent velocity
ūx /u∞ for a turbulent boundary layer on a flat profiles for flow on a flat plate at a local Reynolds number
plate (b) is compared with that for a laminar Rex = 106
(l) (t)
boundary layer (a), both corresponding to a lo- Here, δ m and δ m denote the momentum boundary layer
thickness for laminar (a) and turbulent flow, (b) respectively;
cal Reynolds number Rex of 106 . The turbulent (t) (l)
δ m /δ m ≈ 4.8.
boundary layer thickness is nearly five times that
of the laminar boundary layer, and in turbulent The velocity distribution across these three
flow the velocity profile is more uniform with a regions can be described by the semiempirical
higher ratio of average velocity to maximum ve- relations
locity. Also, the wall velocity gradient and the Laminar sublayer:
corresponding wall friction drag are higher in
the turbulent case. The latter might suggest that a u+ = y + for y + < 5 (2.281)
laminar boundary layer would be more desirable Buffer zone:
in minimizing frictional drag on surfaces; how-
ever, in most cases a turbulent boundary layer u+ = − 3.05 + 5 ln y + for 5 ≤ y + < 30 (2.282)
is preferred because it is more effective in re-
sisting boundary layer separation and increased Turbulent core:
form drag. u+ = 5.5 + 2.5ln y + for 30 ≤ y + (2.283)
For turbulent flow in tubes and along flat sur-
+ +
faces, various flow regions can be identified. At Here, u and y are defined by
distances sufficiently close to the wall, the tur-
u+ ≡ ux /u∗ (2.284)
bulent fluctuations diminish and a laminar sub-
layer is observed. In this region, momentum y + ≡ y u∗ /ν, (2.285)
or energy transfer occurs largely from conven-
tional molecular and laminar convection mech- and u∗ is the friction velocity defined by
anisms. At distances sufficiently remote from -
u∗ ≡ τw / (2.286)
the wall, a fully developed turbulent core is
present where the momentum- and energy-trans- where τ w is the wall shear stress. The ve-
fer mechanisms are largely a result of convective locity distribution represented by Equations
mixing of the turbulent eddies. In the buffer zone (2.281) – (2.283) is commonly referred to as the
between the laminar sublayer and the turbulent universal velocity distribution.
core, the flow is neither laminar nor fully devel- Another form of the velocity distribution that
oped turbulent flow. In this region, both types of is commonly used to describe turbulent flow in
molecular and turbulent transport mechanisms tubes is
are present. 1/n
ūx y
= (2.287)
umax r1
where y is the distance measured from the wall smoothing Equations (1.65) and (1.73) term
and r 1 is the tube radius. Nikuradse [50] ob- by term. Before carrying out these operations,
tained excellent agreement with experimental Equation (1.73) can be put in the equivalent form
observations when n was allowed to vary with
∂
Reynolds number (see Table 6). For Reynolds (u) + ∇ · (uu) = − ∇p − ∇ ·τ + g (2.288)
numbers of ca. 105 , a value of n = 7 is com- ∂t
monly used. Note that Equation (2.287) gives where the equation of continuity has been used
an infinite velocity gradient at the tube wall. As on the left side of Equation (1.73) and Equation
a result, drag force values cannot be predicted (1.84) on the right side. The key time-smoothing
directly from velocity gradients calculations at identities are
the wall.
Fϕ = Fϕ (2.289)
Table 6. Characteristics of velocity profile for turbulent flow in a
tube [50]
Fϕ ψ = Fϕ ψ+Fϕ ψ (2.290)
Red n in Equation (2.287) uavg /umax
4×103 6 0.791 where F is any linear time or spatial derivative

1.1×105 7 0.817 operator (e.g., ∂/∂t, ∇, ∇ ·) and ϕ and ψ repre-
3.24×106 10 0.865
sent scalar, vector, or tensor functions, or com-
binations thereof. By using these identities, the
Although Equation (2.281) – (2.283) and following time-smoothed equations are obtained
(2.287) were developed originally for tube flow, (incompressible fluids):
they are also valid for turbulent boundary layers
on flat plates. In this case, umax in these equa- ∇ ·ū = 0 (2.291)
(t)
tions is replaced by u∞ and r 1 by δ m . Also,
∂ ū
2
because τ w = f uavg /2 for tubes, an expression + ū ·∇ū = − ∇p̄ − ∇ ·
∂t
for uavg /umax must be used to apply the results
to flat plates. As illustrated in Table 6, this ra- τ̄ − u u + g (2.292)
tio for tube flows varies with Reynolds num-
ber. For Reynolds numbers of ca. 105 , a value of If this equation is compared with the form of
uavg /umax ≈ 0.8 is commonly used. Equation (2.288) for incompressible fluids, i.e.,

∂u
+ u ·∇u = − ∇p − ∇ ·τ + g (2.293)
∂t
2.5.2. Time-Smoothed Momentum and
Energy Balances for Turbulent Flow the time-smoothed equation is seen to have the
same form, except that ū and p̄ replace u and p,
The equations of continuity and motion given and τ (t) ≡ τ̄ − u u replaces τ . The compo-
previously are perfectly valid for describing nents of u u are called the Reynolds stresses.
turbulent flow; however, because of the un- Physically, these represent the convective mo-
steady, three-dimensional fluctuations of veloc- mentum flux components associated with the
ity and other dependent variables, the analysis fluctuating part of the velocity.
requires simultaneous solution of the full three- One could expect that just as τ depends on the
dimensional equations of motion along with deformation rate, the Reynolds stresses might be
the equation of continuity. Even if appropriate expressible in terms of the mean velocity and its
boundary and initial conditions could be spec- spatial derivatives. Unfortunately, this does not
ified, such solutions are beyond current mathe- appear to be possible, and when attempted, the
matical capabilities. A less ambitious approach coefficients associated with the mean velocity
is to focus on the time-smoothed quantities and terms and its derivatives are spatially dependent
to describe these variables as a function of posi- and specific to each flow field.
tion and time by using time-smoothed forms of In general, a proper description of the u u
the equations of continuity, motion, and energy. contributions requires a more complete statisti-
The specific forms of the continuity and cal analysis of turbulence. Although progress is
motion equations can be obtained by time- being made in this area, an approach that can be
used in engineering analyses is not yet available. For the exchange of x-momentum between
As a result, only forms of the Reynolds stresses different y layers moving at different velocities
that are valid for specific flows can be obtained. ūx :
This is the approach taken here in restricting at-
d dūx
tention to flow in tubes and along flat surfaces. uy ux = εm ( ūx ) = εm (2.296)
dy dy
Finally, note that the time-smoothed form of
the energy balance Equation (2.191) is where εm is the eddy momentum diffusivity.
Similarly, for the heat flux between different
∂ T̄
cp + ū ·∇T̄ = − ∇ · q̄ + cp u T y layers at different temperatures T̄ :
∂t
(2.294) d dT̄
cp uy T = εT cp T̄ = cp εT (2.297)
dy dy
where q̄ = − λ ∇T̄ . This equation is of the same
form as Equation (2.199), except that q (t) ≡ where εT is the eddy thermal diffusivity.
q̄ + cp u T replaces q = − λ ∇T . Also, this From largely physical arguments, Prandtl
equation neglects viscous heat dissipation, re- [46], [51] was able to relate εm and εT to the
versible work, and heat generation. The quan- motion of discrete fluid elements between lay-
tity cp u T is the heat flux associated with turers with different mean velocities to obtain
bulent fluctuations. As with Reynolds stresses, dū
cp u T must be expressed in terms of the time- x
εm = εT ≡ ε = l2 (2.298)
dy
smoothed quantities and their derivatives before
solutions to Equation (2.294) can be obtained. where l is the Prandtl mixing length. The mix-
Similar to Reynolds stresses, these relations are ing length is a measure of the distance (in the y-
not universal and the coefficients in such expres- direction) that the discrete fluid elements move
sions are spatially dependent and specific to each before they accommodate to the mean velocity
flow. of the surroundings. This quantity is somewhat
analogous to the mean free path in the kinetic
theory of gases. For one-dimensional flow in
2.5.3. Mixing Length Theories tubes and along surfaces (e.g., Fig. 20), the mix-
ing length has been empirically found to increase
One of the common approaches used in relating with distance from the wall. Specifically, the re-
u u and cp u T to time-smoothed quanti- lation
ties is through a mixing length interpretation of
turbulent transport. In particular, this approach l = ky (2.299)
assumes a mechanism for turbulent transport
which involves irregular movement of discrete appears to represent experimental observations
fluid elements in the flow in a manner analogous with the constant k being ca. 0.4.
to the kinetic behavior of molecules in a gas. In summary, for turbulent transport in shear
For the case of unidirectional turbulent flow flows where ūx = ūx (y), the total x-momentum
along a surface as illustrated in Figure 20, where flux in the y-direction can be given by
the time-smoothed entity M (momentum, en- (t) dūx
ergy, mass, etc.) varies with distance y from the τyx = − (ν + ε) (2.300)
dy
surface, the flux arising from the turbulent fluc-
(t)
tuations is given by and the total heat flux qy in the y-direction by
dM̄ (t) dT̄
Flux of Min y direction = − εM (2.295) qy = − cp (α + ε) (2.301)
dy dy
Here εM is the eddy diffusivity associated with where ν and α are the molecular momentum and
the transfer of M by the turbulent fluctuations. thermal diffusivities, respectively, and ε is the
Basically, the fluctuations give rise to the “dif- eddy diffusivity. At positions close to the wall
fusion” of discrete fluid elements that produce a in the laminar sublayer, the fluctuations have
flux of M down the gradient of decreasing M. negligible importance, and ν ε and α ε;
Figure 20. Turbulent transport in unidirectional flow along a surface
whereas in the bulk turbulent field away from q̄y − cp α ddy

T̄
cp α dT̄
the wall, ε ν and ε α for high-intensity tur- τ̄yx
=
− ν dū x
=
ν dūx
(2.302)
dy
bulent flow. In the buffer region between the lam-
inar sublayer and the turbulent core, the molec- or, because q̄y /τ̄yx is assumed to be constant,
ular and eddy diffusivities are generally of the
q̄y qw cp dT̄
same order of magnitude. = = (2.303)
τ̄yx (−τw ) P r dūx
Integration of this equation over the laminar sub-

2.5.4. Turbulent Heat Transfer in layer gives
Tubes – Reynolds, Prandtl, and von Karman
Analogies Pr qw
T̄ξ − Tw = − ūξ (2.304)
cp τw
Results are now presented for estimating heat- where Pr = ν/α. Here the edge of the sublayer is
transfer coefficients for convective heat trans- denoted by y = ξ, and T̄ξ and ūξ are the temper-
fer in tubes under turbulent flow conditions. The ature and velocity at this position.
heat transfer is assumed to arise from tempera- In the turbulent core the eddy momentum and
ture differences between the heated (or cooled) energy transport dominate the molecular trans-
bounding surface and the bulk fluid. The analy- port. As a result,
sis follows that of Prandtl [51] and is aimed
qw − cp εT dy
dT̄
at developing an expression involving the heat- q̄y
= − ≈ (2.305)
transfer coefficient h, the friction factor f , the τ̄yx τw dū
− εm dyx
average velocity uavg , and the properties of the
fluid. or
The key assumptions are (1) the turbulent qw dT̄
flow field is divided into two zones, a laminar − = cp (2.306)
τw dūx
sublayer that extends to y+ = 5 and a turbulent
where εT = εm = ε is assumed as in the Prandtl
core that occupies the region beyond this point;
mixing length theory. Integrating this equation
(2) the velocity profile in the laminar sublayer
from y = ξ, where ūx = ūξ and T̄ = T̄ξ , to the bulk
is given by Equation (2.281); and (3) the ratio
of the fluid, where ūx = uavg and T̄ = T ∞ , gives
q̄y /τ̄yx of the heat and momentum fluxes is con-

stant in both the sublayer and the turbulent core. 1 qw
T∞ − Tξ = − ūavg − ūξ (2.307)
The last assumption implies that the temperature cp τw
and velocity profiles are functionally similar.
In the laminar sublayer where turbulent eddy Adding Equations (2.304) and (2.307) and using
transport is negligible, qw = h (Tw − T∞ ) (2.308)
1 τw 0.0791
τw = f u2avg (2.309) f ≡ 1
= 1/4
(2.314)
2 2
u2avg Red
and, At higher Reynolds numbers (> 105 ), the uni-
- - versal velocity profile can be used to develop an
ūξ = 5 τw / = 5 uavg f /2, (2.310)
expression for the friction factor. In particular,
give if the turbulent core is assumed to extend to the
wall, Equation (2.283) can be integrated over the
N ud h
St ≡ = = tube cross section to obtain the average velocity:
Red P r cp uavg
. u r /
f /2 ∗ 1
- (2.311) uavg = u∗ 1.75 + 2.5 ln (2.315)
ν
1 + 5 f /2 (P r − 1)
Note that
where St is the Stanton number. This equation is
called the Prandtl analogy and relates the heat- - -
u∗ ≡ τw / = uavg f /2 (2.316)
transfer coefficient to the friction factor (or drag
coefficient). The quantities Nud and Red are the thus, Equation (2.315) can be simplified to the
Nusselt and Reynolds numbers based on the tube von Karman friction factor relation, i.e.,
diameter d and the average velocity, i.e., h d/λ
1 -
and uavg d/ν, respectively. √ = 4.07 log Re f − 0.601 (2.317)
For Prandtl numbers of 1 (applicable for f
many gases), Equation (2.311) reduces to This result is quite close to the empirical result
h f of Nikuradse [50] given by
= (2.312)
cp uavg 2
1 -
√ = 4.0 log Re f − 0.40 (2.318)
which is the Reynolds analogy. This result can be f
obtained directly from the above analysis by ne-
Both of these results are for smooth tubes and
glecting the sublayer and allowing the turbulent
are generally used at elevated Reynolds numbers
core to occupy the entire flow region. Hence,
(> 105 ).
uξ = 0 and Tξ = T w in Equation (2.307), and the
For rough tubes, the effects of relative rough-
Reynolds analogy follows directly from Equa-
ness e/d (e ≈ height of wall protuberances) must
tions (2.308) and (2.309).
be included.
√ For Reynolds numbers above the
Von Karman [52, pp. 223 – 227] conducted
value Re f = 0.01d/e, the Colebrook equa-
a more complete analysis including all three
tion can be used to determine f [54]:
zones in the turbulent field (i.e., laminar sub-
layer, buffer zone, and turbulent core). The final
1 4.67 e
result was √ = − 4 log √ + + 2.28 (2.319)
f Re f d
h The Colebrook equation reduces to the Niku-
St ≡ (2.313)
cp uavg radse result when e/d = 0.
f /2 The degree of roughness of a tube is not
= - 8 ;
1+5 f /2 P r − 1 + ln 1+ 56 (P r − 1) always easy to determine accurately. As a re-
sult, pressure drops predicted by substituting the
This analogy includes the Reynolds and Prandtl above results into Equation (2.80) can often in-
analogies as special cases. volve considerable error because of uncertain-
To use the above analogies to estimate heat- ties in estimating e/d. This is particularly true
transfer coefficients, an expression is needed for for tubing susceptible to scaling and corrosion
the friction factor f in terms of the Reynolds and tubing that has been in use for some time.
number and appropriate roughness parameters. In addition to the above analogies, another
For smooth tubes, a useful empirical expres- result can be obtained from the boundary layer
sion for f in the range 4×103 ≤ Red ≤ 105 is results of Equations (2.235) and (2.255). These
the Blasius formula [53] (→ Fluid Mechanics, latter equations can be combined to give
Chap. 3.3.1.):
St P r2/3 = f /2 (2.320) as Eq. 2.226, but with the dependent variables

replaced by time-smoothed quantities),
where f has been substituted for C Dx . This
(t)
equation is identical with the Reynolds analogy δm
=
0.371
(2.323)
1/5
(Eq. 2.312) when Pr = 1. Based on this agree- x Rex
ment at Pr = 1, Colburn suggested the use of
and
Equation (2.320) at higher Prandtl numbers even
for turbulent flow (Colbum analogy). Although 0.0577
CDx = (2.324)
it is strictly valid only for laminar flow, this sim- 1/5
Rex
ple relation has been found to be a useful ap-
proximation for turbulent flow applications par- which are valid up to a local Reynolds num-
(t)
ticularly, where there is no form drag and where ber of 107 . In determining δ m , the turbulent
0.5 < Pr < 50. boundary layer has been assumed to extend to
(t)
The Colburn analogy can be put in another the leading edge of the plate (δ m = 0 at x = 0).
form: Obviously, this can lead to considerable error,
particularly because the laminar boundary layer
F
jH = (2.320a) that exists up to x cr = 2×105 (ν/u0 ) has a square-
2
root dependence on x compared to the 4/5 power
where dependence that results from Equation (2.323).
Regardless, if Equation (2.324) is used in the
jH ≡ St P r2/3 (2.320b) Colburn analogy (with C Dx replacing f and Stx
is the Colburn j factor for heat transfer. The mass replacing St)
transfer analogy of jH will be discussed later. 4/5
N ux = 0.0289 Rex P r1/3 (2.325)
is obtained. Given the restrictions on Equation

2.5.5. Turbulent Momentum and Heat (2.322), this equation is limited to Rex < 107 .
Transferon a Flat Plate Based on the experimental work of
Zhukauskas and Ambrazyavichyus [55],
For a turbulent boundary layer on a flat plate, Whitaker [16, pp. 333 – 336] suggests the use
the wall shear stress can be related to the free of
stream velocity u∞ and the turbulent boundary 1/4
(t) η∞
layer thickness δ m by the Blasius expression: N ux = 0.029 Rex
4/5
P r0.43 (2.326)
ηw
1/4
ν instead of Equation (2.325), where all proper-
τw = 0.0225 u2∞ (t)
(2.321)
u∞ δm ties are evaluated at the free stream tempera-
ture T ∞ . This equation is similar to Equation
This equation follows from Equation (2.325), except for the power dependence on
(t)
(2.314) if d = 2 r 1 → 2 δm , umax → u∞ , and the Prandtl number and the addition of a tem-
uavg /umax ≈ 0.8. It is valid for flat plate perature-dependent viscosity effect. Remember
Reynolds numbers up to 107 . In terms of the that the origin of the 1/3 power dependence
drag coefficient C Dx , this equation can be writ- on Pr in Equation (2.325) was from laminar
ten as boundary theory. In extending this result to
1/4 turbulent boundary layers, some modifications
τw 0.0450 x would be expected. The 1/4 power dependence
CDx ≡ 1
= 1/4 (t)
(2.322)
2
u2∞ Rex δm on (η ∞ /η w ) is different from that for tube flow
where a 0.14 dependence was found. Although
To use Equations (2.321) and (2.322), the tur- such differences are justified on the basis of
(t)
bulent boundary layer thickness δ m must be available data, relatively small experimental er-
determined. If Equation (2.287) is used with rors could cause these differences. As a result,
(t)
n = 7, r 1 → δm , and umax → u∞ in the time- some uncertainty must be associated with the
smoothed momentum integral balance (the same power dependences on Pr and (η ∞ /η w ).
x 
cr L
1  
For a plate of length L, the overall heat-trans-
fer coefficient can be determined from CDL = CDx, lam dx + CDx, turb dx
L  
x  0 xcr
cr L
1   (2.330)
hL = hx,lam dx + hx,turb dx (2.327)
L   Using Equations (2.235) and (2.324) and assum-
0 xcr
ing that Recr = 2×105 give
Using a modified form of Equation (2.252) for
−1/5 −4/5
CDL = 0.072 ReL 1 − 9 200 ReL (2.331)
αx,lam [Eq. 2.252 with (η ∞ /η w )1/4 as a multi-
plier], and Equation (2.326) for hx, turb gives 7
This equation is valid for ReL < 10 . At higher
1/4 Reynolds numbers, the result of Prandtl can
4/5 η∞ be used [56]:
N uL = 0.0361 ReL P r0.43
ηw
( ) 0.455
−4/5 0.473 CDL = (2.332)
· 1 − 17 400 ReL 1− (2.328) [log ReL ]2.58
P r0.1
which is valid for ReL from 106 to 109 .
This equation assumes that the tran-
sition Reynolds number is given by
Recr ≡ (u∞ x cr /ν) = 2×105 . For sufficiently 2.6. Summary of Heat-Transfer
large values of ReL where Recr /ReL 1, Equa- Relations
tion (2.328) can be simplified to
1/4 In Table 7, heat-transfer and friction (or drag)
4/5 η∞ coefficient results are summarized for various
N uL = 0.0361 ReL P r0.43 (2.329)
ηw geometries. They include the flat plate and tube
As with Equation (2.326), all properties in Equa- flow results presented here, as well as results
tions (2.328) and (2.329) are evaluated at the free for heat transfer around cylinders and spheres.
stream conditions. These equations are valid for In addition, free convection results are provided
ReL < 107 , Pr between 0.7 and 380, and viscos- for several common situations.
ity ratios between 0.26 and 3.5.
Whitaker found that the use of Equation
(2.328) versus Equation (2.329) depends on the 3. Transport in Multicomponent
degree of turbulence in the free stream. When Systems
the latter is high, the transition Reynolds number
is less than 2×105 and Equation (2.329) tends Multicomponent transport processes require
to be valid. When the free stream turbulence is consideration of the fact that to the extent mix-
low, Equation (2.328) represents experimental ture compositions are not uniform, diffusion (the
observations more accurately. In addition to this motion of species of the mixture relative to each
effect of free stream turbulence, the roughness other) will be nonzero. In binary systems, diffu-
of the plate also has a significant effect on the sion processes can be analogous to heat transfer.
transition Reynolds number. In particular, very Multicomponent systems are considerably more
smooth plates can exhibit transition values con- complex, however. Useful references on diffu-
siderably above 2×105 . Because such effects are sion and general transport references are given
difficult to characterize in many applications, in [63–67]. An extensive review of methods for
some degree of uncertainty is associated with obtaining diffusion coefficients appears in [68].
the use of Equations (2.328) or (2.329).
If the fluid properties are evaluated at the film
3.1. Diffusive Mass Transfer in Binary
temperature T f ≡ (T w + T ∞ )/2 instead of T ∞ ,
the (η ∞ /η w ) dependence in Equations (2.328) Systems
and (2.329) can be dropped. Such differences 3.1.1. Species Mass Balances
are noted in Table 7.
To calculate the overall drag coefficient on a In considerations of single-component (compo-
plate of length L that extends into the turbulent sitionally homogeneous) systems the equation
boundary layer region, we use of continuity (conservation of total mass)
Table 7. Summary of heat-transfer and friction coefficient results (all properties evaluated at Tf ≡ (Tw − T∞ )/2 unless otherwise noted)
Situation Equation Restrictions Equation

number ( ) or
reference [ ]
Flow over Flat Plates

Heat-transfer coefficients
Laminar, local Nux = 0.332 Rex 1/2 Pr 1/3 constant wall temperature; (2.252)
Rex < 2×105 , 0.6 < Pr < 50
Laminar, local Nux = 0.453 Rex 1/2 Pr 1/3 constant wall heat flux; (2.256)
Rex < 2×105 , 0.6 < Pr < 50
Laminar, overall NuL = 0.664 ReL 1/2 Pr 1/3 constant wall temperature; (2.255)
ReL < 2×105 , 0.6 < Pr < 50
Turbulent, local Nux = 0.029 Rex 4/5 Pr 0.43 (η ∞ /η w )1/4 constant wall temperature; (2.326)
2×105 < Rex < 107 ,
0.7 < Pr < 380; properties
evaluated at T ∞
Turbulent, overall N uL = (2.328)
4/5 −4/5
0.0361 ReL P r 0.43 (η∞ /ηw )1/4 × 1 − 17 400ReL 1− 0.473
P r 0.1
constant wall temperature;

2×105 < ReL < 107 ,
0.7 ≤ Pr ≤ 380; relatively low
free stream turbulence;
properties evaluated at T ∞
Turbulent, overall NuL = 0.0361 ReL 4/5 Pr 0.43 (η ∞ /η w )1/4 same as above except relatively (2.329)
high free stream turbulence
Drag coefficients
Laminar, local C Dx = 0.664 Rex −1/2 Rex < 2×105 (2.235)
−1/2
Laminar, overall C DL = 1.328 ReL ReL < 2×105 (2.236)
Turbulent, local C Dx = 0.0577 Rex −1/5 2×105 ≤ Rex < 107 (2.324)
Turbulent, overall C DL = 0.072 ReL −1/5 (1 – 9200 ReL −4/5 ) 2×105 ≤ ReL < 107 (2.331)
Flow in Tubes
(Properties evaluated at average bulk mean temperature between z = 0 and z = L unless otherwise noted)
Heat-transfer coefficients
Fully developed laminar Nud = 3.658 T w = const.; Red < 2100; (2.203)
z > 0.05 d Red Pr
Fully developed laminar Nud = 4.364 qw = const.; Red < 2400; (2.202)
z > 0.05 d Red Pr
Developing laminar Nud , lm = 1.86 Red 1/3 Pr 1/3 (L/d)−1/3 (η ∞ /η w )0.14 (2.205)
T w = const.; Red < 2400;
intermediate-length tubes
3
Developing laminar N ud,lm = 3.66 + 10.0745 ψ
+ 0.04 ψ 2
Red < 2400 (2.209)
(2.210)
where ψ ≡ (Red Pr)1/3 (L /d)1/3 (η bm /η w )0.14
N ud
Turbulent St ≡ Red P r = Red > 2400 (2.313)
f /2
√
1+5 f /2 P r − 1 +ln 1 + 5 (Pr − 1)
6
Turbulent Nud ,lm = 0.015 Red 0.83 Pr 0.42 (η bm /η w )0.14 Red > 4000; 0.4 < Pr < 600 [57]
Friction coefficients
Fully developed laminar f = 16/Red Red < 2100; z > 0.05 Red d (2.87)
Turbulent f = 0.0791 Red −1/4 2100 ≤ Red ≤ 105 ; smooth (2.314)
tubes

Turbulent 1
√ = − 4 log 4.67
Red
√
f
+ e
d + 2.28 Red > 105 ; smooth (e = 0) and (2.319)
F
rough tubes
Table 7. (Continued)
Situation Equation Restrictions Equation

number ( ) or
reference [ ]
Flow Around Bodies

Flow normal to cylinder N ud = [58]
5/8 4/5
0.62 Re
1/2
P r 1/3 Red 102 < Red < 4×106 ;
0.3 + d
3/4 · 1+ 28200 Red ≡ u∞ d/ν; properties
1+(0.4/Pr)2/3
evaluated at film temperature
Flow past a sphere Nud = 2 + (0.4 Red 1/2 + 0.06 Red 2/3 ) · Pr 0.4 (η ∞ /η w )1/4 [59]
3.5 < Red < 8×104 ;
0.7 < Pr < 380; properties
evaluated at T ∞
Free Convection from Various Geometries

1/4
0.67 Ra
Vertical surface, overall N uL = 0.68 +
L
9/16 4/9 RaL < 109 [60]
1+ 0.492
Pr
2
1/6
0.387 Ra
Vertical surface, overall N uL = 0.825 + L T w = const.; [60]
8/27
10−1 < RaL < 1012
1 +(0.492/P r) 9/16
Vertical surface, laminar, Nux = 0.60 Rax 1/5 qw = const.; [61]

local 105 < Grx Nux < 1011
Vertical surface, laminar, Nux = 0.17 Rax 1/4 qw = const.; [61]
local 2×1013 < Grx Nux Pr < 1016
1/4
0.518 Ra
Horizontal cylinder, N ud = 0.36 + d T w = const.;1 [61]
4/9
laminar, overall 1 +(0.559/P r)9/16 0−6 ≤ Rad ≤ 109
Horizontal cylinder, ud =
N 10−5 ≤ Rad ≤ 1012 [61]
1/6 2
overall  
Rad
0.60 + 0.387 16/9
 1 +(0.559/P r)9/16 
Horizontal plate, down NuL = 0.58 RaL 1/3 T w = const.; 106 < RaL < 1011 [62]
ward facing hot plates or
upward facing cold
plates; overall
Horizontal plate, upward NuL = 0.13 RaL 1/3 T w = const.; RaL < 2×108 [62]
facing hot plates
1/3
or downward facing cold NuL = 0.16 RaL T w = const.; [62]
plates; overall 2×108 ≤ RaL < 1011
∂ ingly, an equation accounting for the amount of

= − ∇ · (u) (3.1)
∂t species A is given by
plays a vital role in establishing relationships ∂A
= − ∇ · (A uA ) + rA (3.2)
between components of velocity. In this form, ∂t
(∂/∂t)x physically represents the accumulation where r A is the rate of production of species A
rate per unit volume of mass; the expression per unit volume in the mixture, A is the mass
(− ∇ · u) represents the net input rate per unit of species A per unit volume of the mixture, and
volume to the volume fixed in space as a result uA is the average velocity of the molecules of
of the mass flux u. species A in the mixture.
An analogous result can be obtained for an in- This equation can also be expressed in terms
dividual species (e.g., species A), however, since of molar concentration by dividing by molecular
individual chemical species are not conserved mass to give
(except for the elements), the net production of
∂cA
A due to reaction must be considered. Accord- = − ∇ · (cA uA ) + RA (3.3)
∂t
Next Page
where cA is the number of moles per volume of Thus, in a mixture, different species may move
species A in the mixture and RA is the molar at different velocities and the mixture velocity is
rate of production of species A by reaction per defined as a weighted average of these individual
unit volume of the mixture. The velocity in this velocities.
equation is the same as in the preceding equa- A parallel set of equations exists for molar
tion. concentrations. Accordingly, the sum of the mo-
An equation of this sort in either mass or lar concentrations of the individual species gives
molar form can be written for each species in n n n
the mixture. When all the equations for all the ∂ci
= − ∇ · (ci ui ) + Ri (3.9)
species of an n-component mixture are added i=1
∂t i=1 i=1
together, the following result is obtained:
n n n Again the summation and derivatives can be in-
∂i
= − ∇ · (i ui ) + ri (3.4) terchanged and the sum of the individual species
i=1
∂t i=1 i=1 concentrations (number of moles of species i per
unit volume of the mixture) gives the total num-
which, with interchange of the summations and
ber of moles of the mixture per unit volume,
derivatives, is
customarily denoted as c. Accordingly, an ac-
n
 n  counting equation for the total number of moles
∂ i n
i=1 in the mixture is
= − ∇·  i ui  + ri (3.5)
∂t
i=1 i=1 ∂c
= − ∇· ci ui + Ri (3.10)
Now, by definition, the sum of the individual ∂t
species’ densities (mass per unit volume of the In terms of moles, however, the net number of
mixture) is the total mass per unit volume of moles produced by reaction is not necessarily
the mixture, which is customarily defined as zero; the total number of moles due to reaction
to be consistent with the notation for compo- is not conserved. Consequently, this total mo-
sitionally homogeneous systems. Furthermore, lar production rate must be included in the to-
the sum of all the individual species production tal molar accounting equation for the mixture.
rates by reaction must be zero, when expressed However, for convenience, a mixture average ve-
in mass units, because total mass is conserved locity is defined such that the summation of the
(i.e., no net generation of total mass occurs). individual species fluxes represents a mixture
Consequently, the equation for the total mixture average flux in terms of the total molar concen-
becomes tration and the mixture molar average velocity.
∂ Accordingly,
= − ∇· i ui (3.6)
∂t n

Because of the similarity of this equation to the c ũ ≡ ci ui (3.11)
total mass conservation equation, the sum of the i=1
individual species fluxes is commonly defined

or, equivalently,
as the product of the total mass density times
an average velocity for the mixture. In fact, this n

becomes a defining relation for what is referred ci ui
i=1
to as the mixture mass average velocity u ũ ≡ (3.12)

n
n
ci
i=1
u ≡ i ui (3.7)
i=1 This molar average velocity is not the same as
or the mass average velocity (Eqs. 3.7 and 3.8) be-
n
cause the individual species are not necessarily
of the same molecular mass. The definition of
i ui
i=1 a molar average velocity for the mixture allows
u ≡ (3.8)

n
i
i=1
Previous Page
the molar accounting equation to be written in this mixture molar average flow, plus the molar
the form rate of production of A per unit volume.
Similarly, a diffusion flux can be defined in
∂c n
= − ∇ · (c ũ) + Ri (3.13) terms of mass fluxes, i.e., the difference between
∂t i=1 the total mass flux of species A and the mass flux
of species A that results from the mixture mov-
Again, the net number of moles produced by re- ing at its mass average velocity:
action is not necessarily zero as it was for mass,
and as a result, this term must remain in the equa- j A ≡ A uA − A u (3.16)
tion. Mass and molar accounting equations are
thus obtained for the individual species, along This mass diffusion flux used in the mass ac-
with statements of the conservation of total mass counting equation for species A gives
for the mixture. Now diffusion must be defined
for the individual species and methods for cal- ∂A
= − ∇ · (A u) − ∇ ·j A + rA (3.17)
culating diffusion fluxes must be introduced. ∂t
Again the accumulation rate of species A at
a point in space results from the mass flux of
3.1.2. Species Diffusion Fluxes species A due to the bulk flow of the fluid (the
mass average velocity of the mixture) plus the
The preceding discussion recognized that each diffusion flux of species A plus the mass rate of
species may be characterized by its own velocity production (per unit volume) of A by reaction.
which, in general, is different from the average In addition to the molar diffusion flux of
velocity of the mixture. Furthermore, the mix- A and the mass diffusion flux of A as defined
ture average velocity may be defined in terms above, a molar diffusion flux of A could be de-
of mass or in terms of number of moles, and fined relative to the mass average velocity ac-
the two velocities in general are different. As a cording to the equation
result, each species has a relative motion with
respect to the mixture average motion. J A ≡ cA uA − cA u (3.18)
This difference in fluxes between each
species relative to the mixture average is referred or a mass diffusion flux of A could be defined
to as diffusion. Because two mixture average ve- relative to the molar average velocity:
locities were defined, one based on number of
moles and one based on mass, two different dif- JÃ ≡ A uA − A ũ (3.19)
fusion fluxes exist for each species, one with re-
Neither of these is as commonly used as the first
spect to the mixture molar average velocity and
two, so they are not considered further here. The
one with respect to its mass average velocity.
point of this discussion is that when talking about
Accordingly, the molar diffusion flux J̃A of
diffusion and diffusion coefficients the velocity
species A can be defined as the difference bet-
used to characterize the mixture must be speci-
ween the total flux of species A and that due to
fied. If the molar average velocity is used, one
the mixture motion on the average [63]:
value for diffusion is appropriate; if the mass
JÃ ≡ cA uA − xA (c ũ) = cA uA − cA ũ (3.14)
average velocity is used, another (different) dif-
fusion is described.
where x A is the mole fraction of species A. Using
this definition of a diffusion flux in the account-
ing equation for species A gives 3.1.3. Fick’s First Law of Diffusion
∂cA
= − ∇ · (cA ũ) − ∇ ·JÃ + RA (3.15) Until now the transport equations presented in
∂t this section have been truly general for multi-
Here, the accumulation rate of the number of component (as opposed to binary) systems. The
moles of A results from the molar flux of A due species accounting equations and the mixture
to the average flow of the mixture, plus the mo- mass conservation equations are correct, inde-
lar diffusion flux of species A above and beyond pendent of whether binary or multicomponent
systems are involved. Likewise, the definitions 3.1.4. Special Cases of Diffusion
of diffusion flux are still valid for multicompo-
nent systems. Using the relations for diffusion molar and mass
However, at this point a relationship is fluxes (Fick’s first law, Section 3.1.3) and the
defined between diffusion driving forces and accounting equations presented in Section 3.1.2
species fluxes. The relationship to be discussed yields the general results that account for species
is restricted to binary systems and is known as A in either moles or mass. Accordingly, in molar
Fick’s first law of diffusion. This law is a lin- units
ear transport equation relating mass transfer or
diffusion driving forces to the diffusion flux. Ac- ∂cA
= − ∇ · (cA ũ) +∇ · (c DAB ∇xA ) + RA (3.21)
cordingly, in a binary system the driving force ∂t
for diffusion (i.e., the reason different species or in mass units
move with different velocities) is the compo-
sitional inhomogeneity (the existence of mole ∂A
= − ∇ · (A u) +∇ · ( DAB ∇wA ) + rA (3.22)
fraction gradients). (Pressure and temperature ∂t
gradients may also induce diffusion [63]. These where wA is the mass fraction of A in the mix-
effects are normally small and are not considered ture. These equations are quite general within
further here.) In the presence of such gradients, the restrictions of Fick’s first law. They do not
species within the mixture move in such a way assume constancy of total molar concentration
as to remove these mole fraction gradients, a or of diffusivities.
motion that occurs spontaneously (implying an Three special cases are of particular interest
increase in entropy of the mixture). [63].
In accordance with a linear relation between
this driving force and diffusion flux, Fick’s first Case 1. If both the mixture mass density
law of diffusion is written as and DAB are constant, then the following result
J˜ = − c DAB ∇xA (3.20) is obtained:
In this equation, ∇x A is the driving force, and the ∂A
= − u ·∇A + DAB ∇2 wA + rA (3.23)
product of the total mixture molar concentration ∂t
and the diffusitivity is the proportionality factor
which may be divided by molecular mass to
required to convert this driving force to a molar
yield a molar accounting equation
flux. The minus sign indicates that the diffusion
flux is in the direction opposite to the direction ∂cA
of increasing mole fraction. The diffusivity is a = − u ·∇cA + c DAB ∇2 xA + RA (3.24)
∂t
parameter that describes how easily species A
moves through the rest of the mixture, species This result, which assumes that the divergence
B – consequently, the notation DAB . of the velocity is zero (the mixture mass density
Similarly, the mass diffusion flux of species is constant), is appropriate for dilute liquid solu-
A can be written in terms of a mass fraction tions at constant temperature and pressure. This
gradient with the proportionality factor being particular form of the equation is also expressed
the product of the mixture mass density and the in terms of mixed quantities; the concentration
same diffusion coefficient as for the molar dif- is given in terms of molar concentration, but the
fusion flux. A priori, the same diffusivity might mixture average velocity is the mass average ve-
not be expected to appear in both the molar locity.
and mass diffusion flux equations. However, this
must be the case for binary systems. Further- Case 2. If the mixture total molar concentra-
more DAB = DBA in a binary system, because tion c and DAB are constant, the mixture conti-
x A = 1 − x B and ∇x A = − ∇x B , and the sum of nuity equation gives
the two species diffusion fluxes must be zero. RA + R B
Consequently, for binary mixtures a single diffu- ∇ ·ũ = (3.25)
c
sivity needs to be reported for any given mixture
composition of A and B.
and the accounting equation for species A be- not complicated by multiple internal energy
comes modes as in the case of thermal conductivity, al-
though the presence of two different molecules
∂cA
= − ũ ·∇cA + c DAB ∇2 xA must be taken into account. Accordingly, the
∂t
Chapman – Enskog equation for diffusivity (in
+ RA (1 − xA ) − xA RB (3.26)
square centimeters per second) in a binary mix-
This result is appropriate for low-density gases ture of gases is
at constant temperature and pressure.
DAB = 1.883 × 10−3 T 3/2 ·
1/2
Case 3. Furthermore, if no chemical reaction Mr,A + Mr,B /Mr,A Mr,B
occurs, if (for liquids) the mixture mass density 2 Ω
(3.28)
p σAB D
is constant, and if the mixture mass average ve-
locity is zero or (for gases) the mixture molar where p is in bar, σ AB is in ångströms, and
concentration is constant and the mixture mo- T is in kelvin. This result incorporates a mo-
lar average velocity is zero (i.e., no bulk motion lecular potential energy function such as the
of the fluid occurs), then Equations (3.25) and Lennard – Jones 12 – 6 function, which may be
(3.26) reduce to the form used for mixtures of nonpolar species. For a bi-
nary mixture the characteristic separation dis-
∂cA tance σ AB is an arithmetic average of the values
= DAB ∇2 cA (3.27)
∂t for the two pure species. Also, the collision in-
This result is known as Fick’s second law of dif- tegral ΩD is a function of k T/εAB , where εAB
fusion and states that the accumulation of species is the geometric mean of the values for the two
A at a point in space results solely from the dif- species. As for viscosity, values of the collision
fusion flux of species A; no convective transfer integral are tabulated or may be calculated by
occurs, nor does any generation or consump- using a relation given by Neufeld et al. [70]
tion as a result of chemical reactions. This re- and presented by Reid et al. [68]. However, the
sult is also called the diffusion equation and is values for calculating diffusivities are different
identical to the partial differential equations (1) from those used for viscosity. For binary mix-
that are obtained for heat conduction in solids tures with at least one polar species, a differ-
of constant heat capacity, thermal conductivity, ent potential function may be used (along with
and density; and (2) that result from the equa- its own values for the molecular parameters) to
tion of motion for a fluid of constant density calculate a different collision integral. Alterna-
and viscosity near a wall suddenly set in mo- tively, the Lennard – Jones collision integral may
tion. This type of agreement between different be modified by an additive contribution due to
modes of transport provides the basis for analo- molecular polarity as manifested by the dipole
gous correlations between certain heat-, mass-, moment [71].
and momentum-transfer problems. That is, the Diffusivities for low-density gases can also
same mathematical equations can govern these be estimated by using empirical relations built
three different modes of transport. Then, with around the basic form of the Chapman – Enskog
analogous geometrical systems and boundary relation. The relation of Fuller et al. [72] is
conditions, exactly the same mathematical prob- applicable to both polar and nonpolar molecules
lem exists, resulting in indentical mathematical and is similar to a group contribution method
solutions. Consequently, the results of many dif- wherein the different structural units of a
fusion problems are available in the heat-transfer molecule are assigned specific diffusion volume
literature, e.g., [67], [69]. increments. The total diffusion volume for each
molecule is calculated and used to determine the
binary diffusivity. Finally, corresponding states
3.1.5. Diffusivities of Gases and Liquids methods also are available for estimating gas dif-
fusivities.
Gases. The diffusivities of gases can be es-
timated quite well by using molecular theory
(similar to viscosity). Diffusion calculations are
Liquids. Theories for estimating liquid dif- Equimolar Counterdiffusion. The term
fusivities are not nearly as successful as for equimolar counterdiffusion means that the two
gases because of the much smaller separation species in the binary mixture diffuse at exactly
distances between molecules, which result in the same molar flow rates per unit area but in
multibody interactions and magnified interac- opposite directions. A diffusion cell schematic
tion forces. The Wilke – Chang method is proba- that approximates ECD is depicted in Figure 21.
bly the most widely used relation for estimating
the diffusivity (in square centimeters per second)
of a solute A at infinite dilution in a solvent B
[73]:
1/2
ϕ Mr,B T
0
DAB = 7.4 × 10−11 (3.29)
ηB VA0.6
Accordingly, M r,B is the molecular mass of the

solvent; η B the solvent viscosity, in pascal sec-
onds, and D0AB the diffusivity when the solute is
at infinite dilution in the solvent. Also, an as-
sociation factor ϕ accounts for the degree of
association exhibited by the solvent. It is 1.0
Figure 21. Schematic of an equimolar counterdiffusion
for nonassociated solvents and increases with (ECD) cell
association: 1.5 for ethanol, 1.9 for methanol,
and 2.6 for water. Other methods are avail- This is a one-dimensional problem for which
able and are summarized and compared in [68]; the mixture molar average velocity (Eq. 3.11)
see also → Estimation of Physical Properties, is zero; hence, the flux of either species occurs
Chap. 6.3.2. only because of its diffusion. If NA is defined as
the total molar flux of species A, from Equation
(3.14)
3.1.6. Theoretical Foundations of
Steady-State Measurement of Diffusion N A = cA uA = cA ũ + JÃ = JÃ (3.30)
or in one dimension using Fick’s first law

To understand the techniques for measurement
of diffusion, two situations are addressed with dyA
NAz = − c DAB (3.31)
respect to gas-phase diffusion that occur as ideal- dz
ized limiting cases. The first is equimolar coun- Now, an accounting of species A (the continu-
terdiffusion (ECD) in which the two species of ity equation, Eq. 3.3) with no reactions and at
a binary mixture have exactly equal and oppo- steady state gives
site molar fluxes. The second is the diffusion of
one species A through a stagnant film of a sec- ∇ ·N A = 0 (3.32)
ond species B (ATSB); the flux of one species
which in one-dimensional form is
is not zero whereas the other is exactly zero.
Both situations are considered to be occurring dNAz
= 0 (3.33)
at steady state. Since they are gas-phase diffu- dz
sion problems at constant pressure the equations and from which the molar flux of species A (and
are given in molar form. In each case analysis similarly of species B) is seen to be invariant
involves using a continuity equation for each with respect to position in the direction of flow.
species (Eq. 3.3), a diffusion flux equation giv- Consequently, Equation (3.31) can be inte-
ing the total flux of a species as the sum of that grated directly (for constant total concentration
due to the mixture molar average flux plus that and diffusivity) to give a linear relation for the
due to diffusion (Eq. 3.14), and finally Fick’s concentration of species A (and hence also of
first law of diffusion (Eq. 3.20). species B) with respect to position in the direc-
tion of flow

yAL − yA0 ATSB Diffusion. For the diffusion of species
yA (z) = yA0 + z (3.34)
L A through a stagnant film of B (ATSB), the sit-
uation is again taken to be constant total pres-
where yA0 and yAL are the mole fractions of A
sure and steady state. Diffusion occurs through
at z = 0 and z = L, respectively. The molar flux
a tube of uniform diameter and length L. In this
in terms of diffusivity and concentrations at the
case, however, the motion of one of the species
ends of the diffusion tube is
is constrained to be zero as in the evaporation of
−c DAB a liquid A from a tube open at one end (Fig. 22).
NAz = ( yAL − yA0 ) (3.35)
L The second gas-phase component is not soluble
This result then can be used to measure diffusiv- in A (or at least A is saturated with B), so its flux
ities if the tube-end concentrations are known as at the interface of liquid A with the gas phase is
a function of time. The above derivation assumes zero. The liquid evaporates at the interface and
a steady state, i.e., the two end-cell concentra- diffuses to the open end of the tube where its
tions do not change with time. The result can concentration is maintained at a reduced level
still be used if the changes in concentration are by a steady flow of fresh gas phase across the
slow compared to the establishment of the con- open end of the tube.
centration profiles in the diffusion cell. By using
this pseudosteady-state assumption the changes
in concentration at the two cell ends can be re-
lated to the flux through the cell by writing a
mass accounting balance for species A in each
cell. Accordingly,
d
(cA0 V0 ) =
dt
Ac DAB
NAz Ac = − (cAL − cA0 ) (3.36)
L
where Ac is the cross-sectional area through
which diffusion occurs and
d
(cAL VL ) =
dt
Ac DAB
−NAz Ac = (cAL − cA0 ) (3.37)
L
from which
d
(cA0 − cAL ) =
dt

Ac DAB 1 1
− (cAL − cA0 ) + (3.38)
L V0 VL
so that
[cAL (t) − cA0 (t)] = [cAL (t0 ) − cA0 (t0 )]

( ) Figure 22. Schematic of “A through stagnant B” (ATSB)
Ac DAB 1 1
· exp − + (t − t0 ) (3.39) diffusion process
L V0 VL
Measuring the concentration difference between For steady state with no reactions in the gas
cells as a function of time gives DAB . The diffu- phase, the continuity of species A in the gas
sion cell itself can consist of a glass frit or even phase requires (as in the equimolar counterdif-
filter paper. In the latter case the cell length is ill- fusion problem) that
defined because of tortuosity and the coefficient
Ac (1/V 0 + 1/VL )/L is determined by calibration
with a material of known diffusivity [65].
dNAz Comparison of ATSB and ECD Results.

0 = − ∇ ·N A = − (3.40)
dz Comparing the ATSB and ECD results shows
that for the same mixture concentration c, dif-
Again, the molar flux of A along the length of
fusivity DAB , and driving force for diffusion
the tube is constant. Likewise, a similar result
dyA /dz, the flux for ATSB is greater than that
is obtained for species B. Because liquid A is
for ECD due to the fact that the mole fraction of
saturated with B, the flux of species B into the
species A is less than unity and hence the driving
liquid at the interface must be zero. Then, be-
force is divided by (1 − yA ). This enhancement
cause this flux is constant along the entire length
is perhaps best understood by looking at Equa-
of the tube, it must be zero everywhere; species
tion (3.42) for the total molar flux of A in terms
B is stagnant. Now, by writing NA (= cA uA ) and
of the bulk flow of the mixture and the diffusion
NB (= cB uB ) as the molar fluxes of species A and
flux. The bulk flow of the mixture is not zero
B, respectively, the combined molar flux for the
for ATSB, whereas it is zero for ECD. Enhance-
mixture is given by (see Eq. 3.11)
ment occurs in the flux of species A out of the
c ũ = cA uA + cB uB = N A + N B (3.41)
tube as a result of this nonzero bulk flow. Note
also that even though B is stagnant, its diffusion
which, combined with Equation (3.14), yields flux, through Fick’s law, is nonzero because its
mole fraction gradient is nonzero. With species
N A = yA (N A + N B ) + JÃ (3.42) B, however, the diffusion flux down the tube
toward the liquid in the bottom of the tube is
i.e., the total flux of A is that fraction due to the exactly counterbalanced by its flow up the tube
total mixture average flow plus the flow due to because of the bulk flow of the gas mixture. The
the diffusion of species A. With species B stag- net effect is that species B is stagnant (N B = 0)
nant, NB = 0 and even though it is in fact diffusing.
In principle, this experimental situation pro-
JÃ vides another method for measuring gas-phase
NA = (3.43)
(1 − yA ) diffusivities. In terms of changes in the amount
which in one-dimensional form is of evaporating liquid in the tube,
dyA dL
NAz dz = − c DAB (3.44) NAz (t) = (3.47)
(1 − yA ) Mr dt
Because of the constancy of NAz along the so that Equation (3.45) becomes
length of the tube, this result can be integrated di-
dL c DAB 1 − yAL
rectly to give either a result for the molar flux of = ln (3.48)
Mr dt L 1 − yA0
A (in terms of tube length, total pressure, diffu-
sivity, and concentrations at the end of the tube) which can be integrated to give

c DAB 1 − yAL 2 c DAB Mr 1 − yAL
NAz = ln (3.45) L2 = ln (t − t0 ) + L 20
L 1 − yA0 1 − yA0
(3.49)
or a result for the concentration profile of species
A along the length of the tube Measuring L as a function of time (by weight)
z/L can then be used to determine DAB . This re-
1 − yAL sult, like the ECD method, rests upon the
yA (z) = 1 − (1 − yA0 ) (3.46)
1 − yA0 pseudosteady-state assumption, in this case that
Note that, contrary to equimolar counterdiffu- the concentration profile and the flux adjust
sion, the concentration profile is nonlinear even rapidly to changes in L. Further complications
though the flux of species A is still constant in this technique involve maintaining constant
along the tube length. temperature in the presence of evaporation and
convection due to differences in the molecular
mass of the two gases [63].
3.1.7. Diffusion with Homogeneous This reaction occurs homogeneously throughout

Chemical Reaction the liquid film in the sense that it takes place ev-
erywhere in the film that species A and B exist
A situation is now considered that involves together. Reaction rate varies with position be-
chemical reaction in addition to diffusion: the cause of variation of the concentration of A with
transfer of a component from a gas phase to position z through the film.
a liquid film followed by diffusion away from As usual, we begin with the equation of con-
the gas – liquid interface and reaction within the tinuity for A which is
film. At a distance δ from the gas – liquid in-
∂cA
terface, the film meets an impermeable solid = − ∇ ·N A + RA (3.52)
∂t
boundary (Fig. 23). As a boundary condition it
is assumed that diffusion of the gas to the liq- For the steady-state condition and for the rate of
uid film is not limiting so that the concentra- production of A given by chemical kinetics, this
tion of the gaseous material in the liquid film equation becomes
at the gas – liquid interface is that established dNAz
by equilibrium with the bulk gas-phase concen- = − k1 cA (z) (3.53)
dz
tration. Species A then diffuses away from the
gas – liquid interface in an attempt to increase This situation differs in a fundamental way from
its concentration within the liquid film. How- the previously described situations in that the
ever, the chemical reaction serves to deplete the flux of A in the diffusion direction is not constant
concentration and a nonlinear steady-state con- because of the depletion of A by the chemical
centration profile is achieved. At the solid – liq- reaction. The concentration of A is a function of
uid interface, the concentration profile must be position z so that the result cannot be integrated
flat; because of the impermeability of the solid to obtain an immediate conclusion about the flux
surface, the flux at that surface is zero. of A. Instead, the flux equation of A is used in
terms of bulk flow in the solution and diffusion:
N A = yA (N A + N B + N C ) − c DAB ∇yA (3.54)
Because species A reacts as it diffuses into the

thin film, a reasonable assumption (depending
on the reaction kinetics versus the diffusion rate)
may be that the concentration of A in the liquid
film is everywhere small so that the bulk flow
(convection) term that contributes to the total
Figure 23. Schematic of diffusion and chemical reaction in flux of species A can be neglected relative to
a liquid film
the diffusion flux term. In this case and for one
The objective of the analysis is to obtain a dimension, the equation becomes
relation for the molar flow rate of A within the dyA
film and the concentration profile of A across the NAz = − c DAB (3.55)
dz
film. For reactions of species A with the liquid
(species B), consider a situation with the reac- Combining this with the continuity equation
tion given by (Eq. 3.53) gives a second-order ordinary differ-
ential equation for the concentration of species
A+B →C (3.50) A
d 2 yA k1
which is characterized by a rate constant k 1 such − yA = 0 (3.56)
that the rate of production of species A is given dz 2 DAB
by the kinetic first-order equation This equation is subject to the boundary condi-
tions at the gas – liquid film interface where the
RA = − k 1 cA concentration in the liquid film is established
(RA < 0 means that A is being consumed) (3.51) by thermodynamic equilibrium (yA = yA0 ) and
at the solid surface (z = δ) where N Az = 0 and
dyA /dz = 0. Imposing these conditions allows in- The situation is depicted schematically in
tegration of the equation to give Figure 24 for a spherical catalyst particle of ra-
. - dius R surrounded by a boundary layer gaseous
yA (z) = yA0 cosh z k1 /DAB − film of thickness δ. Reactant A diffuses through
- - /
the film to the surface where the reaction
tanh δ k1 /DAB sinh z k1 /DAB (3.57) A + A → A2 is assumed to occur very quickly
compared to the diffusion processes. As a re-
The flux of A is a function of position and is sult, at the catalyst surface the concentration of
given by reacting species is assumed to be zero; the react-
- ing species is depleted by reaction as quickly as
NAz (z) = c yA0 k1 DAB · it is delivered to the surface by diffusion. This
. -
− sinh z k1 /DAB + is a binary system with A and A2 as the two
components. Because the reaction occurs at the
- - /
tanh δ k1 /DAB cosh z k1 /DAB (3.58)
solid surface rather than in the gas phase, it is not
relevant to the continuity equation of species A
Note that the concentration profile through the within the gas phase. The role of the reaction sto-
liquid film is exponential in form through the ichiometry and kinetics is to provide a boundary
cosh and sinh functions and that the degree of de- condition on species fluxes at the catalyst sur-
cay depends on the ratio (relative magnitude) of face.
the reaction rate to the diffusion rate. The larger
the reaction rate, the more steeply the profile
falls as the distance into the film away from the
gas interface increases. Conversely, the faster the
diffusion (i.e., the higher the diffusion rate rela-
tive to the reaction rate), the more slowly the
(steady-state) concentration falls or decreases
with increasing distance from the interface.
A similar problem for an infinitely thick liq-
uid film is approached in a similar way except Figure 24. Schematic of diffusion and heterogeneous chem-
that instead of the no-flux boundary condition at ical reaction at a catalyst surface
the solid surface the condition cA → 0 as z → ∞
is used. Such a solution is appropriate even for As for the preceding problems, the objective
liquid films of finite thickness if the reaction rate is to establish quantitative relations for the flux
is large enough compared to the diffusion rate so of reactant A through the stagnant thin film and
that the diffusing species A in fact never “sees” for the concentration profile of A across the film.
the solid surface, i.e., it is depleted by reaction As before, the continuity equation for reacting
before it reaches the solid surface. species A is employed:
∂cA
= − ∇ ·N A + RA (3.59)
∂t
3.1.8. Diffusion with Heterogeneous
Reaction For steady state with no homogeneous reaction,
this gives
The next problem addresses diffusion through
a gas film to a surface at which a reaction oc- ∇ ·N A = 0 (3.60)
curs and from which the reaction product must
diffuse back through the gas phase. This is the which in spherical coordinates is
situation in many catalytic conversion reactions 1 d 2
where a catalyst pellet may be considered to r NAr = 0 (3.61)
r 2 dr
be surrounded by a thin stagnant film through
which a species must diffuse. Because the film which is integrated to give
is stagnant, diffusion rather than reaction kinet-
ics may be the controlling phenomenon. r 2 NAr = constant (3.62)
In this spherical geometry, the flux of a species at the outer extent of the film (i.e., at r = R + δ)
is not constant but is proportional to 1/r 2 . Now is a known value (the concentration in the bulk
because at any position r the spherical surface gas phase). The resulting concentration profile
area is proportional to r 2 , the molar flow rate of is
A rather than the flux is constant, independent  
γ R+δ
of position, according to 1 R+γ δ
yA (r) = 2 1 − 1 − yAδ  (3.69)
2
r 2 NA NA
r2 NAr = constant = = (3.63)
4 π r2 4π
where γ ≡ r − R and
Here N A is the number of moles of species A
R (R + δ) 1
per unit time passing through the entire spher- NA = 8 π c DAB ln 1 − yAδ (3.70)
ical shell at radius r. This molar flow rate is a δ 2
constant, independent of radial position. As be- Now this result is written in terms of an unknown
fore, the result for the molar flux of species A is film thickness δ. It can be evaluated, however, for
written in terms of the convective bulk flow and two limiting cases to obtain limiting or bound-
diffusion: ary concentration profiles and molar flow rates.
If gas flow across the pellet is slow or essentially
N A = yA = N A + N A2 − c DAB ∇yA (3.64) stagnant, then the film thickness goes to infinity
and the results obtained are
which, in one-dimensional form, is
(1− R )
dyA 1 r
NAr = yA NAr + NA2 r − c DAB (3.65) yA (r) = 2 1 − 1− yAδ (3.71)
dr 2
Because of the reaction stoichiometry, the mo- and

lar flow rate of species A can be related to that
of product A2 according to NA = 8 π c DAB R ln 1−
1
yAδ (3.72)
2
N A = − 2 N A2 (3.66)
Alternatively, if the gas velocity is high enough,
These are molar flow rates integrated over the the stagnant film becomes very thin (δ R) and
entire surface of a spherical shell and, as shown results obtained are
above, because of continuity they are indepen- ( γ )
dent of radial position. The fluxes of each of the 1 δ

yA (r) = 2 1 − 1− yAδ (3.73)
species can be written in terms of these molar 2
flow rates so that Equation (3.65) becomes
and

NA NA NA dyA
= yA + 22 − 4 π c DAB (3.67) R2 1
r2 r2 r dr NA = 8π c DAB ln 1− yAδ (3.74)
δ 2
which, because of the relation between the molar
flow rates of A and A2 , gives In these latter equations, the film thickness re-
mains as a parameter, whereas in the stagnant
dr 4 π c DAB dyA film situation the velocity profile and molar flow
NA = (3.68)
r2 1 − 12 yA rate can be calculated directly; as the gas film
becomes very thick, the molar flow rate and
As the molar flow rate is a constant, this result concentration profile become independent of the
can be integrated directly to give a relation for film thickness. At the other extreme, for a very
the concentration profile through the film. In thin film, the molar flow rate becomes inversely
doing so, the boundary conditions are that the proportional to the film thickness; a doubling of
concentration of reactant A is zero at the sur- film thickness halves the molar flow rate.
face of the pellet because it is instantaneously
depleted by the reaction, and the concentration
3.1.9. Perspective liquid film that moves on a solid surface. A sim-

ple example of such a situation is shown in Fig-
The aforementioned results are useful in the con- ure 25, where the gas species A is exchanged
text of this article; not so much for the spe- between a bulk gas phase and a falling liquid
cific problems addressed as for the types of film of component B. This problem is analyzed
approaches that are made to solving diffusion first as steady-state simple absorption with no
problems. In these problems, steady-state sit- chemical reaction. Then, this solution is used to
uations have involved either thin films or in- analyze the more general case in which simulta-
finitely thick films, and slowly changing pro- neous absorption and reaction occur.
cesses have been observed which can be treated
in a pseudosteady-state manner by first solv-
ing the steady-state problem and then integrat-
ing over time to obtain the results as a func-
tion of time. Flat and spherical geometries have
also been observed, although curved geometries,
mathematically, look exactly like flat geome-
tries when the film thickness is small in rela-
tion to the radius of curvature. Therefore, flat
geometry calculations take on an importance
above and beyond their actual application to
specific physical problems. Finally, both homo-
geneous and heterogeneous chemical reactions
have been addressed; homogeneous chemical
reactions occur throughout the phase through
which the diffusion or motion of molecules is
occurring, whereas heterogeneous reactions oc-
cur at a boundary or surface associated with the
diffusion process. As a result, homogeneous re-
action kinetics appear directly in the continuity
equations for the reacting species within the dif-
fusion phase, whereas heterogeneous reaction
kinetics play a role in the fluxes that occur at
interfaces or boundaries of the diffusion region.
Figure 25. Absorption and reaction in a falling liquid film
3.2. Convective Mass Transport In the analysis, A is assumed to be only
slightly soluble in Newtonian liquid B, so that
In the previous examples, motion of the indi- the viscosity and density of the liquid film are
vidual species resulted from the diffusive fluxes not changed appreciably. Under such conditions,
that occur because of concentration gradients. In the film velocity profile is given by (end effects
this section, examples in which species transport neglected)
arises from bulk flow (or convection), as well as
y 2
diffusion, are considered.
uz = umax 1 − (3.75)
δ
3.2.1. Gas Absorption in a Falling Film with The concentration of A in the film varies with
Reaction both y and z, and the species mass balance
(Eq. 3.24) can be written as
A problem encountered in many industrial
∂cA ∂ 2 cA ∂ 2 cA
scrubbers, fixed-bed gas – liquid reactors, and uz = DAB + (3.76)
∂z ∂y 2 ∂z 2
other mass-transfer devices, is the exchange of
a gas species A between a gas mixture and a with the boundary conditions
at z = 0, cA = 0 (3.77) (the y diffusion term). In particular, this requires

that
at z → ∞, cA → cA0 (3.78) 1
ε ≡ 1/2
(3.84)
P eδ
at y = 0, cA = cA0 (3.79)
Equation (3.82) can then be written as
∂cA
at y = δ, = 0 (3.80) 1 ∗2 ∂c∗A ∂ 2 c∗A 1 ∂ 2 c∗A
∂y 1− y = + (3.85)
P eδ ∂z ∗ ∂y ∗2 P eδ ∂z ∗2
The first boundary condition expresses the fact Equation (3.84) indicates that short pene-
that pure B enters at z = 0; the second, that the tration distances (ε 1) are associated with
film is saturated with A after a sufficiently long large Péclet numbers. For the specific case
exposure distance. The third condition gives the in which umax ≈ 0.1 cm/s, δ ≈ 0.1 cm, and
concentration cA0 at the gas – liquid boundary. DAB ≈ 10−5 cm2 /s, the value of Peδ is 103 (or
Generally, unless significant resistance to mass ε ≈ 0.03). Such high Péclet number, short pen-
transfer occurs on the gas side of the interface, etration distance conditions are typical of those
the concentration cA0 is the concentration in encountered in many gas – liquid contact pro-
the liquid that is in equilibrium with the gas. cesses. Under such conditions, Equation (3.82)
The fourth condition simply indicates that no can be reduced to
mass flux exists normal to the solid wall; hence,
the concentration gradient ∂cA /∂y is zero at the ∂c∗A ∂ 2 c∗A
∗
= (3.86)
wall. ∂z ∂y ∗2
By assuming that over some film length z ∼ δ with the boundary conditions
the gas penetrates only a fraction of the distance
into the film (e.g., y ∼ ε δ), the y and z variables at z ∗ = 0, c∗A = 0 (3.87)
can be scaled as
at y ∗ = 0, c∗A = 1 (3.88)
y ≡ ε δ y∗ (3.81a)
at y ∗ → ∞, c∗A → 0 (3.89)
∗
z ≡ δz (3.81b) The solution of Equation (3.86) subject to these
boundary conditions is [63, p. 539]
where y∗ and z∗ are dimensionless quantities of
√ y
order 1. Further, if cA and uz are scaled by

4DAB z/umax
∗ cA 2 2
cA = = 1− √ e−ζ dζ
cA = cA0 c∗A (3.81c) cA0 π
0

and y
= 1 − erf - (3.90)
4 DAB z/umax
uz = umax u∗z (3.81d)
or
Equation (3.76) can be written as
cA y
= erfc - (3.91)
∂c∗A cA0 4 DAB z/umax
2 ∗2 1 1 ∂ 2 c∗A ∂ 2 c∗A
1−ε y = + (3.82)
∂z ∗ P eδ 2
ε ∂y ∗2 ∂z ∗2 where erf and erfc are the error and complemen-
tary error functions, respectively. For a contact
where film of length L and width W , the rate of mass
umax δ transfer (number of moles of A per unit time) to
P eδ ≡ (3.83) the film is given by
DAB
is the mass-transfer Péclet number. WA = (3.92)

If convection is important, the left-hand side L L
∂cA
of Equation (3.82) must be of the same order as NAy |y=0 W dz = −DAB W dz
∂y y=0
the largest diffusion term on the right-hand side 0 0
or, if Equation (3.91) is used, where ϕ ( y∗, z∗) is the cA solution from Equa-
1 tion (3.91). Using Equation (3.92) to determine
4 DAB umax
WA = L W cA0 (3.93) the total gas exchange over a surface of length L
πL and width W gives
If the mass-transfer coefficient kc is defined by
umax
WA = W cA0 -
WA = kc L W cA0 (3.94) k1 /DAB
1
1 √ q
then · + q erf q + · exp (−q) (3.102)
2 π
kc L 2 1/2 2 1/2
ShL ≡ = √ ReL Sc1/2 = √ P eL (3.95) where
DAB π π
where ShL is the Sherwood number, and ReL DaL
q ≡ (3.103)
and Sc are the Reynolds and Schmidt numbers, ReL Sc
respectively, which are defined by In terms of ShL ≡ kc L/DAB , this result can be
umax L ν written as
ReL ≡ , Sc ≡ (3.96)
ν DAB 1/2
ShL = ReL Sc1/2
Hence, for short penetration distances ε (or short
(1 + 2 q) √ 1
contact times or high Péclet numbers), the di- · √ erf q + √ exp (−q) (3.104)
2 q π
mensionless form of the mass-transfer coeffi-
cient (ShL ) varies as the square root of the prod- If q → 0 (no chemical reaction), this equation
uct of ReL and Sc. reduces to Equation (3.95); if q → ∞,
If the chemical reaction
1/2
ShL = DaL = (q ReL Sc)1/2 (3.105)
A+B →C (3.97)
In Figure 26, the results are given for a full
in the film is now considered and a sufficient ex- range of q values. As q increases (higher re-
cess of B is assumed so that a pseudo-firstorder action rates), mass transfer is significantly en-
reaction expression is valid, i.e., hanced (i.e., higher mass-transfer coefficients)
RA = k cA cB ≈ k cB0 cA = k1 cA (3.98) compared to the nonreacting case (q = 0). Many
scrubbers and other absorption processes utilize
the mass balance takes the form absorption with reaction to obtain the most ef-
∂c∗A ∂ 2 c∗A Daδ c∗A
ficient removal of dilute gases from bulk gas
∗
= ∗2
− (3.99) streams.
∂z ∂y Reδ Sc
LIVE GRAPH
where Daδ is the Damköhler number defined by Click here to view
k1 δ 2
Daδ ≡ (3.100)
DAB
Here again, in writing Equation (3.99), the pen-
etration distance is assumed to be small (i.e.,
Peδ ≡ Reδ Sc is large). Also, the boundary con-
ditions are assumed to be the same as given by
Equations (3.87) – (3.89).
The solution to this problem can be expressed
in terms of the solution for the nonreacting case
(Eq. 3.91) by [69, pp. 32 – 33]

cA Daδ ∗
c∗A = = ϕ ( y ∗ , z ∗ ) exp z
cA0 Reδ Sc
∗
z
Daδ Daδ Figure 26. Enhancement of mass transfer with chemical
+ ϕ ( y ∗ , ζ) exp ζ dζ (3.101) reaction in a falling liquid film
Reδ Sc Reδ Sc
0
3.2.2. Mass Transfer in Laminar and L

Turbulent Boundary Layers WA = kc (cA0 − cA∞ ) W dx
0
Consider the convective mass transfer of species = kcL W L (cA0 − cA∞ ) (3.111)
A from a flat or nearly flat surface into a free
stream of species B. Assume that concentration where
changes of A are restricted to a concentration
L
boundary layer of thickness δc . Conceptually, 1
kcL ≡ kc dx (3.112)
this is analogous to the problem illustrated in L
0
Figure 15, except that δc replaces δT , cA∞ re-
places T ∞ , and cA0 replaces T w . is the average mass-transfer coefficient over the
For this problem where cA = cA (x, y), the plate length L.
species mass balance takes the form These results are valid for the laminar part
of the boundary layer. In the turbulent part
∂cA ∂cA ∂ 2 cA (x ≥ x cr = 2×105 ν/u∞ ), the molar flux in the y-
ux + uy = DAB (3.106)
∂x ∂y ∂y 2 direction can be written as
where the x diffusion term [DAB (∂ 2 cA /∂x 2 )] dc̄A
has been neglected compared to the y diffusion N̄Ay = − (DAB + εc ) (3.113)
dy
term (right-hand side of above equation). This
equation is analogous to Equation (2.239) for where N̄ Ay and c̄A are time-smoothed quantities
heat transfer in thermal boundary layers and can and εc is the eddy mass diffusivity. If a Prandtl
be integrated over the boundary layer thickness mixing length expression is assumed for εc , then
to obtain dū
x
εc = εm = εT = ε = l2 (3.114)
δc dy
d
ux (cA − cA∞ ) dy = NAy |y=0 with the mixing length l given by Equation
dx
0 (2.299). Here again, as with energy transfer in
∂cA turbulent flow, DAB ε for the laminar sublayer
= −DAB (3.107)
∂y y=0 next to the wall, DAB ≈ ε in the buffer zone, and
The solution of this equation for δc (x) follows DAB ε in the turbulent core.
in the same way δT was obtained from the inte- Carrying out an analysis analogous to that of
gral form of the energy balance (Eq. 2.240). If a Section 2.5.4 gives the mass-transfer forms of
cubic expression is used for cA in terms of y and the various analogies:
the constants a, b, c, and d are evaluated with Reynolds analogy:
the boundary conditions Shx kc
= = CDx /2 (3.115)
Rex Sc u∞
at y = 0, cA = cA0 (3.108)
Prandtl analogy:
at y = δc , cA = cA∞ (3.109)
Shx CDx /2
= - (3.116)
∂nc Rex Sc 1 + 5 CDx /2 (Sc − 1)
A
at y = δc , = 0 , n = 1, 2, . . . (3.110)
∂y n Von Karman analogy:
the same results can be obtained as for Equations Shx
(2.250) and (2.251), with δc replacing δT , Sc ≡ Rex Sc
= (3.117)
ν/DAB replacing Pr, and Shx ≡ kc x/DAB re- CDx /2
placing Nux . The Blasius solutions (Eqs. 2.252 -
1+5 CDx /2 {Sc − 1 + ln [(1 + 5 Sc) /6]}
and 2.255) also have the same forms for the
mass-transfer results if the same replacements Further, the Colburn analogy can be written as
are made. The mass-transfer rate (number of
moles A per unit time) from the surface is then Shx kc CDx /2
= = (3.118)
Rex Sc u∞ Sc2/3
The last result is obtained directly from laminar 3.3. Mass Transfer Across Interfaces
boundary layer results; however, as noted in Sec-
tion 2.5.4 it can be used as a first approximation In the situations described in the preceding sec-
to the Reynolds analogy for turbulent transport at tions, the rate of mass transfer within a sin-
Schmidt numbers different from 1. All of these gle phase is calculated by using fundamental
analogies can be used for turbulent mass trans- transport relations (mass balances and diffusion
port in tubes if u∞ is replaced by uavg . flux relations) and transport properties (diffusiv-
Equation (3.118) can also be written as ities). Such calculations are possible for well-
defined geometries and flow situations of suffi-
CDx
jD = (3.118a) cient simplicity that can be modeled and calcu-
2
lated a priori and without empiricism.
where This not always the case, however, because a
great many more situations occur in which the
kc Sc2/3 flow of the fluid phases or a complex geometry
jD ≡ (3.118b)
2u∞ prevents exact modeling or calculation. An ex-
is the j factor for mass transfer. When this result ample is forced convection transfer across an in-
is combined with Equation (2.320 a) with C Dx terface. In this case, the situation is described by
replacing f, we obtain using mass-transfer coefficients instead of diffu-
sivities. These coefficients play a role similar to
CDx diffusivities in that they describe the transport
jD =jH = (3.118c)
2 rate of mass that occurs primarily because of
This result is called the Chilton – Colburn anal- molecular motion, but they also allow for other
ogy and connects the mass transfer, heat trans- effects such as the enhancement of mass transfer
fer, and momentum transfer processes in a given because of forced or natural convection. Once
flow geometry. Although Equation (3.118 c) is these coefficients have been determined experi-
obtained directly from analysis of transport on mentally for a number of flow and mass-trans-
laminar boundary layers, it can be used as an fer situations, and correlated by dimensionless
approximation for other geometries and for tur- groups, the coefficients for analogous situations
bulent flows as long as there is no form drag. If can be estimated and used for process design.
form drag is present, the first part of Equation The calculations are complicated, however,
(3.118 c), i.e., jD = jH , can still be used to relate by the dependence of mass-transfer coefficients
mass transfer coefficients to heat transfer coef- on mass flux. For example, in Section 3.1.6 the
ficients if 0.6 < Sc < 2500 and 0.6 < Pr < 100. diffusion of species A through a stagnant film
Finally, analogous to Equation (2.325), B was enhanced, above and beyond pure diffu-
sion, by the net bulk flow of the mixture. Simi-
4/5
Shx = 0.0289 Rex Sc1/3 (3.119) larly, mass-transfer coefficients that apply to low
mass-transfer rates are affected by the species
for mass transfer in turbulent boundary layers. mass fluxes and should be adjusted accordingly
Combining this with the mass-transfer equiva- for the most accurate design calculations at high
lent of Equation (2.252) for the laminar part of mass-transfer rates.
the boundary layer, i.e., Figure 27 shows how mass-transfer coeffi-
1/2 cients that are calculated for low mass-transfer
Shx = 0.332 Rex Sc1/3 (3.120)
rates by using diffusion coefficients or dimen-
yields sionless group correlations can be adjusted for
high mass-transfer rates. Then the coefficients
4/5 −4/5
ShL = 0.0361 ReL Sc1/3 1 − 9170 ReL for mass transfer through films on both sides
(3.121) of an interface can be combined (a process re-
quiring thermodynamic equilibrium between the
for the overall mass-transfer coefficient relation two phases) to give an overall coefficient for
over a plate of length L where L ≥ x cr . Equation transfer between phases.
(3.121) is the mass-transfer equivalent of Equa-
tion (2.328).
Figure 27. Representation of the calculation of overall mass-transfer coefficients showing corrections of the single-phase
coefficients for high mass-transfer rates
The commonly used definitions of mass- transfer. Uniformity of composition is the equi-
transfer coefficients for each side of an inter- librium state in a single phase; if mole fractions
face and for the overall coefficients calculated are not uniform, then a nonequilibrium condi-
from them are given in Section 3.3.1; their function exists and diffusion occurs until uniformity
tional forms based upon theoretical considera- is reached. Two-phase thermodynamic equilib-
tions for low mass-transfer rates or equimolar rium is the equilibrium state across an interface;
counterdiffusion are presented in Section 3.3.2; to the extent that the two phases on opposite sides
and correlations for calculating mass-transfer of an interface are not in equilibrium, mass trans-
coefficients for low mass-transfer rates and the fer tends to occur in such a way as to move the
adjustments that may be made for high mass- system toward equilibrium.
transfer rates are considered in Sections 3.3.3 The degree of departure from equilibrium di-
and 3.3.4, respectively. General references pro- rectly affects the rate of mass transfer. In a single
viding more detailed discussion of mass-transfer phase, the degree of departure from equilibrium
coefficient definitions and calculations include is represented by the mole fraction (or mass frac-
texts in the areas of transport phenomena [63], tion) gradient, and Fick’s first law of diffusion
[74] and chemical engineering unit operations (the most commonly used flux relation) models
[75–79]. the diffusion flux as proportional to this driv-
ing force. The proportionality factor defines the
diffusivity.
3.3.1. Mass-Transfer Coefficients For mass transfer across interfaces or films,
an analogous relationship is normally used to de-
Mass transfer occurs because of an imbalance fine mass-transfer coefficients. The mass-trans-
of concentrations, a departure from equilibrium. fer flux of a species at an interface is modeled
This imbalance provides a driving force for mass as proportional to the driving force (concentra-
tion difference) which exists for that transfer, Likewise, the defining relation for the gas-phase
through a thin film next to the interface. This mass-transfer coefficient for species A based on
situation is depicted in Figure 28. At the inter- the gas-phase mole fractions is
face the two phases are normally assumed to
be in thermodynamic equilibrium. Away from Flux of A = ky ( yAb − yAi ) (3.123)
the interface, however, the bulk concentrations
of the two phases are not necessarily at equi- In each of these equations, a departure from
librium with each other, and possible concen- equilibrium exists that represents the extent to
tration or mole fraction profiles are shown as a which the interface mole fraction (x Ai or yAi )
function of distance from the interface. The ma- differs from that in the bulk fluid (x Ab or yAb )
jority of the concentration change is modeled to of the same phase.
occur over a laminar film region near the inter- Whereas the above relations define mass-
face. The actual concentrations and film depths transfer coefficients for a driving force within
are not known, however, which makes the defi- a single phase at an interface, interphase mass-
nitions quite empirical and dependent on param- transfer coefficients are also defined according
eters such as fluid flow and turbulence. In Fig- to concentration or mole fraction differences that
ure 28, concentration profiles are shown in both exist across the two phases, where the average or
phases and, for simplicity, one phase is called a bulk concentrations are used for each phase. In
gas phase and the other a liquid phase, although this case the mass-transfer coefficients Kx and
this is not a limitation or constraint on the sit- Ky are defined according to the relations
uation. The discussion could just as well be for
Flux of A = Kx (xAe − xAb ) (3.124)
two liquid phases or for a fluid and a solid phase.
The model also normally assumes that concen-
trations at the interface are at steady state; flux Flux of A = Ky ( yAb − yAe ) (3.125)
to the interface through one phase equals that and are called overall mass-transfer coefficients.
away from the interface through the other. They describe the flux in terms of mole fractions
in the bulk phases.
Here, instead of defining a driving force that
exists within one phase or the other, a driving
force that spans the two phases is defined. The
mole fractions and driving forces are shown rel-
ative to a typical interfacial equilibrium curve in
Figure 29. For a mass-transfer coefficient based
on liquid-phase mole fractions, the driving force
that is used is the difference between the actual
mole fraction of A in the bulk liquid phase (x Ab )
Figure 28. Hypothetical concentration profiles across the
and the mole fraction of A that would exist (x Ae )
gas – liquid interface region with the transfer of A from the if the liquid phase were in equilibrium with the
gas to the liquid mole fraction of A in the bulk gas phase. Like-
yAb = mole fraction of A in bulk gas phase; yAi = gas-phase wise, in terms of gas-phase concentrations, mass
mole fraction of A at interface; x Ai = liquid-phase mole frac- transfer of A occurs to the extent that the bulk
tion of A at interface; x Ab = mole fraction of A in bulk liquid
phase gas-phase mole fraction ( yAb ) differs from the
value that would exist ( yAe ) if the gas phase were
Mass-transfer coefficients, then, are defined in equilibrium with the actual bulk liquid-phase
for each of the two phases. The definition of a mole fraction.
liquid-phase mass-transfer coefficient (based on
a liquid-phase mole fraction driving force) is
Flux of A = kx (xAi − xAb ) (3.122)

Next Page
and
1 1 m
= + (3.130)
Ky ky kx
Hence, the overall or combined resistance to

mass transfer through the two phases (1/Kx or
1/Ky ) is equal to the sum of the resistances
through each of the phases individually. Be-
fore summing, however, one of the individual
phase coefficients must be scaled by using the
(local) slope of the equilibrium curve in order
to be consistent with the resistance offered by
the other mass-transfer coefficient. Note that if
kx /m ky , then the gas-phase mass transfer is
limiting and Ky ≈ ky .
Dimensions of Mass-Transfer Coefficients.
Figure 29. Relationships among interface, bulk, and equi-
Because the flux of A is the number of moles of
librium concentrations used in mass-transfer rate equations A per time per (cross-sectional) area, the mass-
transfer coefficients as defined by these relations
The slopes of lines that represent the ratios must also have the dimensions of number of
of mass-transfer coefficients are also shown in moles per time per area. Other definitions us-
Figure 29. If species A does not accumulate at ing different driving force concentration units
the interface, the liquid- and gas-phase relation- are employed, however, and the dimensions of
ships for flux in terms of mass-transfer coeffi- the mass-transfer coefficient vary accordingly.
cients must be equal. Accordingly, For example, number of moles per volume is fre-
quently used for liquid-phase concentrations and
kx (xAi − xAb ) = ky ( yAb − yAi ) (3.126) partial pressure for gas-phase concentration. In
which gives these situations, mass-transfer coefficients may
be defined according to
ky xAb − xAi
− = (3.127)
kx yAb − yAi Flux of A = kc (cAi − cAb ) (3.131)
and the ratio of the interphase mass-transfer co-
efficients is the slope of a tieline connecting the Flux of A = kG ( pAb − pAi ) (3.132)
point with composition coordinates equal to the
liquid- and gas-phase bulk concentrations to a Flux of A = Kc (cAe − cAb ) (3.133)
point with coordinates equal to the equilibrium
interface liquid- and gas-phase concentrations. Flux of A = KG ( pAb − pAe ) (3.134)
Similarly, a ratio can be obtained for the overall
transfer coefficients: Here, k c and K c have the dimensions of volume
per time per area (length per time), and k G and
Kx yAb − yAe K G have the dimension of number of moles per
= (3.128)
Ky xAe − xAb time per area per unit pressure.
In the limit of small driving forces or for a linear
isotherm this ratio is the slope m of a tangent to
the equilibrium curve in the concentration region 3.3.2. Functional Forms of Mass-Transfer
of interest. Coefficient Relations
From the definition of the mass-transfer
coefficients and for a locally linear isotherm In the preceding discussion, the mass flux
(slope = m), through a film is assumed to be proportional
1 1 1
= + (3.129)
Kx kx m ky
Previous Page
to the driving force (the concentration differ- and its adaptations [82], [83]. The penetration
ence) across a film, and this proportionality fac- theory is applicable to a species that is being
tor defines the mass-transfer coefficient. Com- transferred from a gas to a liquid phase; it gives
bining this definition with theoretical models an estimate of the mass-transfer coefficient in
for mass transfer in terms of diffusion coeffi- the liquid phase based upon a nonsteady-state
cients allows calculation of the dependence of situation. The liquid phase is assumed to be a
mass-transfer coefficients on diffusivity. These falling film and the velocity profile of the falling
are only estimates, however, because the situa- film at the gas – liquid interface is essentially flat,
tions are too complex for exact modeling, which i.e., the velocity of the falling liquid is nearly
is why mass-transfer coefficients were defined in independent of penetration depth from the gas
the first place. A complete discussion of several into the liquid as long as the penetration depth
models appears in [75]. is low. This is true if the time that the gas is in
contact with the liquid is short. In this situation,
Two-Film Theory. A particularly simple but any one packet of fluid is in contact with the
useful model for steady-state transfer between gas for a fixed amount of exposure time; there-
two phases, which is frequently used to describe fore, the diffusion of a species from the gas to
mass-transfer coefficients in terms of diffusion the liquid – from the viewpoint of this packet of
coefficients, is the two-film theory of Whitman fluid – is a nonsteady-state process as opposed to
[80]. The concentration profile is taken to be flat the steady-state diffusion of the film theory. This
(independent of position) in the bulk fluid and different type of model gives rise to a mass-trans-
then to vary linearly across a thin film of thick- fer coefficient that is proportional to the square
ness δ up to the interface (Fig. 30). For steady- root of diffusivity:
state mass transfer at low mass-transfer rates the !
results of this model are the same as for equimo- DAB
kx = 2 c (3.136)
lar counterdiffusion (see Section 3.1.6); the mo- π texp
lar flux is directly proportional to the diffusivity,
and the mass-transfer coefficient, in terms of film Here, t exp is the exposure time of a given packet
thickness and diffusivity, is or element of fluid to the gas stream and kx is an
c DAb
average value over this time. Exposure time can
kx = (3.135) be calculated in terms of the fluid velocity at the
δ
gas film interface and the distance of contact of
Hence, this film theory predicts a mass-transfer
the gas and liquid L:
coefficient that is directly proportional to diffu-
sivity through the film. L
texp = (3.137)
uinterface
A third theory, actually a combination of both, is

the film-penetration theory [84]. For some flow
situations, the film theory result is recovered,
whereas for others, the penetration theory’s D1/2
dependence holds, suggesting that different de-
pendencies might be expected in different flow
situations.
3.3.3. Relations for Low Mass-Transfer

Rates
Figure 30. Simplified concentration profiles for the two-
film theory
By using a somewhat different approach, dimen-
sionless group correlations can be postulated to
Other Theories. Other theories relating the exist for mass-transfer coefficients. For exam-
coefficient to diffusion may also be appropri- ple, the Sherwood number (ShAB = kx d/c DAB )
ate. Examples are the penetration theory [81]
can be expressed in terms of a function of the species is obtained as for the equimolar coun-
Reynolds number (Re = d u /η), Schmidt num- terdiffusion situation but for a different reason.
ber (Sc = η/ DAB ), and L/d [63]: The other species is still stagnant, and the bulk
flow is not reduced by the low concentration but
ShAB = f (Re, Sc, L /d) (3.138) rather by transport of the nonstagnant species
that occurs because of reduced bulk flow.
The specific functional form depends on the ac- These two limiting cases (ECD and ATSB)
tual flow situation. provide a basis for understanding the corrections
Furthermore, as discussed in Section 3.2, to mass-transfer coefficients that are made for
analogous correlations exist for heat, mass, and high mass-transfer rates. The mass-transfer co-
momentum transfer because of similarities in the efficients described in the correlations of Table 8
conservation equations that govern all these sit- are defined for equimolar counterdiffusion-like
uations and in the corresponding flux relations. situations; that is, they apply to true equimo-
Consequently, correlations exist for mass-trans- lar counterdiffusion situations or to low transfer
fer coefficients that are very similar to those rate calculations. Evidently, then, if they are to
for heat or momentum transfer (friction loss) be used for ATSB situations, they must be cor-
in analogous situations of geometry and bound- rected in a way similar to the comparison bet-
ary conditions. Results for some specific flow ween equimolar counterdiffusion and ATSB cal-
and mass-transfer situations are summarized in culations; the presence of a stagnant film and
Table 8. Note that in these relations, the depen- high mass-transfer rates provides an induced
dence of the mass-transfer coefficient on diffu- bulk flow that enhances the mass-transfer co-
sivity ranges from about D0.6AB to DAB , corre- efficient. If the low mass-transfer coefficient is
sponding to the D0.5
AB to D AB predicted by the used in a high mass-transfer stagnant film situa-
penetration and film theories, respectively. tion, the mass-transfer rates may be significantly
underestimated.
A common correction to the low mass-trans-
3.3.4. Relations for High Mass-Transfer fer rate – ECD coefficients is to introduce a drift
Rates factor (1 − yA )L analogous to the adjustment of
ECD to ATSB. A common, although not unique,
In Section 3.1.6, two important limiting cases notation is to distinguish between these two
of binary diffusion are considered for a one- mass-transfer coefficients with a prime ( ); how-
dimensional diffusion process. In the case of ever, the notation may be switched with k indi-
equimolar counterdiffusion the flux of each cating ECD rather than ATSB as is done here:
species is the result of diffusion only and is cal-
culated by using Fick’s first law of diffusion; for ky
ky = (3.139)
each species the flux is directly proportional to (1 − yA )L
the mole fraction gradient of that species. For the
case of one species diffusing through a stagnant where (1 − yAi )L is the nonlinear, log-mean av-
film of the other, however, the diffusion of each erage of (1 − yAi ) and (1 − yAb ):
species is the result of the combination of Fick’s (1 − yAi ) − (1 − yAb )
law of diffusion and a bulk flow that is induced (1 − yA )L = (1 − yAi )
(3.140)
ln (1 − yA )
by the diffusion process. For the species that was
defined to be stagnant, the diffusion flux exactly This correction is commonly used for ATSB-
balances its flux due to the mixture bulk flow. like situations and appears in design calculations
For the other species, however, the total flux is such as packed gas-absorption towers where one
that due to Fick’s law of diffusion enhanced by species in the gas phase is absorbed and the oth-
the bulk flow, which results in the Fick’s law flux ers are not.
being divided by (1 − x A ). Instead of a simple ATSB correction to the
In the latter case, if the nonstagnant species mass-transfer coefficient, however, less restric-
is present at low molar concentration (infinite tive theories for flux ratios may be used to make
dilution or approaching infinite dilution), then the adjustment. These are (1) the film theory,
obviously the same result for the flux of this (2) the penetration theory, and (3) the boundary
Table 8. Mass-transfer coefficients a
layer theory. Each of these theories provides a The conservation and accounting equations
means of calculating a correction factor to the and their development are summarized below
mass-transfer coefficient. for compositionally homogeneous systems. The
The situation of ATSB diffusion is actually a purpose is to provide an overall picture relating
specific limiting case of the more complete film conservation laws, accounting equations, U, H,
theory summarized by Bird et al. [63]. They A, G, and second law equations of thermody-
use the film theory to adjust EDC mass-transfer namics, which provide the basics for quantita-
coefficients for the enhancements which result tively understanding transport phenomena (and
from diffusion-induced bulk flow. The model al- other areas of engineering as well) on a macro-
lows for relative fluxes of the two species (A scopic scale, rather than to give handbook-type
and B) that differ from the stagnant B situa- details and examples. General references offer-
tion. For a given flux ratio, adjustments to the ing further discussion of the development and
low mass-transfer rate coefficient can be calcu- application of macroscopic equations include
lated (or, equivalently, the ECD mass-transfer texts in the areas of transport phenomena [98–
coefficient), which would be calculated or esti- 100], thermodynamics [101], [102], chemical
mated from the correlations of the previous sec- engineering unit operations [103], and fluid me-
tion. Again, ATSB situation falls within this less chanics [104].
restrictive film theory.
The penetration theory of Higbie [81] has
also been used to extend the low mass-trans- 4.1. Conservation of Total Mass
fer rate calculations to high mass-transfer rates
Total mass is conserved in the absence of nuclear
due to diffusion-induced enhancement. The re-
conversions or relativistic effects. This means
sults obtained are presented in a similar way to
that for the system and its surroundings together
those for the film theory, and correction factors
the total amount of mass is a constant. Equiv-
are given for a boundary layer theory approach
alently, if the amount of mass contained within
[63]. Qualitatively, the corrections calculated by
the system changes, then the surroundings must
these three theories are very similar although the
change to an equal but opposite extent; there is a
quantitative results are somewhat different. The
one-for-one exchange of mass between the sys-
penetration and boundary layer theories predict
tem and its surroundings as mass moves across
an even larger effect of mass transfer on the co-
the system boundary. Allowing for multiple flow
efficients than does the film theory.
streams into and out of the system, an equa-
tion for the conservation of total mass contained
within the system is
4. Macroscopic Systems
( uavg A)in −
entering streams
The development of conservation and account-
ing equations for macroscopic systems parallels
the development of those for differential systems ( uavg A)out
exiting streams
that led to the partial differential equations of
d
Table 1. Each law or statement is written for a = ( V )system (4.1)
dt
single extensive property (a property that can
be counted, for which the whole is equal to the At each area A where mass exchanges occur
sum of the parts) for a specified region (sys- between the system and surroundings, the fluid
tem) inside a closed-surface boundary and for density and velocity components normal to the
a specified time period (either finite or differen- boundary surface u are appropriately averaged
tial) (Fig. 31). In the case of macroscopic (finite- values. Likewise, the density of the system is
size) systems, either process rate equations are averaged over the system volume V system [98],
obtained, which are ordinary differential equa- [100], [105].
tions, or for a finite time period, an algebraic In addition to a conservation equation for to-
equation is obtained. For conserved properties, tal mass, accounting statements for individual
the generation (or consumption) is always zero. species within the system can be written. If the
system contains n species that together comprise
Figure 31. The concept of accounting for an extensive property – the cornerstone of transport phenomena
Input and output represent an exact exchange with the surroundings; a conserved property has no generation or consumption
term.
the total mass (and could be molecular, ionic, or cause total mass is conserved, the sum of all of
other species), then n accounting equations ex- the generation and consumption terms in the n
ist, one for each species. Because species are species equations must be zero; no net genera-
not necessarily conserved (except for the chem- tion or consumption of mass occurs). Note that
ical elements), these accounting equations must the total mass of each species entering and leav-
allow for any generation or consumption of indi- ing the system is obtained by summing over all
vidual species through chemical reactions. Ac- entering and leaving streams.
cordingly, for each of the n species within the
system,
4.2. Conservation of Linear Momentum
(i uavg,i A)in −
entering streams
Linear momentum is conserved. Given a sys-
tem, the amount of linear momentum contained
(i uavg,i A)out + ri Vsys therein may change only as a result of exchange
exiting streams
of momentum between the system and its sur-
d
= (i V )system (4.2) roundings; linear momentum is not generated
dt
or consumed. Linear momentum may be ex-
The densities and velocities are average values, changed as the result of mass entering or leav-
as discussed above, and ri is an average gen- ing the system and as the result of forces acting
eration rate of species i per unit volume of the on the system by its surroundings. The rate of
system. An equivalent accounting can be done momentum exchange as mass enters or leaves
in molar concentration units (see, e.g., Section the system is the momentum per unit mass u
4.9.3). multiplied by the rate at which that mass enters
Of these n + 1 equations, however, only n are or leaves the system. External forces act upon
independent inasmuch as the total mass must the system either by contact with the system’s
be the sum of the individual species mass (be- surfaces or as body forces, such as gravity, that
act individually on each piece of mass within where Lsystem is the total angular momentum
the system. The momentum of the system then of the system. Again, the entering and leaving
changes according to momenta are actually appropriate integral aver-

ages across the flow cross section, and Lsystem
u2 avg is integrated over the entire volume.
uavg A −
uavg
in
The conservation of angular momentum is
2
not considered further here. It is useful, for ex-
u avg
uavg A ample, for the analysis of torques on pumps and
uavg
out compressors for design purposes [100].
dpsystem
+ F external = (4.3)
dt
The (u2 )avg term arises because the momentum 4.4. An Accounting of Mechanical
flow rate, calculated as the momentum per unit Energy
mass u times the mass flow rate u dA, is in-
tegrated (averaged) over the cross section [98, Mechanical energy accounting can be made for
Chap. 7], [99, Chap. 7]. If the velocity profile finite-sized systems and can be obtained by inte-
across the area is not flat, then (u2 )avg = (uavg )2 . grating the continuum conservation law of linear
If αmom ≡ (uavg )2 /(u2 )avg , where αmom is a momentum. It cannot be obtained from a macro-
measure of the extent to which the velocity pro- scopic linear momentum law and consequently
file is not flat, this equation becomes is an independent equation providing additional
insight into flow situations. In this sense, the set

(uavg )2 (uavg )2 of macroscopic equations differs from the con-

A − A tinuum equations.
αmom αmom
in out
The mechanical energy equation is an ac-
dpsystem
+ F external = (4.4) counting equation, as opposed to a conserva-
dt
tion equation, because mechanical energy is not
For fully developed laminar flow of a Newtonian conserved. Conversion of mechanical energy to
fluid, αmom is 3/4; for turbulent flow, it is nearly thermal or other forms of energy may occur so
unity [106, p. 252]. Also psystem is integrated that the amount of mechanical energy in an iso-
over the entire macroscopic system. lated system is not necessarily constant. Never-
theless, such an accounting is extremely useful
for certain problems, e.g., the design and sizing
4.3. Conservation of Angular of piping systems and flow networks.
Momentum Derivation of the mechanical energy account-
ing equation is complex and lengthy [107]. The
Angular momentum is also a conserved prop- result is stated here for steady-state flow situa-
erty. The angular momentum of a system can tions with one entrance and one exit. Mechanical
change only by exchange with its surroundings. energy is accounted for by the following steady-
A piece of mass possesses angular momentum state equation (expressed as energy per unit mass
that is equal to the cross product of the posi- of flow; the symbolôver a quantity implies “per
tion vector of that piece of mass and its momen- unit mass”):
tum. Consequently, angular momentum enters
1 (u1,avg )2 (u2,avg )2
and leaves with mass. Also, angular momentum g (z1 − z2 ) + − −
2 αKE,1 αKE,2
enters the system as a result of external forces
2
and is equal to the cross product of the position
dp
vector to the point of application of the force + Ŵs + Ŵes − F̂ = 0 (4.6)

with that force: 1
Here αKE ≡ (uavg )3 /(u3 )avg is another measure

r in ×uin ( uavg A)in − r out ×uout ( uavg A)out

of the flatness of the velocity profile, this time
dLsystem
+ (r × F ext ) = (4.5) with respect to kinetic energy. For fully devel-
dt
oped laminar flow of a Newtonian fluid, αKE
is 1/2; for turbulent flow it is nearly unity [106, Heat Q and work W exist at the system bound-
p. 252]. This result holds regardless of heat trans- ary but are not energy possessed by mass. Heat
fer or other thermal effects that may occur. enters the system by either conduction or radia-
Equation (4.6) is referred to as the ex- tion because of a temperature difference across
tended Bernoulli equation (→ Fluid Mechanics, the system boundary. Work is energy transferred
Chap. 3.5.) and through F̂ allows for the irre- when a force acts through a distance upon ele-
versible or dissipative conversion of mechanical ments of the system at the boundary. More prop-
energy to thermal energy in a manner analogous erly, work may be expressed as
to that of Equation (1.80), the mechanical en-
ergy equation for a continuum. These losses are s2
W = F ·ds (4.8)
of the type encountered in flow through pipes
s1
where friction losses result in pressure drop in
a straight run of horizontal pipe. The potential The dot product of the force F with the displace-
energy gz and kinetic energy u2 /2 αKE terms are ment ds provides that the component of force
evaluated (as averages over the cross section) at in the direction of displacement produces work,
the entrance (1) and exit (2) points of the sys- whereas that which is normal to the displace-
tem. The shaft work Ŵ s and the flow work due ment does not. The convention here is that both
to the fluid extra stresses Ŵ es act across the sys- heat and work are positive when energy is added
tem boundary, whereas the friction losses occur to the system.
both within the system (from viscous stresses With energy existing within the system as ki-
inside the pipe) and across the system bound- netic, potential, and internal energy, the conser-
ary (from viscous stresses at the pipe wall). The vation of total energy for a macroscopic system
pressure term dp/ must be integrated along a is expressed in rate forms as
path through the process from the entrance to
the exit, not necessarily an easy task for a com- u2

Û + + g z ( uavg A)
pressible flow. If the flow is incompressible, then 2 αKE in
the extended Bernoulli equation becomes u2

− Û + + g z ( uavg A)
2 αKE
1 (u1,avg )2 (u2,avg )2 out
g (z1 − z2 ) + − d . < P <
/
2 αKE,1 αKE,2 + Ẇ + Q̇ = Û + KE+ E m
dt sys
(p1 − p2 )
+ + Ŵs + Ŵes − F̂ = 0 (4.7) The dots over W and Q imply work rate and heat-

for which the pressure terms also use entrance transfer rate, respectively, rather than a deriva-
and exit values only. Mechanical energy in the tive rate of change of work or heat. Again, prop-
form of (1) upstream kinetic energy, (2) poten- erties of the mass entering and leaving the sys-
tial energy, (3) isotropic and extra stress flow tem are averaged over the flow cross section.
work, and (4) shaft work is either redistributed Usually, the form of the equation is changed
downstream among these forms of mechanical by separating the work required to move mass
energy, converted to work, or lost as mechanical into and out of the system against the pressure
energy by conversion to thermal energy. (isotropic stress) at the boundary (expressed per
unit mass p/) from all other work of the process,
the “nonpressure” work Ẇ np . (The term p/ is
4.5. Conservation of Total Energy commonly referred to as “flow work”. However,
because it represents only the flow work due to
Total energy is conserved. Mass possesses en- isotropic stress and does not include that due
ergy in the form of kinetic, potential, and inter- to extra stress, it is referred here to as pres-
nal energy. When mass enters a system, it brings sure work and all other forms as “nonpressure”
with it energy in these forms, and the rate at work.) The statement is rewritten by combining
which it does so is calculated as the product of the p/ terms with the other inlet and outlet flow
the specific energy in each of these forms (i.e., stream terms and replacing the total work term
the energy per unit mass) and the rate of mass with Ẇ np . The p/ terms are combined with the
flow into the system.
internal energy to give the enthalpy of the flow as thermal energy accounting equations, ex-
streams (Ĥ ≡ Û + p/) and the resulting equa- pressed in terms of thermodynamic state func-
tion is tions rather than the path functions Q̂ and F̂
of Equation (4.11). On the one hand, they re-
u2
Ĥ+ + g z ( uavg A) present relations between thermodynamic state
2 αKE in variables regardless of the path or process used
u2

− Ĥ + + g z ( uavg A) to bring about change; on the other hand, they re-
2 αKE out present thermal energy conversion for a specific
d . < <
/
process.
+ Ẇnp + Q̇ = Û + KE+ P E m (4.10)
dt sys Both statements have intrinsic value in their
The “nonpressure” work includes work associ- own right. Given a change in enthalpy that oc-
ated with volume changes of the system acting curs in a process and is calculated from such
against external forces (a nonsteady-state term), a thermal energy equation, the thermodynamic
all shaft work (compressors, pumps, turbines, relations can be used to express this change in
electric motors or generators, etc.), other forms terms of changes in observable properties such
of energy (electrical, magnetic, etc.), plus – if as heat capacity, temperature, pressure, and vol-
important – any flow work due to extra (non- ume. Hougen et al. [101, p. 508] recognize this
isotropic) stresses at the system boundaries. The separation of mechanical and thermal energy,
last term is frequently neglected. and say that these state functions of a body do not
depend upon “its external position or motion rel-
ative to other bodies.” This result is considered
4.6. An Accounting of Thermal Energy further in Section 4.9.1.
The approach outlined in Sections 4.2, 4.3,
By subtracting the steady-state mechanical en- 4.4, 4.5, and 4.6 for deriving the macro-
ergy equation for one inlet (point 1) and one scopic momentum, mechanical energy, total en-
outlet ( point 2) flow stream (Eq. 4.6) from the ergy, and thermal energy equations is not the
corresponding result for total energy conserva- most common. More frequently, the extended
tion (Eq. 4.10), an accounting of thermal energy Bernoulli equation is hypothesized by consid-
per unit mass is obtained which, although not ering total energy for adiabatic, incompressible
independent from the total and mechanical en- situations or by applying the thermodynamic
ergy equations, can be a useful way of viewing realtions for dÛ or dĤ (e.g., in the form of
thermal effects: Eq. 4.11) to total energy (Eq. 4.10) to obtain
p2 Equation (4.6) or (4.7). The approach given here
dp is preferred because it is more direct and par-
Ĥ2 − Ĥ1 = + Q̂ + F̂ (4.11)
allels the traditional approach used in continua
p1
(Chap. 1). This preference has also been ex-
This result is true regardless of any changes in pressed by Whitaker [105].
elevation, pressure, density, or flow velocity or
the amount of shaft work, as long as a steady
state exists through a single conduit. Further- 4.7. The Second Law of
more, for a reversible situation (F̂ = 0), this re-
sult is readily identified as the thermodynamic Thermodynamics
relation dĤ = T dŜ + dp/, which is integrated to
follow an element of the fluid through the pro- The second law of thermodynamics places con-
cess along the flow path in a sequence of quasi- straints on processes that can occur in macro-
equilibrium steps. For irreversible processes this scopic systems. As discussed for continua, the
thermodynamic relation still holds, but Q̂ and F̂ thermodynamic property of entropy quantifies
together correspond to the integral of T dŜ; both the fact that certain processes are observed to
heat transfer to the system and irreversibilities occur in only one direction. In the context of a
result in an increase in entropy (see Section 4.7). macroscopic law, the entropy contained within a
These thermodynamic relations for dÛ (and, macroscopic system changes through exchange
equivalently, for dĤ, dÂ, and dĜ) may be viewed
with the surroundings and also through genera- Heat transfer is also a one-for-one-exchange
tion within the system as a result of irreversibil- between the system and its surroundings, pro-
ities. On the one hand, accounting for entropy vided the temperatures of the system and the sur-
is similar to accounting for other nonconserved roundings at the boundary (T system, bound and
properties because the entropy of the system T surr, bound , respectively) are the same, this is
may change as a result of generation within the normally the case (however, see the next para-
system, as well as exchange with the surround- graph concerning entropy generation). In this
ings. Unlike other accounting statements (e.g., case, the rate of entropy added to the system
mechanical energy, electrical energy, individual (Ṡ in, system ) due to a rate of heat transfer from
chemical species), however, entropy cannot be the surroundings to the system Q̇ is
consumed within the system; it can only be gen-
Q̇
erated. Also, unlike other accounting relations, Ṡin, system = (4.15)
Tsystem, bound
an independent relation exists for the surround-
ings; the change in entropy of the surroundings and the rate of entropy transfer to the surround-
due to this process arises because of exchange ings (Ṡ in, surr ) due to the same heat transfer is
with the system and also as a result of genera-
Q̇
tion of entropy within the surroundings due to Ṡin, surr = − (4.16)
Tsurr, bound
the process. Again, this generation of entropy
must be positive; it can never be negative. Con- If the temperatures of the system and surround-
sequently, when the two entropy accounting ex- ings at the boundary are the same, then these
pressions for the system and surroundings are two terms cancel exactly and a true exchange
summed, the total entropy change of the system of entropy occurs between the system and sur-
plus surroundings is necessarily positive (or, in roundings.
the limit of a reversible process, equal to zero). The generation of entropy in the system and
These statements are embodied in an ac- surroundings is frequently difficult or impossi-
counting of entropy for a macroscopic system ble to quantify (although not always) but con-
. / . / ceptually is the result of finite driving forces
Ŝ uavg A − Ŝ uavg A for mass, energy, or momentum transfer. Conse-
in out
quently, if temperature, mole fraction, or veloc-
Q̇
+ + Ṡgen ity gradients within the system or surroundings
T system
system are dissipated as a result of heat, mass, or mo-
. /
=
d
Ŝ m (4.12)
mentum transfer within the system, then these
dt system dissipation processes cause a movement toward
and its surroundings a homogeneous condition which necessarily re-
sults in an increase in entropy. Likewise, if heat
. / . /
Ŝ uavg A − Ŝ uavg A or momentum transfer at the system boundary

out in results from finite differences in temperature or
Q̇
+ + Ṡgen
forces, then an entropy increase is associated
T
surr
surr with the heat or momentum transfer due to sub-
d . / sequent temperature or momentum equilibria-
= Ŝ m (4.13) tion within the system and surroundings. For the
dt surr
system and surroundings of homogeneous but
and for the system and surroundings combined different temperatures (T system and T surr ), the

d net total increase in entropy of the universe re-
Ŝ m + Ŝ m ≥0 (4.14) sulting from the two-step heat transfer and sub-
dt system surr
sequent equilibration process is calculated ac-
In these equations, the exchange of entropy cording to
between the system and surroundings is the re-
Q Q
sult of mass ( possessing entropy per unit mass) − ≥0 (4.17)
Tsystem Tsurr
transferring between the system and surround-
ings (values of Ŝ are averaged over the flow cross as though a single-step process of transfer
section). to the system (whose boundary temperature
is T system ) and from the surroundings (with flow from one location to another at a given de-
boundary temperature T surr ) has occurred. sign flow rate. This requires either sufficient up-
Again, because entropy is not conserved, an stream kinetic, potential, and pressure energy or
accounting of entropy for either the system or the addition of energy through a pump. Calcu-
the surroundings alone is not an adequate state- lation of the required upstream energy or pump
ment of the second law of thermodynamics. Fur- work is done by accounting for mechanical en-
thermore, the entropy of a material is a func- ergy through the extended Bernoulli equation
tion of state and consequently can be calculated (Eq. 4.6 for a compressible fluid and Eq. 4.7 for
(with respect to an arbitrarily defined reference an incompressible fluid). For example, to move
value) in terms of heat capacities, equations of water to an elevated storage tank, a pump must
state, and energy changes associated with phase be supplied to overcome the change in potential
changes. Consequently, the entropy exchange energy and any frictional losses of mechanical
associated with mass crossing the system bound- energy due to the flow of water through the pipe.
ary is well defined, and the change of entropy of Kinetic energy changes may also be a factor, al-
the system, given its composition and change in though these are usually relatively small.
state, is also well defined. As mentioned pre- One of the primary factors in such flow cal-
viously, however, the generation of entropy as a culations is determining this mechanical energy
result of irreversibilities is not always as well de- loss term. This is not a calculation that can be
fined. In some cases, such as the diffusive mixing made solely on theoretical grounds. Instead, it
of two ideal gases at equal pressure and tempera- is handled through a dimensionless group cor-
ture, the entropy increase can be calculated from relation for a friction factor f from which the
theoretical considerations. In other cases, how- mechanical energy losses for flow at average ve-
ever, such as the rapid expansion of a gas against locity uavg through a straight section of horizon-
an external force, the entropy increase due to ir- tal pipe of length L and diameter D are calculated
reversibilities cannot be calculated because the according to
expansion is associated with a turbulent velocity
profile that is unpredictable and, because of ve- L u2avg
F̂ = 4 f (4.18)
locity gradients, ultimately results in an increase D 2
in entropy.
The dimensionless group correlation typically
appears in graphic form (the original chart of
4.8. Tabular Summary of the Moody [108] or its modifications) or in analyti-
cal form, convenient for computer use (given by
Macroscopic Equations
Churchill [109]). [Alternative definitions for
The macroscopic equations given in Sections the friction factor in the literature differ from
4.1, 4.2, 4.3, 4.4, 4.5, 4.6, and 4.7 are summa- each other by a factor of 2 or 4. Care must
rized in Table 9. Also given are the number of in- be taken that the dimensionless group correla-
dependent scalar equations that are represented tion for f versus Re and the friction factor def-
in each case and any limitations on the result. inition (e.g., Eq. 4.18) employed are consistent
with each other.]
The friction factor depends on the Reynolds
4.9. Some Examples number of the flow through the pipe and, for
turbulent flow, the roughness of the wall. Addi-
4.9.1. Pressure Drops and Temperature tional losses occur in valves, fittings, and pipe
Changes for Closed Channel Flow bends; relations for calculating these losses also
are found in standard texts on fluid flow.
Perhaps the most basic problem of macroscopic The effect of mechanical energy losses on
fluid mechanics is to calculate the pressure drop the temperature of the fluid is normally quite
or pump requirement (or turbine output) asso- small for liquids, although in some instances it
ciated with fluid flow through a pipe, tube, or may have to be taken into account. The thermal
other closed conduit. The basic design problem energy equation provides a basis for calculat-
specifies a given amount of material that is to ing this effect as discussed in Section 4.6. For
Table 9. Summary of the macroscopic equations
Equation name Equation number Number of independent Comments

macroscopic equations
Total mass (4.1) 1
Species mass (n species) (4.2) n−1
Linear momentum (4.4) 3∗
Angular momentum (4.5) 3∗
Mechanical energy (compressible) (4.6) 1∗∗ steady state, one flow stream
Mechanical energy (incompressible) (4.7) 1∗∗ steady state, one flow stream
Total energy (4.10) 1
Thermal energy (4.11) 0 steady state, one flow stream
Entropy, system (4.12) 1
Entropy, surroundings (4.13) 1
Total entropy (second law of thermodynamics) (4.14) 0 an inequality
∗ One equation for each spatial dimension, e.g., for a two-dimensional situation, only two nontrivial equations exist. ∗∗ Only one of
these two equations can be used in any one situation.
a compressible, single-phase fluid the change As an example, for the flow of oil through
in enthalpy is written in terms of heat capac- the Trans-Alaska pipeline between pump-
ity and thermodynamic p – – T properties by ing stations, the appropriate parameters for
using standard thermodynamic arguments: this problem are D = 1.19 m, L = 107 km,
uavg A = 3.18×105 m3 /d, β = 8.17×10−4 K−1 ,
T2 p2 (∂p)T2 f = 0.00335, and cp = 1.8 kJ kg−1 K−1 [110],
Ĥ2 − Ĥ1 = cp (∂T )p1 + (1 − T β) and the temperature rise is approximately

T1 p1

(4.19) 1 L u2avg
T2 − T1 ≈ 4f
cp D 2
where the temperature integral is at constant
pressure, the pressure integral is at constant tem-
perature, and β is the isobaric coefficient of ther- (1 − β T1 ) = 2.7 K (4.21)
mal expansion [ β ≡ − 1/ (∂/∂T )p ]. There-
fore, by combining Equations (4.11) and (4.19), For comparison, neglecting the fluid compress-
in the absence of heat transfer and for a tem- ibility results in a temperature increase of 3.7 K.
perature-independent heat capacity cp , the net Mechanical energy conversion to thermal energy
temperature change is obtained: in pumps, when present, also contributes to tem-
  perature increases.
p2 p2 Although the temperature increase can be
1  dp (∂p)T
T2 − T1 = F̂ + − (1 − T β) 
cp fairly small for flow of a fluid over a short dis-
p1 p1 tance, it can accumulate and become appreciable
(4.20) if distances are long enough as in a transcon-
tinental pipeline or a continuously circulating
where F̂ is given by Equation (4.18). If the fluid
flow loop. Temperature changes accompanying
is truly incompressible, then β = 0, the two pres-
flow can also contribute to errors in viscosity
sure integrals cancel exactly and the temperature
measurement.
increases in direct proportion to frictional losses.
For compressible fluids, however, this heating is
counteracted by the expansion of the fluid; if
4.9.2. Compressible Flow in a Tube
p2 < p1 , then
p2 If the flow through a closed channel or tube
β T / (∂p)T < 0 is compressible, then accurate design and flow
p1 calculations can be considerably more compli-
cated. The compressible form of the extended
which, if large enough, can result in net cooling. Bernoulli equation must be used (again this is
for steady-state flow situations), and the fric- that obtained for the same pressure difference
tion factor is calculated in the same way as for with isothermal conditions.” Furthermore, they
incompressible flow by using the friction fac- point out that the difference becomes less for
tor correlations. However, the pressure term is long pipes and that “for pipes of length at least
shown as an integral from the entrance of the one-thousand diameters the difference does not
flow channel to the exit. The difficulty of this exceed about 5 %.” Thus, isothermal flow and
calculation is that the density must be known as adiabatic reversible flow are commonly assumed
a function of pressure through the pipe and along to bracket the actual observed situation, and for
the actual flow path of the fluid through the pipe. long pipelines, little difference exists between
Knowing the conditions at the entrance and exit these two extremes.
is not enough; conditions must be known from One other aspect of compressible flow should
one end to the other, along the path taken by the be pointed out. For large pressure drops and high
fluid. Normally, these are unknown because of flow rates, a limit to the flow rate may be ob-
the flow complexity. tained even though the pressure drop is allowed
To handle this situation, idealized approxi- to increase by lowering the downstream pres-
mations to the flow are calculated as limiting or sure. This limit is established by the sonic veloc-
extreme cases. For example, if the flow of an ity of the gas in the pipe. If the gas reaches sonic
ideal gas ( p1 M r = RT 1 1 , where R is the ideal velocity, any further reduction of the down-
gas constant and M r the molecular mass) is adia- stream pressure at constant pipe cross-sectional
batic and reversible (no heat transfer occurs to area results in no additional increase in velocity.
or from the gas, and mechanical energy losses The sonic velocity of the gas at the downstream
are negligible – isentropic flow), the pressure and end, based on thermodynamic principles and in
density are related by terms of the density , pressure p, and specific
entropy Ŝ, is
p p1
= const. = κ (4.22) 1/2
κ 1 ∂p
usonic = (4.26)
where κ is the ratio of the heat capacities, cp /cv , ∂ Ŝ
so that
p2 (κ−1)/κ
dp RT1 κ p2
− = 1− (4.23) 4.9.3. Heterogeneous Reaction in a
(κ − 1) p1
p1 Fluidized-Bed Reactor
A second situation is isothermal flow of an ideal
Consider now the reaction of component A to
gas for which
product B carried out in a well-mixed fluidized-
p RT bed reactor (Fig. 32). Such a conversion might
= = constant (4.24) represent the catalytic cracking of heavy hydro-
Mr
carbons in a refinery process. The reactor stream
and is fed to the fluidized bed as a gas with sufficient
p2
velocity to maintain the catalyst particles in a
dp RT p1 fluidized state. Once inside the reactor, reacting
− = ln (4.25)
p1
Mr p2 species A is converted to product B at the cat-
alyst surface. However, before this reaction can
For the flow of a nonideal gas, the equation of occur, the reactant must first migrate to the sur-
state for that gas can be used instead of the ideal face of the catalyst pellet. Then, after reaction
gas equation of state to obtain corresponding in- at the surface, the product B must migrate to the
tegrals. bulk fluid to be removed from the reactor in the
For adiabatic, nonreversible flow, Coulson exit flow stream. What complicates this situa-
and Richardson [111] give an approach for cal- tion is that the catalyst itself may be porous, so
culating the pressure integral and conclude that that not only does the reactant contact the ex-
“the rate of flow of gas under adiabatic con- terior surface of the catalyst, but part of the re-
ditions is never more than 20 % greater than actant species also diffuses into the micropores
before reacting. Consequently, some reactant is and fixed-bed reactors; this is presented in Ta-
converted at a reduced concentration inside the ble 8. Graphs of these correlations are given in
pores and, therefore, at a lower rate than if it [113], [114].
were converted at the concentration existing at For porous catalysts, determination of the re-
the macroscopic exterior surface of the catalyst. action rate at the catalyst, although primarily a
Calculation of the effective reaction rate requires problem in reaction kinetics, can also be a prob-
considering each of these mass-transfer and re- lem in transport phenomena because of diffusion
action rate processes. in the catalyst pores. The chemical kinetics prob-
To illustrate the concept, the macroscopic lem must be determined from experimental labo-
material balance of reacting species A is con- ratory reactors. Lin provides extensive literature
sidered. Under the assumption of a well-mixed references to studies of a range of industrial re-
fluidized bed, the gas-phase concentration is the actions [113]. The transport problem is normally
same everywhere in the reactor and equal to the addressed by the use of an effectiveness factor
concentration in the exit flow stream. Of course, η. The effectiveness factor adjusts the reaction
this model is an approximation because concen- rate to account for the fact that within the pores
tration gradients exist near the catalyst pellets of a catalyst the reaction occurs at a reduced
due to the heterogeneous reaction. The model rate compared to the pellet’s exterior surface. At
assumes that enough reaction locations of suffi- the catalyst surface, the reaction proceeds at a
ciently small size exist for them to be treated like rate that is dictated by the chemical kinetics and
a homogeneous reaction occurring uniformly by the concentration of the reacting species at
throughout the system volume. An accounting the surface. However, as the reactant becomes
of species A within the fluidized bed in terms of depleted with greater depth into the pores, the
its concentration in the feed stream cAin , the con- reaction rate decreases accordingly; the effec-
centration in the bulk fluid in the bed and outlet tiveness of the catalyst surface within the pores
flow stream cA , and the feed and product vol- is lower than that at the surface.
umetric flow rates (F in and F out , respectively) Calculation of an average (averaged over
is the entire catalyst surface, whether deep in-
side pores or not) effectiveness factor is based
cAin Fin − cA Fout = rA V (4.27)
on combined diffusion and reaction inside the
The amount of A that enters the reactor at con- catalyst pores and was addressed originally by
centration cAin either leaves at concentration cA Thiele [115] and Aris [116] and subsequently
or is converted to products at an effective reac- in many references on reaction and transport
tion rate r A per unit volume. [98], [112], [117]. Such analysis leads to cal-
Although complicated by r A , this result pro- culation of an average effectiveness factor for
vides a clear approach to reactor design. Once a catalyst pellet as a function of a dimension-
an expression for this reaction rate is obtained less variable called the Thiele modulus. This pa-
based on transport and kinetic factors, the prob- rameter depends on the relative rates of the ki-
lem can be completed to obtain the conversion netic reaction to diffusion. If the diffusion rate
in the reactor. Then economic and design cal- into the pores is very high compared to the re-
culations can be made for the reactor in terms action constant, then the fact that some of the
of fractional conversion, space time, and reac- catalyst surface is available only in pores makes
tor volume and flow rates [112], [113]. The key little difference and the effectiveness factor is
to reactor design is to determine the overall re- close to unity. However, if the kinetic reaction
action rate for a given situation. The effect of rate constant is large compared to the diffusion
transport on this effective rate is as follows. rate, then the concentrations, and hence reaction
The transport of species from the bulk of the rates, within the pores are reduced considerably,
fluid in the fluidized bed to the catalyst surface giving a substantially lower effectiveness factor.
can be estimated by using mass-transfer coef- By using the effectiveness factor η to adjust
ficient correlations for fluidized beds. A j fac- for the reaction rate at the catalyst, the reaction
tor correlation has been presented by Chu et al. rate ( per unit volume of catalyst particle) for a
[114] that is applicable to gas – solid and liq- reaction that is first-order irreversible in A with
uid – solid systems and for both fluidized-bed rate constant k is given by
Figure 32. Modeling of the fluidized-bed reactor: macro-scale for the reactor accounting of mass (A), mesoscale for the
mass-transfer rate (B), and microscale for definition and calculation of the effectiveness factor (C)
A) Macroscale: fluidized-bed region is modeled as well mixed and uniform in temperature, composition, and reaction rate;
B) Mesoscale: mass transfer occurs between the bulk fluid and the catalyst surface because of concentration differences; C)
Microscale: diffusion within the catalyst pores reduces the effective reaction rate
rA = η k cAi (4.28) This shows that both the mass-transfer coeffi-

cient to the catalyst and the effectiveness factor –
If a steady state exists at the surface of the cata- rate constant product act as resistances to the
lyst (i.e., no accumulation of materials occurs at conversion of the reactant to the product. When
the catalyst surface), the transport rate of mate- the resistances are added in series, a combined
rials to the pellet equals the reaction rate at the rate constant is obtained.
pellet. For species A then (by using the mass- This result leads to the notion of transport-
transfer coefficients of Section 3.3), limited versus kinetic-limited reactions. If the
kG Sp (cA − cAi ) = η k Vp cAi (4.29)
mass-transfer coefficient is small enough, mass
transfer is the rate limiting step and reac-
where the external pellet surface area S p and the tion kinetics play no role in the overall con-
pellet volume V p are required because k G is per version rate. Likewise, if the kinetic rate
surface area and k is per pellet volume. For a true constant – effectiveness factor product is small
first-order kinetic reaction, the rate constant is a enough (compared to the mass-transfer coeffi-
function of temperature but not of species con- cient), it becomes the limiting part of the rate
centrations. If the reaction is not first order, an process and the mass-transfer coefficient plays
additional functionality depending on the inter- no role in establishing the reaction rate. If both
face concentration exists. This equation can be rate constants are of the same order, then the
solved for the interface concentration in terms overall rate coefficient depends on both the ki-
of the rate constants and the bulk fluid concen- netic and the mass-transfer rate factors.
trations, which can then be used to express the
overall reaction rate of species A in terms of the
bulk phase concentration 5. References
r A = K cA (4.30)
1. R. Aris: Vectors, Tensors, and the Basic
where Equations of Fluid Mechanics, Prentice Hall,
Englewood Cliffs, N.J., 1962.
1
K = 1 1
(4.31)
+
η k (Vp /Sp ) kG
2. L. Brand: Vector and Tensor Analysis, J. 25. M. P. Heisler, Trans. ASME 69 (1947)
Wiley & Sons, New York 1957. 227 – 236.
3. R. B. Bird, W. E. Stewart, E. N. Lightfoot: 26. J. R. Welty, C. E. Wicks, R. E. Wilson:
Transport Phenomena, J. Wiley & Sons, New Fundamentals of Momentum, Heat and Mass
York 1960. Transfer, J. Wiley & Sons, New York 1976.
4. S. Whitaker: Fundamental Principles of Heat 27. L. E. Sissom, D. R. Pitts: Elements of
Transfer, Pergamon Press, New York 1977. Transport Phenomena, McGraw-Hill, New
5. J. C. Slattery: Momentum, Energy and Mass York 1972.
Transfer in Continua, 2nd ed., R. E. Krieger 28. F. W. Kroesser, S. Middleman, Polym. Eng.
Publishing Co, Huntington, N.Y. 1981. Sci. 5 (1965) 1.
6. L. E. Malvern: Introduction to the Mechanics 29. R. W. Flumerfelt, M. W. Pierick, S. L. Cooper,
of a Continuous Medium, Prentice Hall, R. B. Bird, Ind. Eng. Chem. Fundam. 8 (1969)
Englewood Cliffs, N.J., 1969. 354.
7. G. E. Mase: Theory and Problems of 30. J. Happel, H. Brenner: Low Reynolds Number
Continuous Mechanics, McGraw-Hill, New Hydrodynamics, Prentice Hall, Englewood
York 1970. Cliffs, N.J., 1965.
8. R. C. Reid, J. M. Prausnitz, T. K. Sherwood: 31. S. M. Selby: Standard Mathematical Tables,
The Properties of Gases and Liquids, 3rd ed., 16th ed., The Chemical Rubber Company,
McGraw-Hill, New York 1977. Cleveland 1968.
9. S. Chapman, T. G. Cowling: The Mathematical 32. R. B. Bird, R. C. Armstrong, O. Hassager:
Theory of Nonuniform Gases, Cambridge Dynamics of Polymeric Liquids, vol. 1, Fluid
University Press, New York 1939. Mechanics, J. Wiley & Sons, New York 1977.
10. J. O. Hirschfelder, C. F. Curtiss, R. B. Bird: 33. A. B. Metzner, J. C. Reed, AIChE J. 1 (1955)
Molecular Theory of Gases and Liquids, 434.
Wiley Interscience, New York 1954. 34. A. H. P. Skelland: Non-Newtonian Fluid and
11. P. D. Neufeld, A. R. Janzen, R. A. Aziz, J. Heat Transfer, J. Wiley & Sons, New York
Chem. Phys. 57 (1972) 1100. 1967.
12. R. S. Brokaw, Ind. Eng. Chem. Process Des. 35. D. W. Dodge, A. B. Metzner, AIChE J. 5
Dev. 8 (1969) 240. (1959) 189.
13. C. Truesdell: The Elements of Continuum 36. S. Goldstein: Modern Developments in Fluid
Mechanics, Springer Verlag, New York 1966. Dynamics, Oxford University Press, London
14. R. Darby: Viscoelastic Fluids, Marcel Dekker, 1938.
New York 1976. 37. S. Prasad: Non-Newtonian Flow Through
15. W. R. Schowalter: Mechanics of Constricted Geometries, M. S. Thesis,
Non-Newtonian Fluids, Pergamon Press, New University of Houston, Houston, TX, 1978.
York 1978. 38. T. B. Drew: Trans. Am. Inst. Chem. Eng. 26
16. S. Whitaker: Fundamental Principles of Heat (1931) 26.
Transfer, Pergamon Press, New York 1977. 39. H. L. Langhaar, J. Appl. Mech. 64 (1942)
17. R. B. Bird, W. E. Stewart, E. N. Lightfoot: A-55.
Transport Phenomena, J. Wiley & Sons, New 40. W. M. Kays, Trans. ASME 77 (1955) 1265.
York 1960. 41. J. R. Sellars, M. Tribus, J. S. Klein, Trans.
18. A. J. Chapman: Heat Transfer, Macmillan ASME 78 (1956) 441.
Publ. Co., New York 1960. 42. E. N. Sieder, G. E. Tale, Ind. Eng. Chem. 28
19. H. S. Carslaw, J. C. Jaeger: Conduction of Heat
(1936) 1429.
in Solids, 2nd ed., Oxford University Press,
43. H. Hausen, Verfahrenstechnik (Berlin) 4
London 1959.
(1943) 91.
20. L. Brand: Vector and Tensor Analysis, J.
44. H. Schlichting: Boundary Layer Theory, 6th
Wiley & Sons, New York 1947.
ed., McGraw-Hill, New York 1968.
21. J. H. Lienhard: A Heat Transfer Textbook,
45. L. M. Milne-Thomson: Theoretical
Prentice Hall, Englewood Cliffs, N.J., 1987.
Hydrodynamics, 5th ed., Macmillan, New
22. H. P. Gurney, J. Lurie, Ind. Eng. Chem. 15
York 1968.
(1923) 1170.
46. J. Schetz: Foundations of Boundary Layer
23. H. C. Groeber, VDI-Z. 69 (1925) 705.
Theory, Prentice-Hall, Englewood Cliffs, N.J.,
24. A. Shack: Industrial Heat Transfer, J. Wiley &
1984.
Sons, New York 1933.
47. E. Pohlhausen, Z. Angew. Math. Mech. 1 69. H. S. Carslaw, J. C. Jaeger: Conduction of Heat
(1921) 115. in Solids, Oxford University Press, London
48. S. W. Churchill, H. H. S. Chu, Int. J. Heat 1959.
Mass Transfer 18 (1975) 1323. 70. P. D. Neufeld, A. R. Janzen, R. A. Aziz, J.
49. P. S. Klebanoff: “Characteristics of Turbulence Chem. Phys. 57 (1972) 1100.
on a Boundary Layer with Zero Pressure 71. R. S. Brokaw, Ind. Eng. Chem. Process Des.
Gradient,” NACA Report 1247, 1955. Dev. 8 (1969) 240.
50. J. Nikuradse, Ing. Arch. 1 (1930) 150; 72. E. N. Fuller, P. D. Schettler, J. C. Giddings,
VDI-Forschungsh. 361 (1933) 1; Pet. Eng. 11 Ind. Eng. Chem. 58 (1966) 18.
(1940) 164; 11 (1940) 75; 11 (1940) 124; 11 73. C. R. Wilke, P. Chang, AIChE J. 1 (1955) 264.
(1940) 38; 11 (1940) 83. 74. J. R. Welty, C. E. Wicks, R. E. Wilson:
51. L. Prandtl, Z. Angew. Math. Mech. 5 (1925) Fundamentals of Momentum, Heat, and Mass
136. Transfer, 2nd ed., J. Wiley & Sons, New York
52. J. M. Kay, R. W. Nedderman: An Introduction 1976.
to Fluid Mechanics and Heat Transfer, 3rd ed., 75. J. M. Coulson, J. F. Richardson: Chemical
Cambridge University Press, London 1974. Engineering, 3rd ed., vol. 1, Pergamon Press,
53. H. Blasius, VDI-Forschungsh. 131 (1913). Oxford 1977.
54. C. F. Colebrook, J. Inst. Civ. Eng. (London) 76. A. S. Foust et al.: Principles of Unit
133 (1938 – 1939). Operations, 2nd ed., J. Wiley & Sons, New
55. A. A. Zhukauskas, A. B. Ambrazyavichyus: York 1980.
NACA Report 909, 1949. 77. W. L. McCabe, J. C. Smith, P. Harriott: Unit
56. L. Prandtl: “ Über den Reibungswiderstand Operations of Chemical Engineering, 4th ed.,
strömender Luft,” Reports of the Aerol. McGraw-Hill, New York 1985.
Versuchsanst. Göttingen, 3rd Series, 1927; see 78. R. E. Treybal: Mass-Transfer Operations, 3rd
also: “Zur turbulenten Strömung in Rohren ed., McGraw-Hill, New York 1980.
und Längsplatten,” Reports of the Aerol. 79. C. O. Bennett, J. E. Myers: Momentum, Heat,
Versuchsanst. Göttingen, 4th Series, 1931. and Mass Transfer, 2nd ed., McGraw-Hill,
57. W. L. Friend, A. B. Metzner, AIChE J. 4 New York 1974.
(1958) 393. 80. W. G. Whitman, Chem. Metall. Eng. 29
58. S. W. Churchill, M. Bernstein, J. Heat Transfer (1923) 147.
99 (1977) 300. 81. R. Higbie, Trans. Am. Inst. Chem. Eng. 31
59. S. Whitaker, AIChE J. 18 (1972) 361. (1935) 365.
60. S. W. Churchill, H. H. S. Chu, Int. J. Heat 82. P. V. Danckwerts, Ind. Eng. Chem. 43 (1951)
Mass Transfer 18 (1975) 1323. 1460.
61. J. P. Holman: Heat Transfer, 6th ed., 83. P. Harriott, Chem. Eng. Sci. 17 (1962) 149.
McGraw-Hill, New York 1986. 84. H. L. Toor, J. M. Marchello, AIChE J. 4
62. T. Fujii, H. Imura, Int. J. Heat Mass Transfer (1958) 97.
15 (1972) 755. 85. A. L. Hines, R. N. Maddox: Mass Transfer,
63. R. B. Bird, W. E. Stewart, E. N. Lightfoot: Fundamentals and Applications, Prentice
Transport Phenomena, J. Wiley & Sons, New Hall, Englewood Cliffs, N.J., 1985.
York 1960. 86. W. H. Linton, T. K. Sherwood, Chem. Eng.
64. J. C. Slattery: Momentum, Energy and Mass
Prog. 46 (1950) 258.
Transfer in Continua, 2nd ed., R. E. Krieger
87. E. R. Gilliland, T. K. Sherwood, Ind. Eng.
Publishing Co, Huntington, N.Y. 1981.
Chem. 26 (1934) 516.
65. E. L. Cussler: Diffusion Mass Transfer in Fluid
88. P. Harriott, R. M. Hamilton, Chem. Eng. Sci.
Systems, Cambridge University Press, New
20 (1965) 1073.
York 1984.
89. M. J. Christian, S. P. Kezibs, AIChE J. 5
66. E. L. Cussler: Multicomponent Diffusion,
(1959) 61.
Elsevier Scientific Publishing Company, New
90. C. H. Bedingfield, I. B. Drew, Ind. Eng. Chem.
York 1976.
42 (1950) 1164.
67. J. Crank: The Mathematics of Diffusion,
91. R. L. Steinberger, R. E. Treybal, AIChE J. 6
Clarendon Press, Oxford 1956.
(1960) 227.
68. R. C. Reid, J. M. Prausnitz, T. K. Sherwood:
92. F. H. Garner, R. D. Sucking, AIChE J. 4
The Properties of Gases and Liquids, 3rd ed.,
(1958) 114.
93. E. J. Wilson, C. J. Geankoplis, Ind. Eng. Chem. 105. S. Whitaker in N. A. Peppas (ed.): One
Fundam. 5 (1966) 9. Hundred Years of Chemical Engineering,
94. A. Sen Gupta, G. Thodos, AIChE J. 9 (1963) Kluwer Academic Publishers, Dordrecht 1989,
751. pp. 47 – 109.
95. P. N. Dwivedi, S. N. Upadhyay, Ind. Eng. 106. J. C. Slattery: Momentum, Energy, and Mass
Chem. Process Des. Dev. 16 (1977) 157. Transfer in Continua, 2nd ed., R. E. Krieger
96. A. Sen Gupta, G. Thodos, AIChE J. 8 (1962) Publishing Co, Huntington, N.Y. 1981.
608. 107. R. B. Bird, Chem. Eng. Sci. 6 (1957) 123.
97. J. C. Chu, J. Kalil, W. A. Wetteroth, Chem. 108. L. W. Moody, Trans. ASME 66 (1944) 672.
Eng. Prog. 49 (1953) 141. 109. S. W. Churchill, Chem. Eng. (N.Y.) 87 (1977)
Nov. 7, 91.
Transport Phenomena, J. Wiley & Sons, New
110. P. R. Hooker, W. E. Brigham, JPT J. Pet.
York 1960.
Technol. 30 (1978) 747.
99. R. S. Brodkey, H. C. Hershey: Transport
111. J. M. Coulson, J. F. Richardson: Chemical
Phenomena, A Unified Approach,
Engineering, 3rd ed., vol. 1, Pergamon Press,
100. J. R. Welty, C. E. Wicks, R. E. Wilson: Oxford 1977.
Fundamentals of Momentum, Heat, and Mass 112. O. Levenspiel: Chemical Reaction
Transfer, 2nd ed., J. Wiley & Sons, New York Engineering, J. Wiley & Sons, New York
1969. 1962.
101. O. A. Hougen, K. M. Watson, R. A. Ragatz: 113. K.-H. Lin in R. H. Perry, C. H. Chilton (eds.):
Chemical Process Principles, part II, Chemical Engineer’s Handbook, 5th ed.,
Thermodynamics, 2nd ed., J. Wiley & Sons, section 4, McGraw-Hill, New York 1973.
New York 1959. 114. J. C. Chu, J. Kalil, W. A. Wetteroth, Chem.
102. J. M. Smith, H. C. Van Ness: Introduction to Eng. Prog. 49 (1953) 141.
Chemical Engineering Thermodynamics, 3rd 115. E. W. Thiele, Ind. Eng. Chem. 31 (1939) 916.
ed., McGraw-Hill, New York 1975. 116. R. Aris, Chem. Eng. Sci. 6 (1957) 262.
103. W. L. McCabe, J. C. Smith, P. Harriott: Unit 117. C. D. Holland, R. G. Anthony: Fundamentals
Operations of Chemical Engineering, 4th ed., of Chemical Reaction Engineering, Prentice
McGraw-Hill, New York 1985. Hall, Englewood Cliffs, N.J., 1979.
104. F. M. White: Fluid Mechanics, 2nd ed.,
Fluid Mechanics 371
Fluid Mechanics
See also → Mathematics in Chemical Engineering
David V. Boger, Department of Chemical Engineering, The University of Melbourne, Parkville, Victoria
3052, Australia
Y. Leong Yeow, Department of Chemical Engineering, The University of Melbourne, Parkville, Victoria 3052,
Australia
1. Introduction . . . . . . . . . . . . . . . 372 4.1.1. Bingham Type Behavior . . . . . . . . 396

2. Basic Equations of Fluid Mechanics 374 4.1.2. Shear-Thinning (Pseudoplastic) Fluids 397
2.1. Continuity Equation . . . . . . . . . . 375 4.1.3. Shear-Thickening (Dilatant) Fluids . . 398
2.2. Cauchy Equations of Motion . . . . 376 4.1.4. Fluids with Time-Dependent Viscosity
2.3. Energy Transport Equation ( Thixotropic Fluids) . . . . . . . . . . . 398
and Bernoulli Equation . . . . . . . . 378 4.2. Fully Developed Tube Flow . . . . . 399
2.4. Constitutive Equations and 4.2.1. Volumetric Flow Rate – Pressure Drop
Classification of Fluids . . . . . . . . 379 Relationship . . . . . . . . . . . . . . . . 400
3. Newtonian Fluids . . . . . . . . . . . . 379 4.2.2. Generalized Treatment . . . . . . . . . 400
3.1. Deviatoric Stress and Viscosity . . . 379 4.2.3. Velocity Distribution . . . . . . . . . . . 401
3.2. Navier – Stokes Equations . . . . . . 381 4.2.4. Friction Factor – Reynolds Number
3.3. Applications of Navier – Stokes Relationships . . . . . . . . . . . . . . . 402
Equations . . . . . . . . . . . . . . . . . 381 4.3. Viscoelastic Fluid Mechanics . . . . 403
3.3.1. Flow in Pipes . . . . . . . . . . . . . . . 381 4.3.1. Steady Shear Behavior of Viscoelastic
3.3.2. Concentric Cylinder Flow . . . . . . . 383 Fluids . . . . . . . . . . . . . . . . . . . . 405
3.3.3. Creeping Flow Past a Sphere . . . . . . 385 4.3.2. Behavior of Viscoelastic Fluids in Os-
3.4. Some Other Important Flows . . . . 387 cillatory Shear Flow . . . . . . . . . . . 406
3.4.1. Flow Through Granular Beds . . . . . 387 4.3.3. Examples of Constitutive Equations
3.4.2. Fluidization . . . . . . . . . . . . . . . . 388 for Viscoelastic Fluids . . . . . . . . . . 407
3.4.3. Gas – Liquid Flow . . . . . . . . . . . . 389 4.3.4. Extensional Behavior of Viscoelastic
3.5. Mechanical Energy Balance for Fluids . . . . . . . . . . . . . . . . . . . . 409
Macroscopic Systems . . . . . . . . . 391 4.3.5. Accelerating and Decelerating Flows
3.5.1. Fully Developed Tube Flows . . . . . . 392 of Viscoelastic Fluids . . . . . . . . . . 411
3.5.2. Accelerating and Decelerating Flows 393 5. Numerical Methods in Fluid
3.5.3. The Orifice Plate and Similar Flow Mechanics . . . . . . . . . . . . . . . . . 415
Rate Measurement Devices . . . . . . 394 5.1. Finite Difference Method . . . . . . . 415
4. Non-Newtonian Fluids . . . . . . . . . 395 5.2. Finite Element Method . . . . . . . . 417
4.1. Classification of Fluids According to 5.3. General Remarks . . . . . . . . . . . . 420
Viscosity Behavior . . . . . . . . . . . 396 6. References . . . . . . . . . . . . . . . . . 420
Symbols: e rate of strain tensor

exx , exy ,eij components of rate of strain tensor
A cross-sectional area, surface area, ampli-
Ev frictional loss
tude of oscillation
Ev ex losses in valves, fittings, etc.
C loss coefficient
Ev fd losses in fully developed flows
Cd drag coefficient, discharge coefficient
f friction factor
d distance
F force vector
D diameter
Fd drag force
De extrudate diameter
Fi component of force vector
Dhy hydraulic diameter
G volumetric flow rate in gas phase
Dp particle diameter
G storage modulus
Dv vane diameter
G loss modulus
e surface roughness, end correction
372 Fluid Mechanics
h elevation Γ , Γ m torque
H gap between plates δij Kronecker delta
Hv vane height ε porosity
i unit vector in x direction ε̇0 constant extensional rate
I identity matrix η viscosity
j unit vector in y direction η el extensional viscosity
JG superficial gas phase velocity η pl plastic viscosity
JL superficial liquid phase velocity η0 viscosity parameter of Meter, Maxwell,
k thermal conductivity, parameter in the and Oldroyd-B models
power-law equation η dynamic viscosity
k unit vector in z direction η component of complex viscosity
K intercept in the log – log plot of τ w versus θ azimuthal coordinate
8 V /D λ bulk viscosity, time constant
L length, volumetric flow rate in liquid λel extensional viscosity
phase λ1 relaxation time
Le equivalent length λ2 retardation time
L0 initial length density
n flow-behavior index of power law equa- p particle density
tion τ deviatoric stress tensor
n unit outward pointing normal τij component of deviatoric stress tensor
n slope of log – log plot of τ w versus 8 V/D τ rz , τ rθ shear stress
N1 first normal stress τw wall shear stress
p isotropic pressure τy yield stress
q heat flux vector τ 1/2 parameter of Ellis and Meter model
Q volumetric flow rate Φ interpolation function
r radial coordinate ψ1 first normal stress coefficient
r0 plug radius ψ2 second normal stress coefficient
Rc , Rx , Ry residuals Ψ stream function
R, R1 , R2 radius ω 1 , ω 2 , ω angular velocity, vorticity
Re Reynolds number Ω angular velocity
Re generalized Reynolds number for time-
independent fluid
S path joining two points 1. Introduction
t time
T temperature The traditional approach for writing an article
T stress tensor or a text book on fluid mechanics has been to
Tij , Txx , Txy , Txz stress components deal with the Newtonian fluid and the resulting
u velocity vector mechanics associated with such materials. Thus
uf fluidizing velocity the basic tools (in a sequence of events such as
ui , ux , uy , ur , ut , u0 velocity components those illustrated in Figure 1) are treated in de-
U, U 0 , U∞ velocity tail to illustrate how to solve a Newtonian fluid
V average velocity, volume mechanics problem. The laws of conservation
W mass flow rate of mass (continuity equation) and conservation
W s shaft work of momentum (Cauchy momentum equations or
x position vector equations of motion) are established for a gen-
xi components of position vector eral system and in multidimensional form. From
z elevation these equations it then becomes clear that the
α parameter in Meter model solution to any fluid mechanics problem is not
γ shear strain possible unless a relationship is developed bet-
γ0 amplitude of sinusoidal shear strain ween the stress tensor and rate of deformation
γ̇ shear rate tensor, or, between the stresses and velocity gra-
γ̇ 0 amplitude of sinusoidal shear rate dients in the system. Such an equation is termed
Fluid Mechanics 373
the constitutive equation. For Newtonian fluids In Chapter 2 the basic equations for fluid
the relationship between the stress tensor and the mechanics – the continuity equation, the Cauchy
rate of deformation is linear, the proportionality equations of motion, and the energy transport
constant is the viscosity. Substitution of this re- and Bernoulli equations – are established. Chap-
lationship into the Cauchy momentum equations ter 3 deals with Newtonian fluids and Newtonian
leads to the Navier – Stokes equations. Thus the fluid mechanics where the Navier – Stokes equa-
Navier – Stokes equations, in conjunction with tions are developed. In addition, the mechanical
the viscosity, form the basis for the solution of energy balance is established for macroscopic
classical fluid mechanics problems. Much of the systems in order that pipe flow systems can be
effort in classical fluid mechanics is devoted to designed. The emphasis in the article is directed
establishing methods of solution of the Navier – toward pipe flows because the process engineer
Stokes equations. These methods can be analyt- is more concerned with flow in conduits than in
ical in nature and in recent times, of course, are other geometries. Little emphasis is placed on
numerical. While one whole section of this ar- the details associated with turbulence because
ticle is devoted to numerical methods because process engineers are primarily concerned with
of their importance in modern fluid mechanics, turbulent flow in pipes of Newtonian fluids and
no attention is directed towards classical analyt- are not concerned with design of aerofoil struc-
ical methods such as those used in the solution tures, etc.
of boundary layer and slow flow (creeping flow) Chapter 4 concentrates on non-Newtonian
problems. The emphasis is directed towards the fluids. In this chapter fluids are classified accord-
industrial chemist, process scientist, and chemi- ing to their viscosity behavior and are examined
cal engineer who encounter a vast range of mate- in some depth in fully developed tube flow. Vis-
rials in today’s industries where the Newtonian coelastic fluid mechanics are also summarized –
fluid is only one small subset of a vast array of the steady shear and dynamic shear behavior of
fluid behavior which can be observed. Figure 2 viscoelastic fluids are reviewed and examples of
illustrates the range of behavior that can be en- simple constitutive equations are given. The ar-
countered in terms of the viscosity of fluids and ticle is completed with a brief examination of
in terms of whether materials are classified as be- numerical methods in fluid mechanics.
ing inelastic or viscoelastic fluids. It is clear from The emphasis of this article is shifted toward
examination of Figure 2 that a vast range of be- non-Newtonian fluid mechanics, the sequence of
havior in terms of the viscosity of materials can events and tools of importance are illustrated in
be and is observed. An industrial chemist or pro- Figure 3. Here the basic conservation of mass
cess engineer will encounter low molecular mass (continuity equation) and the conservation of
liquids and gases (Newtonian materials) but will momentum (Cauchy momentum equations) re-
also be dealing with polymer solutions, poly- main the equations of fundamental importance,
mer melts, rubbers, mineral suspensions, food but, the relevant constitutive equation in most
products, pharmaceuticals, and energy products cases is still unknown. Thus the Navier – Stokes
such as coal oil and coal water fuels, etc. In such equivalent set of equations in many cases is
systems the viscosity can be constant, but more not known and because any number of consti-
likely will vary with shear rate or rate of flow. tutive equations are available it is not entirely
Viscosity can be a function of shear rate and clear what basic flow property information is
time of shear; or it can be a function of shear required for the most general viscoelastic ma-
rate, time, and thermal history and each of these terial. It is only now (1990) that fluid mechanics
viscosity behaviors can be observed in inelas- problems are solved for the first time for vis-
tic and/or viscoelastic fluids. In addition many coelastic fluids. The solutions evolving now for
materials will not flow until a certain stress is such problems will be extremely important in the
exceeded (e.g., toothpaste). This stress, termed future. It is also of considerable importance to
yield stress, can be present in both inelastic and keep abreast of the numerical software packages
viscoelastic fluids. Therefore, it is important to which have been developed in this area particu-
be aware of the vast range of material behavior larly in regard to the processing of polymers [1],
present in industry. [2].
374 Fluid Mechanics
Figure 1. Newtonian fluid mechanics
Figure 2. Schematic classification of fluid behavior
2. Basic Equations of Fluid

Mechanics
The basic equations of fluid mechanics can be

derived from a small number of fundamental
physical laws such as conservation of mass,
of momentum ( Newton’s second law), and of
energy. Although very general statements of
these laws can be written down (applicable to
all substances, solids as well as fluids), in fluid
Figure 3. Non-Newtonian fluid mechanics
mechanics these laws are formulated in terms of
TH = Thermal history physical variables such as velocity u, pressure
p, temperature T , and density . The resulting
statements may be less general but they are more
directly applicable in analyzing fluid mechani-
cal problems.
Fluid Mechanics 375
2.1. Continuity Equation at time t and its density (x + δx, t + δt) at a later
time t + δt when it is occupying position x + δx,
The requirement that mass be conserved at every it can be seen that D/Dt is the rate of change
point in a flowing fluid imposes certain restric- in density experienced by a fluid element as it
tions on the velocity u and density . Consider an moves about in space. D/Dt should not be con-
arbitrary region in space, of volume V , bounded fused with ∂/∂t which is the rate of change in
by surface A, through which the fluid flows (see density at a fixed point in space. The substan-
Fig. 4). The rate of increase in mass within this tial derivative operator can also be applied to
region is given by the volume integral the velocity u, temperature T , or other proper-
ties associated with a fluid element with a similar
∂
dV (1) physical interpretation of the result.
∂t
V
The rate at which fluid is leaving the region

is given by the surface integral of the out-
ward pointing normal velocity multiplied by the
fluid’s density taken over the surface A

u·ndA= ∇· (u) dV (2)
A V
where n is the unit outward pointing normal at

any point on A. The divergence theorem has been
used to convert the surface integral into a volume
integral. Mass conservation requires the sum of
the rate of accumulation in V and the rate of
outflow from V to be zero:
Figure 4. Fluids flowing through an arbitrary region in space

∂ of volume V and surface area A
+∇· (u) dV = 0 (3)
∂t
V A number of special cases of the continuity
equation are frequently encountered. For exam-
Since V is arbitrary, the integrand itself must ple, under steady-state conditions the equation
vanish at every point in space: reduces to
∂
+∇· (u) = 0 (4) ∇· (u) = 0 (7)
∂t
Equation (4) is usually referred to as the con- Much of the subsequent analyses will be re-
tinuity equation. It is a statement of mass constricted to fluids that are incompressible and ho-
servation in terms of fluid velocity and density. mogeneous. For such fluids the continuity equa-
Expanding the second term and regrouping, the tion takes on a particularly simple form
equation can be written as
∇·u= 0 (8)
∂
+u·∇+∇·u= 0 (5)
∂t In many practical problems the fluid flow can
or be regarded as approximately two-dimensional.
For such problems, Equation 8 (in cartesian co-
D ordinates) takes on the form
+∇·u= 0 (6)
Dt
∂ux (x,y) ∂uy (x,y)
where D/D t is used to represent the operator + =0 (9)
∂ ∂x ∂y
∂t +u·∇.
It is known as the substantial derivative op- Equation (9) and, hence, mass conservation are
erator. By following the change in the density identically satisfied if the velocity components
(x, t) of a fluid element occupying position x are given by
376 Fluid Mechanics
∂Ψ (x,y) ∂Ψ (x,y) where g is the acceleration due to gravity. An-

ux = and uy = − (10)
∂y ∂x other external force is that exerted by the fluid
outside V . This force acts across the closed sur-
where Ψ (x, y), the stream function, is any scalar face A and can be expressed in terms of the
function of x and y. A simple physical interpreta- stress tensor T on the surface. In cartesian co-
tion can be given to Ψ . Consider a line of constant ordinates this stress tensor has nine components
Ψ in the x − y plane, along such a line Txx , Txy , Txz , Tyx , Tyy . . . Tzz , or more con-
∂Ψ ∂Ψ cisely Tij ; i, j = 1, 2 or 3. x 1 , x 2 , x 3 are identified
δΨ = δx+ δy= 0 (11)
∂x ∂y with x, y and z, respectively. Tij is the force per
i.e., unit area in direction j on a surface with normal
in the i direction. The force δF acting on an area
−uy δx+ux δy= 0
dA which has a normal n is given by
or
dy uy
3
= (12) δF =T ·ndA or δFi = Tji nj dA (15)
dx ux j=1
Since dy/dx is the local slope of the line, Equa-

tion (12) shows that the velocity vector is ev- Equation (15) is often referred to as the Cauchy
erywhere tangential to lines of constant Ψ . Such stress principle. For the fluids commonly en-
lines are referred to as streamlines. They give countered, the stress tensor can be taken to be
the instantaneous flow pattern of the fluid. By symmetric, i.e., Tij = Tji for all combinations of
integrating along any path S joining streamlines i and j. Thus, the external force acting through
where Ψ = Ψ A and Ψ = Ψ B , it can be seen that the closed surface A is given by the surface in-

tegral
dΨ
ΨB −ΨA = dS = un dS (13)
dS
S un T ·ndA (16)
A
i.e., volumetric flow crossing S; un is the veloc-
ity component normal to S. Equation (13) shows which is equivalent to
that the difference in stream function between

two streamlines is equal to the volumetric flow
∇·T dV (17)
rate across any line joining the two streamlines.
V
The continuity equation and the stream func-
tion take on different forms when written in non- where the divergence theorem is again used to
cartesian coordinates. Listing of the equations convert the surface integral to a volume integral.
of fluid mechanics in a number of commonly The i component of the vector (∇ · T ) is
encountered coordinates can be found in most
standard textbooks on this subject, e.g., in [3]. 3
∂Tij
A partial list is given in Table 1. (∇·T )i = (18)
j=1
∂xj
2.2. Cauchy Equations of Motion To obtain the equations of motion in terms of

T, u, and ( g), it is convenient to start with a
Before deriving the equations of motion for flu- statement of conservation of momentum which
ids, it is necessary to examine the forces acting asserts that: the rate of change of momentum
on a fluid element as it moves about in space. inside the volume V and the net rate at which
Consider again the arbitrary volume V in space momentum is being convected out of the vol-
(see Fig. 4). One of the external forces acting on ume is equal to the sum of the external forces
the fluid inside V is its weight which is given by acting on the volume. The rate of accumulation
the volume integral is given by

∂ (u)
g dV (14) dV (19)
∂t
V V
Table 1. Continuity and Navier – Stokes equations for incompressible homogeneous fluids in cartesian, cylindrical, and spherical coordinates
Fluid Mechanics
377
378 Fluid Mechanics
The rate at which momentum is being convected needed to relate the local temperature T of the
out is given by the surface integral fluid to variables such as velocity, velocity gradi-
ent, and temperature gradient. Such an equation
u (u·n) dA= ∇· (uu) dV (20) takes the general form
A V
DT ∂
CV = −∇·q − T ∇·u
where u is the momentum per unit volume and Dt ∂T V
u · n is the volumetric flux leaving A. Conserva- +dissipation terms
tion of momentum in V then requires
where q is the heat flux and CV is the heat
capacity at constant volume. This equation sim-
∂ (u)
dV + ∇· (uu) dV plifies to
∂t
V V
DT
= gdV + ∇·T dV (21) Cp =k∇2 T +dissipation terms (25)
Dt
V V
for an incompressible fluid with a heat capac-
Since V is arbitrary, the integrands must be equal ity, Cp , at constant pressure and when the tem-
perature dependence of the thermal conductiv-
∂ (u) ity k can be neglected. In arriving at Equation
+∇· (uu) =g+∇·T (22)
∂t (25), Fourier’s expression for heat conduction
Upon expanding the terms on the left-hand side (q = − k ∇T ) was used to express q in terms of
and regrouping, Equation (22) becomes temperature gradient. Equation (25), the energy
transport equation, is a statement of conserva-
∂ ∂u tion of energy and is a form of the First Law of
u +∇· (u) + +u·∇u
∂t ∂t Thermodynamics. It equates the rate of energy
=g+∇·T (23) transfer to a fluid element by thermal conduction
and the rate of dissipation/conversion of kinetic
From the continuity equation (Eq. 4) the first
energy into thermal energy to the accumulation
group of terms on the left-hand side is zero. The
of thermal energy within the element. The dissi-
second group of terms can be identified as the
pation terms arise as a result of the deformation
product of and the substantial derivative of ve-
suffered by the fluid element. The derivation of
locity. Therefore
the energy transport equation and the exact form
Du of the dissipation terms are given in [3]. In the
=g+∇·T (24) following sections only isothermal flows will be
Dt
discussed. In such flows the dissipation terms
This is the equation of motion for fluids. It is of- are negligible and the energy transport equation
ten referred to as the Cauchy momentum equa- is satisfied. This greatly simplifies the analysis.
tion or equation of motion. The left-hand side is In many flow fields of practical interest, a
referred to as the inertia term. The first term on simple statement of conservation of kinetic and
the right-hand side is the force per unit volume potential energy can be derived. This is obtained
acting on a fluid element arising from gravita- by forming the dot product between the veloc-
tional body force. The second term is the force ity vector u, and the equations of motion (24),
per unit volume acting on the fluid element as a and integrating the result between any two points
result of the spatial variation of the stress tensor. on the same streamline. The resulting equation
The form of the Cauchy equations of motion in takes the form
different coordinate systems can be found in [3].
1 2 p1 1 p2
u + gh1 + = u21 +gh2 + +losses (26)
2 1 2
2.3. Energy Transport Equation and This is one form of the well-known Bernoulli
Bernoulli Equation equation; h, u, and p are the vertical eleva-
tion, the velocity, and the isotropic pressure of
In flow problems where a substantial variation the fluid respectively. Subscript 1 and 2 de-
in temperature occurs, an additional equation is note where these variables are to be evaluated
Fluid Mechanics 379
on the streamline. Losses refer to the conver- mentioned that some authors, particularly those
sion of mechanical (kinetic and potential) en- working on non-Newtonian fluids, define the
ergy into internal (thermal) energy between the rate of strain tensor without the factor of 1/2 as
two points. In deriving this equation, the fluid shown in Equation (27). This difference in the
is taken to be incompressible and the flow to definition can lead to considerable confusion and
be steady. Relaxation of these assumptions will should carefully noted.
result in a more general form of the Bernoulli A convenient way of classifying fluids is ac-
equation [1]. The Bernoulli equation finds many cording to the form of their constitutive equa-
practical applications, especially in flows where tions. For a large class of fluids, the stress ten-
the losses are small or can be estimated with sor T is a linear function of the rate of strain
reasonable accuracy. In many applications the tensor e. Such fluids are referred to as Newto-
spatial average value of the variables at point 1 nian fluids. If T is a non-linear function of e the
and point 2 are used instead of local point val- fluids are said to be non-Newtonian. In chemi-
ues, resulting in further simplification (see Sec- cally more complex fluids, the stress is not only a
tion 3.5). function of e, it also depends on the deformation
or the entire history of deformation suffered by
the fluid. Such fluids may also exhibit solidlike
2.4. Constitutive Equations and elastic behavior and are known as viscoelastic
Classification of Fluids fluids. ( Non-Newtonian and viscoelastic fluids
are treated in greater detail in Chap. 4).
The equations derived from the conservation
laws do not contain any information about the
mechanical properties of fluids. An applied force 3. Newtonian Fluids
or stress acting on fluids with different proper-
ties will result in different flow patterns. Con- 3.1. Deviatoric Stress and Viscosity
versely, the same flow pattern will induce dif-
ferent stresses in different fluids. The diverse In a stagnant fluid, the stress at any point is the
mechanical properties of fluids are described by hydrostatic pressure. This is an isotropic com-
equations that relate the local stress tensor to the pressive stress, i.e., the stress has the same mag-
local flow kinematics. Such equations are known nitude in any direction. Such a stress can be re-
as rheological constitutive equations. presented by
One of the most important kinematic vari-
T = −pI (29)
ables that appear in rheological constitutive
equations is the rate of strain tensor e. This is or in component form
defined as
Tij = − pδij (30)
1. /
e= ∇u+ (∇u)T (27)
2 where I is the identity tensor
 
or in cartesian coordinates 1 0 0
 
0 1 0
1 ∂ui ∂uj
eij = + (28) 0 0 1
2 ∂xj ∂xi
and δij is the Kronecker delta
The rate of strain tensor is a symmetric tensor.
Simple physical interpretations can be given to δij = 1 i = j
the components of e. For example, e11 or exx δij = 0 i= j (31)
is the rate at which a fluid element is being
stretched in the x direction, e12 or exy is the Unless otherwise stated, i and j take on values
rate at which the fluid element is being sheared 1, 2, or 3 in all the equations in this article. The
in the x – y plane. The form of the rate of strain shear components (when i is not equal to j ) of
and other kinematic tensors in different coordi- the isotropic stress are identically zero and the
nate systems can be found in [4]. It should be three normal components take on the same value
380 Fluid Mechanics
p, the magnitude of the pressure; p is a function when dealing with compressible fluids, such as
of the vertical position in the fluid. It is cus- gases, the Newtonian constitutive equation must
tomary to have a negative sign before p so that be modified to allow for compressibility. This is
for hydrostatic compressive stress, the numeri- done by introducing a bulk viscosity λ into the
cal value associated with p is positive. All these Newtonian constitutive equation
are in agreement with the well known nature of
hydrostatic pressure. τ =λ∇·uI +2ηe (34)
For a fluid in motion the stress will, in general,
no longer be isotropic. At any point the stress The bulk viscosity term is zero for incompress-
is a combination of the hydrostatic pressure and ible fluids. This article is concerned almost ex-
the stresses arising from the deformation experi- clusively with incompressible fluids, thus the
enced by the fluid. It is convenient to decompose bulk viscosity term will not appear in all sub-
the stress tensor Tij into an isotropic part – p δij sequent equations and discussions. For further
and a nonisotropic part τij , discussion on compressible flow and bulk vis-
cosity see [5].
Tij = −pδij + τij (32) Specialized instruments known as viscome-
ters have been developed for measuring viscos-
τij , usually referred to as the deviatoric stress ity. The basic principles of such instruments can
tensor, is a consequence of the deformation. For be explained by examining the rate of strain and
a fluid element that has not experienced any de- the deviatoric stress tensors in a fluid contained
formation, the deviatoric stress vanishes. In a between two parallel plates, shown in Figure 5.
stagnant fluid the deviatoric stress is therefore The lower plate is held stationary while the up-
zero and the resulting isotropic stress can be per is moving parallel to itself, with a constant
identified with the hydrostatic pressure. How- velocity u0 . Let F denote the force required to
ever, because of fluid motion, the isotropic com- maintain the motion of the upper plate, A the
ponent of the stress tensor will, in general, be area of the plates, and d the spacing between
different from the hydrostatic pressure. the plates. In this flow, the velocity of the fluid
The nature of the relationship between de- varies linearly from zero at the lower plate to u0
viatoric stress and deformation depends on the at the upper plate. With reference to the coordi-
rheological constitutive equation of the fluid. nates shown, it can be seen that the only nonzero
The constitutive equation completely describes components of the rate of strain tensor are
the deformation arising from a specified devi-
atoric stress and, conversely, gives the stresses 1 dux 1 u0
exy =eyx = = (35)
needed to produce a specified deformation. For 2 dy 2 d
a large class of incompressible fluids the devia- where u0 /d is the velocity gradient across the
toric stress τ is directly proportional to the rate plate spacing. This velocity gradient is often re-
of strain tensor e: ferred to as the shear rate and denoted by γ̇. In
this simple flow field (the steady shear flow) for
τ = 2ηe or τij = 2ηeij (33)
Newtonian fluids, the only nonzero components
where η the constant of proportionality, is a of the deviatoric stress are
property of the fluid and is known as the vis- F
cosity. Equation (33) in the Newtonian consti- τxy =τyx = (36)
A
tutive equation. It is an example of a rheologi-
cal constitutive equation used to relate kinematic By definition, the viscosity is given by
tensors, such as the rate of strain tensor, to the τxy F u0
deviatoric stress. Most commonly encountered η= = /
2exy A d
(37)
low molecular mass liquids and gases follow
the Newtonian constitutive equation, they are In a viscometer F and u0 are measured, and A
called Newtonian fluids. Viscosity is the most and d are obtained from the dimensions of the
important flow property of fluids. It is a strong instrument. From these data the viscosity can be
function of temperature. The SI unit of viscosity calculated. A detailed description of viscometric
is pascal – second. It should be pointed out that techniques is given in [6–8].
Fluid Mechanics 381
∂ui
3
∂ui
+ uj
∂t j=1
∂xj
∂p 3
∂ 2 ui
=− +η +gi (39)
∂xi j=1
∂x2j
The first term on the right-hand side is the

Figure 5. Shearing motion between two parallel plates isotropic pressure term and the second term is
the viscous term. This equation together with
Typical values of viscosity (in Pa s at 20 ◦ C the continuity equation forms a set of four equa-
or as indicated) for several fluids are given in the tions which can be solved to give the three un-
following list. These values show the large varia- known velocity components and the isotropic
tion of viscosity that can be encountered in fluid pressure for any flow of a Newtonian fluid. Equa-
mechanical problems as well as the variation of tion (39), known as the Navier – Stokes equation,
viscosity with temperature. describes the motion of Newtonian fluids. The
Steam (373 K) 1.28×10−5
equivalent forms in some of the more commonly
Carbon dioxide 1.46×10−5 encountered coordinate systems are listed in Ta-
Air (273 K) 1.71×10−5 ble 1. Viscosity is a strong function of tempera-
(293 K) 1.81×10−5 ture in nonisothermal flow, where the variation
(373 K) 2.18×10−5
(473 K) 2.58×10−5
of viscosity with temperature cannot be ignored,
Pentane 2.34×10−4 the Navier – Stokes equations must be modified.
Hexane 3.26×10−4 Thus, it now takes the form
Heptane 4.09×10−4
∂ui
3
Octane 5.45×10−4 ∂ui
Benzene 6.47×10−4 + uj
∂t j=1 ∂xj
Mercury 1.55×10−3
1.79×10−3
∂p ∂
Water (273 K) 3
∂ui
(283 K) 1.30×10−3 =− + η (T ) +gi (40)
(293 K) 1.00×10−3 ∂xi j=1 ∂xj ∂xj
(303 K) 7.98×10−4
Olive oil 8.40×10−2 This equation must now be solved simultane-
Castor oil 9.86×10−2 ously with the continuity equation and the en-
Glycerol (273 K) 1.21×101 ergy transport equation for the unknowns – the
(293 K) 1.49
(298 K) 0.942
three velocity components, the isotropic pres-
(303 K) 0.622 sure, and the temperature. It is assumed that
Low- density polyethylene the variation of viscosity with temperature is a
at zero shear rate known experimentally measured quantity. Vari-
(385 K) 2.65×105
(403 K) 1.05×105 able viscosity adds to the difficulty of solving
(443 K) 2.38×104 the equations describing the flow. The complex-
(463 K) 1.40×104 ity of these equations is such that they often do
not have simple analytical solutions and comput-
ers are used to generate approximate numerical
answers.
3.2. Navier – Stokes Equations
3.3. Applications of Navier – Stokes
When the Newtonian constitutive equation is Equations
substituted into the Cauchy equations of motion
(Eq. 24), the following equation is obtained: 3.3.1. Flow in Pipes
Du Steady flow of Newtonian fluids in pipes is prob-

= −∇p+η∇2 u+g (38) ably the most commonly encountered flow field.
Dt
It is also one of the small number of flow fields
or in cartesian component form for which the Navier – Stokes equations have a
382 Fluid Mechanics
simple analytical solution. In this flow the only

nonvanishing velocity component is that along r2
uz = 2V 1− (46)
the axis of the pipe. It is convenient, in this R2
case, to write down the equations of motion in Thus the velocity profile is a parabola and the
cylindrical coordinates. The axial velocity uz is maximum velocity, which occurs at the centre
a function of the radial coordinate only and is of the pipe, is twice the average velocity. For a
independent of the other coordinates and time. given pipeline, the driving force needed to attain
Examination of the Navier – Stokes equations in a specified average velocity is given by
cylindrical coordinates in Table 1 shows that the
only nontrivial component is ∆p 8ηV
=− 2 (47)
L R

0 =−
∆p
+η
1 d
r
duz
(41)
Equation (45) is the Hagen – Poiseuille equa-
L r dr dr tion. It can be put in a dimensionless form
D∆p
The driving force of this flow is the applied pres- 16 16
f= − 4L
= = (48)
sure gradient ∆p/L; the effect of gravity has been V 2 V D Re
2 η
left out in this equation. Equation (41) can be in-
tegrated to give where D is the diameter of the pipe, Re = V D/η,
and f is as defined by this equation; f is the fric-
1 ∆p 2 tion factor and Re is the Reynolds number. Both
uz = r +A lnr+B (42)
4η L these quantities are dimensionless. Such dimen-
sionless numbers are widely encountered in fluid
where A and B are the constants of integra- mechanical analysis. Equation (48) shows that
tion that can be determined by considering the f is a function of Re only. It will be shown
boundary conditions. The velocity along the axis later that shear stress at the pipe wall is given
of the tube is finite; this then requires A to be by D ∆ p/4 L, while shear rate at the pipe wall
zero. At the pipe wall r = R, it is assumed that is 8 V/D. Thus the ratio of the two measurable
the fluid adheres to the wall, i.e., uz = 0. This is quantities ∆ p D/ 4 L and 8 V/D gives the viscos-
the well known no-slip boundary condition that ity of the fluid. Measurement in pipe flow can be
is normally imposed at the interface between a used for viscosity measurements.
solid wall and a flowing fluid. This boundary For flow in pipes with Re < 2100, the simple
condition is satisfied for relationship between f and Re in Equation (48)
1 ∆p 2 has been confirmed by experimental measure-
B= − R ments. Such flows are known as laminar flows.
4η L
As the Reynolds number is increased above
Thus the resulting velocity profile in the pipe is 2100, the flow gradually loses it steady nature
given by and becomes more and more chaotic. The ex-
pressions derived for the velocity profile, volu-
R2 ∆p r2 metric flow rate, and friction factor are no longer
uz = − 1− 2 (43)
4η L R valid. The chaotic fluid motion associated with
From Equation (43) the volumetric flow rate Q flows at high Reynolds number (Re > 4000) is
through the pipe can be obtained by integrating known as turbulent flow. Turbulent flow is char-
acterized by rapid and apparently random fluc-
R tuations in fluid velocity and pressure. The same
πR4 ∆p
Q= 2πruz dr= − (44) definition of f and Re given in Equation (48) can
8η L
0 be used in turbulent flow. However, the relation-
ship between these two dimensionless numbers
The average velocity V in the pipe is given by in turbulent flow can not be determined analyt-
ically and a number of empirical and semiem-
R2 ∆p
V= − (45) pirical correlations have been developed. In the
8η L
range of 4000 < Re < 105 , experimental data of
In terms of V , the velocity profile in the pipe f versus Re closely follow the empirical Blasius
takes the simple form equation
Fluid Mechanics 383
LIVE GRAPH
f = 0.079Re−1/4 (49) Click here to view
Another equation that can be used to describe

the relationship between f and Re is the von Kar-
man – Nikuradse equation
1 -
√ = 4.0log Re f −0.4 (50)
f
Equation (50) is valid for Re ≥ 4000 [5]. The

constants 4.0 and 0.4 are determined from exper-
iment. Analysis of turbulent flow requires spe-
cial techniques and will not be discussed in this Figure 6. Friction factor for flow in circular pipes at different
article. For further details see [9]. Reynolds number and for different relative pipe roughness
(e/D) [1]
Equations (48) – (50) which relate the friction
factor to the Reynolds number were derived for
pipes with a smooth inner surface. In commer-
cial pipes surface irregularities are invariably 3.3.2. Concentric Cylinder Flow
present – depend on the material of construction
and the manufacturing process. A quantitative
measure of this surface irregularity is the rela-
tive roughness of the pipe which is defined as
the ratio of the average surface roughness e to
the pipe diameter D. The relative roughness has
to be included as an additional factor in the cor-
relations for friction factor. For most commer-
cial pipes the relative roughness is much smaller
than unity and surface irregularities have no no-
ticeable effect on pressure drop as long as the
flow remains laminar. Thus Equation (48) re-
mains valid for rough pipes. In turbulent flow,
the situation is quite different. The friction fac-
tor is altered significantly even for small e/D.
Empirical equations have been developed to re-
late the friction factor to the relative roughness
and the Reynolds number. One example is the
Colebrook equation:

1 e 4.67
√ = −4.0log + √ +2.28 (51)
f D Re f
A disadvantage is that for a given Re and e/D,

Equation (51) must be solved iteratively for f .
Another difficulty in using the Colebrook equa- Figure 7. Flow between two concentric cylinders
tion is the large uncertainty associated with the
relative roughness. Another exact solution of the Navier – Stokes
The friction factor is important in the sizing equation is the one that describes the velocity
of pipelines. It is customary to plot f against Re profile and stresses generated in a fluid contained
in the form of a log – log plot. An example of between the annular gap of two rotating concen-
such a plot is shown in Figure 6 ( Moody chart). tric cylinders (see Fig. 7). This flow is of great
The relative roughness of the pipe is included in practical interest because it is the basis of a large
this plot as an independent parameter. class of commercial viscometers. It is also of
384 Fluid Mechanics
considerable theoretical importance; it is one of The corresponding shear rate and shear stress on
the few flows for which the transition (via a se- the inner wall are
ries of progressively more complicated flows) of
the simple laminar solution to turbulent flow has 2ω2
γ̇rθ2 = (55)
been carefully observed and analyzed theoreti- 1− (R2 /R1 )2
cally.
Γ
To simplify the analysis, the length of the τrθ2 = (56)
2πR22 L
cylinders are assumed to be long compared to
their radii so that the end effects can be ignored.
where L is the length of the cylinder. In viscome-
There is no applied pressure gradient in this flow.
try, these two expressions are combined to yield
Fluid motion is brought about by the rotation
an explicit expression for the viscosity of the
of the cylinders. Let ω 1 and ω 2 denote the an-
fluid:
gular velocity of the outer and inner cylinders

respectively. The corresponding linear velocity τrθ2 Γ 1 1 1
η= = − (57)
of the cylinders are ω 1 R1 and ω 2 R2 , where R1 γ̇rθ2 L 4πω2 R22 R12
and R2 are the respective radii. The only nonva-
nishing velocity component, in cylindrical co- With Equation (57) the viscosity of the fluid can
ordinates, is the azimuthal component uθ . The be calculated from the applied torque per unit
Navier – Stokes equations reduces to height of the cylinders Γ /L and the measured
angular velocity ω 2 . For Newtonian fluids, in
u2θdp principle, only a single reading of the torque to-
− =− (52)
r dr gether with the corresponding angular velocity

d 1 d is needed to determine the viscosity. For non-
0=η (ruθ ) (53)
dr r dr Newtonian fluids, the situation is more complex
Equation (53) can be integrated to give uθ in and a series of data points are needed to deter-
terms of the radial coordinate and the boundary mine the viscosity as a function of shear rate [6].
conditions on the inner and outer cylinder. Using According to the solution of the Navier –
the newly obtained velocity, Equation (52) can Stokes equations, the streamlines should form
in turn be integrated to give the pressure. The a family of circles concentric with the cylinders.
resulting expressions for uθ and p are At low Reynolds number this is indeed the ob-
served flow pattern. However, as the Reynolds
1 2 R12 R22 number is increased (either by increasing the an-
uθ = r R 2 ω2 −R 2
1 ω1 + (ω 1 − ω2 )
R22 −R12 r gular velocity or decreasing the viscosity) this
2 2
R2 ω2 − R12 ω1
2 r −R22 simple flow loses its stability and gives way to
p=p2 + 2 +
R2 − R12 2 a new steady flow in which the streamlines are
spirals whose axes are concentric with the cylin-
r
2R12 R22 (ω1 −ω2 ) R22 ω2 − R12 ω1 ln + ders. A sketch of the new flow pattern, at suffi-
R2
ciently large Re, is shown in Figure 8. The vor-

1 1 tices formed by the fluid are known as Taylor
R14 R24 (ω1 −ω2 )2 −
r 2 R22 vortices. The transition between the two steady
flows can be observed by plotting the torque Γ
where p2 is the pressure at the inner cylinder against the shear rate γ̇ (see Fig. 9). The abrupt
wall. It can easily be verified that the no-slip change in slope of the Γ – γ̇ plot can be used
boundary condition is satisfied at the outer and to locate the transition point accurately. In using
inner cylindrical walls. Equation (57) to obtain the viscosity from con-
In most commercial concentric cylinder vis- centric viscometer measurements, it is important
cometers, the outer cylinder is held fixed while to ensure that all the data points are taken prior
the inner one is rotated at a steady angular ve- to the onset of transition flow. At even higher
locity by an applied torque Γ . For this special Reynolds number, the Taylor vortices in turn
case, the velocity in the annular gap is given by become unstable and are replaced by a series
of progressively more complicated flows, which
1 R12 R22 ω2
uθ = rR22 ω2 − (54) ultimately lead to turbulent flow. The detailed
R22 −R12 r
Fluid Mechanics 385
step by step mapping of the laminar-to-turbulent In making viscosity measurements, it is com-

transition has been investigated experimentally mon practice to use more than one viscometer
and analyzed theoretically with excellent agree- so that the experimental data covers as wide a
ment between the two. range of shear rate as possible. This step is par-
ticularly important if the possibility exists that
the fluid may not be Newtonian (i.e., it has a
viscosity that is a function of shear rate). Fig-
ure 10 shows a log – log plot of shear stress
against shear rate obtained using four different
viscometers. The data at low shear rates were
obtained using a concentric cylinder viscome-
ter. Those at higher shear rates were obtained
from the volumetric flow rate and pressure gra-
dient data from three different capillary tubes.
(Experimental techniques associated with cap-
illary viscometer are described in Section 4.2).
The fact that all the data points, from four dif-
ferent viscometers, fall on the same straight line
with slope equal to unity means that the fluid is
Newtonian over the shear rates covered and the
viscosity can be read off from the intercept of
the straight line with the vertical line at γ̇ = 1.0;
η is, in this case, ca. 0.91 Pa s.
LIVE GRAPH
Click here to view
Figure 8. Taylor vortices [5] (reproduced with permission
of McGraw-Hill)
LIVE GRAPH
Click here to view
Figure 10. Log – log plot of shear stress versus shear rate for
a Newtonian fluid (glycerol at 21.6 ◦ C) obtained using four
different viscometers
D = 5.573 mm, L = 300 mm, L/D = 53.8; D = 5.569 mm,
L = 477 mm, L/D = 85.7; ◦ D = 5.595 mm, L = 700 mm;
L/D = 125.1; concentric cylinder viscometer
3.3.3. Creeping Flow Past a Sphere

Figure 9. Change in slope in the torque – shear rate plot for
flow between concentric cylinders indicating the onset of Steady flow of a Newtonian fluid past a sphere
Taylor vortices [1] has been the subject of numerous investigations.
386 Fluid Mechanics
This flow is of great practical importance in its

own right, but also because it illustrates the steps
involved in the evaluation of the drag force ex-
erted by a flowing fluid on an object. It is also
of considerable theoretical interest because of
the part it played in the development of some
of the modern mathematical techniques, such as
singular perturbation and matched asymptotic
analyses, used in solving flow problems.
The mathematical analysis is greatly simpli-
fied if the inertia terms in the Navier – Stokes
equations are assumed to be small compared to Figure 11. Definitive sketch for flow past a sphere
the viscous terms and thus are ignored. This as-
sumption is valid if the fluid velocity or density In addition, the velocity components have to
is small, its viscosity large, or if the sphere diam- satisfy the continuity equation
eter D is small. These conditions are equivalent 1 ∂ 2 1 ∂
to requiring the Reynolds number Re = U 0 D/η, r ur + (uθ sinθ) (61)
r 2 ∂r rsinθ ∂θ
to be small; U 0 is the undisturbed velocity of the Equations (58) and (61) can be solved to give
fluid at a large distance from the sphere. Flows the following expressions for the velocity com-
with low Reynolds number are often referred to ponents and pressure
as inertialess or creeping flows.

In spherical coordinates, the equations for 3D 1 D 3
ur =U0 1− + cosθ
creeping flow past a sphere are 4 r 22r

3D 1 D 3
∂p 1 ∂ ∂ur uθ = −U0 1− − sinθ
0=− +η 2 r2 + 8 r 4 2r
∂r r ∂r ∂r 2
3ηU0 D
p=p0 − cosθ (62)
1 ∂ ∂ur 2ur D 2r
sinθ − −
r2 sinθ ∂θ ∂θ r2 where p0 is the uniform pressure far from the
sphere. For mathematical details leading to these
2 ∂uθ 2
− 2 uθ cotθ expressions see [1].
r2 ∂θ r
To calculate the drag force on the sphere, the
1 ∂p 1 ∂ ∂uθ
0=− +η 2 r2 + isotropic pressure and deviatoric stress on the
r ∂θ r ∂r ∂r
surface of the sphere must be evaluated. These
are given, respectively, by
1 ∂ ∂uθ 2 ∂ur uθ
sinθ + − 2 2 (58) 3ηU0
r2 sinθ ∂θ ∂θ r 2 ∂θ r sin θ p=p0 − cosθ (63)
D

It is convenient to locate the center of the sphere ∂ uθ 1 ∂ur 3ηU0
τrθ =η r + =− sinθ
at the origin of the spherical coordinates and to ∂r r r ∂θ r=D/2 D
have the undisturbed upstream velocity of the
The other components of the deviatoric stress
fluid parallel to the θ = 0 line (see Fig. 11). In this
are zero on the surface. The drag force F d is ob-
coordinate system, ur and uθ are the only two
tained by integrating the resulting Cauchy stress
nonvanishing velocity components. The Newto-
over the entire surface of the sphere. From the
nian fluid is assumed to adhere to the surface of
symmetry of the problem, it is clear that the drag
the sphere (the no-slip boundary condition), i.e.,
force is in the same direction as the undisturbed
velocity:
ur =uθ = 0 at r=D/2 (59)
π 2π
3ηU0
Fd = −p0 + cosθ cosθ+
Far away from the sphere, u approaches the uni- D
ϕ=0 θ=0
form velocity U 0 , i.e.,

3ηU0
ur =U0 cosθ, uθ = −U0 sinθ as r→∞ (60) sin2 θ R2 sinθdθdϕ= 3πηDU0
D
Next Page
Fluid Mechanics 387
This result is often referred to as Stokes law. One shown in Figure 47) The laminar flow eventually
of the practical applications of Stokes law is the gives way to turbulent flow, and C d is expected
falling ball viscometer. Here the terminal veloc- to change dramatically with Re. Experimentally
ity of a small sphere of known diameter that falls measured drag coefficients as a function of Re
through a fluid is measured. When the sphere has are shown in Figure 12. The validity of Equa-
attained its terminal velocity, the drag force on tions (67) and (68) is restricted to Re less than
the sphere is exactly balanced by it weight, i.e.: ca. unity with the range of validity of Equation
(68) slightly larger than that of Equation (67).
4
Fd = π (D/2)3 ∆g = 3πηDU0 (64) For Re in the range 1 to 103 , C d can be approx-
3
imated by
where ∆ is the difference between the density
of the solid sphere and the fluid. This then yields Cd ≈ 18Re−0.6 (69)
a simple expression which allows the fluid vis-
cosity to be calculated from measurable quan- And for 103 ≤ Re ≤ 2×105 , C d is approxi-
tities such as the densities of the fluid and the mately constant
sphere, and the terminal velocity:
Cd ≈ 0.44 (70)
1 D2 ∆g
η= (65) For a detailed description of the flow phenomena
18 U0
at increasing Re, including the sudden decrease
Usually the drag force F d is expressed in terms in C d at Re ≈ 2×105 , see [1].
of a dimensionless drag coefficient C d obtained
by dividing F d by 12 U02 LIVE GRAPH
Click here to view
and by the cross-sectional area of the sphere
normal to the velocity U 0 ; thus the drag coeffi-
cient is
3πηDU0 24η
Cd = 1 2 πD 2 /4
= (66)
2
U 0 U 0D
In terms of C d and the Reynolds number

Re = U 0 D/η, Stokes law takes the form
Cd = 24/Re (67)
This result was obtained for Re much smaller

than unity: in this case the error incurred is ac- Figure 12. Log – log plot of drag coefficient on a sphere as
a function of the Reynolds number
ceptable for most practical purposes. For larger
Re, the inertia terms can no longer be ignored
and additional terms must be included in the ex-
pression for C d . The result now takes the form 3.4. Some Other Important Flows
of an infinite series in Re, the leading terms are
3.4.1. Flow Through Granular Beds
24 3 9
Cd = 1+ Re+ (lnRe) Re2 +... (68)
Re 16 160
The flow of fluids through granular beds occurs
The validity of this series extends to Re of the or- widely in industry and in nature, some examples
der of unity. The mathematical analysis leading are flow of water down a filter bed, seepage of
to this series is described in [2]. oil through porous underground soil structure,
Expressions (67) and (68) for C d are based and flow of chemicals in a packed bed reactor.
on the assumption that the flow remains steady The key variable in the study of flow through a
and laminar and Re is small. As Re is increased, granular bed is the volumetric flow rate per unit
the flow pattern around the sphere becomes cross-sectional area of the bed, Q/A. This flow
more and more complicated. (See the numer- rate depends on the density and viscosity η
ically generated flow pattern around a cylinder of the fluid, the average size (and shape) of the
Previous Page
388 Fluid Mechanics
particles Dp that make up the bed, the applied 3.4.2. Fluidization

pressure gradient ∆ p/L across the bed, and the
porosity of the bed ε. The relationship between
these variables can be expressed in the general Fluidization is a common operation in the pro-
form cess industry in which a fluid stream, usually
gas, is used to ensure thorough mixing of a bed
∆p/L=f (Q/A,,η,ε,Dp ) of solid particles. The gas stream is passed verti-
cally upward through the solid bed. The pressure
The exact form of the function in this equation drop across the solid bed (or equivalently the up-
is expected to be complex and cannot be de- ward drag force on the particles) increases with
termined from fundamental considerations only. the gas velocity. At a sufficiently high gas veloc-
It must therefore be determined by experimen- ity the drag force becomes equal to the weight
tal measurements. A clearer understanding of of the individual particles and the particles enter
the influence of each of these variables can be a weightless state. Further increase in gas veloc-
achieved by presenting the experimental results ity is not accompanied by an increase in pressure
in a dimensionless form. For the present prob- drop (see Fig. 13), instead the bed begins to ex-
lem, the relevant dimensionless variables are an pand. The bed of solid particles now acquires
appropriately defined friction factor f and an ap- many of the properties normally associated with
propriately defined Reynolds number: a fluid, such as the ability to flow freely; it is said
to be fluidized. The weightless particles move
Dp ε3 ∆p rapidly and randomly throughout the expanded
f= (71)
2 (1−ε) L
U∞ bed, thereby ensuring thorough mixing. This is
exploited, for example, in a fluidized-bed reac-
Dp U∞ tor where the solid particles may be the catalyst
Re= (72) on which an exothermic chemical reaction takes
(1−ε) η
place. The random motion in the fluidized state
U ∞ is the superficial velocity and is defined by results in good particle – particle and particle –
U ∞ = Q/A. From the accumulated data in the lit- wall contact and hence in an efficient removal of
erature, it can be shown that f and Re are reason- the heat of reaction.
ably correlated by the following semi- empirical
expressions:
f = 150/Re for Re<10

150
f = 1.75+ for 10<Re<1000
Re
f = 1.75 for 1000<Re (73)
This set of expressions for f is known as the

Ergun relationship. At low Re, corresponding to
inertialess laminar flow through the bed, the fric-
tion factor is proportional to the reciprocal of Re,
as is the case of laminar flow in a circular pipe.
This appears to be a general property of lami-
nar flow of Newtonian fluids. The Ergun rela- Figure 13. Variation of pressure drop ∆p with flow rate u
in a granular bed showing the leveling of pressure drop after
tionship was based on experimental data – pres- the onset of fluidization (uf )
sure drop in granular beds of spherical particles.
For nonspherical particles, Dp must be replaced One of the key variables in the operation of
by the hydraulic diameter, which is defined by a fluidized bed is the minimum superficial gas
Dhy = 4× volume of particle/surface area of par- velocity uf needed to maintain the particles in
ticle wetted by fluid. For a granular bed of par- the fluidized state. This minimum velocity can
ticles which deviate greatly from sphericity, a be estimated using the Ergun equation (73) for
shape factor may have to be introduced. the pressure drop ∆p in a packed bed. The force
Fluid Mechanics 389
exerted by the gas stream on a bed of solid parti- arrangement of the pipe. Some of the flow pat-
cles of cross-sectional area A is given by A ∆p. terns that can be observed in a gas – liquid stream
At the point of fluidization, this is equal to the flowing up a vertical tube are shown in Figure 14
weight of the bed, i.e. together with the terms used to describe the var-
ious flow regimes.
A∆p= (p −) gAH (1−ε) (74)
where H is the height of the bed and ε is its

porosity; (p − ) is the difference between the
density of the solid particles and the gas; and ∆p
is given by the Ergun equation. Since, in most
fluidized beds, the particle size is small and the
Reynolds number is often < 10, the friction fac-
tor in the Ergun equation can be approximated
by 150/Re. Substituting this result into Equation
(74) gives the following expression for uf
(p −) gDp2 ε3
uf = (75)
150η (1−ε)
The difficulty with using Equation (75) lies in

the uncertainty of estimating the value of ε, the
porosity of the bed at the point of fluidization. In Figure 14. Flow patterns for gas – liquid flow in vertical
the absence of experimental data, ε3 /(1 − ε) can pipes [12]
be approximated by 0.091. For a more accurate A) Bubble flow; B) Slug flow; C) Churn flow; D) Annular
estimation of the minimum fluidization velocity, flow
it is also necessary to take into account the non-
spherical shape of the particles. A large number
LIVE GRAPH
of semi-empirical correlations exist in the lit- Click here to view
erature on fluidization which take into account
these and additional factors [10].
3.4.3. Gas – Liquid Flow
Many industrial operations require the handling

of fluid streams composed of two distinct phases.
The two phases can be a gas and a liquid, two
immiscible liquids, or a suspension of fine solid
particles in a gas or liquid. The flow behavior of
a two-phase stream is considerably more com-
plicated than that of a single-phase fluid. Inves-
tigation of two-phase flow is an active area of
research with an extensive literature. This sec- Figure 15. Map of different flow regimes for gas – liquid
tion provides only a brief qualitative description flow in vertical pipes [11]
of gas – liquid flow in tubes, probably the most In the bubble flow regime (Fig. 14A), ob-
frequently encountered two-phase flow. served at very low gas flow rates, the gas phase
Flow in Vertical Tubes. One of the most dis- exists in the form of many small bubbles dis-
tinctive features of gas – liquid flow is the large tributed in the continuous liquid phase. As the
number of flow patterns that can be observed. gas rate is increased, the bubbles grow and co-
The flow patterns in a pipe for example, depend alesce to form large slugs. The transition from
on the velocity of the two phases, their physical bubble flow to slug flow (Fig. 14B) is gradual.
properties, pipe diameter, and the geometrical
390 Fluid Mechanics
Figure 16. Flow patterns for gas – liquid flow in horizontal pipes [13]
A) Bubble flow; B) Plug flow; C) Stratified flow; D) Wavy flow; E) Slug flow; F) Annular flow; G) Spray
The slug diameter is of the order of the tube di-

ameter. Most of the gas phase now resides within
the slugs with only a small fraction dispersed as JG =G/ πD2 /4
small bubbles in the liquid bridges separating
where L is the volumetric flow rate of the liq-
the slugs. A thin liquid film remains between
uid phase and G is that of the gas phase; D is
the slug and the tube wall. When the gas rate is
the tube diameter. The boundaries between the
increased further this film suddenly becomes un-
various flow regimes are far from well defined.
stable and churn flow (Fig. 14C) takes over. Here
They also depend on the physical properties of
the flow is highly chaotic and the slugs eventu-
the gas and liquid, and on the diameter of the
ally lose their identity. At yet higher gas rates
tube. Like most flow regime maps reported in
the flow becomes more steady. The gas phase
the literature, Figure 15 is based on data col-
now becomes the continuous phase occupying
lected for air – water systems at normal temper-
the central core of the tube with an annular, usu-
ature and pressure in a tube 25 mm in diameter.
ally wavy, liquid film (Fig. 14D) lining the tube
Using this map to determine the flow pattern of
wall. There is also a fine mist of liquid droplets
two-phase systems with vastly different prop-
entrained in the continuous gas phase.
erties or in much larger or smaller tubes is not
One of the objectives of gas – liquid flow
recommended.
experimentation is to determine the conditions
Flow in Horizontal Tubes. As expected, the
for the transition from one flow regime to an-
observed flow patterns of a gas – liquid stream
other. Experimental observations are often sum-
in a horizontal tube differ significantly from that
marized in the form of a flow regime map. Fig-
in a vertical tube. In the horizontal tube the two
ure 15 is a typical map for gas – liquid flow in
phases are more likely to segregate because of
a vertical tube. The horizontal and the vertical
their density difference. Figure 16 is the hori-
axes are the superficial liquid velocity J L and
zontal analogue of Figure 14. Similar terms are
gas phase velocity J G , respectively. These are
used to describe the observed flow patterns at
defined by

increasing gas flow rates. At low gas flow rates,
JL =L/ πD2 /4 the gas phase exists as bubbles (Fig. 16A) which
Fluid Mechanics 391
move along the upper part of the tube at approx- rected at solving the equations of motion for
imately the same speed as the liquid phase. In- two-phase flow and the development of corre-
creasing gas flow will gradually lead to plug lations that can be used in design calculations.
flow (Fig. 16B), where alternate plugs of liq- Details of these can be found in [11–15].
uid and gas move along the upper part of the
tube. In stratified (Fig. 16C) and in wavy flow
(Fig. 16D) the two phases occupy different parts 3.5. Mechanical Energy Balance for
of the tube. In stratified flow the gas – liquid in- Macroscopic Systems
terface is relatively smooth while in wavy flow
the higher gas velocity causes the interface to be- The solution of pipe network flow problems for
come wavy. When the interface becomes grossly a macroscopic system such as that illustrated in
distorted, the gas phase becomes separated into Figure 18 is often of extreme importance. Once
slugs (Fig. 16E) which move through the tube at again the three basic conservation principles are
a higher speed than the liquid phase. In annular required but this time expressed for a system
flow (Fig. 16F), the liquid flows as a thin film of finite size. At steady state the statements of
lining the wall of the tube and the gas flows at a conservation of mass and energy for the control
higher speed in the central core. The liquid film volume shown in Figure 18 are
is thicker at the bottom half of the tube and is
9 : 9 :
generally not smooth. A part of the liquid phase 1 u1 A1 =2 u2 A2 =W (76)
exists as droplets entrained in the gas stream. At
very high gas rates, the liquid film completely and
disintegrates and the liquid phase is carried as 9 3: p2
a fine spray (Fig. 16G) by the high speed gas 1 u dp
∆ 9 : +g∆z + +E v + Ws = 0 (77)
stream. 2 u
p1
LIVE GRAPH
Click here to view
where W is the mass flow rate, the fluid density,
A the cross-section of the flow, u the flow veloc-
ity, z the height above some arbitrary datum, p
the pressure, g the acceleration due to gravity,
W s the shaft work, i.e., pump work, E v the fric-
tion loss, and is used to denote average value.
Each of the terms in Equation (77) has the unit
of energy per unit mass; ∆ refers to the outlet
minus the inlet conditions. Since the velocity u
across any flow cross-section is not in general
uniform, an average velocity V defined by

9 : 1
V= u = udA (78)
A
A
and for tube flow by
Figure 17. Map of different flow regimes for gas – liquid R

9 : 1
flow in horizontal pipes [14] V= u = 2πrudr (79)
πR2
0
The regime map for gas – liquid flow in a hor-
izontal tube is shown in Figure 17. The vertical must be used in the mass and energy balances.
axis is the superficial liquid velocity and the hor- For turbulent flow prior knowledge of the veloc-
izontal axis is the gas velocity. Figure 17 was ity distribution at a particular cross-section is of
constructed from data for air – water mixtures in little consequence because the velocity is essen-
tubes with diameter < 100 mm. tially uniform across the cross-section, i.e.,
Apart from mapping the flow regimes in gas – 9 3:
9 : u V3
liquid flows, considerable effort has been di- u =V and 9 : = =V 2 (80)
u V
392 Fluid Mechanics
and for an incompressible fluid 3.5.1. Fully Developed Tube Flows
p2
dp 1 Consider the control volume shown in Figure 19
= (p2 −p1 ) (81)
for fully developed tube flow. Application of
p1
Equation (84) to this control volume yields
Thus, for turbulent flow of an incompressible
fluid Equation (77) reduces to: p1 − p2
E vfd = (85)

2
V p2 −p1
∆ +g∆z + +E v+Ws = 0 (82)
2 That is, the energy loss per unit mass is simply
the pressure drop divided by the fluid density.
Equation (82) is sometimes referred to as the Application of a force balance to the same con-
mechanical energy balance. If in addition no trol volume yields
shaft work W s crosses the system boundary, then
πR2 (p1 −p2 ) =τw 2πRL (86)
V2 p2 −p1
∆ +g∆z + +E v = 0 (83)
2
or
this is identical to Equation (26), the Bernoulli
equation. Both the mechanical energy balance R (p1 −p2 ) D (p1 −p2 )
and the Bernoulli equation are not generally ap- τw = = (87)
2L 4L
plicable to all flow situations.
For isothermal flow of incompressible fluids and at any radius r
(laminar and turbulent flow, Eq. 76)
9 : 9 : r (p1 − p2 )
τrz = (88)
1 u1 A1 =2 u2 A2 =W 2L
and Elimination of ( p1 − p2 ) from Equations (87)

: 9
and (88) leads to
1 u3 p2 −p1
∆ 9 : +g∆z + +E v + Ws = 0 (84)
2 u r
τrz = τw (89)
R
The problem is to evaluate the terms in Equation
(84) so that the performance of an existing flow Equation (89) indicates a linear distribution of
system can be evaluated or a new flow system shear stress in a tube from zero at the center-
can be designed [16]. line to τ w at the wall. This relationship is valid
The major unknown in Equation (84) is the for Newtonian and non-Newtonian fluids and for
friction loss term E vv. The friction loss term is laminar and turbulent flows.
conveniently split into a contribution due to fully Frictional losses for fully developed flows are
developed flows in long, straight sections of the expressed in terms of the friction factor (Eq. 48).
pipe and an excess contribution due to losses in Combination of Equations (85), (87), and (48)
valves, bends, fittings, expansions, contractions, leads to the Fanning equation:
etc:
2f V 2 L
E vfd = (90)
E v=Evfd +Evex D
E vex is determined from experimental observa- which is the basic equation for defining the fric-
tion whereas E v fd can in some instances be de- tional losses for fully developed flow in pipes.
termined from fundamental principles. The eval- For Newtonian fluids f is given by Equation (48)
uation of E v fd for tube flows is considered in for laminar flow and by Equations (49), (50), and
Section 3.5.1. (51) for turbulent pipe flow.
Fluid Mechanics 393
Figure 18. Generalized representation of a control volume for a flow system
3.5.2. Accelerating and Decelerating Flows

4
1 V2 D2 V22
In any flow system (in addition to fully devel- ∆V 2 = 2 1− = ,
2 2 D1 2
oped flows in long straight pipes) it is essential if D1 >>D2 (94)
that energy losses which occur in the accelerat-
ing and decelerating flow in valves, bends, ex- Also
pansions, contractions, and fittings can be es-
timated. For turbulent flow these losses must E v1,2 =E vfd1,2 + E vex1,2 (95)
be evaluated from available experimental data, Then
whereas numerical simulation results are now
becoming available for some laminar flows. p1 − p2 V2
E vex1,2 = − 2 −E vfd1,2 (96)
As an example consider the flow through a 2
sudden contraction in pipe diameter as is illus- Now E v fd1, 2 will be known at a fixed flow rate,
trated in Figure 20. Application of the mechan- as will V 2 . Hence measurement of p1 − p2 is suf-
ical energy balance (Eq. 84) between stations 1 ficient to define E v ex1, 2 . It is found that the re-
and 2 yields sulting measurements for most situations can be
9 3: generalized in the form
p1 − p2 1 uz
= ∆ 9 : +E v1,2 (91) E vex
2 uz =C (97)
V2
2
Suppose the flow is turbulent, then
where C is the dimensionless loss coefficient.
9 : Loss coefficients are tabulated in many standard
1 u3z 1 V 2 −V12
∆ 9 : = ∆V 2 = 2 (92) handbooks such as in [17]. A great deal of con-
2 uz 2 2
fusion can arise in the use of loss coefficients.
For incompressible flow, conservation of mass Sometimes C is referred to as the number of ve-
(Eq. 76) yields locity heads. This number times V 2 /2 yields the
excess energy loss for that particular fitting. If
2 loss coefficients are used to estimate losses in
D1
V2 =V1 (93) valve and fittings, etc., then the total frictional
D2
loss for a flow system is simply the sum of the
and then individual components:
394 Fluid Mechanics
2f V 2 L CV 2 2 at or just downstream of the plate. Station 1 is

E vtotal = + (98)
D 2 sufficiently far upstream so that the flow there is
Another and perhaps more convenient way to undisturbed by the presence of the orifice plate.
determine E vtotal for a flow system is to use the Neglecting losses due to fluid friction, the av-
Fanning equation in the form erage pressure and velocities between these two
stations are related by Equation (83). In addition,
2f V 2 L 2f V 2 L e from a mass balance
E vtotal = + (99)
D D
where L is the length of straight pipe of di- u1 A1 =u2 A2 (100)
ameter D between fittings and L e the approxi- Combining these two equations leads to
mate length of straight pipe of diameter D which
3
would have the same energy loss as the fitting. 4
4 2∆p
Equivalent length data for various fittings are Q=u1 A1 =A1 4 2 (101)
5 A
available in standard references, for example in A12 −1
2
[18]. A sufficient amount of data for C and L e
have been tabulated for good design of turbulent Equation (101) defines the volumetric flow rate
pipe flow systems. Very little data are available Q, in the pipe in terms of the measured pressure
for laminar flows and almost no results are avail- difference between stations 1 and 2. The losses
able for non-Newtonian fluids in both laminar between 1 and 2 are not taken into consideration.
and turbulent flows. Losses can be accounted for by the incorpora-
tion of an empirical correction factor known as
the discharge coefficient C d into the equation for
volumetric flow rate
3
4
4 2∆p
Q=Cd A1 4 2 (102)
5 A
A12 −1
2
Figure 19. Control volume for fully developed tube flow C d is usually in the range 0.59 – 0.65. Its ex-
act value depends on the geometry of the ori-
fice plate, such as the size and shape of the hole
and the location of the pressure measurement
points. It also depends, to a lesser extent, on the
Reynolds number in the pipe. C d can either be
determined by direct calibration or, in the case
of an orifice plate of standard design, from ta-
bles and correlations published by organisations
such as the ISO.
Figure 20. Schematic diagram for flow through a sudden

contraction
3.5.3. The Orifice Plate and Similar Flow

Rate Measurement Devices
In many chemical plants a simple device known

as an orifice plate, (see Fig. 21) is used to mea-
sure the volumetric flow rate of fluids in turbu-
lent pipe flow. In its simplest form the orifice
plate is a disk with usually (but not always) a
circular hole through which the fluid flows. Con-
sider station 1 upstream of the plate and station
Figure 21. Flow through an orifice plate
Fluid Mechanics 395
A number of other flow measurement devices at point A (Fig. 22A). All of the work done on
based on the Bernoulli equation with an empir- an inelastic fluid is dissipated as heat and cannot
ical correction for losses are also in common be recovered. After removing the force acting
use. Examples are the pitot tube and the venturi on the ideally elastic or Hookean solid, the solid
meter. In each case the volumetric flow rate is particle at point A will recoil to
obtained from the measured pressure difference
using an equation similar to that for the orifice
plate. The value of C d must be determined for
each device.
4. Non-Newtonian Fluids [4], [19]

For fluids such as polymer solutions, molten
plastics, emulsions, suspensions and many oth-
ers, the deviatoric stress tensor may not be di-
rectly proportional to the rate of strain tensor
and the simple Newtonian constitutive equation
does not describe the flow behavior of these flu-
ids. For such fluids, the viscosity, defined as the
ratio of shear stress to shear rate, is now a func-
tion of the rate of strain tensor e:
τ = 2η (e) e (103)
Equation (103) is the generalized Newtonian

Figure 22. Inelastic and viscoelastic fluids
constitutive equation. The viscosity of some A) Viscous, inelastic liquid, work dissipated as heat; B) Elas-
non-Newtonian fluids can change by several or- tic solid, work recoverable; C) Viscoelastic fluid, part of
ders of magnitude as a result of shearing. Such work recoverable
behavior has serious practical consequences for
its original position (Fig. 22B). All of the work
the handling of these fluids. Apart from their
done on an elastic solid is recoverable. For a
variable viscosity, these complex fluids often ex-
viscoelastic fluid partial elastic recovery is ob-
hibit other flow behavior – such as stress relax-
served. The fluid particle at point A recovers to
ation, normal stresses, and stresses that depend
an intermediate position B (Fig. 22C). A portion
on strain history – which are not observed in
of the work done on a viscoelastic fluid is recov-
Newtonian fluids and also cannot be accounted
erable and the remainder is dissipated as heat.
for by the generalized Newtonian constitutive
In fact, the amount of recovery depends on the
equation. Some non-Newtonian fluids exhibit
rate at which the displacement dx is imposed.
some of the characteristics of an elastic solid
In general, increasing the displacement rate in-
and thus are referred to as viscoelastic fluids.
creases the recovery. An inelastic fluid can be
The simple imaginary experiment shown in Fig-
described sufficiently by measuring its viscos-
ure 22 helps to visualize the difference between
ity and by determining the variation of viscosity
inelastic and viscoelastic fluids. Imagine a fluid
with shear rate, time of shear, and, in some in-
confined between two flat plates where a force
stances, thermal history. The viscosity is a steady
is applied to the upper plate, resulting in the dis-
state concept and is also applicable to viscoelas-
placement of a fluid particle just below the upper
tic fluids without any modification. In addition
plate through a distance dx. Also imagine a sim-
to the viscosity, however, there are other fun-
ilar experiment for an elastic solid. The work
damental properties which must be measured
done in displacing the fluid or solid particle a
to adequately characterize a viscoelastic fluid.
distance dx is then F dx. If an inelastic fluid is
The distinction between inelastic and viscoelas-
confined between the flat plates, on removing the
tic fluids is clearly one of time scales. If man-
force F, the fluid particle at point A will remain
396 Fluid Mechanics
ifestation of recoverable elastic deformation is τy

observed on a time scale of interest, then the ma- η= +ηpl for τ ≥τy (104b)
|γ̇|
terial is viscoelastic. In practical terms molecu-
lar relaxation times of < 10−3 s can probably be The stress is undetermined when | τ | < τ y . The
ignored in all cases. Viscoelastic fluids will be term γ̇/| γ̇ | is necessary to ensure that the stress
dealt with in Section 4.3. takes on the same sign as the shear rate and η pl
is the plastic viscosity. The true viscosity η ap-
proaches η pl only when η pl | γ̇ | >> τ y . In con-
4.1. Classification of Fluids According to trast the viscosity for the Bingham and any yield
Viscosity Behavior stress material becomes unbounded as | γ̇ | → 0.
When the shear stress – shear rate function is
In Section 3.1 it has been shown that in one- nonlinear the data are often fit by a Herschel –
dimensional flows the shear rate γ̇ is equal to the Buckley model:
velocity gradient for that flow. Since the viscos-
ity is measured in one-dimensional flows (visco- τy
τ= +k γ̇ n−1 γ̇ for |τ |≥τy (105a)
metric flows) the fluid behavior is classified ac- |γ̇|
cording to the observed shear stress – shear rate τy
behavior in one dimension. A graph of the mea- η= +k|γ̇|n−1 for |τ |≥τy (105b)
|γ̇|
sured shear stress as a function of shear rate is
called the flow curve. The parameters k and n are obtained by plotting
τ − τ y versus γ̇ on logarithmic coordinates. An-
other equation often used to describe yield stress
materials is the Casson equation
1/2
2
τy 1/2
τ= 1/2
+ηpl γ̇ for |τ |≥τy (106a)
|γ̇|
1/2
2
τy 1/2
η= 1/2
+ηpl for |τ |≥τy (106b)
|γ̇|
Typical shear stress – shear rate data for a meat

extract concentrate and for a tomato soup con-
centrate are presented in Figures 24 and 25, re-
spectively. The meat extract behaves like a Bing-
ham solid while the tomato soup concentrate ex-
hibits Herschel – Buckley behavior.
Figure 23. Typical flow curves
LIVE GRAPH
Click here to view
4.1.1. Bingham Type Behavior
Bingham type material exhibits a yield stress.

That is, the shear stress τ must exceed a cer-
tain yield value τ y before the fluid deforms and
flows. Classical Bingham plastic behavior is il-
lustrated in Figure 23 and can be described by

τy
τ= +ηpl γ̇ for τ ≥τy (104a)
|γ̇| Figure 24. Shear stress – shear rate data (flow curve) for a
i.e., meat extract
Fluid Mechanics 397
LIVE GRAPH less entangled and less resistant to deformation
Click here to view
as the deformation rate is increased.
The viscosity of pseudoplastic fluids is typ-
ically plotted versus shear rate on logarithmic
coordinates because the viscosity for such fluids
can change by orders of magnitude over sev-
eral decades of shear rate. The data for the poly-
acrylamide solution shown in Figure 26 are typ-
ical for a macromolecular fluid. The viscosity
approaches a constant value at low shear rates
called the zero-shear viscosity η 0 and a constant
Figure 26. Viscosity as a function of shear rate for a poly-
value in the limit of very high shear rates called
acrylamide solution the infinite shear viscosity η ∞ . Experimental
measurements in both regions can be difficult,
LIVE GRAPH
Click here to view particularly in the infinite shear region. Thus
data are often only available between the two
limits. Between the two limits the shear stress
(or viscosity) is often linear with shear rate over
several decades on logarithmic coordinates. In
this restricted region
logτ = logk+nlogγ̇ (107a)
logη= logk+ (n−1) logγ̇ (107b)
where n is the slope in the linear region of the

plot (n = 0.41 for the data in Fig. 26). Thus
Figure 25. Shear stress – shear rate data (flow curve) for a
tomato soup concentrate
τ =k|γ̇|n−1 γ̇ (108a)
The yield stress is associated with a three-
η=k|γ̇|n−1 (108b)
dimensional structure that must deform elasti-
cally before flow can occur. It is commonly ob- Equation (108) is known as the power law and
served in fine particle suspension systems, espe- sometimes as the Ostwald – de Waele model.
cially at high particle concentrations. Common This law is empirical and must fail for both high
examples are toothpaste, paint, oil well drilling and low shear rates. The factor k is very tem-
muds, foams, and many food and pharmaceuti- perature sensitive (and concentration sensitive
cal products. for suspensions), but n is typically insensitive to
temperature (and concentration) changes.
4.1.2. Shear-Thinning (Pseudoplastic) Fluids Many empirical and semi- empirical equa-
tions have been proposed to represent the vis-
Solutions and melts of flexible macromolecules cosity data for shear-thinning fluids. The Meter
and many suspensions exhibit pseudoplastic model:
shear stress – shear rate behavior such as that il- η 0 − η∞
η=η∞ + α−1 (109)
lustrated in Figure 23 and shown specifically for
1 + τ τ
a polymer solution in Figure 26. Here the ra- 1/2
tio τ /γ̇ (i.e., η) is a decreasing function of γ̇. has four parameters, η 0 , η ∞ , τ 1/2 , and α with
Such a fluid has a shear-thinning viscosity and the following asymptotic behavior
is referred to as pseudoplastic. The decrease of
viscosity with increasing rate of deformation can τ
→ 0, η≈η0 (109a)
usually be attributed to the breakdown of a struc- τ1/2
ture at the colloidal or molecular level. Macro- τ
→ ∞, η ≈ η∞ (109b)
molecules will become more aligned and hence τ1/2
398 Fluid Mechanics
and for suspension is shown in Figure 27 where at the

highest volume fraction of solids (42.5 %) the
τ α−1 viscosity increases with shear rate beyond a crit-
η0
1<< <<
τ1/2 η∞ ical shear rate. The increase in stress observed
at this point is related to a shear-induced struc-
then ture. The phenomena is easily illustrated in the
η 0 − η∞
kitchen by mixing a concentrated suspension of
η= 1−α
|τ |1−α (109c) corn starch and water. Data for shear-thickening
τ1/2
liquids are usually fit by equations such as those
The Meter model exhibits power-law behavior for shear-thinning fluids but with η ∞ = 0 and
in the intermediate region, with α = 1/n; τ 1/2 n > 1 (or α < 1). Dramatic equipment failures
is the stress at which the viscosity is midway have been documented in the processing indus-
between the values of η 0 and η ∞ . If η ∞ is tries where a dilatant fluid response was not an-
taken to be zero, which is often a good approx- ticipated.
imation for molten polymers, then τ 1/2 is the
stress at which the viscosity drops to one-half
the zero-shear value. In this case Equation (109) 4.1.4. Fluids with Time-Dependent Viscosity
is known as the Ellis model. Line (a) through the ( Thixotropic Fluids)
data in Figure 26 is the fit of the Meter model
A special nomenclature is used in cases when
to the data with η 0 = 1.43 Pa s, η ∞ = 0.004 Pa s,
the viscosity varies with the time of shear and
τ 1/2 = 1.21 Pa, and α = 2.43. The power-law fit
the shear rate. A material whose apparent vis-
is line (b) with n = 0.41 (= 1/α). The Ellis model
cosity decreases with the time of shear is said to
follows the Meter model at low shear rates (in-
be thixotropic and one whose viscosity increases
corporating the zero-shear viscosity behavior)
with time of shear is said to be rheopectic. The
and the power-law at higher shear rates.
behavior of these materials depends not only on
LIVE GRAPH the time of shear but also on the past shear and
Click here to view
thermal history. Rheopectic fluids are encoun-
tered very rarely and hence the discussion in this
section will be confined to thixotropic fluids.
Figure 27. Shear stress – shear rate for a titanium dioxide

suspension [20]
4.1.3. Shear-Thickening (Dilatant) Fluids Figure 28. Time dependent fluids
Some suspensions with a high concentration of If the flow curve is measured in a single ex-
solids and with a relatively uniform particle-size periment in which the shear rate is steadily in-
distribution have a viscosity that increases with creased at a constant rate from zero to some max-
shear rate. An example for a titanium dioxide imum value and then decreased at the same rate
Fluid Mechanics 399
to zero shear rate, a form of a hysteresis loop as 4.2. Fully Developed Tube Flow
is shown in Figure 28 is observed. The position
of this loop, its shape, and the area within the
The flow in tubes ( pipes) of circular cross sec-
loop depends on the rate at which the shear rate
tion is the flow field of the greatest interest. For
is increased and decreased as well as the past
non-Newtonian fluids this is not only important
thermal and shear history of the material. This
because of processing applications but also be-
type of measurement has little meaning for the
cause of the extreme importance of tube flow
solution of practical flow problems. What is re-
in the measurement of viscosity. Both laminar
quired is a series of experimentally determined
and turbulent flows will be considered. However,
shear stress – shear rate – time curves which can
because of the sticky, gooey, or highly viscous
then be converted to a series of flow curves with
nature of non-Newtonian fluids, most applica-
time of shear as the parameter. Because of the
tions are in laminar flow. For instance a typical
dependence of these curves on shear and thermal
Reynolds number in polymer processing might
history it is important that the curves represent
be 10−3 . The energy required to reach turbu-
the behavior of a sample of material which has
lent flow for many non-Newtonian fluids is sim-
experienced a history approximately the same as
ply prohibitive. The treatment here is confined
that anticipated for the fluid whose flow behavior
to fully developed tube flows, i.e., flow in long
is to be analyzed.
straight tubes where the velocity profile is not a
The difference between thixotropy and pseu-
function of axial position. Important results re-
doplasticity is thought to be the time element in
quired from the discussion of Newtonian fluids
structural breakdown, which is finite and mea-
include the definition of the friction factor (cf.
surable for the thixotropic fluid and in contrast
Eq. 48)
very small and undetectable for the pseudoplas-
tic fluid. A practical example of time- dependent τw
behavior is the waxy crude oils which in ad- f=
V 2
dition also exhibit a yield stress (see Fig. 29). 2
It should be noted that a fluid can show time-

dependent and viscoelastic behavior (for vis- the general results for the shear stress in tube
coelastic behavior see Section 4.3). Some liquid flow, i.e., Equations (88) and (87)
crystal polymers appear to be rheopectic and vis-
r∆p
coelastic. τrz =
2L
LIVE GRAPH
Click here to view
R∆p D∆p
τw = =
2L 4L
and (Eq. 89)
r
τrz = τw
R
and Equation (44) which defines the volumetric

flow rate
R
Q= 2πruz dr
0
The results obtained for fully developed tube

flow will be valid for time-independent inelastic
Figure 29. Shear stress versus time of shear for an Australian and viscoelastic fluids. Elastic effects are impor-
waxy crude oil at 10 ◦ C and a shear rate of 458 s−1 tant in accelerating and decelerating flows and
in time- dependent flow fields only.
400 Fluid Mechanics
4.2.1. Volumetric Flow Rate – Pressure Drop

Relationship τ 1/n
Q n w n R∆p 1/n
= = (117)
πR3 (3n+1) k (3n+1) 2Lk
Equation (44) can be used to obtain a general re-
lationship between Q and τ w for fully developed For n = 1 Equation (117) reduces to the Hagen –
tube flows. Integration by parts yields Poiseuille equation derived in Section 3.3.1. The
pressure drop for a pseudoplastic fluid is rela-
R
tively insensitive to changes in the flow rate as
Q=π uz r2 − r2 duz (110)
0 compared to a Newtonian fluid. Thus flow rate
measuring devices like the orifice plate that rely
At the tube wall (r = R) uz = 0, then on the measurement of differential pressure are
R not very suitable for shear-thinning fluids, par-
Q= − π r2 duz (111) ticularly if the flow behavior index n is low.
0
Equation (114) can be integrated for any of
the semi-empirical equations which have been
The shear rate in fully developed tube flow is proposed to represent shear stress – shear rate
duz /dr and is a unique function of the shear stress data. The volumetric flow rate – wall shear stress
τrz : results obtained by this integration for a num-
ber of fluids may be summarized as follows
duz
= − f (τrz ) (112) (τ w = R ∆p/2 L):
dr
Q τw
Newtonian fluid = 14
The minus sign is introduced because duz /dr is π R3 η τ 4
Q τw yτ y
negative (uz decreases from a maximum value Bingham plastic π R3
= 4η 1− 43 τw + 13 τw
pl
τw 1/n
at r = 0 to zero at r = R). Then Power-law Q
π R3
n
= 3n+1 k
τwα
Q
Ellis fluid π R3
= 4η1 τw + (α+3)η
0 0 τ1/2 α−1
duz = −f (τrz ) dr (113)
Eliminating r from Equations (111) and (113)

with Equation (89) and then substituting for duz
in Equation (111) with Equation (113) yields 4.2.2. Generalized Treatment
τw If Equation (114) is multiplied by τ 3w and differ-
Q 1 2
= 3 τrz f (τrz ) dτrz (114) entiated with respect to τ w
πR3 τw
0
duz 1 dQ
Equation (114) is an important result which can − =f (τw ) = 3Q+∆p (118)
dr τw πR3 d∆p
be used in two ways: (1) integrated directly for a
particular fluid model such as those represented where f (τ w ) is the wall shear rate γ̇ w . In arriving
by Equations (105), (106), (108), and (109) or at the above, Equation (87) was used to replace
(2) differentiated which leads to the definition τ w by the more directly measurable quantity ∆p.
of the wall shear rate for any fluid. Equation (118) can be rearranged to
Consider the integration of Equation (114)
3n +1 8V
for a power-law fluid. For tube flow of a power- γ̇w = (119)
4n D
law fluid
where
n
duz
τrz = − k (115) dlnτw
dr n = (120)
dln 8V
D
and
and
V is the average velocity in the tube
τ 1/n
f (τrz ) = −
duz
=
rz
(116) V = πQ
R2 .
dr k
Equation (118) and the rearranged form
Substitution for f (τrz ) in Equation (114) and (Eq. 119) is the Rabinowitsch – Mooney equa-
integration leads to tion which enables the calculation of the wall
Fluid Mechanics 401
shear rate from the measurable quantities, R, Q for the shear rate or the 8 V/D range in which they
or V , and ∆ p. Thus measurements in fully de- were determined and cannot be blindly used for
veloped tube or capillary flow can be used to design or process evaluation if the process shear
determine the shear stress (Eq. 87) and the shear rates are out of this range.
rate (Eq. 119 and 120) at the tube wall. Since the
shear stress – shear rate curve is a function of the
material and not the apparatus used, a plot of τ w 4.2.3. Velocity Distribution
versus γ̇ w is one way in which a flow curve can
be determined for any time-independent fluid. For fully developed laminar flow, the velocity
The parameter n is the slope of the log – distribution in a tube for any time-independent
log plot of τ w versus 8 V/D and must not be fluid is obtained by integrating the velocity gra-
confused with the flow-behavior index n in the dient from the tube wall r = R to any radial po-
power law. The flow-behavior index n is con- sition r = r, assuming no slip at the wall:
stant over the range of shear rates for which it is R
defined, whereas n can vary with 8 V/D. Since uz (r) =
−duz
dr (123a)
n in Equation (120) represents the slope of a r
dr
line, the line may be represented by an equation
of the form or
τw
lnτw =n ln8V /D+lnK (121) R
uz (r) = f (τrz ) dτrz (123b)
τw
τrz
If n is not constant, but varies with τ w then
Equation (121) represents the tangent to the For a power-law fluid where f (τrz ) = (τrz /k)1/n
curve at a given point. On the other hand, if n and remembering that τrz = Rr τw
is constant, Equation (121) represents the actual and τrz = r ∆p/2 L yields
relationship between τ w and 8 V/D. When n is
1
constant, it is useful to write Equation (121) in n+1 ∆p n n
uz (r) = n
the form R 2kL n+1

n r n+1
n
8V 1− (124)
τw =K (122) R
D
Comparing Equation (122) to Equation (117) when Equation (123 b) is integrated. In terms of
shows that for a power-law fluid, n = n and the average velocity
n R 1
4n 2π (n+1) ∆p n
k=K (122a) V= ru z dr=R n
3n+1 πR2 2kL
0

It is not necessary to compute the slope of the n
(125)
experimentally determined log – log plot of τ w 3n+1
versus 8 V/D if calculations for laminar tube flow
are to be made. The plot can be used directly and hence

for design or process evaluation, provided that 3n+1 r n+1

n
process conditions are within the range of the uz (r) = V 1− (126)
n+1 R
experimental data. In fact, a single experimental
determination of τ w in a convenient model at a Equation (126) defines the velocity distribution
given value of V/D enables the prediction of the for power-law fluids in fully developed tube
pressure drop in a larger pipe of the same value flow. The velocity gradient at the tube wall is
of V/D.
duz 3n+1 8V
The terms n and K need only be determined = γ̇w = (127)
dr r=R 4n D
when the τ w versus 8 V/D data are to be used for
other laminar flow geometries or for turbulent As expected Equation (127) is identical to Equa-
flow. It is important to realize that n and K , as tion (119) when n = n but more importantly for
determined from the log – log plot, are only valid a Newtonian fluid (n = n = 1)
402 Fluid Mechanics
8V The yield stress of a material can be deter-

γ̇w = (128) mined by extrapolation of the basic shear stress –
D
shear rate data to zero shear rate. However, in
Thus 8 V/D is the wall shear rate for a Newtonian view of the importance of the yield stress special
fluid in laminar tube flow. techniques have been developed for its measure-
For a Bingham material similar calculations ment. In one such technique, a vane is inserted
yield the following velocity distribution: into the fluid (see Fig. 30). The minimum torque
Γ m required to initiate a rotation motion in the
R2 ∆p r2
uz (r) = 1− 0 0 ≤ r ≤ r0 (129a) vane is recorded. The yield stress is then related
4ηpl L R
to this torque by
and

r 2 τ R . r / πDv3 Hv 1
R2 ∆p y Γm = + τy (131)
uz (r) = 1− − 1− 2 Dv 3
4ηpl L R ηpl R
r0 ≤r ≤ R (129b) In deriving Equation (131) it is assumed that the
yielding surface is the cylindrical surface and the
where r 0 = 2 L τ y /∆ p and η pl is the plastic vis-
two end circular disks traced out by the vane. For
cosity of the fluid. Equations (129 a) and (129 b)
short vanes, end effects may become important
show that there is a region of radius r 0 , in the
and must be taken into consideration [21].
center of the pipe, where the fluid moves as a
solid plug with a uniform velocity. The volu-
metric flow rate in a pipe for a Bingham material
is given in Section 4.2.1, where τ y is the yield 4.2.4. Friction Factor – Reynolds Number
stress and τ w is the wall shear stress. This equa- Relationships
tion is only valid when τ w is greater than τ y .
Flow in the pipe will not occur if τ w is less than General procedures applicable to all types of flu-
τ y . Thus ids are of course desirable because of the diffi-
culty in classifying a fluid as one type or another,
∆p 2τy and because of the tendency of some fluids to
> (130)
L R change from one type to another with chang-
is necessary for the initiation of flow in a pipe ing shear rate, temperature, or composition. At
for yield stress materials. present generalizations are established only for
time-independent fluids.
Laminar Flow. For laminar flow of Newto-

nian fluids in circular pipes, the friction factor
satisfies the relation (see Section 3.3.1 and Equa-
tion (48))
16
f=
Re
with the Reynolds number defined as

Re = (D V )/η. For the laminar flow of any time-
independent fluid in a tube, the wall shear stress
is given by
n
8V
τw =K (132)
D
where, in general, K and n are not constant, but

Figure 30. The vane used for yield stress measurement depend on 8 V/D. When Equation (132) is sub-
Dv = vane diameter; H v = vane height stituted into the defining equation for the friction
factor one obtains
Fluid Mechanics 403
appeared to begin at Re of about 2100, 2700

16
f= (133) and 3100, respectively. Others have examined
Re
the flow transition question for non-Newtonian
where fluids but the conservative conclusion remains:

Dn V 2−n Re ≤ 2100 (135)
Re = (134)
K 8n −1
has been accepted and is used to establish
which is a generalized Reynolds number valid
whether the flow is laminar or turbulent for a
for all time-independent fluids. In the special
non-Newtonian fluid.
case where n = 1 and K = η, Equation (134) re-
duces to the Reynolds number for a Newtonian
fluid. For a power-law fluid n = n and Equation Turbulent Flow. The friction factor chart for
(122 a) is valid. time-independent inelastic fluids is reproduced
in Figure 31. The friction factor is defined by
LIVE GRAPH !
Click here to view 1 4.0 .
/ 0.4
= log Re f 1−n /2 − 1.2 (136)
f (n ) 0.75 n
Equation (136) reduces to the von Karman –

Nikuradse equation (50) for Newtonian fluids
when n = 1. The solid lines in Figure 31 are
based on experimental results, and the dashed
lines are extrapolations made using Equation
(136). The constants in Equation (136) were
evaluated from experimental data. If the fluid
does not obey the power law with an n and
K which vary with 8 V/D, then a trial-and-error
procedure is required to calculate f, τ w , or ∆p.
Figure 31. Friction factor design chart for non-Newtonian First a value of ∆p is assumed, then the approx-
fluids imate values of n and K are found from the
—— Experimental regions; – – – extrapolated regions laminar flow curve (τ w versus 8 V/D) at the as-
sumed τ w . From these parameters, Re is cal-
Transition Flow. So far only the laminar culated and f is obtained from Figure 31. If the
flow of non-Newtonian fluids in tubes has been pressure drop calculated from the friction factor
considered and the important question, when is does not agree with the original assumed value,
the flow laminar, has been avoided. For New- another iteration is carried out. The process con-
tonian fluids, the question is answered by cal- verges quickly.
culating the Reynolds number and comparing
it to the empirically determined value of 2100
below which the flow is laminar. A similar crite- 4.3. Viscoelastic Fluid Mechanics
rion has been sought for non-Newtonian fluids
by Metzner and Reed [22] and Dodge and Materials such as molten plastics, solutions of
Metzner [23]. Metzner and Reed first con- synthetic macromolecules and many biological
sidered that stable laminar flow in tubes usually fluids – apart from possessing the properties nor-
ends when the friction factor becomes < 0.008, mally associated with purely viscous fluids –
which corresponded to a generalized Reynolds also exhibit a range of behavior which is nor-
number of 2100. In the later work by Dodge mally associated with elastic solids. For this rea-
and Metzner, which led to the generalized f – son such materials have been given the name vis-
Re chart shown in Figure 31, laminar flow was coelastic fluids. In a viscoelastic fluid the stress
found to end at generalized Reynolds numbers generated by deformation is no longer a simple
which increase slightly as n decreases. At n val- function of the instantaneous rate of strain. It
ues of 1.0, 0.726, and 0.38, the transition region also depends, as in solids, on the strain and, for
Next Page
404 Fluid Mechanics
Figure 33. Extrudate swell by a viscoelastic fluid

Figure 32. Rod-climbing by a viscoelastic fluid
large strains, on the strain history experienced often referred to as the Weissenberg effect. When
by the fluid. As discussed earlier, in a purely a viscoelastic fluid is extruded from a capillary
viscous fluid, all the energy required to produce (see Fig. 33) the resulting fluid stream may swell
the deformation is dissipated as heat while in a up to several times the capillary diameter. This
perfectly elastic solid this energy is stored and phenomenon is known as extrudate swell. New-
is completely recovered when the forces acting tonian fluids also exhibit extrudate swell at small
on the solid are removed. In a viscoelastic fluid, Reynolds number, but the increase in diameter
this energy is partly dissipated and partly stored, is only 13 %. Large extrudate swell is observed
the ratio of dissipation to storage depends on the in polymer extrusion and clearly has to be taken
fluid, the nature of the deformation, and the his- into account in the design of extrusion shaping
tory of the deformation. Thus, depending on the dies. Figure 34 shows a tubeless syphon, where
flow, a viscoelastic fluid may exhibit, in varying a viscoelastic fluid is being sucked vertically up-
degrees, the elastic properties of solids and the wards into a tube. The suction tube can be lifted
viscous properties of fluids. to a large height (well over four to five tube diam-
It is therefore not surprising that some of the eters in the case shown) above the viscoelastic
flow behaviors of viscoelastic fluids have no par- fluid without the syphoning action being inter-
allel in purely viscous fluids. A number of these rupted. In comparison, for a purely viscous fluid,
viscoelastic phenomena are reproduced in Fig- syphoning ceases as soon as the tube is lifted
ures 32, 33, 34, and 35. Figure 32 shows a rod out of the fluid. The tubeless syphon illustrates
slowly rotating in a beaker filled with a vis- the large tensile stress that can be sustained in a
coelastic fluid. The rotation causes the viscoelas- viscoelastic fluid. Figure 35 is a comparison of
tic fluid to climb up the rod. Under similar con- the streamline patterns formed by a Newtonian
ditions, a purely viscous fluid is undisturbed by fluid and a viscoelastic fluid as they flow through
the slow rotation and its surface remains essen- a pipe contraction. Figure 35A shows a Newto-
tially flat. Rod climbing by a viscoelastic fluid is nian fluid; Figures 35B – D show a viscoelastic
Previous Page
Fluid Mechanics 405
fluid at increasing flow rate. For the Newtonian Some of the more fundamental aspects of vis-
fluid, two small recirculating vortices can be ob- coelastic fluid mechanics will be discussed in
served at the contraction plane. The size of the the next section. The treatment is, however, of a
Newtonian vortex, shown at low Reynolds num- more descriptive nature.
ber, is not very sensitive to changes in flow rate.
For viscoelastic fluids, the situation is quite dif-
ferent. At low flow rates the viscoelastic vortices 4.3.1. Steady Shear Behavior of Viscoelastic
are approximately of the same size as those for Fluids
the Newtonian fluid, but they rapidly increase in
size, up to four times the size of Newtonian vor- Under steady shear the shear stress Txy gener-
tex, as the flow rate is increased. The flow then ated in a viscoelastic fluid is related to the shear
becomes unstable and the vortices begin to pul- rate by
sate, growing and decreasing in size in some er-
Txy =η (γ̇) γ̇
ratic manner. Although the streamline pattern of
the Newtonian fluid can be obtained by solving where η is the shear-rate dependent viscosity of
the Navier – Stokes equations, attempts to un- the fluid. Figure 26 is the plot of the viscosity of a
derstand the viscoelastic flow patterns have so solution of polyacrylamide, a typical viscoelas-
far been, at most, only partially successful [24]. tic fluid. Like most non-Newtonian fluids, most
The most likely source of the problem here is the viscoelastic fluids exhibit shear thinning, and,
present inability to describe, with the necessary over a range of shear rates, behave like a power-
degree of accuracy, the complex rheological be- law fluid. However, if the normal components of
havior of the viscoelastic fluid when it undergoes the stress tensor in the x direction, Txx , and in the
shearing and stretching deformation as it flows y direction, Tyy , are measured, it will be found
through the contraction. that they are, in general, not equal. This is not
observed in Newtonian and generalized Newto-
nian fluids. The difference in Txx and Tyy is re-
ferred to as the first normal stress difference N 1 .
Similarly, it will be found that Tyy and Tzz are
unequal, and the difference Tyy − Tzz is known
as the second normal stress difference. The first
and second normal stress difference are related
to the shear rate by
Txx − Tyy =ψ1 (γ̇) γ̇ 2
Tyy − Tzz =ψ2 (γ̇) γ̇ 2
The functions ψ 1 and ψ 2 are known as the first

and second normal stress coefficients, respec-
tively. They are a function of the shear rate γ̇: η,
ψ 1 and ψ 2 are known as the viscometric func-
tions of the fluid which together describe the
response of the viscoelastic fluid under steady
shear. ψ 1 is measured in special viscometers,
which measure the normal stress, as well as the
shear stress, exerted by the test fluid when it
is being sheared [8]. Figure 36 is a plot of the
first normal stress difference exhibited by a poly-
acrylamide solution. For comparison, the shear
stress is also included in Figure 36. It can be
Figure 34. Viscoelastic fluid being sucked up (tubeless seen that the normal stress is very much larger
syphon) than the shear stress which means that this vis-
coelastic fluid can be expected to behave quite
differently from a purely viscous shear-thinning
406 Fluid Mechanics
Figure 35. Comparison of the flow patterns exhibited by a Newtonian fluid and by a viscoelastic fluid
A) Newtonian fluid; B) – D) Viscoelastic fluid at increasing flow rates
fluid with similar shear stress versus shear rate ciated with viscoelastic fluids. Boger fluids are
behavior. The second normal stress difference is used extensively in the comparison of experi-
usually much smaller than the first normal stress mentally observed elastic response of fluids with
difference and is very difficult to measure accu- that predicted by viscoelastic constitutive equa-
rately. It is not normally reported in the literature. tions. They play an important role in the devel-
LIVE GRAPH
opment and selection of such constitutive equa-
Click here to view tions.
4.3.2. Behavior of Viscoelastic Fluids in

Oscillatory Shear Flow
In steady shear motion the viscoelastic fluid is

subjected to a constant rate of strain which does
not reveal the dependence of the current stress on
the strain history. Viscoelastic behavior under a
time-dependent rate of strain is frequently stud-
ied experimentally by putting the fluid through
Figure 36. Normal stress versus shear rate for a viscoelastic an oscillatory shear flow, such as that generated
fluid when the fluid is sheared between two parallel
a) Shear stress τ ; b) First normal stress difference N 1 plates: one of the plates is held stationary and the
In laboratory investigations of viscoelasticity, other oscillates sinusoidally with a frequency ω.
it is very useful to be able to isolate the effects The resulting shear rate and shear stress both
of shear thinning and fluid inertia from that of have the same frequency ω, but there is a phase
fluid elasticity so as to concentrate on the lat- difference between them. If the oscillatory shear
ter. For this purpose, a class of special test flu- strain is represented by
ids have been developed. They are commonly γ =γ0 sin (ωt) (137)
referred to as Boger fluids or ideal elastic flu-
ids. Typically, they are prepared by dissolving where γ 0 is the amplitude of the sinusoidal shear
a high molecular mass solute in a highly vis- strain, then the shear rate experienced by the
cous Newtonian solvent. The resulting solutions fluid is given by
are characterized by their near constant viscos-
γ̇ =γ0 ωcos (ωt) = γ̇0 cos (ωt) (138)
ity, over a wide range of shear rates, and they
exhibit all the elastic properties normally asso- γ̇ 0 (= ω γ 0 ) is used to denote the amplitude of the
sinusoidal shear rate.
Fluid Mechanics 407
It is customary to express the resulting shear the steady and oscillatory data. An example of
stress in the form these is the Cox – Merz rule which relates η (γ̇)
to η (ω) and η (ω):
Txy (ω) =γ0 G (ω) sinωt+G (ω) cosωt (139) . /1/2

η (γ̇) = η (ω)2 +η (ω) (143)
The terms associated with G (ω) and G (ω) are ω=γ̇
the in-phase and the out-phase component of the The Cox – Merz rule is often used to extend the
shear stress. G (ω) is usually referred to as the steady shear viscosity data to large shear rates
storage modulus of the fluid, it is related to the where only oscillatory measurements have been
storage of energy. G (ω) is the loss modulus of carried out. Further details and the limitations of
the fluid and is connected with energy dissipa- this and other similar relationships are given in
tion. As indicated above, G (ω) and G (ω) are [4].
functions of ω, and for small amplitude oscilla- G (ω) and G (ω) or equivalently η (ω) and
tory shear, they are independent of γ 0 . For purely
η (ω) are measured with special viscometers
viscous fluids G (ω) is zero. in which one of the shearing surfaces can be
G (ω) and G (ω) are material properties of a driven sinusoidally [8]. A typical set of oscilla-
viscoelastic fluid. Two other material functions, tory data is shown in Figure 37. These data were
related to G (ω) and G (ω) are also in common extracted from a comprehensive study carried
use. These are the complex viscosity of the vis- out on polyethylene [25]. Oscillatory measure-
coelastic fluid, defined by ments are now routinely carried out by polymer
manufacturers as a means of characterizing their
η (ω) =G (ω) /ω (140a)
products.
and LIVE GRAPH
Click here to view
η (ω) =G (ω) /ω (140b)
The function η (ω) is called the dynamic viscos-

ity of the fluid; η (ω) does not seem to have a
generally accepted name. For a Newtonian fluid
η (ω) is equal to the viscosity of the fluid and
η (ω) is zero. It is evident that a large number of
material functions are needed just to describe the
behavior of viscoelastic fluids in shear. At low
shear rates and low angular frequencies, the ma-
terial functions for steady-shear and oscillatory
shear are related to one another. The dynamic Figure 37. Storage and loss modulus of a low density poly-
viscosity at very low frequencies is related to the ethylene [25]
steady shear viscosity at very low shear rates by Storage modulus G ; Loss modulus G
lim η (ω) = lim η (γ̇) (141)

ω→0 γ̇→0 4.3.3. Examples of Constitutive Equations
for Viscoelastic Fluids
Furthermore, the storage modulus at very low
frequencies is related to the first normal stress Numerous constitutive equations have been
coefficient ψ 1 (γ̇) at very low shear rates by proposed to describe the diverse relationship,
observed in viscoelastic fluids, between the
2G (ω) N1 (γ̇)
lim = lim = lim ψ1 (γ̇) stresses and the various kinematic quantities
ω→0 ω2 γ̇→0 γ̇ 2 γ̇→0
(142) used to measure the strain and the rate of strain
experienced by the fluid. One of the earliest
These limiting relationships are very useful for viscoelastic constitutive equations is the linear
checking the consistency of experimental data Maxwell equation. In shear flow, the stress Txy
on viscoelastic fluids. A number of other empir- and the shear rate γ̇ are related by a constitutive
ical relationships have been developed to relate equation of the form
408 Fluid Mechanics
dTxy t, the transient terms can be ignored. The result-

λ +Txy =η0 γ̇ (144)
dt ing sinusoidally fluctuating stress can be written
in the form
λ and η 0 are the two material parameters of the
linear Maxwell equation where λ is the time con- η0 ω η0 λω 2
Tyx =γ0 2 2
cosωt+ 2 2
sinωt (149)
stant of the fluid and η 0 is its viscosity. Under 1+λ ω 1+λ ω
steady shear, the stress is not a function of time,
From the definition of G (ω) and G (ω) and of
hence the first term on the left-hand side van-
η (ω) and η (ω) it can then be seen that for a
ishes and the linear Maxwell equation reduces
linear Maxwell fluid
to the Newtonian constitutive equation where the
stress is related to the shear rate via the viscosity η0 λω 2 η0 ω
η 0 . However, the introduction of the time con- G (ω) = G (ω) = (150a)
1+λ2 ω 2 1+λ2 ω 2
stant λ means that, in general, the stress is no
η0 η0 λω
longer a unique function of the instantaneous η (ω) = η (ω) = (150b)
1+λ2 ω 2 1+λ2 ω 2
shear rate. For example, during the start up of the
shear flow or in oscillatory shear test, the stress By choosing the appropriate value for the vis-
is out of phase with the instantaneous shear rate. cosity η 0 and time constant λ, these functions
In particular, in oscillatory shear test the os- can provide an adequate description of the ob-
cillation of the top plate is given by A sin ω t. served behavior of real viscoelastic fluids. The
The velocity of the top plate is linear Maxwell equation does not satisfy all the
requirements of modern continuum mechanics
u0 =Aωcosωt for a theoretically sound constitutive equation.
Numerous modifications of the Maxwell equa-
For most viscoelastic fluids of practical interest,
tions can be found in the literature. Some of
experimental conditions are such that the inertia
the modifications were made so as to satisfy
terms in the Cauchy equations of motion, Equa-
the requirements of continuum mechanics, oth-
tion (24), are small and can be ignored. As a
ers resulted from improved understanding of the
result, the velocity variation across the gap sep-
molecular structure and dynamics of the poly-
arating the plates is linear and the velocity profile
mer constituents of viscoelastic fluids [4], [26].
is given by
A constitutive equation that has been very
Aωy popular is the Oldroyd-B equation. It relates the
u (y,t) = cos (ωt) (145)
H deviatoric stress tensor τ to the strain tensor γ
by an equation of the form
where H is the gap between plates. The shear
rate is given by
λ1 τ (1) +τ =η0 γ (1) +λ2 γ (2) (151)
Aω
γ̇ (t) =
H
cos (ωt) =γ0 ωcos (ωt) (146) where λ1 and λ2 are the relaxation and retar-
dation time of the Oldroyd-B fluid, respectively
where γ 0 = A/H is used to denote the ampli- and η 0 is, as before, the viscosity of the fluid.
tude of the shear strain. According to the linear Subscripts (1) and (2) are used to denote the first
Maxwell constitutive equation, the stress exerted and second convected derivatives of the stress
by the fluid on the oscillating top plate is given and the strain tensor. The definition of the con-
by vected and other derivatives can be found in [4].
dTxy The introduction of these derivatives is required
λ +Txy =γ0 ωcos (ωt) (147) by the theory of constitutive equations in contin-
dt
uum mechanics. The derivative γ (1) is equal to
This equation can be solved to give the rate of strain tensor e. The Oldroyd-B equa-
tion satisfies all the requirements of continuum
η0 ωcosωt η0 λω 2
Txy =γ0 + sinωt mechanics. In terms of the three material param-
1+λ2 ω 2 1+λ2 ω 2
+transient terms (148)
eters, λ1 , λ2 , and η 0 the viscometric functions
(i.e., the steady shear properties) and the oscil-
The transient terms decay away exponentially. latory behavior of the Oldroyd-B equation can
As oscillatory measurements are taken at large be shown to be
Fluid Mechanics 409
agreement between experimental observations

η=η0 ψ1 = 2η0 (λ1 − λ2 ) ψ2 = 0 (152a)
and theoretical predictions could be observed
η0 (λ1 − λ2 ) ω 2
for the first time. It has also been possible to re-
G (ω) = late the parameters in the constitutive equations
1+ (λ1 ω)2
to the physical properties of the constituents of
η0 ω 1+λ1 λ2 ω 2
G (ω) = (152b) Boger fluids.
1+ (λ1 ω)2
LIVE GRAPH
η0 1+λ1 λ2 ω 2 Click here to view
η (ω) =
1+ (λ1 ω)2
η0 (λ1 − λ2 ) ω
η (ω) = (152c)
1+ (λ1 ω)2
As with the linear Maxwell equation, the pa-

rameters of the Oldroyd-B equations are chosen
so that these functions give an approximate de-
scription of the measured viscometric and os-
cillatory properties of real fluids. It is interest-
ing to note that both linear Maxwell and the
Oldroyd-B equations give a constant viscosity.
This means that these equations are particularly
suitable for describing the rheological behavior
of viscoelastic fluids that are not shear-thinning.
In Figure 38 the measured G (ω) and η (ω) for a
silicone oil are plotted against ω. This fluid can
be regarded as a non-shear-thinning viscoelas-
tic fluid ( Boger fluid). The expression for these
two quantities according to the Maxwell and the
Oldroyd-B equations are also plotted on the fig- Figure 38. Comparison of the observed normal stress and
ure. Standard procedures have been applied to storage modulus of a silicone oil against that predicted by
extract the fluid parameters of these two con- the Maxwell and the Oldroyd-B constitutive equations, fluid:
silicone oil
stitutive equations [27]. The Oldroyd-B equa- ◦ N 1 , Pa; 2 G , Pa; • η, Pa s; η , Pa s
tion provides a better description of the rheolog-
ical behavior of this viscoelastic fluid than the
simpler Maxwell equation. For comparison, the 4.3.4. Extensional Behavior of Viscoelastic
steady shear data for this silicone oil are also in- Fluids
cluded in Figure 38. The experimental data con-
firm the limiting relationship between N 1 and In many of the flow fields encountered in indus-
2 G and between η and η at low γ̇ and ω. trial processes the fluid undergoes a stretching
The linear Maxwell and the Oldroyd-B equa- deformation. A specific example is the deforma-
tions are just two examples of the large number tion suffered by a fluid element when it is forced
of viscoelastic constitutive equations in the lit- to flow through a channel or tube of gradually
erature. The construction of constitutive equa- or abruptly changing cross-sectional area. This
tions is guided by the principles of continuum kind of deformation is usually referred to as ex-
mechanics and by the understanding of the dy- tensional deformation. In extensional deforma-
namical properties of the macromolecules and tion the macromolecules in the viscoelastic fluid
the solvent that make up the viscoelastic fluids. are being stretched and may generate large ten-
For more details on these and related topics see sile stresses as a result of this. The behavior of
[28], [29]. a viscoelastic fluid in extensional deformation
One of the recent developments in viscoelas- can be quite different from its behavior in shear
tic fluid mechanics is the use of Boger fluids deformation.
to gain a physical understanding of constitu- An idealized flow field that can be used to in-
tive equations. With these ideal test fluids good vestigate the extensional behavior of a viscoelas-
410 Fluid Mechanics
tic fluid is shown in Figure 39. The tensile stress

Tzz applied to stretch the specimen of test fluid,
in the form of a circular cylinder, is measured.
The applied stress Tzz is varied so that the ax-
ial velocity gradient is uniform within the fluid
sample and remains constant in time, i.e.,
duz 1 dL
ezz = = ε̇0 = (153)
dz L dt
where ε̇0 is the constant extensional rate, which Figure 39. Schematic diagram of extensional flow
can be identified with the ratio of the instanta- An important extensional property of a vis-
neous rate of increase in length of the fluid sam- coelastic fluid is its extensional viscosity η el . In
ple dL (t)/dt to its instantaneous length L (t). It terms of the idealized extensional measurement
can be assumed that the azimuthal velocity com- described above, η el is defined by
ponent in the test specimen is zero. The conti-
nuity equation for an incompressible fluid then Tzz − Trr
ηel = (157)
requires the velocity components in the axial and ε̇0
radial directions to be given by The difference between the normal stress in the
axial direction Tzz and that in the radial direc-
uz = ε̇0 z tion Trr gives the deviatoric tensile stress arising
1 from the extensional deformation. The defini-
ur = − ε̇0 r
2 tion of extensional viscosity is analogous to the
uθ = 0 (154) definition of shear viscosity. Like its shear coun-
The rate of strain tensor, in cylindrical coordi- terpart, the extensional viscosity is in general a
nates, is given by function of the extensional rate ε̇0 .
The extensional viscosity predicted by differ-

ε̇ ent constitutive equations can be found in the
0 0 0
literature [30]. The extensional viscosity of a
e= 0 − 12 ε̇0 0 (155)
Newtonian fluid with constant viscosity η 0 is rel-
0 0 − 12 ε̇0
atively simple to obtain. The total normal stress
A characteristic of extensional flow is the van- in the axial and the radial directions are given by
ishing off-diagonal elements in the rate of strain duz
tensor. This idealized constant-rate fluid stretch- Tzz = −p+2η = −p+2η0 ε̇0
dz
ing experiment, known as the steady axisymmet- dur
ric extensional flow, is the extensional equivalent Trr = −p+2η = −p − η0 ε̇0
dr
of steady shear flow. It is a difficult experiment to
carry out and consequently reliable extensional Hence
properties of fluids are difficult to obtain. One of Tzz −Trr
ηel = = 3η0 (158)
the difficulties becomes apparent when Equation ε̇0
(153) is integrated to give
According to this result, the extensional viscos-
ε̇0 t ity of a Newtonian fluid is three times its shear
L=L 0 e (156)
viscosity. This result has been verified experi-
where L 0 is the initial length of the cylindrical mentally by Trouton in 1906 and extensional
fluid test specimen. The exponential increase in viscosity is often referred to as Trouton viscos-
length of the test specimen makes it very difficult ity [31]. The extensional viscosity of viscoelastic
to sustain measurement for a period long enough fluids is, in general, much larger than three times
for the effects of initial conditions to be ignored. it shear viscosity.
Specialized rheometers have been designed to The extensional viscosity obtained for the
overcome this and other related problems [8]. Oldroyd-B equation can be shown to be
However, good elongational flow measurements
(1−λ2 ε̇0 ) (1 + 2λ1 ε̇0 )
are rare. ηel (ε̇0 ) = 3η0 (159)
(1+λ1 ε̇0 ) (1 − 2λ1 ε̇0 )
Fluid Mechanics 411
At low extensional rate, the Newtonian result of rates of > 103 s−1 are easily obtained in the cap-
3 η 0 is again obtained. As the extensional rate illary rheometer. This is one of its main advan-
is increased, the extensional viscosity increases tages over conventional rotation instruments.
rapidly. This large extensional viscosity is in Assuming that the flow is laminar and that the
agreement with the observed extensional behav- fluid is a time-independent inelastic or viscoelas-
ior of viscoelastic fluids. However, according to tic fluid, corrections to the measured pressure
the Oldroyd-B equation, the extensional viscos- drop ( pgas − patm ) for pressure- driven rheome-
ity grows without bound as the extensional rate ters and ( papp − patm ) for ram- driven rheome-
approaches λ1 /2. This singularity in the relation- ters may have to be made due to the following
ship between extensional rate and extensional effects:
viscosity is physically unrealistic and is an in-
dication that the Oldroyd-B equation must be 1) Head of fluid above the tube exit
modified. Comparison of the measured exten- 2) Kinetic energy effects
sional viscosity with that predicted by a consti- 3) Tube entrance and exit losses
tutive equation provides an additional test of the 4) Weight of filament after exit (this will be ig-
validity of the constitutive equation. nored here)
It is clear that fluid elasticity has greatly in-
creased the complexity of fluid motion. There pgas −patm = ∆pfd1 +∆pen +∆pfd2
are a large number of flow phenomena which
+∆pex +∆KE +∆P E (160)
are only observed in viscoelastic fluids. Many
of these have practical implications for industrial Equation (160) is a mechanical energy balance
processes. For further details on the mechanics written between surface 0 and 2 as shown in Fig-
of viscoelastic fluids see [4], [19], [26]. ure 40: ∆pfd1 and ∆pfd2 are the fully- developed
flow pressure drops in the reservoir and tube,
respectively; ∆pen is the entry loss over and
4.3.5. Accelerating and Decelerating Flows above the fully-developed flow loss for the flow
of Viscoelastic Fluids into the tube; and ∆pex is the exit loss over and
above the fully-developed flow loss for flow out
Fluid elasticity does not affect the energy re- of the tube to the atmosphere; ∆KE and ∆PE are
quirements for fully- developed/laminar tube the kinetic and potential energy losses, respec-
flow. However, in accelerating and decelerating tively. Kinetic and potential energy effects can
flows, such as in the entrance and exit of a tube, normally be neglected for polymer melts and for
the influence of fluid elasticity becomes quite concentrated solutions and suspensions. In ad-
pronounced. Entrance and exit effects are condition, the reservoir diameter is usually much
veniently discussed with reference to the capil- greater than that of the downstream tube, so
lary rheometer, an important instrument for the that the fully- developed pressure drop in the up-
measurement of fundamental flow properties of stream tube or reservoir can also be neglected.
fluids. Thus, Equation (160) becomes
One essential feature of the capillary vis-
cometer is that the wall shear stress can be pgas −patm = ∆pen +∆pfd2 +∆pex (161)
directly determined from the measured fully-
developed flow pressure drop (see Eq. 87). How- where
ever, for a laboratory-scale capillary viscome- 2τw L
ter it is more practical to measure the overall ∆pfd2 =
R
pressure drop from the upstream fluid reservoir
to the exit of the tube, rather than the pressure If high L/R capillary tubes are used for the pres-
drop in the tube itself. Schematics of a pressure- sure drop – flow rate measurements (L/R ≥ 200),
driven and a ram-driven capillary rheometer are fundamental shear stress – shear rate data can be
shown in Figure 40. In the pressure-driven in- determined directly with the capillary rheometer
strument, the independent variable is the shear because
stress, whereas in the ram-driven instrument the 2τw L
independent variable is the shear rate. Shear >> ∆pen +∆pex (162)
R
412 Fluid Mechanics
Figure 40. Schematic diagram of (A) pressure and (B) ram driven capillary rheometers
Therefore
R (pgas −patm ) pgas −patm
τw = (163) τw = (168)
2L 2 (L/R+e)
i.e., the wall shear stress can be directly deter-
mined from the measured pressure drop, and the The end correction e is determined by first
wall shear rate is specified by the Rabinowitsch – plotting ( pgas − patm )/(2 L/R) versus 8 V/D on
Mooney equation log – log coordinates. Different lines or curves
such as those illustrated in Figure 41 will be ob-
3n +1 8V tained for different L/R tubes. From such a graph
γ̇w = (164)
4n D pgas − patm can be determined as a function of
where L/R for various values of 8 V/D. A linear plot of
pgas − patm versus L/R is then made for various
dlnτw values of 8 V/D. The end correction e is the in-
n = (165)
dln 8V
D tercept on the abscissa of this plot (see Fig. 42).
The end correction is then a known function of
However, for many materials in tubes with a high
8 V/D and hence the corrected value of τ w can
L/R ratio, the pressures required to obtain shear
be computed as a function of 8 V/D from Equa-
rates of interest are prohibitive, and methods
tion (168) whereas the true shear rate can be
have been derived to correct for entry and exit
computed with the aid of Equation (164) and
effects when low L/R capillary tubes are used.
the slope of a log – log plot of τ w versus 8 V/D
The method most commonly used is that first
(Eq. 165).
suggested by Bagley in 1957 [32]:
The capillary rheometer is an important in-
2τw L e strument for the measurement of the shear stress
∆pen +∆pex = = 2τw e (166)
R as a function of shear rate, particularly for
molten polymers where measurements can be
where e is the dimensionless extra length of tube
made at processing shear rates. It is also an in-
which defines the exit and entry losses in excess
strument for determining quantitative measure-
of the fully-developed flow losses.
ment of fluid elasticity. For instance, the end cor-
pgas −patm = 2τw (L/R+e) (167)
rection is strongly influenced by the elasticity of
the fluid. Figure 43 shows end correction results
and for molten polymers while Table 2 lists the end
Fluid Mechanics 413
Figure 41. First plot of capillary rheometer data for deter- Figure 42. Determination of the end correction
mination of the end effect
correction for inelastic power-law fluids as de- also highly elastic. Even higher end correction
termined from the numerical solution of the tube values than those illustrated for molten poly-
entry and exit flow problem [34]. mers in Figure 43 have been observed for con-
centrated polymer solutions. The end correction
Table 2. The end correction for inelastic power-law fluids
is used to differentiate between different poly-
Power-law index, ∆pen /2 τ w ∆pex /2 τ w e mers and in fact to distinguish between different
n grades of the same polymer (see curves d and e
1.0 0.588 0.246 0.834 in Fig. 43).
0.5 1.34 0.26 1.60 Significantly different behavior is indeed ob-
0.3 1.76 0.28 2.04
0.167 2.33 0.59 2.92
served in inlet and exit flows of inelastic and
viscoelastic fluids. Figure 44 shows streamline
photographs obtained for an inelastic Newto-
LIVE GRAPH nian fluid (Fig. 44A) and for an elastic fluid
Click here to view
which shows no shear thinning (Fig. 44B). Both
fluids have identical viscosities. Flow is from
left to right in the photographs and represents
flow from the reservoir into the tube of a cap-
illary rheometer. For the inelastic Newtonian
fluid a small secondary flow is present in the
corner of the reservoir. This cell remains essen-
tially constant in size with increasing flow rate
and ultimately disappears for Reynolds numbers
> ca. 0.1 when the fluid inertia starts to become
important. For the viscoelastic fluid of the same
viscosity (2000 Pa s) the secondary flow is much
Figure 43. Typical values of the end correction as a function larger. The size of the secondary flow grows
of shear rate [33] with increasing flow rate for Reynolds numbers
a) Polystyrene; b) Poly(methyl methacrylate); C) Low-
density polyethylene MFI 2.0; d) High- density polyethylene < 0.1 and continues to grow until the flow be-
MFI 0.25; e) High- density polyethylene; f ) Polyacetal comes unstable. For a molten polymer being ex-
truded through a die, the flow instability results
In the absence of fluid elasticity, the end cor- in a distorted extrudate. The flow phenomena,
rection increases as a result of the shear-thinning called melt fracture, represents an upper limit
characteristics of the fluid, but not to the extent of on the rate at which a molten polymer can be
the values observed for many commercial poly-
mers which in general are shear-thinning and
414 Fluid Mechanics
extruded. Similar flow instabilities are not ob- where the subscript w indicates that the stresses
served in tubular inlet flows for inelastic fluids. are to be evaluated at the wall shear rate for fully-
developed flow. Die swell ratios of 2 or more are
not unusual in the processing of molten poly-
mers. Since the die swell depends not only on
the particular polymer but also on the operating
conditions such as temperature and flow rate, the
industrial problems related to extrudate swell are
particularly complex and challenging.
Fluid elasticity does not effect the energy
requirements for fully-developed laminar tube
flow, that is
fviscoelastic =finelastic (169)
The equivalent conclusion, however, is not ap-
plicable for viscoelastic fluids in turbulent flow.
Here considerable reduction in the friction factor
below the expected inelastic value is observed.
This drag reduction phenomenon, first observed
by Toms in 1948, has received considerable at-
tention in the literature because of its possible
commercial significance. Parts per million of
certain polymers dissolved in water can reduce
the friction factor considerably; drag reduction
by as much as 90 % has been observed. Figure 45
shows some friction factor – Reynolds number
data for a very dilute aqueous polymer solution.
The data agrees with the laminar flow predic-
Figure 44. Comparison of entry flow patterns for a New-
tonian and a non-shear thinning elastic fluid with the same
tion but deviates from the solvent line character-
viscosity ization for turbulent flow for Reynolds numbers
Reservoir to tube diameter ratio is 7.67 > 104 .
A) Newtonian; B) Non-shear thinning elastic
LIVE GRAPH
For a viscoelastic fluid the exit flow from a Click here to view
capillary tube also differs significantly from that
of an inelastic fluid. For fully-developed flow of
a viscoelastic fluid in a tube, a tension along the
streamlines associated with the deviatoric nor-
mal stresses is present. When the fluid passes
through the exit of the tube to the atmosphere,
it will relax the tension along the streamlines by
contracting in the longitudinal direction. For an
incompressible fluid, this results in a lateral ex-
pansion of the fluid. This relaxation phenomena
results in extrudate swell (see Fig. 33), where
the diameter of the extrudate De is significantly
greater than the internal tube diameter. For large
Figure 45. Friction factor – Reynolds number data for Boger
tube length to diameter ratios the extrudate swell fluids, distilled water, and a solution of 296 ppm by weight of
can be estimated as follows [35]: polyethylene oxide in distilled water in an 8.46 mm-diameter
pipe [36]. (Reproduced by permission of the American In-
stitute of Chemical Engineers c 1975 AIChE)

1/6
De 1 τ11 −τ22 2 Boger fluid; ◦ Distilled water; • 296 ppm by weight poly-
= 0.1+ 1+ ethylene oxide
D 2 2τ12 w
Fluid Mechanics 415
5. Numerical Methods in Fluid Subscripts are used to indicate the grid point at
Mechanics which the variable is to be evaluated. The error
incurred in this approximation is dependent on
Many of the flows of practical importance have the size of the grid ∆x. It approaches zero as ∆x
irregular geometry and their boundary condi- approaches zero. A similar approximation can
tions are often mathematically difficult to han- be obtained for ∂uy /∂y. It is common practice
dle. Furthermore, the fluid properties may vary to make ∆y equal to ∆x. The finite difference
rapidly with flow and thermal conditions. These approximation of the incompressible continuity
complications mean that the set of equations that equation at the grid point (i, j ) is
describe the fluid motion are unlikely to have
an analytic solution. Even in those rare cases uxi+1,j +uyi,j+1 −uxi−1,j −uyi,j−1 = 0 (171)
where an analytic solution can be found, it may
be in a form, that is not convenient for practical
use, e.g., as a slowly converging infinite series. This is an algebraic equation for the unknowns
For such flows, it is necessary to obtain an ap- uxi+1, j , uxi−1, j etc. A similar equation can
proximate numerical solution to the governing be written down for each of the grid points,
equations. Numerical methods have always been 1 ≤ i ≤ Ni and 1 ≤ j ≤ Nj , where Ni and Nj are
used, but their development has been greatly ac- the number of grid points in the x and y direc-
celerated due to the availability of modern digi- tions, respectively.
tal computers that perform the repetitive calcu-
lations. Computational fluid mechanics is now
a well established subject capable of producing
highly accurate predictions of the fluid motion
at great speed. The ever increasing computing
power combined with the graphical capabilities
of modern computers has established numerical
solution of fluid mechanical problems as an ex-
tremely effective way of generating and present-
ing information about fluid flows. In this short
section, the principles of two general numeri-
cal methods for solving the steady-state Navier –
Stokes equations and the continuity equation in
two dimensions will be described. Further de-
tails are given in [37–41].
5.1. Finite Difference Method

Figure 46. Finite difference grid
(→ Mathematics in Chemical Engineering,
Chap. 7.3.)
At the grid point (i, j ), ∂ 2 ux /∂x 2 , a typical
In the finite difference method, the partial deriva- second derivative, can be approximated by the
tives in the governing equations are approxi- finite difference:
mated by finite differences. To do this, the flow
field of interest is divided into a regular grid as
∂ 2 ux uxi+1,j +uxi−1,j −2uxi,j
shown in Figure 46. = (172)
∂x2 i,j ∆x2
At any grid point (i, j ), the first derivative
∂ux /∂x in the continuity equation can be approx-
imated by Replacing all the partial derivatives by their fi-
nite difference approximations, the following fi-

∂ux uxi+1,j −uxi−1,j nite difference equivalent of the x- component
= (170)
∂x i,j 2∆x of the Navier – Stokes equation is obtained:
416 Fluid Mechanics
the unknown velocity components. These equa-

tions are not easy to solve directly. In one of
uxi+1,j −uxi−1,j
uxi,j + the numerical procedures developed to deal with
2∆x
the nonlinear terms, the typical inertia term ux

uxi,j+1 −uxi,j−1 ∂ux /∂x is approximated by
uyi,j
2∆y

pi+1,j −pi−1,j uxi+1,j +uxi−1,j −2uxi,j
= +η
2∆x ∆x2  
∂ux
(n) (n)
(n−1)  uxi+1,j −uxi−1,j 
uxi,j+1 +uxi,j−1 −2uxi,j ux ≈ uxi,j (175)
+η (173) ∂x 2∆x
∆y 2
A similar finite difference equation can be writ-

ten for the y- component of the Navier – Stokes
equation. The finite differences have converted Here the superscript n is used to denote the val-
the differential equations describing the fluid ues of the unknowns at the nth iteration. At the
flow to a set of simultaneous algebraic equations nth iteration the values of the (n − 1)th iteration
for the unknown velocity components and pres- are already known. This way the nonlinear terms
sure at the grid points. After the incorporation of are approximated as linear ones and the finite
the boundary conditions, they can, in principle, difference equations become a set of linear al-
be solved for the unknown variables. However, gebraic equations for which many computation-
because of the complexity of the Navier – Stokes ally efficient methods of solution are available.
equations, the success of the finite difference The calculation is terminated when the differ-
method depends critically on how the finite dif- ence between two successive iterations is less
ference equations are handled. They often have than some preassigned small tolerance. To start
to be completely reorganized and rewritten in the iterative procedure, it is necessary to sup-
various forms that are numerically and compu- ply the zeroth iteration of the unknown vari-
tationally more manageable. For example, in this (0)
ables ui, j , etc. In the absence of any informa-
description of the finite difference method, the tion, these zeroth iteration values can be taken
physical variables ux , uy and p appear explic- to be zeros. Convergence of this straightforward
itly. The finite difference method can be refor- iterative scheme is not guaranteed and even if
mulated in terms of the stream function Ψ , or a it converges, it may require a large number of
combination of stream function and the vorticity iterations. Convergence, for example, becomes
ω. For two-dimensional flow ω is defined as the slower and slower as the Reynolds number of
z component of curl of the velocity vector: the flow is increased and may fail completely
∂ux ∂uy
when the Reynolds number becomes too large.
ω= − + (174) Many numerical procedures have been devel-
∂y ∂x
oped to improve the convergence performance.
In two-dimensional flows, the stream function Iterative procedures have also been developed to
or stream function-vorticity formulations are, in deal with the nonlinearity introduced by variable
fact, used in preference to the velocity – pressure fluid properties.
formulation. Further details, particularly regard- Figure 47 shows the streamlines of the flow
ing the choice of numerical schemes for han- of a Newtonian fluid past a cylinder at increas-
dling the resulting equations, can be found in ing Reynolds number obtained by finite differ-
the references listed. ence computation using the stream function –
In this introductory description of the finite vorticity formulation [42]. Numerical conver-
difference method, the partial derivatives are ap- gence at a Reynolds number as high as 100
proximated by central differences. Other finite was achieved by a specially developed itera-
difference approximation schemes can be ap- tion scheme. The effects of increasing Reynolds
plied. Irrespective of the finite difference scheme number show up clearly in the increasing size
employed (because of the inertia terms on the of the recirculating wake behind the cylinder.
left-hand side of the Navier – Stokes equations) These numerical results are in excellent agree-
the resulting algebraic equations are nonlinear in ment with the available experimental data.
Fluid Mechanics 417
Figure 47. Streamlines around a cylinder at increasing Reynolds number obtained by finite difference computation [42] (re-
produced with permission of Cambridge University Press)
A) Re = 5; B) Re = 7; C) Re = 10; D) Re = 20; E) Re = 40; F) Re = 70; G) Re = 100.
5.2. Finite Element Method In finite element approximation, the flow field
(→ Mathematics in Chemical Engineering, of interest is again subdivided by a grid into
Chap. 7.5., Chap. 7.6.) a large number of small connected domains of
different shapes and sizes known as elements.
The finite element technique was originally de- (Following the general practice in finite element
veloped by structural engineers for calculating computation, the grid points, referred to as the
the stresses and strains in structures of complex nodal points, are identified by a single subscript
shapes. It has been generalized and developed i instead of the double subscripts i, j in finite dif-
as a numerical technique for solving differential ference.) The unknown variables, ux , uy , and p
equations, particularly partial differential equa- are approximated by series of the form
tions. As with the finite difference method, the
N
differential equations for the unknown variables ux (x,y) = uxi Φi (x,y)
are converted into a set of algebraic equations i=1
which can then be solved for the unknown vari-

N
ables at discrete points. The application of finite uy (x,y) = uyi Φi (x,y) (176)
i=1
element computation to fluid mechanics started

in the early 1960s and has since been greatly
N
refined. A brief description of the finite ele- p (x,y) = pi Ψi (x,y)

i=1
ment technique based on the Galerkin approach
will be presented here. The mathematical prin- where N (and N , see below) is the total num-
ciples and numerical details of the Galerkin fiber of nodal points in the grid; uxi , uyi , and pi
nite element method, particularly the handling of are unknown numerical coefficients to be deter-
boundary conditions, can be found in [37–41]. mined; Φi (x, y), for i = 1 to N, and Ψi (x, y) for
418 Fluid Mechanics

i = 1 to N are two sets of known functions de-
N
N
∂Φi
uxi Φi uyi +
fined for each of the nodal points. They are usu- i=1 i=1
∂x
ally referred to as the interpolation functions.
While one is free to choose the form of these

N
N
∂Φi
functions, Φi (x, y) and Ψi (x, y) are usually re- uyi Φi uyi
∂y
stricted to simple functions such as low-order i=1 i=1
N
polynomials. In many finite element computa-

N
∂Ψi ∂ 2 Φi
N
∂ 2 Φi
tions Φi (x, y) are taken to be quadratic functions + pi −η uyi + u yi
i=1
∂y i=1
∂x2 i=1
∂y 2
of x and y and Ψi (x, y) to be linear functions of x
=Ry (x,y) (177b)
and y. Both Φi (x, y) and Ψi (x, y) take the value
of unity at the nodal point i and decrease to zero
N
∂Φi
N
∂Φi
at all the neighboring nodes surrounding node uxi + uyi =Rc (x,y) (177c)
i=1
∂x i=1
∂y
i. These functions are also defined to be identi-
cally zero beyond these neighboring nodes, i.e., In general the series representations do not
Φi and Ψi are nonzero only in those elements satisfy the governing equations and leave be-
which have node i as one of its nodal points. The hind residuals Rx (x, y), Ry (x, y), and Rc (x, y).
quadratic interpolating function Φi (x, y) is also These residuals are functions of the unknown
defined to be zero at the midpoints (the mid-side coefficients uxi , uyi , pi , as well as x and y. An
nodes) of each side of the elements that have approximate solution is obtained by finding the
node i as one of its nodes. The total number set of the unknown coefficients that minimize,
of nodes N for the quadratic interpolation func- in some sense, these residuals. In the case of
tions includes the mid-side nodes. Thus N , the Galerkin finite element method, this is done by
total number of nodes for the linear interpola- requiring the Rx (x, y) and Ry (x, y) to be orthog-
tion function, is < N. In order that the series onal to all the Φi (x, y) and Rc (x, y) to be orthog-
representation approaches the true solution as onal to all the Ψi (x, y) over the region of interest,
N and N become large, the interpolation func- i.e.,
tions have to satisfy a number of mathematical
requirements. For example, all the interpolation Rx (x,y) Φk (x,y) dA= 0 k= 1toN (178a)
functions have to be continuous across the com- A

mon boundary of two adjacent elements.
Ry (x,y) Φk (x,y) dA= 0 k= 1toN (178b)
Typical examples of the interpolating func-
A
tions for quadrilateral and triangular elements
are shown in Figure 48. In the finite element Rc (x,y) Ψk (x,y) dA= 0 k= 1toN (178c)
method, elements of different sizes and shapes
A
can be mixed relatively easily. This greatly sim-
plifies the discretization of irregularly shaped A is the area occupied by the flow field. After
flow fields and is the major advantage of the performing the integration, these become a set
finite element method over the finite differ- of algebraic equations which can be solved for
ence method. When the series representations the unknown coefficients uxi , uyi , pi . It will
(Eq. 176) are substituted in the equations of mo- be found that the number of independent al-
tion and the continuity equation, the following gebraic equations, after taking into considera-
are obtained: tion the boundary conditions, is exactly equal to
N the number of unknown numerical coefficients

N
∂Φi
uxi Φi uxi + in the series representation. From the definition
i=1 i=1
∂x of the interpolation functions, it is clear that at

node j, x = xj and y = yj , the only nonzero terms

N
N
∂Φi in the series representation are Φj (xj , yj ) and
uyi Φi uxi Ψj (xj , yj ) where they take on the value of unity.
i=1 i=1
∂y
N
Hence

N
∂Ψi ∂ 2 Φi
N
∂ 2 Φi
+ pi −η uxi + u xi ux (xj ,yj ) =uxj Φj (xj ,yj ) =uxj (179a)
i=1
∂x i=1
∂x2 i=1
∂y 2
=Rx (x,y) (177a)
Fluid Mechanics 419
Figure 48. Typical finite element linear and quadratic interpolation functions
and p appearing explicitly in the finite element

uy (xj ,yj ) =uyj Φj (xj ,yj ) =uyj (179b)
computation scheme.
p (xj ,yj ) =pj Ψj (xj ,yj ) =pj (179c)
Thus the numerical coefficients in the series re-

presentation are also the values of the unknown
velocity components and pressure at the nodal
points.
A considerable amount of algebraic manipu-
lation and numerical integration must be carried
out to set up and solve these algebraic equations.
Some of these steps require considerable inge-
nuity in computer programming. In a well de-
signed finite element computer package most of
these are taken care of by the computer requiring
a minimal amount of human intervention. Be- Figure 49. Finite element mesh and streamlines in a branch-
ing channel at increasing Reynolds number obtained by finite
cause of the inertia terms and variable fluid prop- element computation
erties, the algebraic equations are again nonlin- A) Finite element mesh; B) Streamlines for Re = 10; C)
ear in the unknown coefficients. A procedure Streamlines for Re = 100
similar to that outlined above for handling the
Figure 49 shows the streamlines obtained by
set of nonlinear algebraic equations arising from
finite element computation for the flow in a
the finite difference method can also be applied
branching channel. The finite element grid em-
here, the details for implementing the iterative
ployed is shown in Figure 49A. The use of a
procedure may, of course, be quite different.
small number of triangular elements together
In the finite element method ux , uy , and p
with rectangular elements has made the dis-
appear explicitly in the computation. It is again cretization of the irregularly shaped flow field a
possible to formulate a finite element scheme relatively simple task. A Newtonian fluid, trav-
where the unknown variable is the stream func- eling vertically upwards, enters the channel as a
tion or a combination of stream function and vor- single stream and leaves as two separate streams,
ticity. In the case of viscoelastic fluids, it is also generally of unequal size. The effects of in-
common practice to have the deviatoric stress creasing Reynolds number, based on upstream
components τxy , τxx , and τyy as well as ux , uy ,
420 Fluid Mechanics
channel width, now show up as a recirculating 3. R. B. Bird, W. E. Stewart, E. N. Lightfoot:

zone in the branch channel. At low Reynolds Transport Phenomena, J. Wiley & Sons, New
number, the flow is divided equally between the York 1960.
two branches (Fig. 49B). As the Reynolds num- 4. R. B. Bird, R. C. Armstrong, O. Hassager:
ber is increased (Fig. 49C), the flow through the Dynamics of Polymeric Liquids, 2nd ed.,
straight channel increases at the expense of the vol. 1, J. Wiley & Sons, New York 1987.
branch channel. 5. H. Schlichting: Boundary-Layer Theory, 7th
ed., McGraw-Hill, New York 1977.
6. K. Walters: Rheometry, Chapman and Hall,
London 1975.
5.3. General Remarks 7. R. W. Whorlow: Rheological Techniques, Ellis
Horwood, London 1980.
Both the finite difference method and the finite 8. J. M. Dealy: Rheometers for Molten Plastics,
element method are now routinely used to solve Van Nostrand, New York 1982.
fluid flow problems. A detailed discussion of the 9. J. O. Hinze: Turbulence, 2nd ed.,
relative merits of these two methods would not McGraw-Hill, New York 1975.
serve a very useful purpose and is certainly out 10. D. Kunii, O. Levenspiel: Fluidization
of place here. It is, however, generally agreed Engineering, R. E. Krieger Pub. Co.,
that the principles of the finite difference method Huntington 1977.
are easier to understand and simpler to imple- 11. J. M. Kay, R. M. Nedderman: Fluid Mechanics
ment on computers. In contrast the finite ele- and Transfer Processes, Cambridge
ment method can cope with irregular flow fields University Press, Cambridge 1985.
very efficiently, better than the finite difference 12. Y. Taitel, A. E. Dukler, AIChE J. 26 (1980)
method. 345.
13. G. E. Alves, Chem. Eng. Progr. 50 (1954) 449.
The development of a computer program to
14. J. M. Mandhane, G. H. Gregory, K. Aziz, Int.
solve a nontrivial flow problem numerically is
J. Multiphase Flow 1 (1974) 537.
a major undertaking that requires expertise not 15. P. Griffith: “Two-Phase Flow,” in W. M.
only in fluid mechanics, but also in numerical Rohsenow, J. P. Hartnett, E. N. Ganic (eds.):
analysis, computer programming, and organiza- Handbook of Heat Transfer Fundamentals,
tion. It is not a task that can normally be carried 2nd ed., McGraw-Hill, New York 1985.
out by a single person working in isolation. A 16. F. A. Holland: Fluid Flow for Chemical
number of commercial software packages spe- Engineers, E. Arnold, London 1973.
cially designed for solving fluid flow problems 17. R. H. Perry, D. W. Green: Perry’s Chemical
are now available. Some of these packages are Engineers Handbook, 6th ed., McGraw-Hill,
very well designed and simple to use. Most of New York 1984.
them incorporate special procedures for deal- 18. A. S. Foust et al.: Principles of Unit
ing with highly nonlinear flow problems. They Operations, 2nd ed., J. Wiley & Sons, New
usually have built-in computer graphics for ef- York 1980.
ficient presentation of the large amount of nu- 19. H. A. Barnes, J. F. Hutton, K. Walters: An
merical results generated by these packages. In- Introduction to Rheology, Elsevier,
telligent use of these computing tools coupled Amsterdam 1989.
with a sound understanding of the physics and 20. A. B. Metzner, M. Whitlock, Trans. Soc.
Rheol. 2 (1958) 239.
mathematics of fluid mechanics has lead rapidly
21. Q. D. Nguyen, D. V. Boger, J. Rheol. (N.Y.) 29
to advances in the solution of flow problems that
(1985) 335.
would otherwise be intractable. 22. A. B. Metzner, J. C. Reed, AIChE J. 1 (1957)
434.
23. D. W. Dodge, A. B. Metzner, AIChE J. 5
6. References (1955) 189.
24. D. V. Boger: “Viscoelastic Flows Through
1. M. M. Denn: Process Fluid Mechanics, Contractions,” in J. L. Lumley, M. Van Dyke,
Prentice-Hall, Englewood Cliffs 1980. H. L. Reed (eds.): Annual Review of Fluid
2. S. W. Churchill: Viscous Flow the Practical Mechanics, vol. 19, Ann. Reviews Inc., Palo
Use of Theory, Butterworths, Boston 1988. Alto 1987.
Fluid Mechanics 421
25. J. Meissner, Pure Appl. Chem. 42 (1975) 553. 35. R. I. Tanner, J. Polym. Sci. Part A-2 8 (1970)
26. R. B. Bird, C. F. Curtiss, R. C. Armstrong, O. 2067.
Hassager: Dynamics of Polymeric Liquids, 2nd 36. P. S. Virk, AIChE J. 21 (1975). 625.
ed., vol. 2, J. Wiley & Sons, New York 1987. 37. T. J. Chung: Finite Element Analysis in Fluid
27. G. Prilutski, R. K. Gupta, T. Sridhar, M. E.
Dynamics, McGraw-Hill, New York 1978.
Ryan, J. Non-Newtonian Fluid Mech. 12
(1983) 233. 38. M. M. Gupta: “Numerical Methods for
28. M. Doi, S. F. Edwards: The Theory of Polymer Viscous Flow Problems,” in A. S. Mujumdar,
Dynamics, Oxford University Press, Oxford R. A. Mashelkar (eds.): Advances in Transport
1986. Processes, vol. 1, Wiley, New York 1980.
29. R. L. Larson: Constitutive Equations for 39. A. J. Baker: Finite Element Computational
Polymer Melts and Solutions, Butterworths, Fluid Mechanics, McGraw-Hill, New York
Boston 1988. 1983.
30. C. J. S. Petrie: Elongational Flows, Pitman, 40. O. C. Zienkiewicz, K. Morgan: Finite
London 1979. Elements and Approximation, Wiley & Sons,
31. F. T. Trouton, Proc. R. Soc. London A 77 London 1983.
(1906) 426.
41. M. J. Crochet, A. R. Davies, K. Walters:
32. E. B. Bagley, J. Appl. Phys. 28 (1957) 624.
33. J. A. Brydson: Flow Properties of Polymer Numerical Simulation of Non-Newtonian
Melts, Butterworth, London 1970. Flow, Elsevier, Amsterdam 1984.
34. D. V. Boger, R. K. Gupta, R. I. Tanner, J. 42. S. C. R. Dennis, G. Z. Chang, J. Fluid Mech.
Non-Newtonian Fluid Mech. 4 (1978) 239. 42 (1970) 471.
Design of Experiments 423
Design of Experiments
Sergio Soravia, Process Technology, Degussa AG, Hanau, Germany (Chaps. 1 – 3)
Andreas Orth, University of Applied Sciences, Frankfurt am Main, Germany; Umesoft GmbH, Eschborn,
Germany (Chaps. 4 – 7)
1. Introduction . . . . . . . . . . . . . . . . . 423 4.4. Using Regression Analysis to Fit

1.1. General Remarks . . . . . . . . . . . . . 423 Models to Experimental Data . . . . . 444
1.2. Application in Industry . . . . . . . . . 424 5. Methods for Assessing, Improving,
1.3. Historical Sidelights . . . . . . . . . . . . 425 and Visualizing Models . . . . . . . . . 444
1.4. Aim and Scope . . . . . . . . . . . . . . . 425 5.1. R2 Regression Measure and
2. Procedure for Conducting Experimen- Q2 Prediction Measure . . . . . . . . . . 445
tal Investigations: Basic Principles . . 425 5.2. ANOVA (Analysis of Variance) and
2.1. System Analysis and Clear Definition Lack-of-Fit Test . . . . . . . . . . . . . . 446
of Objectives . . . . . . . . . . . . . . . . 426 5.3. Analysis of Observations and
2.2. Response Variables and Experimental Residuals . . . . . . . . . . . . . . . . . . . 448
Factors . . . . . . . . . . . . . . . . . . . . 426 5.4. Heuristics for Improving Model
2.3. Replication, Blocking, and Performance . . . . . . . . . . . . . . . . . 449
Randomization . . . . . . . . . . . . . . . 427 5.5. Graphical Visualization of Response
Surfaces . . . . . . . . . . . . . . . . . . . . 450
2.4. Interactions . . . . . . . . . . . . . . . . . 428
6. Optimization Methods . . . . . . . . . . 451
2.5. Different Experimental Strategies . . 428
6.1. Basic EVOP Approach Using Factorial
2.6. Drawback of the
Designs . . . . . . . . . . . . . . . . . . . . 451
One-Factor-at-a-Time Method . . . . . 429
6.2. Model-Based Approach . . . . . . . . . 451
3. Factorial Designs . . . . . . . . . . . . . . 430 6.3. Multi-Response Optimization with
3.1. Basic Concepts . . . . . . . . . . . . . . . 430 Desirability Functions . . . . . . . . . . 452
3.2. The 22 Factorial Design . . . . . . . . . 432 6.4. Validation of Predicted Optima . . . . 453
3.3. The 23 Factorial Design . . . . . . . . . 435 7. Designs for Special Purposes . . . . . . 453
3.4. Fractional Factorial Designs . . . . . . 436 7.1. Mixture Designs . . . . . . . . . . . . . . 454
4. Response Surface Designs . . . . . . . . 441 7.2. Designs for Categorical Factors . . . . 456
4.1. The Idea of Using Basic Empirical 7.3. Optimal Designs . . . . . . . . . . . . . . 457
Models . . . . . . . . . . . . . . . . . . . . 441 7.4. Robust Design as a Tool for Quality
4.2. The Class of Models Used in DoE . . . 442 Engineering . . . . . . . . . . . . . . . . . 458
4.3. Standard DoE Models and 8. Software . . . . . . . . . . . . . . . . . . . 459
Corresponding Designs . . . . . . . . . 443 9. References . . . . . . . . . . . . . . . . . . 459
1. Introduction tal parameters are varied in an intelligent and

balanced fashion so that a maximum of infor-
1.1. General Remarks mation is gained from the analysis of the ex-
perimental results. In most cases, the time and
Research and development in the academic or money spent on the experimental investigation
industrial context makes extensive use of exper- will be greatly reduced. In all cases, an optimal
imentation to gain a better understanding of a ratio between the number of experimental trials
process or system under study. The methodol- and the information content of the results will
ogy of Design of Experiments (DoE) provides be achieved.
proven strategies and methods of experimental DoE is a powerful target-oriented tool. If
design for performing and analyzing test series it is properly employed, creative minds with
in a systematic and efficient way. All experimen- a scientific and technical background will best
424 Design of Experiments
deploy their resources to reach a well-defined – Low costs to ensure adequate profits
goal of their studies. In contrast to what re- – Short development periods for new or im-
searchers sometimes fear, experimenters will proved products and production processes
not be hampered in their creativity, but will (time to market)
be empowered for structuring their innovative
Quality engineering techniques are powerful
ideas. Of course, adopting DoE requires disci-
elements of modern quality management sys-
pline from the user, and it has proved very help-
tems and make it possible to reach these goals.
ful to take the initial steps together with an ex-
One important challenge in this context is not
pert with experience in the field. The rewards
to ensure quality downstream at the end of the
of this systematic approach are useful, reliable,
production line, but to ensure product quality by
and well-documented results in a clear time and
a stable and capable production process which
cost frame. A comprehensible presentation and
is under control. By this means, ongoing tests
documentation of experimental investigations is
and checks to prove that the product conforms
gratefully acknowledged by colleagues or suc-
to specification requirements are avoided. This
cessors in research and development teams. The
can be realized by knowing the important and
application of DoE is particularly essential and
critical parameters or factors governing the sys-
indispensable when processes involving many
tem and through the implementation of intelli-
factors or parameters are the subject of empiri-
gent process management strategies.
cal investigations of cause – effect relationships.
A methodical approach, sometimes referred
DoE is a scientific approach to experimen-
to as off-line quality engineering [24], [31], fo-
tation which incorporates statistical principles.
cuses even further upstream. By considering
This ensures an objective investigation, so that
quality-relevant aspects in the early stages of
valid and convincing conclusions can be drawn
product and process development, quality is en-
from an experimental study. In particular, an
sured preventively in terms of fault prevention
honest approach to dealing with process and
[30], [39]. Naturally, there is considerable cost-
measurement errors is encouraged, since exper-
saving potential in the early stages of product
iments that are repeated under identical condi-
and process design, where manufacturing costs
tions will seldom lead to the same results. This
are fixed to a large extent. The losses incurred for
may be caused by the measuring equipment, the
each design modification of a product or process
experimenter, changes in ambient conditions, or
gradually increase with time. In addition, design
the natural variability of the object under study.
errors with the most serious consequences are
Note that this inherent experimental error, in
known to be committed in these early stages.
general, comprises more than the bare repeata-
As an outstanding quality engineering tool,
bility and reproducibility of a measurement sys-
DoE occupies a key position in this context.
tem. DoE provides basic principles to distin-
The emphasis is on engineering quality into the
guish between experimental error and a real ef-
products and processes. At the same time, DoE
fect caused by consciously changing experimen-
opens up great economic potential during the en-
tal conditions. This prevents experimenters from
tire development and improvement period. It is
drawing erroneous conclusions and, as a conse-
well-known that the implementation and use of
quence, from making wrong decisions.
corresponding methods increases competitive-
ness [4], [23], [29], [37], [40]. DoE is applied
successfully in all high-technology branches of
1.2. Application in Industry industry. In the process industry, it makes essen-
tial contributions to optimizing a large variety of
In industry, increasingly harsh market condi- procedures and covers the entire lifecycle of a
tions force companies to make every effort to product, starting from product design in chem-
reach and maintain their competitive edge. This ical research (e.g., screening of raw materials,
applies, in particular, in view of the following finding the best mixture or formulation, opti-
goals: mizing a chemical reaction), via process devel-
– Quality of products and services in confor- opment in process engineering (e.g., test novel
mance to market requirements technological solutions, determine best oper-
ating conditions, optimize the performance of eral years now. They essentially support the gen-
processes), up to production (e.g., start up a eration, analysis, and documentation of experi-
plant smoothly, find an operating window which mental designs. Experience has shown that such
meets customer requirements at low cost, high software can be used by experimenters once the
capacity, and under stable conditions) and appli- basic principles of the methods applied have
cation technology (give competent advice con- been learned. A list of software tools is given
cerning the application of the product, customize in Chapter 8.
the properties of products to specific customer Despite these stimulating developments, the
needs). In particular, technologies like high- majority of scientists and engineers in industry
throughput screening or combinatorial synthe- and academic research have still not yet used
sis with automated workstations require DoE to DoE.
employ resources reasonably.
1.4. Aim and Scope

1.3. Historical Sidelights
The target group of this article consists of scien-
The foundations of modern statistical experi- tists and engineers in industry or academia. The
mental design methods were laid in the 1920s intention is
by R. A. Fisher [16] in Great Britain and
were first used in areas such as agricultural – To give an insight into the basic principles
science, biology, and medicine. By the 1950s and strategies of experimental design
and 1960s, some of these methods had already – To convey an understanding of the important
spread into chemical research and process de- design and analysis methods
velopment where they were successfully em- – To give an overview of optimization tech-
ployed [3], [13], [34]. During this period and niques and some advanced methods
later, G. E. P. Box et al. made essential contribu- – To demonstrate basically the power of
tions to the advancement and application of this proven methods of DoE and to encourage
methodology [4–9]. their use in practice
In 1960, J. Kiefer and J. Wolfowitz ini- References for further reading and detailed
tiated a profound research of the mathematical study are given on all subjects. In particular,
theory behind optimal designs, and in the early [7], [27], and [33] may be regarded as stan-
1970s the first efficient algorithms for so-called dard monographs on DoE in their respective lan-
D-optimal designs were developed. guages.
Around the same time, G. Taguchi inte-
grated DoE methods into the product and pro-
cess development of numerous Japanese compa-
nies [38]. One of his key ideas is the concept of 2. Procedure for Conducting
robust design [24], [31], [39]. It involves design- Experimental Investigations: Basic
ing products and processes with suitable param- Principles
eters and parameter settings so that their func-
tionality remains as insensitive as possible to un- DoE should become an integral part of the regu-
avoidable disturbing influences. Taguchi’s ideas lar working tools of all experimenters. The meth-
were discussed fruitfully in the United States ods provided by this approach may be used in
during the 1980s [4], [18], [22], [24] and caused experimental investigations on a smaller scale
an increasing interest in this subject in Western as well as in large projects which, depending on
industries. At the same time, another set of tools, their importance and scope, may involve putting
which in general is not suitable for chemical or together an interdisciplinary team of appropri-
chemical engineering applications, became pop- ate size and composition. It proved to be ad-
ular under the name of D. Shainin [2], [26]. vantageous to also include staff who take care
The 1980s also saw the advent and spread of the equipment or facility on-site. They of-
of software for DoE. Various powerful software ten bring in aspects and experiences with which
tools have been commercially available for sev-
Figure 1. Three essential phases characterize the basic structure of a DoE project
the decision-makers involved are largely unfa- 2.2. Response Variables and
miliar. Moreover, involving, for instance, labo- Experimental Factors
ratory staff in the planning phase of experiments
has a positive effect on their motivation. A DoE Each experiment can be regarded as an inquiry
project essentially subdivides into three charac- addressed to a process or system (see Fig. 2).
teristic phases: the design or planning phase, the Naturally, it must be possible to record its an-
actual experimental or realization phase, and the swer or result in terms of measurable or quantifi-
analysis or evaluation phase (Fig. 1). It should able response variables (dependent variables).
be stressed that the design phase is decisive be- Response variables must be selected such that
cause it is this phase that determines the level the characterization of the interesting properties
of information attainable by the analysis of the of the system is as complete and simple as pos-
experimental results. For more information on sible. Let us consider a batch reaction, for in-
this subject and on basic principles of DoE, see stance. In this case it is certainly not only the
[11], [19], [21]. conversion of starting material that is of inter-
est as a test result; other potential response vari-
ables could be the concentration of undesired
2.1. System Analysis and Clear byproducts or the duration of the reaction (ca-
pacity). For some system characteristics, such
Definition of Objectives
as foaming during stirring operations or the vi-
sual impression of a pigment, there are often no
A system analysis involves collecting all exist-
measurable quantities. In these cases, it may be
ing information about the system to be examined
helpful to assess the results by a subjective rat-
and describing the current situation. A precise
ing (e.g., 0: no foam or very beautiful pigment,
formulation of the problem and a clear definition
1: some foam or beautiful pigment, up to about
of the objectives are very important prerequisites
7: very much foam or very ugly pigment). When
for a successful procedure and for attaining use-
the response variables are selected, it is impor-
ful results from an experimental investigation.
tant to ask questions about the reliability of the
Experiments should never be conducted for their
corresponding values: How much do the results
own sake but are to provide objective and reliable
vary if the experimental runs are conducted un-
information, particularly, as a sound basis for de-
der conditions that are as identical as possible?
cisions to be made. A clear statement of objec-
Ideally, a detailed analysis of the measurement
tives is crucial, since the experimental strategy
system is available which, in particular, provides
and hence the design of the experiments is essen-
information on repeatability and reproducibility.
tially influenced by the goals to be reached (see
The results of experimental runs, i.e., the val-
Section 2.5). This sounds trivial but is frequently
ues of response variables, are affected by vari-
not handled carefully enough in practice. The
ous factors. In practically all applications there
actual planning or even the performance of ex-
are disturbing environmental factors, which may
perimental trials should not start until all of the
cause undesired variations in the response vari-
aforementioned points have been settled satis-
ables. Some of them are hard to control or uncon-
factorily.
trollable, others simply may not even be known.
Examples of such variables are different batches
of a starting material, various items of equipment
with the same functionality, a change of experi- risk of misleading interpretation of the results is
menters, atmospheric conditions, and – last but minimized.
not least – time-related trends such as warming- Replicates serve to make results more reliable
up of a machine, fouling of a heat exchanger, and to obtain information about their variability.
clogging of a filter, or drifting of a measuring A genuine replicate should consider all possible
instrument. environmental influences leading to variations
within the response variables, i.e., the whole
experiment with its corresponding factor-level
combination should be repeated from the be-
ginning and with some time delay in between.
The results of data analyses must always be seen
in the light of this inherent experimental error.
Hence, replication does not mean, for instance,
analyzing a sample of a product several times.
This variability of a response variable is solely
a measure of the precision of the analytical test
Figure 2. Input – output model of a process or system procedure (laboratory assistant, measuring in-
However, besides collecting and discussing strument).
the uncontrollable and disturbing variables, it is It is of crucial importance that environmen-
essential to collect and weigh up those factors or tal factors and experimental factors of interest do
parameters that can be controlled or adjusted (in- not vary together such that changes in a response
dependent variables), such as temperature, pres- variable cannot be unambiguously attributed to
sure, or the amount of catalyst used. The decision the factors varied. For example, if two catalyst
as to which of these experimental factors are to types were to be compared at various reaction
be kept constant during a test series and which temperatures and if two differently sized reac-
are to be purposefully and systematically varied tors were available for this purpose, it would be
must also be carefully weighed up. The entire unwise to conduct all experiments with one cat-
scientific and technical system know-how avail- alyst in the smaller reactor and all experiments
able by then from literature and experience, as with the other catalyst in the larger reactor. If, in
well as intuition, must decisively influence not this case, the results differed from each other, it
only the choice of the factors to be varied (one would be impossible to decide whether the cat-
should focus on the important ones here accord- alyst type or the reactor type or both caused the
ing to the latest knowledge) but also the deter- deviations. The objective of blocking is to pre-
mination of the experimental region, i.e., of the determine relatively similar blocks – in this case,
specific range over which each factor will be var- the two reactors – in which test conditions are
ied (e.g., temperature between 120 and 180 ◦ C more homogeneous and which allow a more de-
and pressure between 1200 and 1800 mbar). A tailed study of the experimental factors of inter-
good experimental design will efficiently cover est. Regarding the selection of the catalyst type
this experimental domain such that the questions and reaction temperature, the experiments to be
related to the objectives may be answered when conducted in each of the two reactors must be
the experimental results are analyzed. similar in the sense that variations in the values
of a response variable can be interpreted cor-
rectly.
2.3. Replication, Blocking, and It is not always possible, however, to clearly
identify unwanted influences and to take them
Randomization into account, as is the case when blocking is
used. Yet these side effects can be counterbal-
To take the effects of disturbing environmen- anced by a general use of randomization. Here,
tal variables into account and decrease their imin contrast to systematically determining which
pact to a large extent, the principles of replica- experiments are to be conducted, the order of the
tion, blocking, and randomization are employed. experiments is randomized. In particular, false
Moreover, by considering these principles, the assignments of time-related trends are avoided.
Let us consider a rectifying column, for instance, about the joint effects of experimental factors,
in which the effects of operating pressure, reflux that is, their interactions. Two variables are said
ratio, and reboiler duty on the purity of the top to interact if, by changing one, the extent of im-
product are to be examined. Let us assume that pact on a third, namely, a response variable, de-
the unit is started up in the morning and that the pends on the setting of the other variable. In
whole test series could be realized within one other words, interaction between two experi-
day. Now, if one conducted all experiments in- mental factors measures how much the effect of
volving a low reflux ratio before those involving a factor variation on a response variable depends
a high reflux ratio, the effect of the reflux ra- on the level of the other factor. Interactions are
tio could be falsified more or less by the unit’s often not heeded in practice, or they are stud-
warming up, depending on how strong this influ- ied at the price of spending large amounts of
ence is (poor design in Fig. 3). Such an uncon- time and money on the associated experimen-
trolled mixing of effects is prevented by choos- tal investigation. In addition, what interaction
ing the order of the experimental runs at random actually means is often not clearly understood.
(good design in Fig. 3). In particular, interaction is not to be confused
with correlation. Two variables are said to be
correlated if an increase of one variable tends
to be associated with an increase or decrease of
the other. Especially factorial experimental de-
signs (see Chap. 3) allow, among other things,
a quantitative determination of interactions bet-
ween varied experimental factors.
2.5. Different Experimental Strategies

When processes are to be improved or novel
Figure 3. Time-related effects caused, e.g., by instrument technical solutions are to be tested, but also
drifts may falsify the analysis of the results when factor set- when plants are started up, several factors are
tings are not changed randomly (poor design). If environ- often varied, in the hope of meeting with short-
mental conditions vary during the course of an experiment, term success, by using an unsystematic itera-
their effect will be damped or averaged out by randomizing
the sequence of the experiments (good design) tive trial-and-error approach until satisfactory
results are eventually produced. The expenditure
The decisive reason for employing the princi- involved quickly takes on unforeseeable propor-
ples of replication, blocking, and randomization tions without affording important insights into
is therefore to prevent the analysis of system- the cause-and-effect relationships of the system.
atically varied experimental factors from being The result of this procedure is that, in the end, a
unnecessarily contaminated by the influences of comprehensible documentation is not available,
unwanted and often hidden factors. While block- and objective, reliable reasons for process op-
ing and randomization basically do not involve erations or factor settings are missing. Further-
additional experimental runs, each replicate is a more, very little is known in most cases about
completely new realization of a combination of the impact of factor variations. Experimenting
factor settings. An appropriate relation between in this way might be acceptable for orientation
the number of experimental runs and the relia- purposes in a kind of pre-experimental phase.
bility of its results must be established here on However, one should switch to a judicious pro-
an individual basis. gram as soon as possible.
To study causal relationships systematically,
the experimental factors or parameters are usu-
2.4. Interactions ally varied separately and successively, and the
values of a response variable (product, process,
To avoid an overly limited view on the behav- or quality characteristic), such as the yield of
ior of systems, it is of great importance to know a chemical product, are shown in a diagram
(see Fig. 4). This one-factor-at-a-time method vestigated as evenly as possible, while ensur-
(see Section 2.6), however, provides only few in- ing to the largest possible extent that changing
sights into the subject under study because the values in a response variable can be attributed
effect of a particular factor is only known at a unambiguously to the right causes. Information
single factor-level combination of the other fac- of crucial importance is frequently obtained by
tors. The response variable may have quite an- a simple graphical analysis of the data without
other shape if the levels of the remaining factors having to employ sophisticated statistical anal-
are set differently. If the experimental factors ysis methods, such as variance analysis or re-
in their effect on a response variable do not act gression analysis. On the other hand, the best
additively according to the superposition prin- statistical analysis is not capable of retrieving
ciple, i.e., if the factors influence each other in useful information from a badly designed series
their effect on the response variable by existing of experiments. It is therefore decisive to con-
interactions, a misinterpretation of the results is sider basic DoE principles right from the begin-
easily possible, particularly when optimum con- ning, above all, however, before conducting any
ditions are to be attained. experiments.
When statistical experimental design meth-
ods are used, all considered factors are varied in
a systematic and balanced way so that a maxi- 2.6. Drawback of the
mum of information is gained from the analy- One-Factor-at-a-Time Method
sis of the corresponding experiments. This may
comprise the statistically sound quantitative de- A crystallization process is used in the follow-
termination of the effects of factor variations on ing to illustrate the deficiency of the frequently
one or several response variables (see Chap. 3) used one-factor-at-a-time method. Factors influ-
or a systematic optimization of factor settings encing this system are, for instance, crystalliza-
(see Chap. 6). Depending on the experimenter’s tion conditions such as geometry of the crystal-
intention, the following questions can be an- lizer, type and speed of the agitator, temperature,
swered: residence time, and concentrations of additives
like crystallization and filter aids, as well as of
– What are the most important factors of the two presumed additives A and B. Possible re-
system under investigation? sponse variables may be bulk density, abrasion,
– To what extent and in which direction does hardness, and pourability of the crystallization
a response variable of interest change when product. Let us assume the simple case that the
an experimental factor is varied? effects of the two experimental factors – additive
– To what extent is the size and direction of the A and additive B – on the material’s bulk density
effect of a factor variation dependent on the are to be systematically examined with the aim
settings of other experimental factors (inter- of obtaining a maximum bulk density. As men-
actions)? tioned before, the experimental factors are usu-
– With which factor settings does one obtain ally examined and/or optimized separately and
a desired state of a response variable (maxi- successively. In the example considered here,
mum, minimum, nominal value)? one would therefore begin by keeping factor B
– How can this state be made insensitive to dis- constant and varying A over a certain range until
turbing environmental factors or how can an A has been optimally adjusted in terms of a max-
undesired variability of a response variable imum bulk density and enter the result in a dia-
be reduced (robust design)? gram (see Fig. 4). The optimal value for A would
The question of which experimental strategy then be selected and kept constant. The same
should be chosen from a comprehensive range procedure would then be employed for B. The
of methods will be governed by the objectives result of this is a presumably optimal setting for
to be achieved in each individual case, taking, A and B, and hasty experimenters would jump
e.g., system-inherent, financial, and time-related to the conclusion that, in this case, after varying
boundary conditions into account. Every project A between 15 and 40 g/L and B between 5 and
has its peculiarities. Carefully planned experi- 17.5 g/L, the highest bulk density is obtained by
ments cover the experimental region to be in- setting A to 33 g/L and B to 8.5 g/L and that its
value is approximately 825 g/L. However, the some uneasiness for experimenters using this
response surface in Figure 4, which shows the method for the first time. But by using two-level
complete relationship between both experimen- factorial designs, a balanced coverage of the in-
tal factors and the response variable, reveals how teresting experimental region is achieved very
misleading such a conclusion can be. This dras- economically. Moreover – owing to the special
tic misinterpretation is based on the, in this case, combination of factor levels – it is also possible
false assumption that the effect of varying one to gain deeper insights from the associated indi-
factor is independent of the settings of the other vidual values of the response variables. A deci-
factor. For instance, by using the response sur- sive advantage of the two-level factorial designs
face, one can show that the bulk density val- is that they allow the effects of factor variations
ues take on a decidedly different shape com- to be systematically and reliably analyzed and
pared to the first diagram when varying A for quantified and that they provide information on
B = 15 g/L. The following should be noted: If how these effects depend on the settings of the
there are interactions between experimental fac- other experimental factors. These insights are
tors, the one-factor-at-a-time method is an un- gained by calculating so-called main effects and
suitable tool for a systematic analysis of these interaction effects. In the calculation of these ef-
factors, which holds true in particular when fac- fects, all experimental results can be used and are
tor settings are to be optimized. If such interac- included to form well-defined differences of cor-
tions can definitely be ruled out, it might well be responding averages (see Figs. 6 and 9), thereby
used. In chemistry, however, it is rather the rule increasing the degree of reliability. The essential
that interactions occur. results of this effect analysis can be visualized
by simple diagrams (see, e.g., Fig. 7).
In a factorial design, not only continuous ex-
3. Factorial Designs perimental factors, such as temperature, pres-
sure, and concentration, which can be set to any
3.1. Basic Concepts intermediate value, but also discrete or categor-
ical factors, such as equipment or solvent type,
The statistical experimental designs most fre- may be involved. If at least one categorical vari-
quently used in practice are the two-level facto- able with more than two levels is involved or if
rial designs. These designs are called two-level curvatures in the response variables are expected
because there are only two levels of settings, a and to be explored, factorial designs with more
lower (−) and an upper level (+), for each of than two levels may be used, e.g., 3n designs, in
the experimental factors. A full two-level fac- which all factors are studied at three levels each,
torial design specifies all combinations of the or hybrid factorial designs with mixed factor lev-
lower and upper levels of the factors as settings els like the 2 × 32 design, in which one factor is
of the experimental runs (2n design, where n de- varied at two levels, and two factors at three lev-
notes the number of factors). Their principle is els [27]. However, especially in the case of con-
illustrated by a simple example of a chemical tinuous factors, other so-called response surface
reaction for which the influence of 2 (22 design) designs are more efficient (see Chap. 4). In the
and 3 (23 design) experimental factors on the following, the expression “factorial designs” al-
product yield is to be examined (Sections 3.2 and ways refers to two-level factorial designs.
3.3). For a growing number of factors, the num- For the sake of simplicity, replicates are ne-
ber of runs of a full factorial design increases glected in the following examples, and variabil-
exponentially, and it provides much more infor- ity in the process and in measurement are as-
mation than is generally needed. Particularly for sumed to be very small. Note, however, that
n > 4, the number of experimental settings can being aware of the impact of experimental er-
be reduced by selecting a well-defined subgroup ror on the reliability or significance of calcu-
of all 2n possible settings of the factors without lated effects is an essential principle of DoE and
losing important information. This leads to the crucial to drawing valid conclusions. Variabil-
fractional factorial designs (Section 3.4). ity within individual runs having the same set-
The restriction of initially using just two lev- tings of the experimental factors will propagate
els for each experimental factor often causes and cause variability in each calculated variable,
Figure 4. The one-factor-at-a-time method can lead to misinterpretations in systems that are subject to interactions
Figure 5. Example of a 22 factorial design, including a graphical and a tabular representation of the experimental settings and
results
e.g., main effect or interaction effect, deduced which contain the settings of the experimental
from these single results. Experimental designs, factors form the so-called design matrix. The
particularly the factorial designs, minimize error resultant values of the response variable y ob-
propagation. tained for the settings A−B−, A+B−, A−B+,
and A+B+ are referred to as yA−B− , yA+B− ,
yA−B+ , and yA+B+ respectively. They are en-
tered in the column of the response variable and
in the corresponding positions of the graph.
Due to the special constellation of the exper-
imental runs, it is possible to see how y changes
when factor A is varied at the two levels of B
and what happens when factor B is varied at
the two levels of A. Figure 5 reveals that, at the
lower temperature of 70 ◦ C (B−), an increase of
the catalyst quantity from 100 g (A−) to 150 g
(A+) increases the response variable yield by
2 %, while at the higher temperature of 90 ◦ C
(B+), increasing the catalyst quantity enlarges
the value of the response variable by 18 %, i.e.,
Effect of AforB−
= EB− (A)
= yA+B− − yA−B−
= +2%
Effect of AforB+
= EB+ (A)
= yA+B+ − yA−B+
= +18%
Accordingly, the individual effects of a tempera-

ture increase can be determined for the different
catalyst quantities:
Effect of BforA−
= EA− (B)
= yA−B+ − yA−B−
Figure 6. Calculation of the two main effects and the inter-
= +14%
action effect in a 22 factorial design
Effect of BforA+
Factorial designs are treated in most text- = EA+ (B)
books on DoE, e.g., [7], [25], [27], [33], [36].
= yA+B+ − yA+B−
= +30%
3.2. The 22 Factorial Design

As mentioned before, key results of a fac-
Let us suppose the influence of two factors – cat- torial design are obtained by the calculation of
alyst quantity A and temperature B – on yield y of main effects and interaction effects (Fig. 6). The
a product in a stirred tank reactor is to be exam- main effect of a factor is a measure of the extent
ined. Figure 5 shows the two levels of both fac- to which a response variable changes on aver-
tors involved, as well as a tabular and a graphical age when this factor is varied from its lower to
representation of the associated experimental 22 its upper level. To calculate this main effect, all
factorial design. The – in this case two – columns experimental results obtained at the upper (+)
and lower (−) level of the factor are averaged, were not 92 but 76 %, there would be no in-
and the result at the lower setting is subsequently teraction between A and B. The effect of a
subtracted from that at the upper. This leads to variation of one of the two factors on the re-
the following equations: sponse variable would be independent of the ad-
justment of the other factor. In this case, the
Main effect of A two individual effects would be identical for
= ME (A) each factor, i.e., EB− (A) = EB+ (A) = + 2 % and
=
yA+B− + yA+B+
−
yA−B− + yA−B+ EA− (B) = EA+ (B) = + 14 %. The corresponding
2 2 lines in the interaction diagrams would then be
(yA+B− − yA−B− ) + (yA+B+ − yA−B+ ) parallel. It seems reasonable now to determine
=
2 a quantitative measure for the interaction of two
EB− (A) + EB+ (A) factors as the difference of these individual ef-
=
2 fects, i.e.,
= 10%
Interaction effect between AandB
Main effect of B
= IE (AB)
= ME (B)
1
yA−B+ + yA+B+ yA−B− + yA+B− = [EB+ (A) − EB− (A)]
= − 2
2 2
(yA+B+ − yA−B+ ) − (yA+B− − yA−B− )
(yA−B+ − yA−B− ) + (yA+B+ − yA+B− ) =
= 2
2
yA+B+ + yA−B− yA−B+ + yA+B−
EA− (B) + EA+ (B) = −
= 2 2
2
(yA+B+ − yA+B− ) − (yA−B+ − yA−B− )
= 22% =
2
1
= [EA+ (B) − EA− (B)]
The expressions preceding the numerical re- 2
sults in the calculations above show that the main = IE (BA)
effect of a factor can also be calculated from the = +8%
mean of the individual effects involved. The two
calculated results can now be read as follows: From these sequences of expressions it can be
When the catalyst quantity A is increased from seen that the interaction between A and B could
100 to 150 g, the yield increases on average by be equally defined through the difference of the
10 % from 60 + 74
= 67% to 62 + 92
= 77%. individual effects of A or the individual effects of
2 2 B, giving the same numerical result each time.
The temperature B has a stronger impact on
the response variable yield within the range of Moreover, the expression in the middle shows
70 – 90 ◦ C. An increase in temperature leads to that the interaction between A and B – as is the
an average increase in yield of 22 %. The main- case for the main effects – is nothing but the
effect diagrams in Figure 7 illustrate these rela- difference of two averages (this is basically the
tions graphically. reason why a factor of 12 is introduced in the defi-
The effect of a factor variation is strongly de- nition). This corresponds to the difference of the
pendent on the respective setting of the other averages of the results located on the diagonals
factor. This was already shown in Figure 5 and in Figure 6.
is further illustrated by the two interaction di- The calculation of the two main effects and
agrams in Figure 7. The four lines in these di- of the interaction effect is also represented geo-
agrams correspond to the four edges of the re- metrically in Figure 6. The corresponding anal-
sponse surface, also shown in Figure 7. This in- ysis table contains columns of signs, which al-
teraction is a typical case of a synergetic inter- low calculation of these effects. Each effect may
action. A simultaneous increase of A and B has be computed as the sum of signed response val-
a clearly higher impact on the response vari- ues divided by half the number of experiments,
able than the additive superposition of the in- where the signs are taken from the column of the
dividual effects, EB− (A) and EA− (B), would desired effect. Note that the signs of the interac-
lead one to expect. If the value of yA+B+ tion column AB can be generated by a row-wise
Figure 7. Diagrams of main effects, interactions, and response surfaces illustrate conspicuously important relations governing
the system
multiplication of the main-effect columns A and tor range, in our example, to 125 g of catalyst
B. Today, however, the effects do not need to be and 80 ◦ C. This isolated additional experimental
computed like this anymore. Specific DoE soft- point gives a rough impression of the behavior
ware tools (see Chap. 8) use methods such as of response variables inside the experimental re-
those described in Section 4.4 and yield numer- gion of interest. If the result in the center point
ical and graphical results more easily. does not correspond to the mean of the results
A final interpretation of the experiments obtained in the corner points of the factorial de-
could read as follows: The catalyst shows a not sign, then the response surface of the response
yet satisfactory activity at the lower tempera- variable will have a more or less pronounced
ture (70 ◦ C). An increase of the catalyst quantity curvature that depends on the magnitude of this
from 100 to 150 g gives a slight improvement deviation. The graph in Figure 5 shows a result
but does not yet yield satisfactory values. The of 70 % at the center point, which is slightly be-
situation is a different at the higher temperature low the 72 % obtained by averaging the four re-
(90 ◦ C), where the catalyst clearly performs bet- sults of the factorial design. Thus, the response
ter. In addition, an increase in the catalyst quan- surface must be imagined as slightly sagging in
tity at this temperature has a strong impact on its middle. Of course, with this single additional
yield. experiment, it is impossible to determine which
If all experimental factors are continuous, it of the experimental factors is (are) ultimately
will be possible and useful to perform experi- responsible for the curvature. This question can
mental runs at the center point. It is obtained only be settled by a response surface design (see
by setting each factor to the midpoint of its fac- Chap. 4).
The analysis shown for one response variable two-factor interactions, where n denotes the
is performed for each response variable so that number of factors. For three factors there are
the effects of factor variations on every response
3
variable are finally known. =3
2
two-factor interactions, namely, AB, AC, and
3.3. The 23 Factorial Design BC. The calculation of a two-factor interaction
in a 23 factorial design will be demonstrated for
The concepts and notions introduced in the Sec- AB. This interaction is obtained by calculating
tion 3.2 can be generalized to three or more fac- the two-factor interaction IEC− (AB) at the lower
tors. Let us suppose that, in addition to the ex- level of factor C and the two-factor interaction
ample in Section 3.2, not only the effects of tem- IEC+ (AB) at the upper level of factor C, and
perature and catalyst quantity but also the impact then by averaging these two values:
of changing the agitator type on the yield are to
Interaction effect between AandB
be examined. In analogy to Figure 5, the experi-
mental factors with their respective two settings = IE (AB)
as well as the 23 factorial design, which is ob- =
IEC− (AB) + IEC+ (AB)
tained by realizing all possible combinations of 2
60 + 92 62 + 74
57 + 82 59 + 67

factor settings, are represented in graphical and 2
− 2
+ 2
− 2
=
tabular form in Figure 8. 2
By comparing the values at the ends of the 60 + 92 + 57 + 82 62 + 74 + 59 + 67
= −
various edges of the cube in Figure 8, it is pos- 4 4
sible to perform a very elementary analysis. For = +7.25%
each factor, the effect of its variation can be stud- A two-factor interaction in a factorial design
ied for the four different constellations of the with more than two factors is obtained by tak-
other two factors. For example, the change from ing the average of all individual two-factor in-
the current to the new agitator type does not lead teractions at the different constellations of the
to the presumed improvement in yield. This may other factors. The calculation of IE(AB) is also
be verified by looking at the four edges going illustrated in Figure 9, where it is seen to be the
from the front face to the back face of the cube. difference of averages between results on two
The deterioration is particularly severe at high diagonal planes. Due to the inherent symmetry
temperature where the yield decreases from 74 of the design, the calculation of the other two-
to 67 % (for the lower level of catalyst) and from factor interactions, IE(AC) and IE(BC), can be
92 to 82 % (for the upper level of catalyst). performed in a similar way. This leads to the
More detailed information about the specific respective columns of signs within the analysis
and joint effects of the factors is obtained by table in Figure 9 and to the corresponding diag-
calculation of the main effects and interaction onal planes within the cube.
effects introduced in Section 3.2. Now, if the interaction between A and B at the
The main effect thereby indicates how much lower level of C differs from their interaction at
a response variable is affected on average by a the upper level of C, there will be a three-factor
variation of a factor and is measured as the dif- interaction, which is defined by the difference of
ference in the average response for the two factor these two individual two-factor interactions:
levels. Figure 9 illustrates this for the factors A
IE (ABC)
(catalyst) and B (temperature). The main effect
1
for C (agitator type) is obtained analogously by = [IEC+ (AB) − IEC− (AB)]
2
calculating the difference of the two averages at
1 57 + 82 59 + 67
the back face and the front face of the cube. = −
2 2 2
The interaction effect of two factors, more
60 + 92 62 + 74
precisely, the two-factor interaction was intro- − −
2 2
duced in Section 3.2. Generally, there will be
62 + 74 + 57 + 82 60 + 92 + 59 + 67
n n· (n − 1) = −
= 4 4
2 2 = −0.75%
Figure 8. Example of a 23 factorial design, including a graphical and a tabular representation of the experimental settings and
results. The experimental settings for agitator type “current” correspond to the 22 factorial design in Figure 5
Note that this result can also be obtained by using Even though three-factor interactions may re-
the column of signs corresponding to the three- ally exist in some cases, it is seldom that they
factor interaction ABC in Figure 9. As in the play an essential role. So, if their absolute value
case of two-factor interactions, the signs within is clearly higher than most of the main effects
this column are obtained by a row-wise multi- and two-factor interactions, it seems reasonable
plication of the signs of the main effect columns to conclude that the experimental error is of a
A, B, and C. Obviously, the three-factor interac- magnitude that does not allow the reliable esti-
tion is also the difference of two averages (as in mation of most of the effects (perhaps because
the case of the two-factor interaction presented they are very small) and/or that at least one re-
in Section 3.2, this is the reason why the factor sponse value has been corrupted by a gross sys-
of 12 is introduced in the definition). They are tematic error.
obtained by averaging the results located at the If, on the whole, systematic errors can be
vertices of the respective two tetrahedra which excluded, it is a legitimate practice to neglect
make up the cube. higher-order interactions, such as three- and
The numerical results of all effects obtainable four-factor interactions, because main effects
from the 23 factorical design are summarized in tend to be larger than two-factor interactions,
the following: which in turn tend to be larger than three-factor
interactions, and so on. Moreover, if no infor-
ME(A) = 9.25 %
ME(B) = 19.25 % mation about the magnitude of the experimental
ME(C) = − 5.75 % error is available, it will be possible to obtain
IE(AB) = 7.25 %
IE(AC) = − 0.75 %
a rough estimate of this error by using higher-
IE(BC) = − 2.75 % order interactions, like five-, four-, and even
IE(ABC) = − 0.75 % three-factor interactions.
Note again that numerical results like these

and graphical results like those of Figure 7 are 3.4. Fractional Factorial Designs
easily obtained by using specific DoE software
(see Chap. 8). Diagrams of main effects and in- For a growing number n of experimental factors,
teraction effects may also be generated for fac- the number of experimental settings 2n increases
torial designs with more than two factors. exponentially in a full factorial design. Simul-
Figure 9. Calculation of main effects and interaction effects in a 23 factorial design shown for the main effects of A and B
and their two-factor interaction AB
taneously, the proportion of higher-order inter- lating these effects leads to the same expression.
actions increases rapidly. For instance, if n = 5, It is actually the sum ME(C)+IE(AB) of both ef-
there are 5 main effects, 10 two-factor interac- fects. It can also be verified that ME(A) is con-
tions, and 16 interactions of higher order. Obvi- founded with IE(BC), and ME(B) with IE(AC).
ously, if n is not small, there is some redundancy This is an example of a so-called resolution III
in a full factorial design, since higher-order inter- design.
actions are not likely to have appreciable mag- A slightly different situation occurs when
nitudes. At this point, the following questions considering the 24−1 design (see Fig. 11). Here
arise: the main effects are confounded with three-
– Is it possible to reduce the amount of exper- factor interactions, e.g. ME(A) with IE(BCD),
imental effort in a sophisticated way so that and the two-factor interactions are confounded
the most important information can still be with each other, e.g., IE(AC) with IE(BD). This
obtained by analysis of the data? is an example of a resolution IV design. The
– Is it possible to study more experimental fac- 25−1 design also shown in Figure 11 is an ex-
tors instead of higher-order interactions with ample of a very efficient resolution V design.
the same number of experimental settings? The resolution of a fractional factorial design
largely characterizes the information content ob-
The answer in both cases is “yes”. It leads tainable by analyzing the results of a fractional
to the 2n−k fractional factorial designs, where factorial design:
2n−k denotes the number of experimental set-
tings, n the number of experimental factors, – A fractional factorial design of resolution III
and k the number of times by which the num- does not confound main effects with each
ber of settings has been halved compared to other but does confound main effects with
the corresponding complete 2n design with two-factor interactions.
the same number of experimental factors (1/2k – A fractional factorial design of resolution IV
· 2n = 2n−k ). The application of fractional fac- does not confound main effects with two-
torial designs yields a reduction in experimental factor interactions but does confound two-
effort, which is adapted to the complexity of the factor interactions with other two-factor in-
system under investigation and to the informa- teractions.
tion required. – A fractional factorial design of resolution
Once the experimental runs have been per- V does not confound main effects and two-
formed, fractional factorial designs are analyzed factor interactions with each other but does
like full factorial designs, except that fewer val- confound two-factor interactions with three-
ues are available. As introduced in Sections 3.1, factor interactions.
3.2, and 3.3, effects are obtained by calculat- The resolution of the most important frac-
ing corresponding differences of averages. How- tional factorial designs can be seen in Table 1.
ever, by doing so, one will discover that effects Designs of resolution III are used in the early
are confounded. Confounding is defined as a sit- stages of experimental investigations to gain a
uation where an effect cannot unambiguously be first insight into the possibilities and behaviors
attributed to a single main effect or interaction. of systems. Particularly beneficial are saturated
Let us consider the 23−1 design, in which the designs for 2n − 1 factors in which all degrees
effects of three factors are studied with four ex- of freedom of a 2n design are exploited. The
perimental settings (see Figure 10). This is an above-mentioned 23−1 design is an example of
example of a half-fraction factorial design (see such a design in which three factors are studied
Figure 11). By calculating the main effect of C with four experimental settings. It is “generated”
[ME(C) on the left-hand side of Fig. 10] the out- by replacing all columns of signs in the analy-
come is not the difference between the averages sis table of Figure 6 by experimental factors, i.e.,
of four (as in the case of the 23 design) but the the settings of factor C at the top of Figure 11 are
averages of only two results which are calcu- determined by the column of the two-factor in-
lated. A similar situation occurs when calculat- teraction AB in the analysis table of Figure 6. A
ing the interaction between A and B [IE(AB) on further important example of a saturated design
the right-hand side of Fig. 10]. Moreover, calcu- is the 27−4 design, which allows seven factors
Figure 10. Example of a 23−1 fractional factorial design. In the top section the experimental settings and results are shown in
geometrical and tabular form. In the bottom section the problem of confounding is illustrated: Calculating ME(C) and IE(AB)
leads to the same expression, which is actually the sum of both. It is not possible to determine whether the calculated value is
caused by the main effect of C, by the interaction effect of A and B, or by both
Table 1. The 2n−k (fractional) factorial designs with a maximum of 32 experimental settings and their resolution. 2n−k denotes the number
of experimental settings, n the number of experimental factors, and 1/2k the factor by which the number of settings has been reduced compared
to the corresponding full factorial design with the same number of experimental factors.
Resolution Number of experimental settings
4 8 16 32
III 23−1 25−2 – 27−4 29−5 – 215−11 217−12 – 231−26

IV 24−1 26−2 – 28−4 27−2 – 216−11
V 25−1
VI 26−1
Full 22 23 24 25
to be studied with eight experimental settings. the analysis results. Calculated main effects may
It is generated by replacing AB by D, AC by also be two-factor interactions of other factors.
E, BC by F, and ABC by G in the heading of Resolution IV designs are employed to gain
the columns of signs used for the calculation of unambiguous information about the individual
effects in Figure 9. With resolution III designs impact of the experimental factors, while unam-
special care must be taken when interpreting biguous information about their two-factor in-
teractions is not yet required. Designs of resolu-
Figure 11. Geometric representation of the most important half-fraction factorial designs and their respective tabular repre-
sentation, i.e., their design matrices
tion III and IV are mostly used to find out which only confounded with higher-order interactions,
factors play an important role. This technique which in most cases can be neglected. Particu-
of isolating the important factors is sometimes larly when n > 4, experimental settings can be
referred to as screening. halved to achieve designs of at least resolution
Using designs of resolution V or higher does V.
not lead to any loss of decisive information, since Fractional factorial designs support the itera-
the main effects and two-factor interactions are tive nature of experimentation. The experimen-
tal runs of two or more fractional factorial de- variable is a response, and the x variables are ex-
signs conducted sequentially may be combined perimental factors. A set of coefficients is used
to form a larger design with higher resolution. to describe how the y variables depend on the x
In this way it is possible to resolve ambiguities variables. Often a process or experimental sys-
by the addition of further experimental runs. tem can only be adequately described by more
Half-fraction designs possess an interesting than one response, in which case there will be
and useful projection property: the omission of one model for each response, and each model
one arbitrary column in the designs always leads will have its own set of coefficients.
to a full factorial design with respect to the re- Coefficients are estimated from experimen-
maining columns or factors. So, if a factor proves tal data which are collected in a corresponding
to have no significant effect on a response vari- experimental design. Estimating model coeffi-
able, the remaining factors can be analyzed as in cients from experimental data is called model
the full factorial design. For example, the omis- fitting and represents the principle task of sta-
sion of factor B in the 24−1 design of Figure 11 tistical analysis to be performed as soon as re-
leads to a 23 design for the factors A, C, and D. sponse values from experiments are available.
This may be verified by examining the three re- An equally important task consists of assessing
maining columns in the table but also by pushing the quality of a fitted model, as an important step
the upper faces of the two cubes into the lower towards qualifying it for use in prediction and
faces. optimization or whatever other purpose. In fact
it is often possible to improve the performance
of a model by taking small corrective measures
4. Response Surface Designs such as those described in Section 5.4.
The important ideas behind empirical mod-
In some situations factorial designs in which all eling are:
factors are varied by only using two settings are – The model must describe the entire behavior
not adequate for describing the behavior of an of the process or experimental system that
experimental system, because a more detailed is relevant to answering the questions of the
insight is needed to predict its responses or to experimenter.
find optimal factor settings. In this case, it is of- – The experimental design is based on the
ten necessary to extend factorial designs and to model and determines which information
do additional experiments at other points in the can be extracted from the experimental re-
experimental domain. To decide which points sults. Statistical analysis is only the tool for
to use, response surface designs are used [5], extracting this information.
[28]. These designs are based on mathematical – Neglecting experimental design essentially
models that describe how responses depend on means missing out on finding all the rele-
experimental factors. vant answers. Picking the wrong design also
means missing out on relevant answers.
– Enlarging the scope of the questions always
4.1. The Idea of Using Basic Empirical means extending the model and adding ex-
Models periments to the design.
Using models and setting up designs in this
A model is a way to describe a part of reality;
fashion requires that one proceed in the sys-
ideally it is much simpler and more manageable
tematic way that has been described in Chap-
than that which it describes, but it should never-
ter 2. There are several additional aspects that
theless adequately fulfill a predefined modeling
play an important role in modeling:
purpose. Since a model can only be an approx-
imate description of the original, it is important – Definition of the experimental domain in
to be aware of this purpose when constructing which the model should be useful for pre-
models (see Chap. 2 for typical goals in con- diction
junction with DoE). Models used in DoE are – Selection of the correct model type
polynomials in several variables, in which the y
Next Page
– Choice of the experimental design that corre- this coding can be understood as a simple lin-
sponds optimally to the experimental domain ear transformation of the factor range onto the
and to the model type chosen interval [− 1, + 1]. This transformation is called
– Estimation of coefficients by regression scaling and centering; the corresponding equa-
analysis tion is:
– Qualification and refinement of the model by
continued statistical analysis xcentered & scaled = 2 (x − xcenter ) / (x max − xmin ) .
– Validation of model predictions by confirma-
tory experiments Since x center = (x max + x min )/2, x max transforms
– Use of the model for the purpose of finding into + 1 and x min transforms into − 1 (or sim-
optimal factor settings ply + and − respectively, when using factorial
designs). Centering and scaling allows the influ-
ences of different factors with different scales
to be compared. In the following discussion it
4.2. The Class of Models Used in DoE is assumed that all factors are either coded or
scaled and centered in this fashion.
The class of models that is normally used in DoE The b are the coefficients that are estimated
contains only models which are linear with re- by regression after the experiments have been
gard to the unknown coefficients. This is why, in completed. A question that arises is: How do cal-
order to estimate coefficients, linear regression culated effects in a factorial design as described
methods can efficiently be used [15]. Nonlin- in Chapter 3 compare to estimated coefficients
ear or first-principle models, such as mechani- of linear or interaction terms in a fitted model?
cal models, reaction-kinetic models, and more The answer to this question is quite interest-
general dynamic models are only rarely used ing. Estimating coefficients by multiple linear
directly when designing experiments; they are regression and calculating effects for factorial
commonly approximated by simple polynomial designs as described in Chapter 3 are mathemat-
models at the cost of restricting the domain of ically equivalent. In fact, coefficients are simply
validity of the model. A direct generation of op- half of the corresponding effects: Calculating a
timal designs for nonlinear models, i.e., models main effect of a factor ME(A) means estimating
that are nonlinear in the parameters that are to the difference ∆y in the response that has been
be estimated, is sometimes possible. However, provoked by changing the factor A from its lower
it is particularly important that such models are to its upper level. In contrast, the correspond-
very accurate, that experimental errors are small ing coefficient, bA , is the geometrical slope of
and that initial estimates of the parameters are the curve describing the dependency of y upon
already available. It is this last point that often x, i.e., ∆y/∆x. Since DoE is based on scaled
makes setting up the correct design very difficult and centered variables, ∆x is exactly 2. So bA
[8]. can be estimated by ME(A)/2. This is also true
Polynomial models used in DoE are built up for interaction effects: bAB can be estimated by
as a sum of so-called model terms: IE(AB)/2. Estimators are often denoted by ˆ, so
b̂A = IE (AB) /2. The constant b0 can be es-
y = b0 + bA xA + bB xB + bAB xA xB + timated by calculating the mean of all response
bAA x2A + bBB x2b + ε values.
For the example that was discussed
This is an example of a quadratic model for two in Section 3.2, the model equation is
factors A and B, containing a constant term b0 , y = b0 + bA x A + bB x B + bAB x A x B and the es-
linear terms bA x A and bB x B , an interaction term timated coefficients are:
bAB x A x B , quadratic terms bAA x 2A and bBB x 2B ,
and an error term ε. b̂0 =
1
(74 + 92 + 70 + 60 + 62) = 71.6%
The x represent the settings of the factors in 5
the experimental domain. In factorial designs, b̂A = ME (A) /2 = 5%
they are coded as − 1 and + 1. When factors have b̂b = ME (B) /2 = 11%
continuous scales, like temperature or pressure, b̂AB = IE (AB) /2 = 4%
Previous Page
Figure 12. Examples of response surfaces of standard models for two factors: linear (A), interaction (B), and quadratic (C)
models
The benefit of using coefficients lies in the Standard models for two and three factors are
greater generality of the response surface mod- shown in Table 2, examples of response surfaces
els. These allow: are shown in Figure 12.
– Prediction of response variables within the Adding isolated interaction terms to linear
experimental region models, taking away interaction terms from in-
– Use of quadratic models for modeling max- teraction models, taking away square terms from
ima and minima quadratic models, or even adding cubic terms
– Use of mixture models for modeling formu- like bAAB x 2A xB , bABC x A x B xC , or bAAA x3A ,
lations (see Section 7.1) to quadratic models gives nonstandard models
– Use of dummy variables for modeling cate- which can also be used for DoE. Nonstandard
gorical factors (see Section 7.2) models are also obtained when mixture com-
– Correcting factor settings when prescribed ponents are investigated together with normal
settings cannot be exactly met in the experi- factors, or when so-called dummy variables (in-
ment dicator variables) are used to code categorical
– Nonstandard domains for the model (and the factors that have three or more settings.
design) that are subject to additional con- Optimal designs for standard and nonstan-
straints dard models are:
– Linear models: resolution III factorial de-
signs or so-called Plackett – Burman designs
4.3. Standard DoE Models and (which are very similar to factorial designs)
Corresponding Designs if no interactions are present
– Interaction models with only some interac-
For standard DoE models the designs can be cho- tion terms: resolution IV factorial designs
sen off the peg. This means that the design struc- or so-called D-optimal designs (see Sec-
ture is predefined and available in the form of a tion 7.3); resolution IV designs are also used
design table (see, e.g., Fig. 11 for half-fraction for linear models when interactions may be
factorial designs). For nonstandard models an present but are assumed to be unimportant
optimal design has to be generated by using a – Interaction models with all interaction terms:
mathematical algorithm (see Section 7.3). resolution V (or higher) factorial designs or
Standard DoE models are D-optimal designs
– Linear models (i.e., linear with regard to – Quadratic models: central composite de-
the factor variables), containing the constant signs (CCD; see below) or so-called
term and linear terms for all factors involved Box – Behnken designs
– Interaction models, which additionally con- – All nonstandard models: D-optimal designs
tain interaction terms of the factors involved (see Section 7.3)
– Quadratic models, which, in addition to all
interaction terms, contain quadratic terms
Table 2. Standard models for two and three factors
Linear model Interaction model Quadratic model
Two factors y = b0 + bA x A + bB x B . . .+ bAB x A x B . . .+ bAA x 2A + bBB x 2B

Three factors y = b0 + bA x A + bB x B + bC x C . . .+ bAB x A x B + bAC x A x C + bBC x B x C . . .+ bAA x 2A + bBB x 2B + bCC x 2C
Factorial designs are discussed in detail in 4.4. Using Regression Analysis to Fit
Chapter 3. Central composite designs (CCD) are Models to Experimental Data
extensions of factorial designs, in which so-
called star points and additional replicates at the Factorial designs are orthogonal for linear and
center points are added to allow estimation of interaction models which means that coefficients
quadratic coefficients (see Fig. 13 and Table 3). can be estimated independently of each other.
The number of star points is simply twice the This is why calculating effects as described in
number of factors and, ideally, the number of Chapter 3 is so easy. For more complex models
replicates at the center is roughly equal to the and designs, the analysis will be based on mul-
number of factors. The distance α from the cen- tiple linear regression (MLR) and its variants,
ter point to the star points should be greater than such as stepwise regression, variable subset se-
one, i.e., the star points should be outside the do- lection (VSS), ridge regression (RR), and partial
main defined by the factorial design. A star dis- least squares (PLS) [17]. All of these methods
tance α = 1 is sometimes used; then star points represent ways of fitting the model to the data, in
lie in the faces of the factorial design. A good al- the sense of minimizing the sum of squared dis-
ternative to a CCD is the Box – Behnken design, tances from measured response values to model
in which no design points leave the factorial do- values (Fig. 14). They differ in that the mini-
main [5]. Box – Behnken designs do not contain mization procedure is subject to different con-
a classical factorial design as a basis. straints, and their performance differs only in the
case of badly conditioned designs, i.e., when the
design is not really adequate for estimating all
Table 3. Design matrix of a CCD for two factors. The run Nos. 1 to
4 form the factorial design, Nos. 5 to 8 the star points, and No. 9 the
model coefficients.
center point. If yi stands for the observed response value
No. A B y
at experiment i and ŷi represents the predicted
value at that point, then the least-squares esti-
1 −1 −1 mates for the coefficients (b0 , bA , bB , bAB , ...)
2 1 −1 2
3 −1 1 are those for which Σ (yi − ŷi ) is minimized
4 1 1
5 − 1.41 0
(remember: ŷi depends on the b̂ values).
6 1.41 0
7 0 − 1.41
8 0 1.41
9 0 0 5. Methods for Assessing, Improving,
and Visualizing Models
CCDs are normally used with full factorial There are many statistical tools that allow a basic
designs, and sometimes with resolution V de- judgement of whether a fitted model is sound. A
signs. Another class of designs, called Hartley useful selection of these is:
designs [20], are similar to CCDs and are based
on resolution III factorial designs. When, as is – The regression measure R2 to check the qual-
sometimes done in industrial practice, only some ity of fit
quadratic terms are added to an existing interac- – The prediction measure Q2 to check the po-
tion model, it is useful to include star points only tential for prediction and to prevent so-called
for those factors for which quadratic terms have over-fit, which means that the model is so
been added. close to the data that it models experimental
errors
Figure 13. Central composite design for two factors (left) and three factors (right)
Figure 14. How least-squares regression works: squared distances from the model to the observed values are minimized
– Analysis of variance (ANOVA), to compare 5.1. R2 Regression Measure and Q2

the variance explained by the model with Prediction Measure
variance attributed to experimental errors
and to check for significance The regression measure R2 is the quotient of
– Lack-of-fit test (LoF) to assess the adequacy squared deviations due to the model, SSreg =
2
of the model Σ (ŷi − ȳ) , and the total sum of squared de-
– Analysis of the residuals to find structural viations of the measured data about the mean
2
weaknesses in the model and outliers in the value ȳ, SStot = Σ (yi − ȳ) , i.e.,
collected data
R2 = SSreg /SStot .
These methods are used both to qualify mod-
els for prediction and optimization purposes and If ordinary least squares is used for fitting the
also to find indications of how to improve the model, R2 = 1 − SSres /SStot , where SSres =
2
models in the sense of increasing their reliability. Σ (yi − ŷi ) , because SSres = SStot − SSreg ,
The different statistical methods are explained the sum of squared residuals. An example for
and ways to interpret and use them toward model the calculation of R2 is given in Figure 15 and
improvement are discussed. Table 4. R2 is always between 0 and 1 and should
be as close as possible to 1; how close it should
be depends upon the context of the applica-
tion. When a measuring device is calibrated, R2
should be above 0.99, whereas when the output may not be the case if the design is saturated or
of a chemical reaction with several influencing almost saturated, which means that the number
factors is examined, R2 may well be around 0.7 of experiments that have been carried out equals
and still belong to a very useful model. or only slightly exceeds the number of terms in
the model. In this case, Q2 may underestimate
the quality of the model, because leaving out sin-
gle measurements may destroy the structure of
the design.
It is more dangerous, however, to overesti-
mate the quality of a model, which may happen
if many experiments are replicated. In these ex-
periments ŷî will be very close to ŷi because
only one of the measurements is left out in the
calculation of ŷî . This means that PRESS may
be unduly close to SSres , and Q2 unduly close to
R2 . Nevertheless, Q2 is normally quite a useful
Figure 15. From the example in Section 3.2: observed val- measure to prevent overfit.
ues yi and predicted values ŷi from a model with coeffi-
cients b̂0 = ȳ = 71.6, b̂A = 5, b̂B = 11, b̂AB = 4
(see Section 4.2), so that ŷi , yi − ŷi andyi − ȳ can be
calculated 5.2. ANOVA (Analysis of Variance) and
2
R is a deceptive measure because it is prone Lack-of-Fit Test
to manipulation: by adding terms to a model, it
will always be possible to get a value of R2 that Analysis of variance, usually abbreviated as
is almost one, without really improving the qual- ANOVA, is a general statistical tool which is
ity of the model. On the contrary, many models used to analyze and compare variability in dif-
with a very high R2 tend to “over-fit” the data, ferent data sets. It becomes a powerful tool that
i.e., they model the experimental errors. This is can be used for significance testing when as-
a common and unwanted phenomenon because sumptions about the error structure underlying
it decreases the prediction strength of a model. the data can be made. In the context of DoE,
Especially when a design is not orthogonal, one ANOVA can be used to complement regression
should be wary of over-fit. analysis and to compare the variability caused
To counteract overfit and improve the reliabil- by the factors with the variability due to experi-
ity of model predictions it is useful to consider mental error.
the prediction measure Q2 . The calculation of Strictly speaking, “analysis of variance”
Q2 is similar to that of R2 , except that in the sec- should be referred to as “analysis of sum of
ond equation, the prediction error sum of squares squares” or, even more correctly, “analysis of
(PRESS) is used instead of SSres : the sum of squared deviations”, because it is ac-
tually this sum of squares that is decomposed
Q2 = 1 − PRESS/SStot (Fig. 17).
2 However, the aim of ANOVA is to see to what
Here, PRESS = yi − ŷî , where ŷî is the extent the variability in the measured data is ex-
prediction for the ith experiment from a model plainable by the model and to judge whether the
that has been fitted by using all experiments ex- model is statistically significant. To make this
cept this ith one. In a sense yi − ŷî is a fair comparison, SSreg and SSres must first be made
measure of prediction errors. PRESS is always comparable by considering the degrees of free-
greater then SSres , and therefore Q2 is always dom.
smaller then R2 . The relationship between Q2 Already when R2 is calculated, it is ar-
and R2 and an example for the calculation of Q2 guable that the number of terms in the model
are given in Figure 16 and Table 5. p and the number of runs in the design N
In good models, Q2 and R2 lie close together, should be considered in the calculation, and that
and Q2 should at least be greater than 0.5. This R2adjusted = 1 − [(N − 1)SSres ]/[(N − p)SStot ]
Table 4. Calculation of R2 for the example above: SSres = 3.2, SSreg = 648, SStot = 651.2, hence R2 = 1 − SSres /SStot = 0.995. This is a
very good value for the regression measure R2 .
A B yi ŷi yi − ŷi yi − ȳ
1 − − 60 59.6 0.4 − 11.6

2 + − 62 61.6 0.4 − 9.6
3 − + 74 73.6 0.4 2.4
4 + + 92 91.6 0.4 20.4
5 0 0 70 71.6 − 1.6 − 1.6
Squared sum SSres = 3.2 SStot = 651.2
Figure 16. How Q2 relates to R2 : PRESS ≥ SSres and Q2 ≤ R2 ; ŷi is usually between yi and ŷî
Table 5. Calculation of Q2 for the example above: PRESS = 260 and Q2 = 1 − 260/651.2 = 0.601. This is quite a reasonable Q2 value. Hence,
there is no indication of over-fit.
A B yi yi y i − yi yi − ȳ
1 − − 60 52 8 − 11.6
2 + − 62 54 8 − 9.6
3 − + 74 66 8 2.4
4 + + 92 84 8 20.4
5 0 0 70 72 −2 − 1.6
Squared sum 260 651.2
should be used instead of R2 = 1 − SSres /SStot . nificant under the assumption that the residuals
But since R2adjusted normally lies somewhere can be used to estimate the size of random ex-
between R2 and Q2 , these two are quite suffi- perimental error. MSreg = SSreg /(p − 1) is com-
cient for a first model assessment. In any case, pared to MSres = SSres /(N − p), also called the
N − 1 is the total number of degrees of freedom mean square error (MSE), by subjecting them to
(of variation with respect to the mean value), a so-called F-test for significance. If the quo-
p − 1 is the number of degrees of freedom of the tient, F emp = MSreg /MSres , is greater than 1,
model (not counting the constant), and N − p then there is reason to suspect that the model
is the so-called residual number of degrees of is needed in order to explain the variability in
freedom. the experimental data. If this has to be proven
“beyond a reasonable doubt” (i.e., for statisti-
cal significance), F emp must be greater than the
theoretical value of F crit (p − 1,N − p,γ), which
is always greater than 1, where γ is the desired
level of confidence.
Taking the square root of MSres furnishes a
reasonable estimate of the standard deviation of
Figure 17. Decomposition of SStot into SSreg and SSres a single measurement, provided N − p is not too
ANOVA compares the model to the residuals small and MSres does not change dramatically
and tells us whether the model is statistically sig- when terms with small coefficients are added
to or removed from the model. This number is 5.3. Analysis of Observations and
called the residual standard deviation (RSD or Residuals
SDres ).
In the example that has been used Ideally, when models are fitted to data, the model
SSreg = 648, p − 1 = 3, hence MSreg = 216. describes all of the deterministic part of the mea-
SSres = 3.2, n − p = 1, hence MSres = 3.2. F emp sured values and the part due to experimental
MS
can be calculated as Femp = MSreg , but a com- error is reflected by the residuals. It is a pre-
res
parison to F crit (3, 1, 95 %) is not meaningful, sumption in linear modeling, i.e., when using
because there is just one least squares fitting as a criterion, that the exper-
√degree of freedom. Also
the estimate RSD = MSres = 1.789 should imental error is
not be taken too seriously in this example. – Identically (i.e., evenly) distributed over all
The lack-of-fit test addresses the question of measurements
whether the model may have missed out on some – Statistically independent of the measured
of the systematic variability in the data. This test value, the order of the experiments, the pre-
can only be performed if some of the experimen- ceding measurement, the settings of the fac-
tal runs have been replicated: When replicates tor variables, etc.
are present, SSres can be further decomposed
into a pure error part SSp.e. and a remaining To verify this assumption and to detect out-
lack-of-fit part SSlof (Fig. 18). liers, a rudimentary examination of residuals
should always be performed as a step toward
qualifying the model. The most important tests
for residual structure are:
– Test for influence of single observations on
the model
– Test for normal distribution and test for out-
Figure 18. Decomposition of SSres into SSlof and SSp.e. liers
– Test for uniform variance
The corresponding significance test – Test for independency of measurement er-
compares MSlof = SSlof /(N − p − r) to rors
MSp.e. = SSp.e. /r, where r is the total number
of replicates of experimental runs in the design. These tests can be performed formally as de-
(A replicate count does not include the original scribed above for ANOVA and lack-of-fit test-
run: if there are five runs at the center point, ing. However, formal testing of hypotheses of
then one of these runs is counted as the original the type necessary here usually requires a very
and the four others as replicates; hence, r = 4; if high number of residual degrees of freedom
a design consisting of eight runs is completely N − p. Since this number is actively and con-
replicated, there are eight runs that have each sciously kept low in DoE, these tests do not of-
been replicated once, hence r = 8.) ten yield useful results. This is why it is com-
As in ANOVA, a quotient MSlof /MSp.e. mon practice to plot observations and residuals
greater than 1 means that there may be a in different types of graphs in order to detect
structural weaknesses and to find hints on what
lack of fit although the evidence is still weak,
whereas a quotient greater than F crit (N − p − r, the problem might be and on how to avoid it.
r, 1 − α) > 1 means a significant lack of fit at the Common plots are:
error probability level α. – Observed values versus predicted values to
The lack-of-fit test method can be regarded as see whether there are observations that had
a good complement to the Q2 prediction measure undue influence on the model
because the former works well when many repli- – Ordered residuals in a normal probability
cates are involved, while the latter makes sense plot to detect outliers and indications of a
when there are only few replicates. Of course, possibly nonnormal distribution of residuals
the latter situation is more common in DoE. – Residuals versus predicted values in order to
spot inhomogeneities in variance
– Residuals versus different factor variables to pure error if experiments have been repeated;
detect weaknesses in the model check that no important factors and interac-
– Residuals versus run order to check latent tions are missing in the model.
influences of time and autocorrelation – R2 is high but Q2 is very low (below 0.4, i.e.,
There is a further systematic approach to cop- tendency for over-fit): remove very small and
ing with possible inhomogeneities in variance insignificant terms from the model (they may
that was proposed by G. E. P. Box and D. R. reduce the predictive power of the model);
Cox in 1964 and that can be summarized in the check for dominating outliers (by compar-
so-called Box – Cox plot: In addition to fitting ing observed and predicted values) and try
a model to the response y, they suggest fitting fitting the model without them (remember,
models to the transformed response (yλ − 1)/λ however, that for screening designs with few
for different λ and then to choose λmax such that residual degrees of freedom, Q2 may be low
residuals are closest to normally distributed. The although the model is good).
Box – Cox plot, displays performance of a trans- – There are clear outliers in the normal proba-
formation against λ. It is a practical way of find- bility plot: usually these outliers have not had
ing indications of what type of transformation much influence on the model (otherwise they
to the response data may be useful. would be seen when comparing observed and
predicted values), however, they often lead
to low R2 values; check what happens when
they are removed from the model; check the
5.4. Heuristics for Improving Model
records, repeat the experiment; mistrust pre-
Performance dictions of the model in the vicinity of such
outliers; consider that the outlier may con-
An interesting although somewhat dangerous as-
tain important information (maybe this is a
pect of DoE and statistical analysis is that of
new and better product).
“pruning” models. What is meant by this is the
– There is some structure in a plot showing
following: When a model displays some weak-
residuals versus a factor variable (Fig. 19):
nesses in the analysis phase explained above,
this is a sign that the model is too weak and
there is often the possibility to improve the per-
should be expanded; this can usually not be
formance of a model by simple measures that do
done without enlarging the design.
not require additional experiments:
– In rare cases of analysis it may be observed in
– Excluding model terms with insignificant co- a plot displaying residuals versus predicted
efficients values that residuals are not homogeneous;
– Introducing a transformation this may be the case when a response varies
– Excluding observations that seem to unduly over several orders of magnitude and the
dominate the model or that lie far away from size of errors is either proportional to the
the model response values or satisfies some other re-
– Include one or two terms in the model with- lation. Indications of this can also be seen
out overstressing the design, i.e., without in the Box – Cox plot if the optimal expo-
having to perform further experiments nent λmax deviates significantly from unity.
Of course there are always situations in which A transformation of the response, e.g., tak-
a model remains inadequate and further experi- ing logarithms or square roots, may be the
ments must be performed to reach the objectives. correct measure.
The following is a set of heuristics, which may Sometimes, the measures suggested above
help to improve a model in one of several possi- do not lead to a stable model; outliers seem be
ble situations that may arise during the analysis present in spite of all attempts to improve the sit-
phase: uation, there are bends and curves in the normal
– R2 and Q2 are both small (i.e., there is just probability plot, coefficients are not significant
bad fit): check for outliers using a normal but also not negligible, and so on. This is usually
probability plot; check that the response val- an indication that not enough experiments have
ues correspond to the factor variables; check
Figure 19. Standardized residuals are residuals divided by RSD = SDres (see Section 5.2). When plotted against a factor
variable they may give an indication of how a model can be improved
been done. It is the authors’ recommendation in 5.5. Graphical Visualization of

this case to either Response Surfaces
– Reduce all “manipulation” to a minimum When statistical tests such as those described
(eliminate only obvious outliers from the above detect no serious flaws in the model, it is
data and very small coefficients from the useful to plot the model by reducing it to two or
model), and use the model knowing that it three dimensions and by representing it as a con-
is weak but may still be useful, or to tour diagram (see Fig. 20) or a response surface
– Strip the model down to linear, find the op- plot (see Fig. 12).
timal conditions and repeat a larger design When the model consists of more than two
here. factors, surplus factors are set constant, usually
In any case the heuristics above cannot repair to their optimum level, i.e., where responses are
a model that is simply incorrect, and care must optimal. Setting a factor constant corresponds
be taken not to succumb to the temptation of sys- to slicing through the experimental domain and
tematically perfecting such an incorrect model. reducing its dimension by one. An interesting
This is usually not the purpose of modeling. possibility is setting a third factor constant at
three levels, and placing the three contours side
by side.
Figure 21. Superimposed contour plot for two responses

used for finding specification domains for the two factors
x A and x B , given the specifications for the responses Y (1)
Figure 20. Contour plot of yield, showing the dependency and Y (2)
on catalyst and temperature (for the data from Fig. 6 and
Fig. 15). It can be seen that there is an interaction between Visualizing models is particularly interesting
the two factors when the modeling involves several responses,
because contour diagrams can be used to find
specification domains for the factors when spec-
ification ranges for the response variables have
been imposed (e.g., by the customer of the chem- The direction of maximal improvement of a
ical product to be produced; see Fig. 21). response can be deduced from these effects and
can subsequently be used to find a new position
for a second factorial design. At this new posi-
6. Optimization Methods tion the second factorial is repeated until signif-
icant effects or a satisfactory result is obtained.
A major purpose of using response surface mod- This procedure can be repeated until a stable op-
eling techniques is optimization. There are sev- timum is found (Fig. 22).
eral approaches to optimization depending on
the complexity of the situation. Single-response
optimizations are easier to handle and are treated 6.2. Model-Based Approach
in Sections 6.1 and 6.2. Multi-response opti-
mization requires weighting the different re- When it is less difficult to establish the signif-
sponses according to their importance. This can icance of a model, as is usually the case on a
be quite difficult, and the relevant techniques are laboratory scale or in a pilot plant, the model
treated in Section 6.3. can directly be used for optimization. Gradients
of the polynomial models are calculated from
the model coefficients because they point to the
6.1. Basic EVOP Approach Using directions of maximum change in the responses.
Factorial Designs These directions are then used in an iterative
search for a maximum or minimum, as was pro-
A very basic approach to optimization was proposed by Box and Wilson [9].
posed in the 1960s by G. E. P. Box and N. R. For quadratic and interaction models, it
Draper [6]. It is known as Evolutionary Op- makes sense to use conjugate gradients, which
eration, or EVOP (and has nothing to do with correct the direction of maximum change by the
evolution strategy or genetic optimization algo- curvature of the model function (Fig. 23). In this
rithms). When performing optimization experi- way the search for an optimum can often be ac-
ments in a running production unit, it is not pos- celerated. When a predicted optimum lies within
sible to vary factors over very large domains. the experimental domain, it is usually quite a
Hence, effects will be small and very hard to good estimate of the real optimum, particularly
detect against an underlying natural variability when a response surface model has been used.
of the response. The idea is to simply repeat a When it is outside of the domain, where, by con-
small factorial design for, for instance, two fac- struction, the model is most probably not ade-
tors, as often as is necessary so that the random quate in describing the process or system under
noise can be averaged out and the effects become study, it should be validated in the fashion de-
apparent. scribed in Section 6.4.
Figure 23. How the conjugate gradient compares to the gra-

dient
Figure 22. Example of a moving EVOP design (22 factorial
design with a center point) that has found a stable optimum
on the right
(j )
6.3. Multi-Response Optimization with values leave more room to move within ymin
Desirability Functions (j )
and ymax .
To build one desirability function for all re-
In an industrial environment, it is usually not sponses, the geometric mean is usually taken:
sufficient to maximize or minimize one response
. /1/k
only. A typical goal is to maximize yields, min- D (y) = d1 y (1) ·d2 y (2) ·...·dk y (k)
imize costs, and reach specification intervals or
target values for quality characteristics. But how
should one proceed when these goals are contra- By substituting the y by the predicted values
dictory? This question arises quite frequently in of the model functions, desirability D becomes
practice. a function of the factor variables, D = D(x). To
For example, yield, cost, and the quality char- find the best possible factor settings, this func-
acteristics are used as responses in an exper- tion D should be maximized by using any effi-
imental design. The design should be chosen cient mathematical optimization procedure.
to allow adequate models to be fitted to all re- In many typical applications, production cost
sponses. For each response, a model will be fit- and yield tend to increase simultaneously, and
ted to its corresponding measured data. Now op- the optimizer, in trying to raise yield and lower
timization can be started. Before being able to cost, reaches an optimum somewhere within the
apply any mathematical optimization algorithm, experimental domain. Then it is essential to have
the goal of the optimization has to be translated good information about the quality of predic-
from a multidimensional target to a simple max- tions in the interior of the domain. It may be
imization or minimization problem. This can ef- necessary to fit a quadratic model to obtain such
fectively be done by using desirability functions. good predictions.
A desirability function dj (y(j) ) for one response In a similar fashion, quality characteris-
y(j) , measures how desirable each value of this tics are often contradictory, e.g., more textile
response is. A high value of dj (y(j) ) indicates strength means less skin and body comfort;
a high desirability of y(j) . Many types of de- again, the optimizer will find an optimal com-
sirability functions have been proposed in liter- promise, which means suboptimal settings for
ature (e.g., [14]). Two-sided desirability func- the individual responses within the experimen-
tions are used if a target value or a value within tal domain.
specification limits is to be reached (Fig. 24, Often, the predicted optimum is at the bor-
left), whereas one-sided desirability functions der of the experimental region. It is in fact quite
are used if the corresponding response is to be typical that, in cases where linear or interac-
maximized (Fig. 24, right) or minimized. tion models are used and no compromises as
An example of a two-sided desirability func- described above are necessary, two or more cor-
tion is: ners of the experimental domain are found to be
locally optimal. From a mathematical point of
(j) (j)
dj y (j) = 0 f or y (j) > ymax or y (j) <ymin , view this seems to present a problem, but in fact
it is a very promising situation for further im-
(j) s (j) (j) s
dj y (j) = y (j) − ymin / ytarget − ymin provement of the product or the process under
(j) (j) study. Although the models were made to work
f or ytarget > y (j) > ymin ,
inside the experimental region, they often also
t t give very useful information just outside the ex-
(j) (j) (j)
dj y (j) = ymax − y (j) / ymax − ytarget
perimental domain.
(j) (j)
f or ymax > y (j) > ytarget . To be able to make a compromise between
different y, it is sometimes more practical to use
(j )
This function depends on a target value ytarget , a desirability functions dj that are not exactly 0 for
(j )
minimum acceptable value ymin , a maximum ac- y(j) > y(j) max or y(j) < y(j) min , but only close to
(j ) 0. This allows the comparison of factor settings
ceptable value ymax , and two exponents s,t > 0
for which desirability would otherwise be zero,
(Fig. 24, left). High values of s and t emphasize
the importance of reaching the target; smaller
Figure 24. Two responses with corresponding desirability functions: a two-sided desirability function for y(1) (target value
(1)
ytarget desired) and two different one-sided desirability functions for y(2) (maximization of y(2) desired)
because some of the y are outside of specifica- intervals is only correct for qualified models as
tion. In any case, constructing desirability func- explained in Chapter 5.
tions is quite a delicate task, and it is useful to Confidence intervals of this type must be mis-
play around with the desirability function when trusted if there is a significant lack of fit or if Q2
looking for an optimum. is very low. They should also be mistrusted if
When extrapolating outside the domain of x, residuals of observed responses in the vicinity
remember that predictions using the model de- of the predicted optima are very large.
teriorate when the experimental region is left. In this case and when predicted optima are
This means that predicted optima outside the re- outside the experimental domain, further exper-
gion must always be validated by further experiments are inevitable. A good strategy for this
iments. is to find a sequence of experimental settings
for which the predictions gradually improve (ac-
cording to the model). This sequence will start
6.4. Validation of Predicted Optima within the experimental domain and will typi-
cally leave it at some point (see Fig. 25). Exper-
There are several reasons why predicted optima iments in this sequence should be carefully per-
from empirical models should always be vali- formed and checked against predicted results.
dated by further experiments: This procedure will usually lead to very good
– Errors in observed responses propagate into results. It should be emphasized, however, that
predictions of the model and hence into the these experiments are purely confirmatory in na-
position of the predicted optima ture, they may lead to better products and better
– The model may be insufficient to describe the processes but they will not lead to better (fitted)
relevant behavior of the experimental system models.
under study and lead to bad predictions of
optima
– The desirability function used in multire- 7. Designs for Special Purposes
sponse optimization may not correctly depict
all aspects of the real goal The design methods that have been discussed
– Predicted optima may lie outside the initial until now cover many situations in which the
experimental domain, where the quality of cause and effect relationship between several
the model is doubtful factors and one or more responses of an exper-
– Predicted optima may be unsatisfying in that imental system are investigated. However there
not all responses lie near the desired values are cases where further methods are necessary
or within specified ranges. to solve modeling problems. Four characteristic
situations are treated in this chapter:
It is possible within the scope of linear mod-
eling to calculate confidence intervals for all re- – Designs for modeling and optimizing mix-
sponses, and hence to get a good idea of the qual- tures are used in product optimization
ity of prediction. This calculation of confidence
Figure 25. Predicting optima based on the model for increasing domains: A strategy in optimization consists of predicting a
series of optima while slowly increasing the domain. Experiments should be performed at these predicted optima for validation
purposes. In this way either a satisfactory optimum is reached or a further design is employed
– Designs for categorical factors may be used 7.1. Mixture Designs

for raw product screening and for imple-
menting blocking (as described in Sec- All designs described above assume that all fac-
tion 2.3) tor variables can be set and varied independently
– So-called optimal or D-optimal designs of each other in an arbitrary manner. This is the
which are implemented for advanced mod- typical situation in process optimizations, where
eling when nonstandard models or irregular factors are technical parameters such as temper-
experimental domains are to be investigated atures, pressures, flow rates, and concentrations.
– Robust design techniques have the aim of However, when the goal is to model the proper-
not only optimizing response values but also ties of a mixture in order to find optimal ratios for
response variability. its components, then this factor independence
may no longer be presumed. There are many
Further interesting topics, such as branches of the chemical industry and rubber
– Nested designs, where the levels of factor B industries where mixtures are investigated, and
depend on the setting of factor A [7], [27] there is a whole range of characteristic problems:
– The field of QSAR (quantitative structure – Optimizing the melting temperature of a
activity relationships), which is becoming metal alloy
more and more interesting in conjunction – Reducing cost in producing paints while
with the screening of active ingredients in keeping quality at least constant
medicines – Optimizing the taste of a fruit punch or the
– The whole field of DoE for nonlinear dy- consistency of a yogurt
namic models involving differential alge- – Increasing adhesion of an adhesive
braic equations – Finding the right consistency of a rubber
and others, cannot be treated here. The advanced mixture for car tires
reader is invited to research on his own, particu- These are cases where experimental design
larly on the latter two themes, which are still in methods must be modified to cope with the
constant motion (both of them incidently make fact that all components of the mixture must
extensive use of D-optimal designs to be shortly add up to unity, i.e., for three components,
discussed in the following). x A + x B + x C = 1. Nevertheless there are useful
models and designs for mixtures. They are based
on the so-called mixture triangle or the mixture
Figure 26. For three-component mixtures the cube is no longer the appropriate geometrical object for modeling the experi-
mental domain. The equation x A + x B + x C = 1 defines a triangle. Unfolding this triangle leads to the mixture triangle for three
factors (left).
Mixtures with four components can be modeled by a simplex; setting one of the factors constant again leads to a triangle for
the others, e.g., x D = 0.5, i.e., x A + x B + x C = 0.5 (right)
simplex when four or more components are in- which consists of experiments at the corners, at
volved (Fig. 26). the centroid (equal amounts of all components)
All simplices have the following properties, and midpoints of the axes from the corners to the
which facilitate analysis and the visualization of centroid (Fig. 27, Table 6). Details can be found
results: in [12].
– Response plots can be generated based on
the mixture triangle (as contour plots).
– A simplex is very similar to the cube in that
its boundaries and also its sections parallel to
its boundaries are again simplices in a lower
dimension. This allows contour plots to be
used in the mixture triangle even in situa-
tions where more than four components are
involved; just set the surplus factors constant
and put the three important ones into the mix-
ture triangle.
– Lower and upper levels of the mixture fac-
tors can be visualized geometrically as cut- Figure 27. Geometrical view of an axial simplex design for
ting off parts of the simplex. An active upper three-component mixtures
level means cutting off a corner, an active
lower level means cutting off the base (or
Table 6. Design matrix for an axial simplex design for three mixture-
side) of a simplex. When upper levels are components
active, the experimental domain is no longer
Run no. Comp. A Comp. B Comp. C
a regular simplex, but only a subset thereof,
a so-called irregular mixture region. 1 1 0 0
2 0 1 0
The best experimental designs for regular 3 0 0 1
4 0.6666 0.1667 0.1667
mixture regions are so-called simplex lattice de- 5 0.1667 0.6666 0.1667
signs. Simplex lattice designs place experiments 6 0.1667 0.1667 0.6666
7 0.3333 0.3333 0.3334
at the corners and along edges and axes of a sim-
plex. Depending on the complexity of the model
that is to be fitted, different strategies in picking When investigating mixtures, it is important
out the points are used. The most typical design to keep in mind that, although it is possible to
for a linear model is the axial simplex design correlate changes in the responses to changes in
the factor settings, it is principally impossible – The supplier of a raw material, who may in-
to tell which factors have caused these changes fluence some of the quality characteristics of
in the responses, because whenever one fac- an end product
tor has changed, at least one other factor has – The date or the time of the year may influ-
also changed. So which one should be made re- ence how well a process will perform
sponsible? Example 1: A fruit punch containing – Different persons doing the same experi-
pineapple, grapefruit, and orange juice seems ments
to become more tasty when pineapple juice – The type of catalyst or solvent
is added. Example 2: A long drink containing – Mutants of a strain of bacteria in a fermen-
pineapple and orange juice and vodka seems tation process
to become less bitter when pineapple juice is
All these are possible influencing factors that
added. Is it possible, in the two examples, to at-
cannot be quantified in a satisfactory manner.
tribute the change in taste to the change in the
(In the case of investigating solvents it would
amount of pineapple?
be a very good idea to consider polarity as a
When mixtures are modeled and optimized,
quantifiable factor instead of just the type of sol-
it is not always necessary to use simplex designs
vent.) Hence, particularly when more than two
and corresponding models. There are principally
instances of a categorical variable must be con-
three ways to proceed, only one of which in-
sidered, new design techniques are necessary.
volves using simplex designs:
Typical questions that arise in conjunction
– Define component ratios as factors and use with categorical or discrete factors are:
the classical factorial design or a CCD (in-
stead of ratios, any other transformation – How large is the impact of a qualitative fac-
leading to independent pseudocomponents tor? Is it significant?
can be used). – If so, which instance yields the best results?
– Use a simplex design, as described above, – Does the categorical factor interact with
or D-optimal design, as described in Sec- other factors? Are there interactions between
tion 7.3. different categorical factors?
– Identify a filler component, for example, – Is a possible optimum for the other (contin-
x C , which does not have an effect on any uous) factors robust with respect to varying
of the responses, use a factorial design, a the categorical factor? If so, where does it
CCD, or a D-optimal design for the remain- lie?
ing components (together with the constraint If there are just two instances or categories
x A + x B ≤ 1, if necessary), and regression of a qualitative factor, it is easy to encode them
analysis for a model in which the filler vari- as “−” and “+” and to use factorial designs. The
able does not appear. categorical or qualitative factor can then be used
Analyzing mixture designs requires some in calculations like a continuous quantitative fac-
care, because due to the dependencies amongst tor. Effects and coefficients can be calculated in
the mixture factors the models must be adapted the usual way, and they measure how large the
to the situation. H. Scheffé and D. R. Cox were influence of changing categories is. The same
the pioneers who developed ways to use models is true for interactions with other factors; they
correctly for the mixture problem. Details can- measure how the influence of these factors on the
not be included here. The reader is referred to responses changes when changing categories.
the literature [10], [12], [33], [35]. Treating categorical factors with three or
more instances is much more delicate. Within
generalized linear modeling, it is possible to treat
factors with three or more instances by increas-
7.2. Designs for Categorical Factors
ing the number of dimensions of the problem.
Not all factors that influence a product or a pro- Dummy variables are used to differentiate bet-
cess can be quantified. Examples of nonquantifi- ween instances: Let p1 , p2 be two dummy vari-
able or so-called categorical (or discrete) factors ables and encode instances i1 , i2 , i3 in the fashion
are: shown in Table 7.
Table 7. How to encode three instances of a categorical factor by

By additionally setting c3 = − c1 − c2 the
using two dummy variables same measure has been found for instance i3 .
Coding for p1 p2
For the example shown in Figure 28 the co-
efficients are c0 = 9, c1 = − 3, c2 = − 1, c3 = 4.
Instance i1 1 0 Designs for categorical variables will nor-
Instance i2 0 1
Instance i3 −1 −1 mally be adapted to the problem at hand and
generated by a computer algorithm. In fact opti-
mal designs, as described in Section 7.3, should
Geometrically the three instances become
be used.
three points in the two-dimensional coordinate
It is interesting to note that dummy variables
system of the dummy variables. The coded de-
can be used to model interactions: Just use these
sign with example values for a response y as well
variables in interaction terms of a model. The co-
as the corresponding geometrical visualization
efficients then measure by how much the effect
is shown in Figure 28.
of another factor varies from a given instance to
its mean effect taken over all instances (i.e., its
main effect). It would go beyond the scope of
this article to go into details about this, in partic-
ular about calculation of degrees of freedom. A
short digression on dummy variables and their
use for modeling blocking can be found in [15].
7.3. Optimal Designs

The usual procedure in planning an experimen-
tal design is to identify factors and responses,
to determine ranges for the factors, and then
to choose a standard design amongst those that
Figure 28. Geometrical and tabular representation of the have been discussed. This design may be fac-
design and the response values torial, Plackett – Burman, CCD, Box – Behnken,
Simplex, or the like. However, in some situations
Now the advantage of using dummy variables none of the standard designs are suitable. Such
becomes apparent: Analysis of data can be done situations typically are:
using the same regression methods as described
in Section 4.4, and the interpretation of results, – Use of nonstandard models
although being somewhat different, is still rela- – Use of nonstandard experimental domains
tively straightforward: (i.e., constraints involving more than one fac-
The model has the form tor)
– Special restrictions on the number of runs or
y = c0 + c1 p1 + c2 p2 tests that can be performed
– Use of mixture designs when either upper
where c1 and c2 are coefficients pertaining to the factor levels are active (this means that the
dummy variables p1 and p2 . regular simplex structure is corrupted) or
Model predictions for the instances i1 , i2 , i3 when normal continuous factors are to be in-
become: vestigated in the same design
– One or more categorical factors with three or
ŷ (i1 ) = c0 + c1 more discrete settings are present.
ŷ (i2 ) = c0 + c2 In these cases it is common practice to gener-
ŷ (i3 ) = c0 − c1 − c2 ate a design by using a mathematical algorithm
that maximizes the information that the design
So the coefficients c1 , c2 are actually a measure will contain. Such designs depend on the model
of the extent to which instances i1 and i2 differ to be used and on the experimental domain to be
from the mean c0 . covered.
Criteria involved in optimizing designs are tors and predicting process behavior or quantifi-
based on the extended design matrix, usually able product characteristics. A typical applica-
denoted by X, which is built up of the design tion of DoE techniques is toward finding con-
matrix and extended by a column for each term ditions, i.e., factor settings, for which not only
in the model. The basic idea behind optimal de- quantifiable responses are optimal (usually in a
signs is to ensure that there are no correlations multivariate way as described in Section 6.3) but
between the columns of this X matrix. For if also the variability of response values is minimal
there are correlations here, then the influence of with respect to disturbing or environmental fac-
the terms involved cannot be resolved (this sit- tors that act during production or field use of the
uation is similar to that described in Section 7.1 product. Typically, these influences can not all be
in conjunction with mixture components, which controlled or are too expensive to be controlled
are always correlated). even during the experimentation phase.
Working with optimal designs (Fig. 29) in- Doing DoE with the goal of reducing vari-
volves: ability is known as robust design. In a robust
– Defining the experimental domain (includ- design, control factors or design factors are var-
ing possible constraints) ied in a design as described above, typically in a
– Choosing the appropriate model screening design, and experiments are repeated
– Specifying experiments that the experi- at each trial run so as to estimate the standard
menter explicitly wants to perform or has deviation (or variance) at each trial. This dis-
already performed persion measure is employed as a new response
– Selecting the optimization criteria for the de- value. Statistical analysis and optimization tools
sign such as those described above are then used to
– Specifying approximately how many exper- quantify and finally to minimize variation, while
imental runs can be performed. at the same time improving product characteris-
Typically not just one design is generated, tics.
but a whole number of designs of differing size Taguchi [18], [24], [38] introduced an addi-
(test or run number). This makes it possible tional idea into robust design, namely, the con-
to evaluate designs by comparing the optimal- cept of so-called noise factors or environmental
ity criteria for different designs. Typical crite- factors [3], [24]. These are introduced as per-
ria are D-optimality, G-optimality, A-optimality, turbing factors in a designed experiment with
and E-optimality. They are essentially variance- the idea that they simulate possible external in-
minimizing design criteria in the sense that the fluences which may effect the quality of prod-
variances of model predictions or model coeffi- ucts after they have left the plant. These factors,
cients are minimized. The most commonly used which will in fact increase the standard devia-
criterion is D-optimality, which leads to a maxi- tion, are varied in a second experimental design
mized determinant of the squared X matrix. For which is performed for each of the trial runs in
more details, in particular, for further optimality the design for the design factors. To distinguish
criteria, the reader is referred to special literature between the two designs, the design for the envi-
on optimal designs [1], [32]. ronmental factors is sometimes called outer ar-
Optimal designs will have a high quality if a ray and that for the design factors is called inner
sufficient number of experimental runs or tests array. The use of outer arrays is recommended,
has been allowed for. They are analyzed by re- when noise factors can rather cheaply be varied
gression analysis like other designs, and the cor- independently of the controlled factors.
responding models can be used for prediction Example: During the production of CDs a
and optimization purposes. transparent coating is applied to protect the op-
tical layer. CDs are placed onto a turntable, a
droplet of lacquer is applied, and the CD is spun
7.4. Robust Design as a Tool for Quality to spread the lacquer. Parameters to be varied
Engineering are the size of the droplet, the speed and the ac-
celeration of the turntable and the temperature
Sometimes the goal of investigation goes be- in the room. CDs are to be subjected to different
yond estimating the effects of influencing fac-
Figure 29. An optimal design with constraints and inclusion of some old experiments
Table 8. A design for a quality engineering problem, using a 24−1 factorial with center point as inner array and a 22 factorial as an outer
array.
Run Design factors; A, B, C, D Environmental factors: H, T Mean Variance
H=− H=− H=+ H=+

T=− T=+ T=− T=+
A B C D y1 y2 y3 y4 y-mean y-var
1 − − − −
2 + − − +
3 − + − +
4 + + − −
5 − − + +
6 + − + −
7 − + + −
8 + + + +
9 0 0 0 0
10 0 0 0 0
11 0 0 0 0
extreme climatic conditions in order to simu- 2. K. R. Bhote: Qualität – Der Weg zur Weltspitze
late their performance in the field. This is to be (World Class Quality), IQM, Großbottwar
done in a climate chamber. Factors to be varied 1990 (American Management Association,
in the corresponding outer array are humidity New York 1988).
and temperature in the climate chamber. For the 3. S. Bisgaard: Industrial Use of Statistically
inner array a 24−1 factorial design with 3 re- Designed Experiments: Case Study References
alizations at the center point is chosen, for the and Some Historical Anecdotes, Quality
outer array a simple 22 full factorial (Table 8). Engineering 4 (1992) no. 4, 547 – 562.
Results from the four experiments in the outer 4. G. E. P. Box, S. Bisgaard: The Scientific
Context of Quality Improvement, Quality
array are taken together, and the mean and the
Progress June (1987) 54 – 61.
variance are calculated and subjected to effect
5. G. E. P. Box, N. R. Draper: Empirical
calculation or regression analysis. Model-Building and Response Surfaces, John
Wiley & Sons, New York 1986.
6. G. E. P. Box, N. R. Draper: Evolutionary
8. Software Operation – A Statistical Method for Process
Selected DoE software and suppliers are listed Improvement, John Wiley & Sons, New York
1969.
in Table 9.
7. G. E. P. Box, W. G. Hunter, J. S. Hunter:
Statistics for Experimenters – An Introduction
to Design, Data Analysis, and Model Building,
9. References John Wiley & Sons, New York 1978.
1. A. C. Atkinson, A. N. Donev: Optimum 8. G. E. P. Box, H. L. Lucas: Design of
Experimental Designs, Oxford University Experiments in Nonlinear Situations,
Press, Oxford 1992. Biometrika 46 (1959) 77 – 90.
Table 9. A selection of DoE software tools and providers (as of March 2002).
Tool Company WEB link
Design-Expert Stat-Ease Inc. http://www.statease.com

D.o.E. FUSION S-Matrix Corp. http://www.s-matrix-corp.com
ECHIP ECHIP Inc. http://www.echip.com
JMP, SAS/QC SAS Institute Inc. http://www.sas.com
MINITAB Minitab Inc. http://www.minitab.com
MODDE Umetrics http://www.umetrics.com
Starfire, RS/Series Brooks Automation Inc. http://www.brooks.com
STATGRAPHICS Plus Manugistics Inc. http://www.statgraphics.com
STATISTICA StatSoft Inc. http://www.statsoft.com
STAVEX AICOS Technologies AG http://www.aicos.com
9. G. E. P. Box, K. B. Wilson: On the 20. H. O. Hartley: Smallest composite designs for

Experimental Attainment of Optimum quadratic response surfaces, Biometrics 15
Conditions, J. Roy. Statist. Soc. B 13 (1951) (1959) 611 – 624.
1 – 45. 21. C. D. Hendrix: What every technologist should
10. J. Bracht, E. Spenhoff: Mischungsexperimente know about experimental design,
in Theorie und Praxis (Teil 1 und 2) Qualität CHEMTECH March (1979) 167 – 174.
und Zuverlässigkeit (QZ) 39 (1994) no. 12, 22. J. S. Hunter: Statistical Design Applied to
1352 – 1360, Qualität und Zuverlässigkeit Product Design, Journal of Quality Technology
(QZ) 40 (1995) no. 1, 86 – 90. 17 (October 1985) no. 4, 210 – 221.
11. D. E. Coleman, D. C. Montgomery: A 23. ISO 3534-3: 1999 (E/F):
systematic approach to planning for a designed Statistics – Vocabulary and symbols – Part 3:
industrial experiment (with discussion), Design of experiments.
Technometrics 35 (1993) no. 1, 1 – 27. 24. R. N. Kacker: Off-Line Quality Control,
12. J. A. Cornell: Experiments with Parameter Design, and the Taguchi Method
Mixtures – Designs, Models, and the Analysis (with discussion), Journal of Quality
of Mixture Data, 2nd ed., John Wiley & Sons, Technology 17 (October 1985) no. 4,
New York 1990. 176 – 209.
13. O. L. Davies (ed.): The Design and Analysis of 25. R. L. Mason, R. F. Gunst, J. L. Hess: Statistical
Industrial Experiments, 2nd ed., Oliver & Design and Analysis of Experiments with
Boyd, London 1956. Applications to Engineering and Science,
14. G. Derringer, R. Suich: Simultaneous John Wiley & Sons, New York 1989.
Optimization of Several Response Variables, 26. B. Mittmann: Qualitätsplanung mit den
Journal of Quality Technology 12 (Oktober Methoden von Shainin, Qualität und
1980) no. 4, 214 – 219. Zuverlässigkeit (QZ) 35 (1990) no. 4,
15. N. R. Draper, H. Smith: Applied Regression 209 – 212.
Analysis, 3rd ed., John Wiley & Sons, New 27. D. C. Montgomery: Design and Analysis of
York 1998. Experiments, 5th ed., John Wiley & Sons,
16. R. A. Fisher: The Design of Experiments, 8th New York 2000.
ed., Oliver & Boyd, London 1966. 28. R. H. Myers, D. C. Montgomery: Response
17. I. E. Frank, J. H. Friedman: A Statistical View Surface Methodology: Process and Product
of Some Chemometrics Regression Tools, Optimization Using Designed Experiments,
Technometrics 35 (May 1993) no. 2, John Wiley & Sons, New York 1995.
109 – 148. 29. A. Orth, M. Schottler, O. Wabersky:
18. B. Gunter: A Perspective on the Taguchi Statistische Versuchsplanung, Serie: Qualität
Methods, Quality Progress (June 1987) bei Hoechst, Hoechst AG 1993.
44 – 52. 30. T. Pfeifer: Qualitätsmanagement: Strategien,
19. G. J. Hahn: Some Things Engineers Should Methoden, Techniken, Hanser, München 1993.
Know About Experimental Design, Journal of 31. M. S. Phadke: Robuste Prozesse durch Quality
Quality Technology 9 (January 1977) no. 1, Engineering (Quality Engineering Using
13 – 20. Robust Design), gfmt, München, 1990
(Prentice Hall, London, 1989).
32. F. Pukelsheim: Optimal Design of 37. S. Soravia: Quality Engineering mit

Experiments, John Wiley & Sons, New York statistischer Versuchsmethodik,
1993. Chem.-Ing.-Tech. 68 (1996) no. 1 + 2, 71 – 82.
33. E. Scheffler: Statistische Versuchsplanung und 38. G. Taguchi: System of Experimental Design,
-auswertung – Eine Einführung für Praktiker, vol. I and II, Kraus International Publications,
3., neu bearbeitete und erweiterte Auflage von New York 1987.
“Einführung in die Praxis der statistischen 39. J. Wallacher: Einsatz von Methoden der
Versuchsplanung”, Deutscher Verlag für statistischen Versuchsplanung zur Bestimmung
Grundstoffindustrie, Stuttgart 1997. von robusten Faktorkombinationen in der
34. K. H. Simmrock: Beispiele für das Auswerten präventiven Qualitätssicherung,
und Planen von Versuchen, Chem.-Ing.-Tech. Fortschr.-Ber. VDI Reihe 16 Nr. 70,
40 (1968) no. 18, 875 – 883. VDI-Verlag, Düsseldorf 1994.
35. R. D. Snee: Experimenting with mixtures, 40. DuPont Quality Management & Technology:
CHEMTECH (November 1979) 702 – 710. Design of Experiments – A Competitive
36. E. Spenhoff: Prozeßsicherheit durch Advantage, E. I. du Pont de Nemours and
statistische Versuchsplanung in Forschung, Company 1993.
Entwicklung und Produktion, gfmt, München
1991.
Computational Fluid Dynamics 463
Computational Fluid Dynamics

Anja R. Paschedag, Technische Universität Berlin, Germany
1. Introduction . . . . . . . . . . . . . . . 464 4.1. Basics . . . . . . . . . . . . . . . . . . . . 475

2. Procedure . . . . . . . . . . . . . . . . . 464 4.2. Finite Volume Method . . . . . . . . 476
3. Modeling . . . . . . . . . . . . . . . . . 465 4.3. Pressure Correction Methods . . . 480
3.1. Transport Equations . . . . . . . . . 466
4.4. Lattice Boltzmann Method . . . . . 480
3.2. Initial and Boundary Conditions . 467
5. Interpretation . . . . . . . . . . . . . . 480
3.3. Turbulent Flow . . . . . . . . . . . . . 469
3.4. Multiphase Approaches . . . . . . . 472 6. Industrial Application . . . . . . . . 482
4. Numerics . . . . . . . . . . . . . . . . . 475 7. References . . . . . . . . . . . . . . . . 484
Symbols Sφ source in general transport

equation
A m2 cell surface (FVM) T N ·m torque
CBC1 . . . CBC4 constants of mathematical T K temperature
expressions for boundary t s time
conditions u J /m3 specific internal energy
Cµ , Cε1 , Cε2 constants in k − ε model V m3 volume
c mol/m3 concentration v m/s velocity
cp J /(kgK) specific heat capacity x m position vector
C Courant number
D m2 /s diffusion coefficient αi volume fraction of phase i
F N force m2 /s molecular transport
F general function coefficient
f weighting factor in time δ unit tensor
discretization ε m2 /s 3 energy dissipation rate
G filter function (LES) κ Pa · s dilatational viscosity
g m/s 2 gravitational acceleration λ J /(msK) heat conductivity
I kg · m2 moment of inertia µ Pa · s dynamic viscosity
Jφ molecular flux µt Pa · s turbulent viscosity (RANS)
k m2 /s 2 turbulent kinetic energy ρ kg/m3 density
m kg mass τ N/m2 Newtonian shear stress
n normal vector τs N/m2 turbulent stress tensor (LES)
N number of nodes τt N/m2 turbulent stress tensor
P̂ m2 /s 3 source term in transport (RANS)
equation for k φ general transport quantity
p N/m2 pressure m/s rotational speed of particles
q̇ J /(m2 s) heat flux density
r residual
Re Reynolds number Indices
Sc source in concentration
B, E, N, P , S, T , W nodes of the FVM grid
equation
b, e, n, s, t, w cell faces of the FVM
Shr source in temperature
grid
equation
Pi i th particle parcel
Su source in energy equation
464 Computational Fluid Dynamics
Computational Fluid Dynamics (CFD) is a modeling fluid dynamic processes is called com-
numerically based tool for the prediction of flow putational fluid dynamics (CFD). A high com-
field, concentration and temperature distribu- plexity of the mathematical models is needed
tion. Its main parts are mathematical model- for a sufficient description of the relevant inter-
ing, discretization, numerical solution of the dis- actions in reactive flows occurring on different
cretized equations and the interpretation of nu- time scales. Even if not all aspects can be con-
merical results. sidered in detail to keep the equation system in
Basic equations in all mathematical models a manageable frame, the complex mathematical
for CFD are balances for momentum and total models are far from being able to be solved an-
mass determining velocity, pressure and density alytically. Therefore, numeric methods play an
field. Depending on the case considered they important role in CFD and many applicants as-
are supplemented by mass balances for single sociate CFD mainly with its numerical aspects.
species and a heat balance. Additional models But the subject is defined much wider: formu-
are required to describe e.g. turbulence, mul- lation of the mathematical model, visualization
tiphase flows, chemically reactive systems and and interpretation are all essential parts of the
other special cases. tool.
Basis for the discretization of the balance
equation is the discretization of a space – the
grid generation. Most codes can handle unstruc- 2. Procedure
tured grids. Nevertheless, certain requirements
concerning grid structure have to be fulfilled to This chapter sketches the general steps of a CFD
get stable convergence and an accurate solution. simulation. It gives an overview of the proce-
Traditionally, most CFD codes use finite volume dure and the relation of the individual parts. The
discretization for the balance equations, even if points mentioned here are described in more de-
finite element algorithms are of increasing rel- tail in the following chapters.
evance for simulations with adaptively moving As with all investigation methods, the formu-
grids and for coupling CFD with structural dy- lation of the exact question is a crucial point for
namics simulations. A new approach for simu- the entire CFD procedure. The question includes
lations with high resolution in space and time is the target value and its accuracy, the dependen-
the lattice Boltzmann method. cies of importance and possible approximations
Finally, the numerical results have to be and assumptions which can be made. Also the
graphically presented and interpreted. Because range in space and time to be considered is a part
of the huge amount of numerical data provided of it. All significant physical parameters or the
by each simulation this cannot be done with a range of their variation have to be specified to-
general method. It must always be analysed in gether with the physical state at the boundaries
reference to a certain research question. Errors and at the initial time. The formulation of the
caused by the model formulation and by the nu- question determines the effort and the time re-
merical scheme have to be analyzed in order to quired to solve the problem and should be there-
judge the accuracy of a simulation. Quantitative fore as strict as necessary and as weak as possi-
estimates are required for an adequate interpre- ble.
tation of the results. The mathematical model can be formulated
based on the question posed. Its central ele-
ments are balance equations for mass, momen-
1. Introduction tum and energy. These are supplemented by ad-
ditional model equations if necessary. All partial
The increasing pressure on development time differential equations require initial and bound-
and product quality in industrial process devel- ary conditions for their solution. Parameters and
opment stimulates the application of numerical constants in the equations have to be speci-
methods in addition to traditional experimental fied in a way that the model is mathematically
ones. In many cases the numerical tools can save closed. For this purpose, additional laws, like an
time and costs if they are used complementary to equation of state or temperature dependencies
experimental methods. The simulation tool for of physical properties (e.g. density, viscosity)
might be required. Not always can the most exact changes at the molecular level. Discontinuous
mathematical formulation be solved with rea- jumps are found only at interfaces. Therefore,
sonable effort. In such cases, additional model in some points, modeling of multiphase systems
assumptions such as averaging procedures, re- requires different approaches than modeling of
duction of the number of variables or restriction single-phase systems.
of the range in space and time considered have For an easier understanding of the following
to be introduced. discussion a few terms shall be defined:
The resulting system of differential, integral
– Balance quantities
and algebraic equations is too complex to be
Quantities governed by laws of conservation
solved analytically. Therefore, numerical algo-
can be balanced. In general, mass, momen-
rithms are applied to derive a system of linear al-
tum and energy are such balance quantities.
gebraic equations which provides an approxima-
For detailed considerations masses of differ-
tive solution of the original mathematical model.
ent chemical species or different kinds of en-
In most cased this discretization is performed
ergy can be balanced separately. In such bal-
using the finite volume method or the finite ele-
ances source terms for possible conversions
ment method. Specialized methods exist for cer-
appear. Balance quantities are extensive val-
tain applications. A relatively new alternative to
ues.
classic discretization algorithms are statistical
– Transport quantities
methods like the Lattice Boltzmann method.
While the basic step of balancing is an integral
As a result of the great complexity of the
consideration of the balance quantities, differ-
mathematical model, the numerical solution of
ential transport equations can be derived from
the governing equations must be post-processed
the original balances. Transport equations de-
to extract the information necessary to answer
scribe the distribution and the transport of in-
the original question. Most often this informa-
tensive values, either mass based (mass frac-
tion can best be presented in a graphic plot, but
tion, specific energy) or volume based (den-
the data to be plotted are usually not the direct
sity, concentration), which are the so-called
solution of the model. Relevant data have to be
transport quantities.
selected, linked, transformed, and in some cases
– Independent variables
statistically treated and normalized to create a
Independent variables in transport equations
data set which allows the user to answer the ques-
are normally the three spacial directions and
tion.
time. In special cases symmetry can be used
Last but not least, the accuracy of the numeri-
to reduce the number of spacial directions, in
cal result has to be judged, even if the simulation
the case of stationary considerations, time is
is not erroneous in an obvious sense. Starting
not considered. For certain model approaches
from the setup of the mathematical model over
additional independent variables have to be
all numerical steps up to the postprocessing, in-
included. In probability density models, e.g.
accuracies are introduced or at least accepted.
for micromixing, the species composition is
Only a rough quantitative error estimation can
an additional independent variable, in popu-
prove if the solution provided is accurate enough
lation balances particle properties such as the
for the question considered.
characteristic diameter take this functionality.
– Parameters
All known values in the transport equations –
3. Modeling besides transport quantities and independent
variables – are called parameters. ’Known’
The central CFD modeling approach is to bal- has to be understood in a mathematical sense:
ance momentum, mass and heat. This approach the solution of the equations is only possi-
is based on the continuity hypothesis which ble if values for the parameters are given. In
states that all balance quantities and physical the physical sense the determination of these
parameters change continuously within each values might be problematic or only possible
phase. Consequently, limiting considerations with help of an additional equation.
for infinitesimally smallvolumes never consider
3.1. Transport Equations The velocity itself is not the transport quantity
here but rather the volume based momentum ρv.
Transport equations are derived based on bal- The stress tensor τ plays the part of the molecu-
ances. For the general transport quantity φ the lar flux. It is a function of the velocity gradient,
transport equation reads: but this functionality can not be expressed in a
general form because it depends on the rheologic
∂φ
= −∇(vφ) − ∇Jφ + Sφ properties of the fluid. In many applications a
∂t (1) Newtonian fluid can be assumed and τ can be
(a) = (b) + (c) + (d) expressed in the following way:

Term (a), the time derivative, codes transient 2
τ = −µ ∇v + (∇v)T − κ − µ (∇ · v)δ (4)
changes. Term (b) models the convective trans- 3
port with v being the convective velocity. Term
(c) in this general form is the molecular trans- µ is the viscosity which is independent of shear
port term including the molecular flux vector Jφ . stress and time in Newtonian fluids. κ is the di-
In certain cases, in particular in turbulence mod- latational viscosity, which in most real cases has
eling, structurally similar terms can occur which no influence on the flow.
are numerically treated in the same way but have The last two terms of Eq. (3) are the source
different physical meanings. Finally, term (d) is terms to be considered in most cases. The pres-
the source term. The kinds of sources which oc- sure term is of highest importance. It has a dual
cur depend strongly on the transport quantity φ. role in the structure of the equation. As men-
In the momentum balance these are forces, in tioned, it can be seen as a source term, but it also
the energy balance these are exchange rates to could be counted as a special type of stress and
other types of energy and in mass balances for included together with τ in a general stress term.
single species these are conversion rates due to The first concept is applied here because it pro-
chemical reactions. vides a more suitable structure for the discussion
Detailed derivations and discussions of the of numerical methods.
transport equations can be found in [1], see also Gravity acts in all systems and is therefore
→ Transport Phenomena. also written here. In special cases other forces
acting on a fluid like electromagnetic forces or
Continuity equation. A basic physical law centrifugal forces also have to be considered.
is the conservation of mass. From this the con- Two things complicate the numerical han-
tinuity equation can be derived: dling of the equation of motion. The first is
the nonlinear structure of the convective terms.
∂ρ While in other transport equations the velocity
= − ∇ (ρv) (2)
∂t can be handled like a parameter, in the equa-
tion of motion it is the unknown. The second
As there is no molecular mass transfer rel-
problem occurs from the pressure term. There
ative to the convective velocity (with its mass
is no transport equation available for pressure.
based definition) and no source of mass in a non-
In compressible fluids an equation of state is
relativistic system, this equation contains only
used additionally which allows one to calculate
the terms (a) and (b) of Eq. (1) with density ρ
the pressure if the density field is known from
being the transport value.
the equation of continuity. The solution of these
three coupled equations (one of which has three
Equation of motion. CFD considers trans-
components) is numerically not handsome, but
port phenomena in fluids, so the convective ve-
possible without significant problems. In incom-
locity is a central quantity. This becomes obvi-
pressible systems the density is constant and an
ous also from Eq. (1) where velocity is the only
equation of state cannot be used to determine the
general, φ-independent value contained. The ve-
pressure. The remaining equation for the pres-
locity is determined by the equation of motion:
sure is the equation of continuity, but it does
∂ρv not contain the pressure. The relation can be de-
= −∇ (ρvv) − ∇ τ − ∇p + ρg (3) scribed in the way that only the velocities which
∂t
satisfy the equation of motion with the right pres- equation for the temperature field. For the ap-
sure gradient also satisfy the equation of conti- plication of turbulence modeling, a certain part
nuity. of the kinetic energy is of interest. This second
case is discussed in Chapter 3.3, only the inter-
Navier-Stokes equations. A special and nal energy is considered here. Internal energy
commonly used version of the equation of con- covers the kinetic energy of atomic and molec-
tinuity and the equation of motion are obtained ular motion, potential energy of intermolecular
for Newtonian fluids with constant density and interactions, energy of chemical bonds and nu-
constant viscosity. The equations simplify to: clear energy. Not all aspects of this energy can
be determined absolutely. Therefore, only differ-
Equation of continuity: ences in the internal energy between two states
are discussed. Balancing of the internal energy
∇v = 0 (5) gives:
Equation of motion: ∂ρu

= −∇(ρuv) − ∇ q̇ − (ττ : ∇v) − p(∇ · v) + Su
∂t
∂v
ρ = −ρv∇v + µ∇ 2 v − ∇p + ρg (6) (a) = (b) + (c) + (d) + (e) + (f )
∂t
(8)
This equations are called Navier-Stokes equa-
tions. They are of restricted validity because with
changes in temperature as well as changes in the (a) temporal change
chemical composition effect density and veloc- (b) convective transport
ity. Nevertheless, they are a reasonable approach (c) heat conduction
in many cases. (d) increase by viscous dissipation
(e) increase by compression
Concentration equation. The equation of (f ) conversion from other types of energy
continuity results from the overall mass balance.
If a multi-component system is considered and If an incompressible fluid is considered, in
the concentration of the different species is of in- addition viscous dissipation, radiation and other
terest for the simulation, separate transport equa- kinds of energy conversion can be neglected and
tions have to be solved for them. As the global the mixing enthalpy is also negligible the only
mass balance is solved in all cases, the number potential source is the enthalpy of a chemical re-
of additional equations needed for a complete action Shr . Density, heat conductivity and heat
description is one smaller than the total number capacity values are calculated for the mixture
of species in the system. The transport equation in the case of a multi-component system. With
for a concentration c reads: these assumptions the temperature equation can
be derived to the form of a commonly used equa-
∂c tion:
= −v∇c + ∇(D∇c) + Sc (7)
∂t
∂ρcp T
= −v∇(ρcp T ) + ∇(λ∇ρcp T ) + Shr (9)
D is the molecular diffusion coefficient and Sc ∂t
is the source term resulting from a chemical re-
action. It is expressed via the chemical reaction cp is the heat capacity and λ the heat conduc-
kinetics which in many cases include nonlinear tivity. If the assumptions cannot be upheld as
expressions and dependencies between concen- described above, extended forms of the temper-
trations of different chemical species. ature equations must be derived.
Energy equation. Formulating of energy

equations is a large area because there are many 3.2. Initial and Boundary Conditions
different forms of energy which can be converted
into each other. For CFD the equation of the in- Partial differential equations cannot be solved
ternal energy is usually considered to obtain an without initial and boundary conditions. In a
mathematical sense this can be interpreted as

such that the solving of a differential equation area relevant
requires its integration and to perform this the for simulation
integration constants must be determined. Con-

sequently, the number of additional conditions
needed for each independent variable is equal
to the number of derivatives. Therefore, in time
only one condition is needed, which in most
cases is given at the initial time while for the
space coordinates two conditions are required unsuitable location
which are realized normally by one condition at for boundary conditions
each boundary point. suitable location

for boundary conditions
For the initial conditions values of the trans-
port quantities φ must always be given. These Figure 1. Location of boundary conditions
values may vary in space but cannot be a func-
tion of φ. – Wall
Three different types of boundary conditions Most model systems are bounded at least
are possible: partly by solid walls. They can be fixed or
Dirichlet condition
moving (e.g. wall and stirrer of a stirred ves-
sel). Walls considered here are impermeable
φ|BC = CBC1 fixed value of φ given at the for mass fluxes but may possibly conduct heat.
boundary To prevent convective fluxes through the wall
the normal velocity component is set to zero
Neumann condition
or equal to the normal velocity of the moving
∂φ wall. Assuming no slip conditions, the tan-
= CBC2 derivative of φ normal to the
∂n BC gential velocity is equal to the wall velocity,
boundary is given
which is zero with fixed walls. If slip is con-
Cauchy condition sidered, the gradient of the tangential velocity
components normal to the wall is zero.
∂φ
+CBC3 φ|BC = CBC4 combination of value
∂n BC To avoid diffusive fluxes through the wall the
and derivative of φ is concentration gradient normal to the wall is
given
set to zero.
In a finite region of the boundary a Dirichlet For heat transfer different types of walls have
condition is required. to be considered. The definition of tempera-
The use of these boundary conditions can be ture boundary conditions at walls is an ap-
segregated in relation to the physical nature of proximation in most cases, because neither
boundaries. The ones most often used are pre- the physical conditions are well known there
sented here, but for special flow situations other nor are they easy to control. Adiabatic walls
types can also be defined. It is not always easy to are modeled using a zero temperature gradient
find the expression required and in some cases normal to the wall. At walls of fixed temper-
a setup is more easily obtained by moving the ature this temperature is given as boundary
boundary location than by constructing a com- condition. Heat fluxes across a wall can be
plex formulation at the original location. An ex- described using Neumann or Cauchy condi-
ample is shown in Figure 1. tions.
– Outlet
– Inlet No assumptions about the quantities of the
It is assumed that the conditions at the inlet transport values can be made for outlet condi-
are known. Therefore, fixed values are given tions. However, it is assumed that the flow is
at the inlet for all transport quantities. These uniform and no further sources occur. In that
fixed values may vary along the inlet, e.g. a case velocities tangential to the outlet are zero.
parabolic velocity profile can be given for a For all other unknowns (normal velocity, con-
laminar flow in a tube.
centrations, temperature) zero gradients nor- Reynolds numbers with the present computing
mal to the outlet are used. Furthermore, for power.
incompressible flows the mass flow at each In most cases the exact structure of the tur-
outlet has to be specified to preserve the total bulent flow is of minor interest and information
mass. on local averaged values is sufficient. Unfortu-
It is not always easy to find a location at which nately, such an averaging can not be done in a
outlet boundary conditions can be specified simple way because the coarse scale structure of
with sufficient accuracy. Special problems oc- the flow interacts strongly with the small scale
cur in turbulent flows if vertex structures are structure. Special attention has to be given to
not averaged but resolved and the assump- chemically reactive flows. Chemical reactions
tions for the velocity field do not hold. In such can take place only if the species are mixed
a case, boundary conditions for the pressure on the molecular scale. A model averaging this
are stated instead of velocity conditions. The scale brings the danger of overestimating the rate
strong coupling between pressure and veloc- of fast chemical reactions.
ity described in context of the equation of mo- Two general modeling approaches for turbu-
tion allows one to solve these equations with lent flows are used nowadays: Reynolds averag-
this type of boundary conditions. ing (Reynolds averaged Navier-Stokes – RANS)
– Symmetry and large eddy simulations (LES). RANS mod-
Some systems show symmetries which allow eling is based on averaging all transport quanti-
one to reduce the model space and conse- ties over all scales of turbulent fluctuations. This
quently the numerical effort. Symmetry can allows one to use relatively coarse grids and
be utilized if it holds not only for the geome- can be applied on geometrically large systems
try, but also for the flow and for all transport with reasonable effort. The influence of turbu-
variables. lent structures is included in additional models.
Symmetry is given when all gradients normal Large eddy simulations work with a grid size
to the symmetry plane are zero and the veloc- which allows the direct resolution of the large
ity component normal to the symmetry plane scale part of the turbulence structures. Since the
is zero, too. large eddies contain the major amount of tur-
bulent energy, the return in accuracy is super-
proportional to the increase in effort with this ap-
3.3. Turbulent Flow proach. The filter width is a function of the grid
spacing and can therefore be influenced by the
While laminar flow is characterized by parallel user. Nevertheless, sub-grid scale models (SGS
stream lines in a turbulent flow, vertex structures models) are required also for LES. The numer-
of a large size range are found causing highly ical effort for large eddy simulations is signif-
frequent fluctuations in all transport variables. icantly larger than for RANS simulations and
All the equations introduced up to now are valid can be handled at the moment only on high per-
in laminar as well as in turbulent flows, as long formance parallel computers. Figure 2 gives an
as the conditions mentioned hold. The greatest impression of the resolution of turbulent eddy
problem in the simulations of turbulent flows is structures by the different methods.
that the resolution of the high frequent fluctu- LES and RANS are illustrated in more de-
ations requires a fine numerical grid and small tail for the equation of motion. Concentration
time steps. The number of grid cells N needed and energy equations can be handled in a simi-
for a three-dimensional simulation can be esti- lar way, but all turbulence models are developed
mated by in the first step for momentum transport. Thus
the mass and energy transport models use pro-
N = 53 Re9/4 (10) portionality approaches in most cases based on
the parameters computed for momentum trans-
with Re being the Reynolds number of the flow. port.
Such simulations of turbulent flows, called di-
rect numerical simulations (DNS) are possible Reynolds averaging. Reynolds averaging is
only for small academic cases and relatively low based on the assumption that scales of the main
a) Direct numerical b) Large eddy c) Reynolds averaged

simulation simulation simulation
Figure 2. Resolution of turbulent eddy structures by different modeling approaches
flow and of turbulent fluctuations differ signif- 2

τ t = µt [∇v + (∇v)T ] − ρkδ (14)
icantly. Therefore, each transport quantity can 3
be split up into a time averaged value φ and a
fluctuating value φ in such a way that possible δ is the unit tensor and k is the turbulent kinetic
macroscale fluctuations of φ are included in φ energy defined by
while turbulent fluctuations are covered by φ :
1
k= v ·v (15)
2
φ = φ + φ (11)
In contrast to the molecular viscosity, µt is the
In accordance with the goal of RANS to obtain eddy viscosity, which is not a material constant
averaged values, the transport equations are av- but depends on the flow structure. The k − ε
eraged. This yields for the Navier-Stokes equa- model expresses this dependence as a function
tions: of the turbulent kinetic energy k and its dissipa-
tion rate ε:
∇v = 0
(12) k2
∂v
ρ = −ρv∇v +∇ττ t + µ∇ 2 v − ∇p + ρg µt = Cµ ρ (16)
∂t ε
where an additional term including the Reynolds with

stress tensor τ t occurs.
µ
  ε= |∇v + ∇vT |2 (17)
2ρ
ρvx vx ρvx vy ρvx vz
 
−ττ t = ρv × v = ρvy vx ρvy vy ρvy vz  (13)
k and ε computed by their own transport equa-
ρvz vx ρvz vy ρvz vz
tions. The original model by Launder and Spald-
ing [4] uses the following form:
With this term the averaged equation of motion
is not closed because the velocity fluctuations
∂ρk µt
are unknowns. = −∇(vρk) + ∇ ∇k + P̂ − ρε
∂t σk
There is a large number of approaches to
model the Reynolds stress tensor. To explain all (18)
of them is beyond the scope of this article. A de-
∂ρε µt ε ε2
tailed presentation is given by Pope [2]. There- = −∇(vρε) + ∇ ∇ε + Cε1 P̂ − Cε2 ρ
∂t σε k k
fore, only the most commonly used concept of
the eddy viscosity approach together with the
with the production term P̂ defined as
k − ε model will be sketched. Boussinesq [3] in-
terprets the effect of the Reynolds stress tensor in µt
analogy to the Newton stress tensor. Therefore, P̂ = − |∇v + ∇vT |2 (19)
2
it can be expressed proportionally to the gradient
of the averaged velocity with a proportionality The constants of the model are listed in Table 1.
factor µt called eddy viscosity:
Table 1. Constants of the k − ε model and Meneveau et al. [8] are based on this idea
Cµ Cε1 Cε2 σk σε and extend upon it. For this approach two sim-
0.09 1.44 1.92 1.0 1.3 ulations on different grids are carried out. The
sub-gid scale model is adapted to the differences
The k − ε model is valid for fully devel- in the predictions of both models. In this way
oped isotropic turbulence. If this condition is not parameters of the sub-grid scale model can be
given, either extended RANS models or large varied in time and space and dissipation effects
eddy simulations are required for an acceptable are described. Such models are interesting for
flow prediction. cases in which constant parameters are only a
rough approximation. The major drawback of
Large eddy simulations. A high accuracy this method is its numerical effort which is sig-
alternative to Reynolds averaging is given by nificantly higher than for the other methods.
large eddy simulations. In this approach the
transport values are filtered with a filter func- Micromixing models. If systems with fast
tion G(x, x ): chemical reactions are to be simulated, a de-

scription of the mixing state on the microscopic
(x) =
φ G(x, x )φ(x )dx (20)
level is required. Neither Reynolds averaging
nor large eddy simulation provide such an de-
scription because they average or filter small
G describes the influence of the value of φ in scale fluctuations. A remedy is the use of mi-
at position x.
position x on the filtered value φ cromixing models which provide information
Several forms of G are possible, but it is always about the micromixing quality as a function of
a function of the grid size. turbulence quantities, like eddy viscosity or tur-
Filtering the equation of motion gives: bulent kinetic energy dissipation.
∂
v A widespread micromixing model is the
ρ = −ρ v − ∇ττ s + µ∇ 2
v∇ v − ∇p
+ ρg (21) probability density function approach (PDF) [9],
∂t
[10]. It considers the possible mixing states of a
In this equation the sub-grid scale Reynolds fluid of certain composition and gives for each
stress tensor τ s occurs. Its meaning is analo- computational cell a probability density function
gous to the Reynolds stress tensor in RANS but it for each state in a way that the integral compo-
considers only the effect of unresolved sub-grid sition in this cell is satisfied. For a mixture of
scale structures. only two species A and B this is shown in Fig-
Eq. (21) can be solved only if τ s is expressed ure 3. The local probability density functions are
as a function of filtered values. For this purpose computed from transport equations for the PDF.
so-called sub-grid scale models (SGS models) Each mixing state is related to a certain chem-
are used. ical reaction rate. The integral of the reaction
SGS models of the Smagorinsky type are rates over the whole composition space gives the
widespread [5]. They are similar to the eddy vis- total reaction rate in the appropriate numerical
cosity models in RANS, apart from the fact that cell.
they consider only sub-grid scale effects. In their Alternative micromixing models are
structure they do not use information about the
eddy structure of the resolved scales. Similarity – Eddy break up model [11]
models like the one from Bardina et al. [6] are This is a simple empirical model which as-
based on the assumption that there is a similarity sumes binary chemical reaction with only one
in the eddy structures of different scales. There- product. It is mainly applied for the modeling
fore, the analysis of the resolved structure can of combustion.
be used to model the sub-grid scale. This mod- – Flamelet model [12], [13]
els fail to describe the dissipation at the small- This model assumes the chemical reaction in
est eddy scales because this effect is not found a two-dimensional laminar layer. It was devel-
at larger scales. So they have to be combined oped for premixed and non premixed flames
with other models to cover this aspect. Dynamic with a different definition of the reaction layer
models like the ones from Germano et al. [7] for both cases.
0 1
cA
A B xA =
cA +cB
a) Distribution of species A (black) and B b) Probability density function of mixing be-
(white) in a turbulent flow with incomplete tween A and B
micromixing
Figure 3. Modeling micromixing in a computational cell with probability density function approach
– Engulfment model [14] Vi

αi = (22)
This model assumes that a fluid is mixed into V
another one of different composition by the
formation of a rotational cylinder. Within the The sum of all volume fractions must be one:
cylinder diffusion is the dominant mixing pro-
αi = 1 (23)
cess and the composition changes proportion-
i
ally to the change of cylinder size.
The assumption that the continuum hypotheses
holds for disperse systems implies that changes
3.4. Multiphase Approaches of properties in a particle are not resolved. This
means for example in a temperature distribution
Multiphase systems are characterized by inter- that each particle is characterized by a mean tem-
faces at which the fluid properties change dis- perature, but the different mean temperatures
continuously. This requires extensions of the of all particles determine a particle temperature
model approaches introduced up to now for their field of the system. If this approach is insufficient
application to multiphase systems. At the begin- for the description of a system, e.g. because the
ning of this chapter multiphase systems will be temperature gradient at the interface is needed to
classified to describe the appropriate model for determine the heat transfer between the phases
each type. exactly, it cannot be modeled with the approach
One type of classification refers to the geo- for disperse systems.
metric structure of the system (see Figure 4). An important property of disperse systems
If one phase consists of solid or fluid particles is the size distribution. Many phase interactions
with a small size compared to the total system like buoyancy force or heat transfer rate depend
the system is called a disperse system. The par- on particle size and therefore the particle size
ticles form the disperse phase while the other distribution is needed to determine these inter-
phase is called the continuous one. For model- actions exactly. The easiest case from the point
ing disperse systems, an extended form of the of modeling are monodisperse systems, which
continuum hypotheses is applied. Properties of means that all particles have the same size. For
both phases are considered to be continuously some applications the differences in the inter-
distributed over the whole system; specific prop- actions do not need to be resolved, and this ap-
erties of single particles are not relevant. The proach can be used. If the size distribution has to
central property in that case is the volume frac- be considered the particle size becomes an addi-
tion α which for phase i is defined as the ratio tional independent variable in the system, which
of the volume of this phase, Vi and the total vol- increases the complexity of the mathematical
ume V :
discontinuous coarse disperse fine disperse
monodisperse
with size distribution
Figure 4. Geometric structure of multiphase systems
system significantly. Size distributions are rel- particles and also between particles and walls
evant for all cases where the size range of the have to be considered, one speaks of four-way
particles is very wide or where the size distribu- interactions.
tion changes in the course of the process e.g. by If in a multiphase system a disperse phase
nucleation, evaporation, agglomeration or sim- cannot be defined clearly because the extension
ilar processes. The computation of particle size of all phases is too large to neglect gradients of
distributions is based on the solution of popula- the transport values in it, the system is called
tion balances. This model approach is not dis- a discontinuous multiphase system. The way to
cussed here further but details can be found e.g. model such a system is to use the approaches in-
in [15–17]. troduced in the previous chapter for single-phase
Another characteristic of a disperse system systems and additionally to describe the condi-
is the relative velocity between the phases. If tion at the interface. This works well if the extent
the differences in gravitational forces are small of each single-phase region covers a significant
compared to the momentum transfer between the part of the total domain.
phases, both phases have nearly the same veloc- The conditions at the interface act as bound-
ity. This is the case for phases with similar den- ary conditions for the balances in both phases.
sities or for systems with very small particles. Therefore, two conditions have to be defined for
Another description refers to the interac- each transport variable in each point. One is the
tions during momentum transfer. If particles are equilibrium of fluxes, the other is the relation
moved with the continuous phase but do not sig- between the values of the transport quantity. As
nificantly influence the flow field of this phase neither momentum nor mass or energy can be
it is called a one-way interaction. Systems with accumulated at the interface, the fluxes must be
one-way interactions do not have to be modeled equal on both sides. The ratio of the values de-
with multiphase approaches. The flow field is pends on the quantity considered. As a result
modeled with the single phase equations and the of the non-slip condition the tangential veloci-
volume fraction can be handled like a concen- ties are equal. Unless there is a significant mass
tration. The term two-way interaction is used, if transfer over the interface (e.g. melting or evap-
there is a relative velocity between both phases oration) this holds also for the normal velocity,
which causes a reciprocal momentum transfer. otherwise source terms must be considered in the
If in addition the volume fraction of the disperse stress balance at the interface. Thermal equilib-
phase is so high that interactions between the rium at the interface states that the interfacial
temperature for both phases is the same. The resent the particle phase with its volume frac-
distribution of chemical species is not equal in tion and properties. For each of this parcels P i
equilibrium but described by a distribution coef- the path and the velocities (convective and ro-
ficient. Detailed explanations and equations for tational) are determined by ordinary differential
such systems can be found e.g. in Deen [18] and equations:
Slattery [19].
dxP i
= vP i
Euler/Euler. The Euler/Euler method is used dt
for modeling disperse systems. It utilizes contin- dvP i
mP i = Fi (24)
uous transport equations for each phase. These dt
equations are based on single phase equations ωP i
dω
but weighted with the volume fraction and ap- IP i = Ti
dt
pended with source terms describing the phase
interaction [20]. xP i is the position of the parcel, vP i and ω P i its
For the equation of motion the interactions convective and rotational velocity, Fi the forces
between phases are forces. In all systems with acting between the phases, IP i the moment of
a relative velocity between the phases the drag inertia and Ti the torque.
force plays a major role. It is the main force The velocity of the continuous phase and the
which prevents the continuous increase in the particle phases are corrected in an iterative pro-
relative velocity between the phases. Further cedure considering interactions based on current
forces which have to be considered depending on particle paths. The particle parcels only give a
the properties of the phases are the virtual mass statistical representation of the particle phase if
force, the Basset force or other forces caused by their characteristics are averaged over a reason-
different relative velocities at different points of able time interval. The time interval for averag-
the particle surface, such as the Saffman force ing has no limits in the stationary case aside from
and the Magnus force. giving statistically reliable results. For transient
Mass and heat transfer between the phases investigations the time interval of averaging de-
determine the interaction terms in the concen- termines the time resolution of the simulation.
tration and temperature equations. For systems If statistical reliability is insufficient, the time
with a significant mass transfer over the interface steps of the particle simulation must be reduced.
it must be considered that heat and momentum The forces for phase interaction in the second
are also transferred together with that mass. equation of (24) are the same as those mentioned
The Euler/Euler approach is preferably used for the Euler/Euler approach. Mass and energy
for systems with high volume fractions of the transfer also have to be considered along the par-
disperse phase or for relatively large particle ticle paths and statistically evaluated.
sizes because there are no formal restrictions Consideration of the particle paths reduces
for these properties. Models for the changes in the volume fraction and particle sizes which can
turbulence caused by phase interaction are not be handled by this method. The volume of a par-
well developed yet. Size distributions can be de- cel can not be larger than the smallest grid cell.
scribed only with a high numerical effort be- For high volume fractions there is a danger of
cause most forces change as a function of the having more than one parcel in a cell at a time
particle size and therefore the size distribution which further restricts the volume ratio between
must be divided into size classes whereby each a cell and a parcel. Reasonable results are there-
class is handled as an individual phase. fore only obtained for very low volume frac-
tions, usually in the range of 1%, exceptionally
Euler/Lagrange. Alternatively, the Euler/ up to 5%. The numerical effort of the method
Lagrange approach can be used for disperse sys- increases with the volume fraction, because ad-
tems. In this approach the continuous transport ditional parcels have to be introduced.
equations are also used for the continuous phase On the other hand, this method provides bet-
and extended by interaction terms. The disperse ter models of the influence of particle on turbu-
phase is modeled differently: particle parcels are lence than the Euler/Euler approach. Defining
defined and distributed in a way that they rep- parcels with different properties allows one to
model size distributions with only a small addi- have been introduced. It is obvious that the cou-
tional effort. A detailed description of the Eu- pled system of integrodifferential equations and
ler/Lagrange method is given by Crowe et al. algebraic equations can be solved analytically
[21] and by Sommerfeld and Krebs [22]. only for a very small number of limiting cases.
For all practically relevant situations only a nu-
Grid adaptation to interface. The best way merical, computer based solution is possible.
to model a discontinuous multiphase system is The basic idea of a numerical solution is to
to define the reference system in a way that the replace the partial differential equation which is
interface has a fixed position in space. In that continuously defined over the range in space and
case the grid can be constructed so that the in- time with a system of algebraic equations which
terface is located at grid lines. The interfacial gives the solution only at defined discrete points
conditions can then be applied easily. or for discrete intervals. For the finite differ-
In most cases interfaces move and the ref- ence method (FDM) values at single points are
erence system cannot be defined as described computed, for the finite volume method (FVM)
above. In this case the location of the interface characteristic values are determined, which are
is a part of the solution of the model. To incorpo- constant for a numerical cell, and for the finite
rate the interfacial conditions as with boundary element method (FEM) parameters of a polyno-
conditions the grid can be adapted to the new mial function over a cell yield the solution. All
location of the interface. As long as the dislo- these are available for separate times. A com-
cation is small, this affects only the cell layer pletely different approach used with the lattice
close to the interface and the numerical error in- Boltzmann method will be described separately.
troduced is small. For large dislocations the cells As the solution of the algebraic equations,
near the interface would be deformed severely called the discretized equations, is fixed to cer-
and it is necessary to add or delete cells. Detailed tain points or elements is space and time, the
descriptions of adaptive methods are given by discretization of space and time is the first step
Ferziger and Peric̆ [23]. to be performed. Time is a one-dimensional co-
ordinate, and so it can simply be split into inter-
Volume of fluid. If there is a strong move- vals, i.e. time steps. The time step size can vary
ment of the interface, the grid adaptation method over the total time period considered. Stability
is numerically laborious and erroneous. An al- and accuracy of the procedure on the one side
ternative is to locate the interface at an arbitrary and computing time on the other side depend on
position of the grid. Different methods act in the time step size chosen in relation to the space
this way (segment method [24], marker and cell discretization (see Chapter 4.2).
method [25]). The most popular method is the The discretization of the three-dimensional
volume of fluid method first presented by Hirt space offers much more possibilities. The two
and Nichols [26]. A volume fraction is defined discretization methods mainly used in CFD,
and a transport equation is solved for it similarly FVM and FEM, require the subdivision of the
to the Euler/Euler method. The volume fraction total model space into non overlapping cells. In
in most cells is either zero or one and the in- the ideal case the grids formed out of this cells
terface is located in the cells where the volume meet the following requirements:
fraction lies between these values. The exact lo-
cation of the interface is determined by the vol- – Geometrical requirements
ume fraction in the cell. The direction of the The outer border of the grid should fit as
interface is normal to the gradient of the volume closely as possible to the physical borders of
fraction. the system to introduce the boundary condi-
tions at the correct location. In the case of sim-
ple geometrical structures this is not a prob-
4. Numerics lem but it might become one for jagged struc-
tures. The more variable cell shapes are ac-
4.1. Basics cepted by a CFD code the easier such struc-
In the previous section mathematical models for tures can be described without extensive re-
the description of transport processes in fluids finement close to the boundaries.
– Physical requirements but for simple geometries they can be generated

To achieve sufficient accuracy in the solution easily.
the grid size should increase in areas of steep In unstructured grids no global grid faces or
gradients and especially where they are vary- lines are defined, but the domain may be divided
ing. This criterion has the major problem that in any way. This offers many more possibilities
it can be fulfilled precisely only if the solution for grid fitting, but it normally cannot be done
is known. In many cases general physical un- without an automated grid generator.
derstanding of the flow investigated is suffi- For some simulations it is necessary to per-
cient to estimate where local grid refinement form grid adaptation in the course of the simu-
is necessary. In other situations preliminary lation. Reasons might be, for example, moving
computations on a rough grid give an orien- boundaries (as in stirred vessels), moving of
tation for grid improvements. interfaces which have to be tracked or strong
The simulation of turbulent flows requires a transient changes in the solution which requires
few grid cell layers parallel to the boundary local changes in refinement. If the new structure
for an appropriate modeling of the laminar of the grid depends on the numerical solution,
sub-layer. the numerical effort for the adaptation strategies
– Numerical requirements is relatively high. Nevertheless, in many cases
The numerical requirements depend mainly with grid adaptation a significant improvement
on the numerical method used and the way it in accuracy and efficiency of a simulation can
is implemented in the code. The crux of the be gained.
matter is whether a structured grid is needed
or an unstructured one is allowed. Especially The model equations can be discretized based
for unstructured grids a wide variety of cell on the discretization of space and time. Dif-
shapes can be imagined but not every one is ferent methods are available varying in their
supported by every code. Nearly all unstruc- mathematical approach and in the range of ap-
tured solvers can handle tetrahedral and hex- plication where they are used. An insight shall
ahedral cells separately or in combination in be given here for two methods: the finite vol-
one grid. In some cases more general formu- ume method and the lattice Boltzmann method
lations of polyhedral cells are available but with stress on the first of the two. In accordance
are not standard. with the overview character of this contribution,
From a numerical point of view serious jumps the methods cannot be discussed in detail, but
in the size of adjacent grid cells should be references for further reading will be given.
avoided. Furthermore, cells should not tend A third widespread method is the finite el-
to degenerate, which means that the ratio of ement method. It is extensively explained in
volume to surface gets too small. → Mathematics in Chemical Engineering and
→ Fluid Mechanics and therefore not discussed
In many cases very large numbers of cells
here.
would be needed to meet all requirements suffi-
ciently. This might push the computational effort
to an unrealistic level. Therefore, a reasonable
4.2. Finite Volume Method
compromise has to be found.
The major distinction of grid types is made Historically, the most common numerical
between structured and unstructured ones. A method in CFD is the finite volume method
structured grid is defined by three bands of grid (FVM). It is also used by the presently widest
faces, where the faces of one band do not in- distributed commercial CFD codes FLUENT,
tersect with each other but with the faces from CFX and Star-CD. Its success in CFD is related
the other bands. There is no restriction on the to physical equivalents in the approach.
shape of the faces or the coordinate system in The fundamental concept is the considera-
which they are defined. The cell shape in struction of grid cells (also called control volumes) in
tured grids are hexahedral, sometimes with one which all physical parameters and system char-
collapsed cell face. Structured grids have only acteristics are assumed to be constant. The bal-
restricted applicability to complex geometries ance equations are integrated over each of this
cells. For volume sources these integrals can be we consider here the stationary form. The veloc-
solved directly considering these sources as con- ity field is assumed to be known as well as the
stant over the cell. The volume integrals of the molecular transport coefficient which might
transport terms are transformed into surface in- vary in a known way over the analyzed space.
tegrals using the theorem of Gauss. As the physi-
cal properties are constant within each cell, they ∂φ ∂φ ∂ ∂φ ∂ ∂φ
0 = −vx − vy + + + Sφ
can also considered to be constant along each ∂x ∂y ∂x ∂x ∂y ∂y
cell face, which permits the surface integral to (25)
be resolved. The value or the derivative of the
solution at the cell face is contained in the ex- For reasons of simplicity the integration is
pressions gained. While the values are constant shown here for a equidistantly structured grid.
within each cell, they jump unsteadily at the cell But there is no general restriction – finite volume
faces and the values and derivatives at the faces discretization can also be carried out for non-
have to be expressed by the values in the cells equidistant and unstructured grids. Note that in
which are fixed at certain reference points, i.e. the two-dimensional case the ’volume’ for inte-
the nodes. gration is a face and the ’volume surface’ is a
This approach is, in general terms, the re- line.
verse of the derivation of the transport equa- For the grid the compass notation as shown
tions, where a finite model volume is consid- in Figure 5 is normally used [27]. The nodes are
ered initially and fluxes over the boundaries and marked with capital letters, P being the one of
volume sources are balanced. In the second step the cell considered. The points at cell faces are
the limiting expression for the model volume ap- marked by lower case letters. The final linear
proaching zero is determined. This analogy re- equation system can contain only values with
veals another advantage of the method in a phys- capital letter indices, values with lower letter in-
ical sense: as the surface integral of the transport dices are not defined and have to be replaced by
terms expresses the fluxes over the cell surface, the former ones.
a numerical error in the determination of these Integration of Eq. (25) over the control vol-
fluxes does not violate the integral conservation ume gives
of the balanced property. The laws of conser-
vation of mass, momentum and energy are the ∂φ ∂φ ∂ ∂φ
0=− vx dV − vy dV + dV
fundamentals of modeling for CFD, and there- ∂x ∂y ∂x ∂x
V V V
fore a method upholding this laws inherently has
∂ ∂φ
been most widely accepted by engineers. + dV + Sφ dV (26)
∂y ∂y
Nowadays, this advantage of FVM is no V V
longer significant, firstly, because the accuracy
of all methods has been increased so that for Conversion of volume integrals of the transport
well designed grids the error in the computation terms and resolution lead to:
of fluxes is small compared to other errors in
the course of simulations and secondly, because 0=− nvx φdA − nvy φdA
advanced grid techniques, like certain types of A A
unstructured grids or sliding grids do not uphold
∂φ ∂φ
this advantage exactly. Nevertheless, it is still the + n dA + n dA
∂x ∂y
most widely distributed CFD method and shall A

A
therefore be described here as an example. More + Sφ dV
details can be found e.g. in [15],[27–29]. (27)
V
Discretization in space. We first consider 0 = − (vx Aφ)e + (vx Aφ)w − (vy Aφ)n + (vy Aφ)s
the general shape of a transport equation for the
∂φ ∂φ ∂φ
quantity φ. For purposes of simplicity only the + A − A + A
∂x e ∂x w ∂y n
two-dimensional version is used, but the exten-
∂φ
sion to three dimensions is straightforward. The − A + SV
∂y s
discretization in time will be mentioned later, so
NW N NE
WW W P E EE
ww w e ee
s
SW S SE
ss
SS
Figure 5. Nomenclature in a two-dimensional grid for finite volume method
Ae , Aw , An and As are the cell faces crossing e, ity vector is nearly parallel to the face normal
w, n and s and n is the face normal. vector.
Finally, the values and the derivatives of φ at – Central Differencing Scheme – CD
the cell faces have to be replaced as a function of
the values at the nodes. The derivatives are ap- δxW w φW + δxwP φP
φw = (30)
proximated using the central difference which is δxW P
accurate to the second order, e.g.
This scheme is only conditionally stable but
it is second order. Central schemes give nor-
∂φ φ − φW
A = w Aw P (28) mally a better approximation of steep slopes
∂x w δxW P
but they show significant non-physical oscil-
where δxW P is the distance between the points lations of the solution. In the worst case these
W and P . oscillations can build up and lead to a diverg-
To express the values of φ various approaches ing solution. CD schemes are stable and ad-
are used which differ in their stability and accu- visable for diffusion-dominated processes.
racy. Most of them are asymmetric and depend – Quadratic Upstream Interpolation for Con-
therefore on the flow direction. We discuss them vective Kinetics – QUICK
for cell face w and a velocity vx,w from W to P .
1 6 3
– Upwind Differencing Scheme – UD φw = − φW W + φW + φP (31)
8 8 8
φw = φW (29) QUICK is the basis for most third-order

schemes used today. With a combination of
This scheme is unconditionally stable, but it is central and upwind aspects it joints properties
only accurate for the first order. It is the only of both schemes discusses above. Oscillations
scheme which does not produce any over- occur, but to a lesser extent than with the CD
shots or undershots without additional limiter scheme. QUICK has a much wider range of
and therefore guarantees the solution to be in stability than CD but restrictions remain for
the physically meaningful range (no negative systems without significant diffusion terms.
concentrations etc.). On the other hand, the To improve this third-order scheme various
numerical error is relatively large. It has the advancements have been developed. The main
effect of smoothing strong changes in the gra- advantage is gained from the combination
dients – a property called numerical diffusion. with so-called limiters. Limiters are exten-
The error can be minimized if the local veloc- sions of the numerical scheme which prevent
t t t
t+ t
x x x
WW W P E EE WW W P E EE WW W P E EE
a) explicit b) implicit c) Crank-Nicolson
Figure 6. Discretization in time – coupling of values according to different methods
the formation and pronunciation of local ex- aPt+t φPt+t =

trema but keep the numerical accuracy of a t+t
aE [f φE t ] + a [f φ t+t + (1 − f )φ t ]
+ (1 − f )φE W W W
scheme. t+t t ] + a [f φ t+t + (1 − f )φ t ]
+aN [f φN + (1 − f )φN S S S
For the source term a linear approach in φ is
+aPt φPt (36)
used:
in which the coefficients aPt+t and aPt depend
SV = S0 + S1 φ (32)
on f linearly. ai are the coefficients resulting
from space discretization and from Eq. (34).
For different values of f different methods
Discretization in time. For transient cases a
can be derived. The most common ones are
time derivative of the transport quantity also
shown in Figure 6.
occurs in the equation. If the two-dimensional
Eq. (25) is extended in this way one obtains: – f = 0 – explicit method
This method is numerically simple to use be-
∂φ cause only independent linear equations are
= (33)
∂t derived. It is of first-order accuracy. On the

∂φ ∂φ ∂ ∂φ ∂ ∂φ
−vx − vy + + + Sφ other hand, it is only conditionally stable. For
∂x ∂y ∂x ∂x ∂y ∂y
applications in which the flux is dominated
The philosophy for the time discretization is the by the convective part (and this is the ma-
same as for the discretization in space: The equa- jor part of all CFD applications) the Courant-
tion is integrated over the grid cell as well as over Friedrich-Lewy criterion determines the sta-
the time interval. The integration of the left hand bility range:
side can be performed easily: |v|t
1 ≥ C = (37)
t+t
x
∂φ
dtdV = V (φPt+t − φPt ) (34)
∂t C is the so-called Courant number.
V t
– f = 1 – implicit method
For the time integral of the right hand side a lin- This method is unconditionally stable and also
ear relation to the values of φ at the old and the first-order accurate. If a final state of a process
new time step is assumed: is more interesting than the transient behav-
ior, this method can be used with relatively

t+t
large time steps.
φdt = [f φ t+t + (1 − f )φ t ]t (35)
– f = 0.5 – Crank-Nicolson method
t
This method is second-order accurate. It is
f is a weighting factor between zero and one. conditionally stable but larger Courant num-
For a space discretization which needs only the bers than in the explicit method can be han-
values of φ in P and its direct neighbor points dled. It is used if a high accuracy in time is
the discretized equation reads: required.
4.3. Pressure Correction Methods the equations. To provide sufficient statistics the
method requires a relatively fine grid and small
One of the crucial points of fluid dynamic mod- time steps, on the other hand it performs much
eling are the nonlinearities in the equation of mo- faster on a fine grid than FVM does on the same
tion and the lack of an explicit pressure equation grid. The grid used is completely regularly struc-
for incompressible flow. This has been outlined tured but the location of wall boundaries is not
in connection with the equation of motion. restricted to the grid lines. Therefore, the method
There are different approaches to deal with is suited for geometries with sophisticated wall
this problem. The directly coupled solution of shapes like porous media. While some years ago
the equation of motion and the equation of conti- the grid requirements caused a impassable nu-
nuity is possible but is mathematically instable, merical effort, such a method can be handled to-
especially for the finite volume method and is day on parallel computers. It is especially suited
seldom used. Also, the approach of an artificial for simulations which require a fine grid to han-
compressibility is only successful and efficient dle the models, like large eddy simulations of
in a few cases. The most commonly used alter- turbulent flows.
natives are pressure correction schemes. They For lattice Boltzmann simulations a number
breakup the velocity and pressure into an esti- of numerical particles with properties like ve-
mated value and a corrective part. Starting with locity, temperature and concentrations are dis-
an estimated pressure field, they compute an tributed over the grid in a way that averaging
estimated velocity field, or vice versa, using of their properties gives the initial conditions of
the equation of motion. For the velocities in the flow. The simulation consists of a first step in
front of the derivatives in the convective terms which the particles move due to their individual
(see Eq. (6)) estimates are used. Reorganization velocities. In a second step collisions between
of the discretized momentum balance gives an particles and also between particles and walls
equation for the pressure correction as a function are interpreted according to collision rules. The
of velocity correction. With the help of this equa- collision rules describe the change in the proper-
tion the discretized continuity equation can be ties of each of the particles in the collision. They
transformed into a pressure correction equation. have to be formulated in a way that they cause
Iterative solution of all these equations lead to a statistical changes so that the averaged property
stepwise approach of velocity and pressure. It is field fulfills the transport equations [30], [31].
important to update the ’parameter-velocity’ in As the method is still relatively new, not all
the convective term and other dependent param- models can be used yet but the current develop-
eters in each iterative cycle. If necessary, cou- ment is rapid.
pled equations (e.g., turbulence models) have to
be solved at the end of each step.
One of the most basic pressure correc- 5. Interpretation
tion algorithms is the SIMPLE algorithm from
Patankar [27]. Because it does not converge sta- As mentioned in Chapter 2, the volume of com-
bly, a significant under- relaxation has to be used. puted data of a CFD simulation is too large to
Reversed algorithms have been developed since interpret the numbers directly. In a graphic visu-
then, but the underlying basic principles are the alization the data are much easier to compre-
same. hend. A basic step of a suitable visualization
is an appropriate reduction of the data. Three-
dimensional transient data cannot be visualized
4.4. Lattice Boltzmann Method at once, and the visualization of the velocity
vector field can not be realized effectively in a
A numerical method which has undergone a two-dimensional plane. But not all aspects of
rapid development during recent years is the lat- the data field are relevant to answering the ini-
tice Boltzmann method (LBM). It differs greatly tial question. Relevant data, however, can be ex-
from FVM because it is not a discretization of tracted, data can be averaged or combined to
the transport equations but a statistical method derive meaningful results. To transfer informa-
which gives an average result for the solution of tion into a graphical presentation requires that
the figure be clearly readable and quantitative. in space and time only approximations based
Aspects of data reduction (location of a slice, on the values at the nodes can be used.
chosen velocity components) have to be marked The solution of the discrete equations at the
and a legend must be given which allows quan- nodes differs from the solution of the con-
titative interpretation of colored figures. tinuous equations at the same points. This is
Visualization is not only useful to find the re- caused by the assumptions and approaches
sult of the simulation. It also helps to detect er- used in the course of discretization. While this
rors. For this purpose the whole data field should is valid for all discretization schemes, it can be
at least be scanned roughly. As the aim of this most easily explained for the finite difference
procedure is to find irregularities in the solution, method (FDM) (see also → Fluid Mechanics
the layout of the presentation is of minor inter- Chap. 5 and → Mathematics in Chemical En-
est, but a quantitative interpretation of the data gineering or [32]). According to this method,
must be possible. the approximation is derived from the Taylor
series where only the first terms are consid-
To judge the results all errors of the simulation ered. The neglected terms give the discretiza-
must be analyzed and as well as possible and tion error. The procedure is based on the as-
quantified. The main categories are: sumption that the following terms in the Tay-
lor series are decreasing. Therefore, the dis-
– Modeling errors cretization error can be approximated by the
Modeling errors refer to the differences be- first neglected term. This term is proportional
tween the values of all quantities in a real to the grid size with a certain power. This
physical system and the values resulting from power is the so-called order of accuracy. The
an exact solution of the mathematical model. more terms considered the higher the order
Not all physical relations can be reproduced of the scheme. The order of a scheme is also
exactly in a mathematical formulation. Fur- used for other discretization methods. It states
thermore, not all mathematical models can by which power the discretization error is re-
be solved numerically with reasonable ef- duced in relation to the reduction of the grid
fort. Therefore, additional assumptions and size. This means that a scheme of higher or-
restrictions are introduced which increase the der is not always more accurate than a scheme
modeling error. Examples are the application of lower order if the schemes are derived in
of turbulence models, the neglect of tempera- a completely different manner. But the influ-
ture dependencies of parameters or simplified ence of grid size reduction is greater for the
approaches for boundary conditions. scheme of higher order.
A quantitative estimate of the modeling errors – Truncation of iterative procedures
is very difficult. If the mathematical model Iterative procedures are used on different lev-
can be solved analytically (at least for a limit- els for the solution of the discrete equations.
ing case) and the corresponding quantities can Normally the linear algebraic equation sys-
be measured, a direct comparison is possible. tems are solved iteratively. Also, the coupling
Even in this case the measurement error from between the equations is often handled itera-
the experiment has to be regarded. In most tively. The most important example of this are
cases such a direct comparison is not possible the pressure correction schemes (see Chap-
and one is restricted to experience from simi- ter 4.3). Iterative procedures approach the so-
lar cases or to comparison of different model lution asymptotically. They are terminated if a
approaches for the same situation. certain accuracy is reached. Criterion for ter-
– Discretization errors mination is the residual. It can be defined in
Discretization errors refer to the difference two different ways. The first alternative is the
between the solution of the continuous math- difference in the solution between two itera-
ematical model and the discretized equations. tions. This value is easily determined, but it is
The discrete solution is computed only for dangerous because for slow convergence the
the nodes (which are representative for a cer- differences between two iterations is small,
tain volume according to FVM) and for time ever far away from the solution. The second
steps. For the locations between these points
alternative can be used if the problem can be before a new kind of applications is tackled. Of-
formulated as: ten additional models can be implemented by
user coding, but the effort to do so is great and it
F(x) = 0 (38) should be checked before beginning if another
code provides a better foundation for the case
The residual of the nth iteration rn is then de- considered.
fined as: To illustrate different modeling requirements,
some examples for applications in chemical en-
F(xn ) = rn (39) gineering will be presented. This cannot give a
complete overview of the most current usage of
Both definitions of the residual give values CFD in chemical engineering but gives an im-
for each node. For a truncation criterion dif- pression of the variety of applications.
ferent statistical methods are used to derive – Tubular reactor
a characteristic value. This can be either the Tubes without internals have a simple geo-
maximum, the average or a weighted average metric structure. They are a part of nearly
of the value itself or of a normalized one. all technical apparatuses as inlet and outlet
– Representation errors pipes and in some cases they are used as
In the computer all numbers are represented reactors. Problems in modeling occur from
with a limited number of digits. This might re- the large ratio between length and diameter,
sult in significant errors, e.g., if a small differ- which requires a compromise in meshing be-
ence of large numbers is computed. Normally, tween number of cells and shape of cells. In
this type of error is of minor importance in some cases the number of cells can be reduced
CFD simulations. by utilizing symmetry properties of the sys-
The different types of errors are usually ad- tem.
ditive. Therefore, it does not help to improve the Tubular reactors are often used to mix non-
accuracy of one aspect if the error in this re- Newtonian fluids or, in a jet configuration, to
gard is smaller than other errors. In most cases mix Newtonian fluids very fast down to mi-
for simulation the limiting factor for error re- croscopic levels. For non-Newtonian fluids,
duction is the modeling error. All other errors e.g. in polymerization processes, chaotic mix-
are usually small by comparison. A quantitative ers [33] consisting of tubular loops or static
judgment has a higher priority than indifferent mixers [34], [35] within the tubes are used. In
formulations such as ’grid independence’. both cases the geometry of the flow becomes
much more complicated. Especially for static
mixers sufficient flexibility is only provided
6. Industrial Application by unstructured grids.
In jet flows the modeling of turbulence is of
CFD is a tool of increasing importance in in- high importance. As tubular reactors are rel-
dustrial applications. The expertise of industrial atively narrow, wall effects have a significant
users is mainly in the field of fluid dynamics or influence on the flow. Therefore, in most cases
chemical engineering, not in numerics or pro- special wall models have to be used which
gramming. Therefore, industrial problems are increases the modeling and numerical effort.
solved with commercial codes which are avail- Furthermore, turbulence in tubes is often non-
able at high level with regard to modeling and isotropic. This reduces the applicability of
numerics. Furthermore, such codes have a user RANS simulations.
friendly interface and support which allows even – Stirred vessel
inexperienced users to obtain first results quite Stirred vessels are widely used in chemical
fast. Commercial codes are continuously being engineering for single phase and multi-phase
developed and achive more or less the state of the flows. The flow field is markedly inhomo-
art. Nevertheless, the different codes are special- geneous and transient. Characteristic of all
ized in different fields of application and there- stirred vessel configurations is the combi-
fore it is necessary to check the available models nation of static and moving elements. In the
simplest case the static parts are rotationally in connection with the Lagrangian approach
symmetric. Then they can be modeled as a than with the Eulerian approach.
moving wall in a rotating reference frame – Membrane module
[36]. If there are baffles, the rotational sym- One of the newest apparatuses used in chem-
metry is broken and extended approaches are ical engineering is the membrane module. Its
used. A good overview about this approaches numerical simulation is at the very beginning
is given by Brucato et al. [37]. If only the sta- because of the variety of aspects which have
tionary solution averaged over a high number to be considered. These are for instance:
of stirrer evolutions is interesting, the power
Flow through a porous medium
input from the stirrer can be included in source
Coupling of two flow regions
terms. This system can be solved for the sta-
Multi-phase flow
tionary case on a fixed grid. For more detailed
Non-Newtonian fluids
simulations the grid is divided in two overlap-
Fouling
ping or non-overlapping parts. One of them
is moving with the stirrer, the other is static. Presently the modeling approaches do not
As the stirrer motion has to be resolved suffi- consider all of this aspects. The main stress
ciently in time, only small time steps can be is on modeling the two flow regions divided
used and the simulation becomes relatively by the porous membrane under certain pres-
extensive. sure conditions [46], [47].
RANS simulations often do not give a suf-
ficient description, especially in presence of It is obvious from this listing that the qualified
chemical reactions, because the flow field is application of CFD can not be performed with-
inhomogeneous. As the fine resolution re- out well founded knowledge of applicable mod-
quired for large eddy simulations is numeri- els and some insight into the numerical proce-
cally extensive, a remedy is to apply the lattice dures.
Boltzmann method [38]. The development of refined products like fine
– Precipitation reactor chemicals and active agents will be of growing
Precipitation is usually simulated to predict importance in the chemical industry and CFD
the particle size distribution in the system will play an important part in the design of the
[39], [40]. The initial supersaturation in pre- necessary apparatuses. This requires the consid-
cipitation processes is high and therefore nu- erations of parallel and consecutive chemical re-
cleation and particle growth start at a high rate. actions of different rates and simulations of mul-
This requires appropriate turbulence model- tiphase systems including the prediction of par-
ing, including micromixing models [41]. The ticle size distributions. Consequently, emphasis
particles are very small, so only one-way cou- in CFD development for this field will be put on
pling is relevant and the simulation can be car- models and solution methods for fine spatial and
ried out as pseudo-single-phase. On the other temporal resolution and for a detailed descrip-
hand, the solution of the population balance tion of physics.
must be integrated into the simulation [15]. The advances in CFD interact strongly with
– Bubble column the hardware development. On one hand the
Bubble columns are a typical example for two available computing power determines which
phase flows. The difference in density be- mathematical models and which numerical
tween gas and liquid causes a relevant rel- methods can be used with reasonable numeri-
ative velocity between the phases. Depend- cal effort, on the other hand it affects the direc-
ing on bubble size and volume fraction, ei- tion of development of new models and meth-
ther Euler/Euler [42], [43] or Euler/Lagrange ods. Due to the fast pace at which new pow-
[44], [45] approaches are used. In most prac- erful compute hardware evolves and becomes
tical applications the requirements for the La- available, model development does not restrict
grangian approach are not met because the itself to quantitative refinement but regularly in-
volume fraction is too high. But to describe cludes new fields of research. Latest improve-
the non-uniform bubble size population, bal- ments are Large eddy simulations of turbulent
ances have to be solved. This is much easier flows instead of Reynolds averaged approaches
and models for multiphase systems. A new trend 13. N. Peters: “A spectral slosure for premixed tur-
in the field of numerical methods is the applica- bulent combustion in the flamelet regime”, J.
tion of the lattice Boltzmann method. Further Fluid Mech. 242 (1992) 611.
innovations can be expected. 14. J. Bałdyga, J.R. Bourne: Turbulent Mixing and
Chemical Reactions, John Wiley & Sons Ltd.,
Chinchester 1999.
15. A.R. Paschedag: CFD in der Verfahrenstechnik:
7. References Allgemeine Grundlagen und mehrphasige An-
wendungen, Wiley-VCH, Weinheim 2004.
1. R.B. Bird, W.E. Steward, E.N. Lightfoot: Trans- 16. D. Ramkrishna: Population Balances. Theory
port Phenomena, 2nd ed., John Wiley & Sons, and Application to Particulate Systems in Engi-
New York 2002. neering, Academic Press, San Diego 2000.
2. Pope S.: Turbulent flows, Cambridge University 17. A. Gerstlauer, A. Mitrović, S. Motz, E.-D.
Press, Cambridge 2000 Gilles: “A population balance model for crystal-
3. J.V. Boussinesq: “Essa sur la theories des lization processes using two independent parti-
eaux courantes”, Mém. prés. par div. savants cle properties”, Chem. Eng. Sci. 56 (2001) 2553.
à l’acad. sci. de Paris 23 (1877) 1. 18. W.M. Deen: Analysis of Transport Phenomena,
4. B.E. Launder, Spalding D.B.: “The numeri- Oxford University Press, New York 1998.
cal computation of turbulent flows”, Computa- 19. J.C. Slattery: Advanced Transport Phenomena,
tional Methods in applied mechanics and Engi- Cambridge University Press, New York 1999.
neering 3 (1974) 269. 20. D.A. Drew: “Mathematical modeling of two-
5. J. Smagorinsky (1963): “General circulation ex- phase flow”, Ann. Rev. Fluid Mech. 15 (1983)
periments with the primitive equations, part I: 261.
the basic experiment”, Monthly Weather Rev. 91 21. C.T Crowe., M. Sommerfeld, Y. Tsuji: Multi-
(1963) 99. phase flows with droplets and particles, CRC
6. J. Bardina, J.H. Ferziger, W.C Reynolds: Im- Press, Boca Rato 1998.
proved turbulence models based on large eddy 22. M. Sommerfeld, W. Krebs: “Particle dispersion
simulation of homogeneous, incompressible, in a swirling confined jet flow”, Part. and Part.
turbulent flows, Technical Report TF-19, Ther- Syst. Characterization 7 (1990) 16.
mal sciences div., Dept. of Mech. Engg., Stan- 23. J.H. Ferziger, M. Peric̆: Computational Meth-
ford Univ., Stanford, CA. 1980. ods for Fluid Dynamics, 2nd rev. ed., Springer
7. M. Germano, U. Piomelli, P. Moin, W.H. Berlin 1999.
Cabot: “A dynamic subgrid scale eddy viscosity 24. B.D. Nichols, C.W. Hirt: “Calculating Three-
model”, in: Proc. Summer workshop, Center for Dimensional Free Surface Flows in the Vicin-
turbulent research, Stanford CA 1990. ity of Submerged and Exposed Structures”, J.
8. C. Meneveau, T.S. Lund, W.H. Cabot: “A La- Comput. Physics 8 (1971) 434.
grangian dynamic subgrid-scale model of tur- 25. F.H. Harlow, J.E. Welch: “Numerical calcula-
bulence”, J. Fluid Mech. 319 (1996) 353. tion of time-dependent viscous incompressible
9. J. Bałdyga: “A Closure Model for Homoge- flow of fluid with free surface”, Phys. Fluids 8
neous Chemical Reactions”, Chem. Eng. Sci. 49 (1965) 2182.
(1994) 1985. 26. C.W. Hirt, B.D. Nichols: “Volume of fluid
10. R.O. Fox: “On the Relationship between La- (VOF) method for the Dynamics of Free Bound-
grangian Micromixing Models and Computa- aries”, J. Comput. Physics 39 (1981) 201.
tional Fluid Dynamics”, Chem. Eng. Process 37 27. S.V. Patankar: Numerical Heat Transfer and
(1998) 521. Fluid Flow, Hemisphere Publ. Co. Washington
11. B.F. Magnussen, B.W. Hjertager: “On the struc- 1980.
ture of turbulence and a generalised eddy dissi- 28. H.K. Versteeg, W. Malalasekera: An intriduc-
pation concept for chemical reaction in turbu- tion to computational fluid dynamics. The finite
lent flow”, in: 19th AIAA Aerospace Meeting, volume method, Longman, Harlow 1995.
St. Louis, USA. 1981 29. C.A.J. Fletcher: Computational Techniques for
12. A. Linan: On the internal structure of lami- Fluid Dynamics, vol 1+2, Springer, New York
nar diffusion flames, Technical Note, Inst. nac. 1988.
de tec. aeron., Esteban Terradas, Madrid, Spain 30. Frisch U., D. d’Humieres, B. Hasslacher: “Lat-
1961. tice Gas Hydrodynamics in Two and Three Di-
mensions”, Complex Systems 1 (1987) 649
31. Succi S.: The Lattice Boltzmann Equation for Taylor-Couette Reactor Using CFD”, AIChE J.
Fluid Dynamics and Beyond, Oxford Univer- 47/3 (2001) 664.
sity Press, Oxford 2001 40. Paschedag A.R.: “Modelling of Mixing and
32. J.D.Anderson Jr.: Computational Fluid Dynam- Precipitation Using CFD and Population Bal-
ics: the basics with applications, McGraw-Hill, ances”, Chem. Eng. Tech. 27/3 (2004) 232.
New York 1998. 41. D.L. Marchisio: Precipitation in Turbulent Flu-
33. A. Birtigh, G. Lauschke, W.F. Schierholz, D. ids, PhD thesis, Politecnico di Torino 2002.
Beck, Ch. Maul, N. Gilbert, H.- G. Wagner, 42. A. Sokolichin, G. Eigenberger: “Applicability
C.Y. Werninger: “CFD in der chemischen Ver- of the standard k − ε turbulence model on the
fahrenstechnik aus industrieller Sicht”, Chem. dynamic simulation of bubble columns: Part I
Ing. Tech. 72/3 (2000) 175. Detailed numerical simulations”, Chem. Eng.
34. Th. Avalosse, M.J. Crochet: “Finite Element Sci. 54 (1999) 2273.
simulation of mixing: 2. Three-dimensional 43. L.I. Zaichik, V.M. Alipchenkov: “A kinetic
flow through a Kenics mixer”, AIChE J. 43/3 model for the transport of arbitrarydensity par-
(1997) 563. ticles in turbulent shear flows”, in: Proc. of Tur-
35. E.S. Mickaily-Huber, F. Bertrand, P. Tanguy, T. bulence and Shear Flow Phenomena 1, Santa
Meyer, A. Renken, F.S. Rys, M. Wehrli: “Nu- Barbara 1999.
merical simulations of mixing in an SMRX 44. A. Lapin, A. Lübbert: “Numerical simulation
static mixer”, Chem. Eng. J. 63 (1996) 117. of the dynamics of two-phase gas- liquid flows
36. F. Bertrand, P.A. Tanguy, E. Brito de la Fuente, in bubble columns”, Chem. Eng. Sci. 49 (1994)
P. Carreau: “Numerical modelling of the mixing 3661.
flow of second-order fluids with helical ribbon 45. L. Sanyal, S. Vásquez, S. Roy, M.P. Dudukovic:
impellers”, Comp. Methods Appl. Mech. Engng. “Numerical simulation of gas-liquid dynamics
180 (1999) 267. in cylindrical bubble column reactors”, Chem.
37. A. Brucato, M. Ciofalo, F. Grisafi, G. Micale:
Eng. Sci. 54 (1999) 5071.
“Numerical prediction of flow fields in baf-
46. D.E. Wiley, D.F. Fletcher: “Techniques for com-
fled sirred vessels: A comparison of alternative
putational fluid dynamics modelling of flow in
modelling approaches”, Chem. Eng. Sci. 53/21
membrane channels”, J. Membrane Sci. 211
(1998) 3653.
(2003) 127.
38. J. Derksen, H.E.A. Van den Akker: “Large eddy
47. C.A. Serra, M.R. Wiesner: “A comparison of
simulations on the flow driven by a Rushton tur-
rotating and stationary membrane disk filters
bine”, AIChE J. 45/2 (1999) 209.
39. D.L. Marchisio, A.A. Barresi, R.O. Fox: “Simu- using computational fluid dynamics”, J. Mem-
lation of Turbulent Precipitation in a Semi-batch brane Sci. 165 (2000) 19.
Model Reactors and Their Design Equations 487
Model Reactors and Their Design Equations

Vladimir Hlavacek, Laboratory for Ceramic and Reaction Engineering, Department of Chemical
Engineering, University of Buffalo, Buffalo, NY 14260, United States
Jan A. Puszynski, Laboratory for Ceramic and Reaction Engineering, Department of Chemical Engineering,
University of Buffalo, Buffalo, NY 14260, United States
Hendrik J. Viljoen, Laboratory for Ceramic and Reaction Engineering, Department of Chemical Engineering,
Jorge E. Gatica, Laboratory for Ceramic and Reaction Engineering, Department of Chemical Engineering,
1. Introduction . . . . . . . . . . . . . . . 489 4.5. Flow Field Description . . . . . . . . . 517

2. Batch Reactors . . . . . . . . . . . . . . 490 4.5.1. Boundary Conditions . . . . . . . . . . 518
2.1. Homogeneous Systems . . . . . . . . . 490 4.5.2. Permeability and Inertia Coefficient . 518
2.1.1. Isothermal Reactors . . . . . . . . . . . 490 4.5.3. Thermal-Expansion Coefficient . . . . 518
2.1.2. Nonisothermal Reactors . . . . . . . . . 490 4.5.4. Mass-Expansion Coefficient . . . . . . 519
2.2. Nonhomogeneous Systems . . . . . . 493 4.6. Thermomechanical Effects in the
2.2.1. Gas – Liquid Reactions . . . . . . . . . 493 Reaction System . . . . . . . . . . . . . 519
2.2.2. Solid – Solid Reactions . . . . . . . . . 494 4.7. Numerical Simulation . . . . . . . . . 520
2.2.3. Solid – Gas Reactions . . . . . . . . . . 496 4.7.1. Discretization of the Physical Domain 520
3. Continuous Stirred-Tank Reactors 4.7.2. Discretization of the Governing Equa-
(CSTR) . . . . . . . . . . . . . . . . . . . 498 tions . . . . . . . . . . . . . . . . . . . . . 521
3.1. Isothermal Homogeneous System . 498 5. Optimization of Chemical Reactors 522
3.2. Isothermal Heterogeneous Reactors 502 5.1. The Objective Function for Chemi-
3.3. Nonisothermal Continuous Stirred- cal Reactors . . . . . . . . . . . . . . . . 522
Tank Reactors . . . . . . . . . . . . . . 502 5.2. Elementary Optimization Problems 523
3.4. Cascade of Tank Reactors . . . . . . 505 5.2.1. Optimization of a Batch System . . . . 523
4. Packed-Bed Reactors . . . . . . . . . 507 5.2.2. Optimization of a Continuous System
4.1. Mass and Energy Balances . . . . . . 507 (CSTR) . . . . . . . . . . . . . . . . . . . 524
4.1.1. The Single-Particle Model . . . . . . . 508 5.2.3. Optimization of Complex Systems:
4.1.2. The Two-Phase Model . . . . . . . . . . 509 Illustrative Example . . . . . . . . . . . 524
4.1.3. The One-Phase Model . . . . . . . . . . 509 5.3. Optimization of Reactors by the
4.1.4. Boundary Conditions . . . . . . . . . . 510 Search Method . . . . . . . . . . . . . . 524
4.2. Values of the Parameters . . . . . . . 511 5.4. Optimum Temperature Profile and
4.2.1. Average Bed Porosity . . . . . . . . . . 511 Optimization of Multistage Reactors 527
4.2.2. Effective Transport Coefficients . . . . 512 5.5. Optimization of a Multibed Adia-
4.2.3. Wall Heat-Transfer Coefficient . . . . 513 batic Reactor with Heat Exchange
4.3. Further Simplifications . . . . . . . . 513 Between Catalytic Stages . . . . . . . 528
4.4. Parametric Sensitivity . . . . . . . . . 515 6. References . . . . . . . . . . . . . . . . . 529
Symbols c concentration, kmol/m3

cJ molar concentration of species J,
a activity
kmol/m3
a thermal diffusivity, m2 /s
cp , cv heat capacity per unit mass at con-
a interfacial area per unit volume, m2 /m3
stant pressure and volume, respectively,
A heat transfer area, m2
J kg−1 ◦ C−1
B, B∗ dimensionless adiabatic temperature
rise
488 Model Reactors and Their Design Equations
cpm specific heat capacity of the cool- Pe vL /D1 ; Péclet number for longitudi-
ing/heating medium nal dispersion
C reduced concentration, c/c0 Peh vL cp /λ; Péclet number for heat dis-
Cp , Cv molar heat capacity at constant persion
pressure and volume, respectively, Pet vd t /Dt ; Péclet number for transverse
J kmol−1 ◦ C−1 dispersion
d characteristic dimension, diameter, m Pr µ cp /λ; Prandtl number
dI diameter of impeller Q amount of heat, J
D diameter of reactor, m Q̇ heat flow, W
D coefficient of molecular diffusion, m2 /s r cylindrical or spherical coordinate, m
e particle emissivity R rate of reaction
Ea activation energy R gas constant, 8.314 J mol−1 K−1
E (t) residence time distribution function or RJ molar rate of production of J per
frequency function, s−1 unit volume of the reaction phase,
F molar flow rate kmol m−2 s−1
g gravitational acceleration, m/s2 | R |J molar rate of conversion per unit
h overall heat-transfer coefficient, volume of the reaction phase,
W m−2 K−1 kmol m−3 s−1
H enthalpy, J Re v d/ν; Reynolds number
HJ molar enthalpy of species J, J/kmol Rep v d p /ν; Reynolds number in packed
∆H r heat of reaction at constant pressure bed related to particle diameter
as associated with the stoichiometric s ratio of reaction rate constant
equation S surface, m2
(∆H r )J heat of reaction at constant pressure for Sc ν/D; Schmidt number
the conversion of or to one molar unit St α/ cp v; Stanton number for heat
of J, J/kmol transfer
J component St K G /v or K L /v; Stanton number for
J molar flux, kmol m−2 s−1 mass transfer
JJ molar flux of species J, kmol m−2 s−1 St UA/ cp Φv ; modified Stanton number
k homogeneous reaction veloc- t time, s
ity constant, dimension depends t off-line time, s
on the kinetics; for nth order: t∗ reaction time, s
m3(n−1) /(kmol(n−1) s) T temperature, K or ◦ C
∗
K chemical equilibrium constant T optimum reaction temperature, K or ◦ C
KD ratio between two concentrations T average radial temperature for a two di-
KL mass-transfer coefficient, m/s mensional model
L length, m ∆T ad adiabatic temperature rise of a reaction
m total mass of a system, kg mixture after complete conversion, ◦ C
e
mJ mass of species J in a system, kg T equilibrium temperature
MJ molar mass of species J, kg/kmol u internal energy per unit mass, J/kg
n sequence number of a tank reactor in a u average internal energy (over the reac-
cascade or of a bed in a multibed reactor tor volume), J/kg
n outward unit vector on S u linear velocity, m/s
N number of revolutions (impeller) per us control volume velocity, m/s
unit time UJ molar internal energy of species J,
N QI dimensionless constant J/kmol
Nu αd/λ; Nusselt number ∆U r heat of reaction at constant volume as
p total pressure, Pa associated with a stoichiometric equa-
P permeability tion, J
∆Pr pressure drop across the reactor (∆U r )J heat of reaction at constant reaction
Pe total pressure in the bulk stream volume for the conversion of or to one
molar unit of J, J/kmol
v velocity, m/s τ average residence time in reactor sys-

vF front velocity, m/s tem, s
vr relative velocity; velocity of one phase Φ flow rate
relative to another phase, m/s ΦP production rate, kg/s; kmol/s
V volume, m3 ΦmJ mass flow rate for species J, kg/s
Vr volume of reaction mixture, m3 Φc circulation rate
VR reactor volume, m3 Φv volumetric flow rate, m3 /s
wJ mass fraction of species J ψ shape factor
W mass of the catalyst
W amount of work, J
Ẇ rate of work done on the surroundings, Subcripts
W 0 initial
x direction of propagation, m av average
xJ mole fraction of species J in any phase A, B reactants
x coordinate, m c coolant, continuous
yJ mole fraction of species J in any gas e equilibrium
phase only used in connection with x J ext extern
for the liquid phase f fluid
z flow direction, m fus fusion
Z dimensionless coordinate in the direc- F fluid phase
tion of flow, z/L g gas
α heat-transfer coefficient, W m−2 K−1 G gas phase
β̄ dimensionless heat-transfer coefficient i interface
γ ratio between kinetic and mass-transfer ign ignition
rates J arbitrary species
γ temperature factor E/RT a ; index a l liquid, longitudinal
varies, depending on situation L liquid phase
γ̄ dimensionless activation energy L at the outlet of a tubular reactor of length
δ̄ dimensionless parameter L
δ displacement vector m medium, mass
ε porosity n output of the nth tank reactor in a cascade,
ε̄ dimensionless parameter or of a segment n
ϑ dimensionless temperature r reaction, radial direction
Θ dimensionless time s solid
Θc dimensionless cooling temperature S solid phase
ζ relative degree of conversion, fraction t transverse
of reactant converted v volumetric
ζ̄ average conversion w wall
κ ratio between reaction rate constant z axial direction
λe effective thermal conductivity,
W m−1 K−1
λ thermal conductivity, W m−1 K−1
λ Lamé constant 1. Introduction
µ Lamé constant
µ dynamic viscosity, Ns/m2 Reactor modeling represents a simultaneous so-
ν kinematic viscosity, m2 /s lution and analysis of mass, energy, and momen-
ν stoichiometric coefficient tum transfer equations along with reaction rate
ξJ degree of conversion of species J and equilibrium data. Sometimes additional in-
η effectiveness factor formation (e.g., of economic nature in reactor
density, specific mass, kg/m3 optimization calculations) must be also included
σ Stefan – Boltzmann constant, in the reactor model.
5.67×10−8 J m−2 K−4 s−1 Important goals of reactor modeling are [1]:
1) Scale-up of experimental laboratory units to form (Eq. 2.2) and the reaction time t that is re-
pilot-plant size quired for a certain degree of conversion can be
2) Scale-up of pilot-plant units to full scale size obtained by integrating Equation (2.1).
3) Prediction of behavior of different reactor
feedstocks and new catalysts ξJ
dξJ
4) Prediction of transients in reactors for better t= (2.2)
M J RJ
control 0
5) Optimization of steady-state operating con- If the density of the reaction mixture remains
ditions constant during the course of the reaction, the in-
6) Better understanding of the system that may tegration is simplified. In the case of irreversible
lead to process and design improvements nth-order reactions integration gives
Reactor modeling in the hands of a practi-
(1 −ξJ )1−n − 1
tioner is a powerful tool and can result in faster, t= , n = 1. (2.3)
k (n − 1) cJn−1
more economical process design. It should al- 0
ways be coupled with pilot-plant experiments

and process development. ln (1 −ξJ )
The most important parts of reactor model- t= ,n= 1 (2.4)
−k
ing are described in this article; namely, simu-
lation of batch and continuous stirred-tank re- The rate equations of reversible first-order re-
actors, tubular systems, and packed beds. Some actions with initial concentrations cJ0 and cP0
elements of optimization of chemical reactors and rate constants k 1 and k 2 for the forward and
are presented as well. backward reactions respectively, can also be in-
tegrated:
. cJ +cP0
/
2. Batch Reactors ln (1 −ξJ ) (k1 +k2 ) −k2 0c
J0
t= (2.5)
− (k1 +k2 )
2.1. Homogeneous Systems
The general problem in reactor design is to cal-
2.1.1. Isothermal Reactors culate the volume of a reactor for a certain aver-
age rate of production. The volume can be ob-
Batch reactors are usually operated as closed tained from the required degree of conversion
systems with no net inflow or outflow of mass. and the corresponding reaction times. In batch
The systems are also well-mixed and no spatial operation, a certain time is used for filling, heat-
gradients exist. The material balance for a com- ing, cooling, and cleaning and during this time
ponent J in a batch reactor which meets these no production occurs. If t denotes this off-line
conditions, is: time and ΦP denotes the desired production of
product P, the reactor volume is
dmJ dξJ
dt
=m
dt
=MJ RJ Vr (2.1) νA ΦP (t +t )
VR = (2.6)
νP MP cA0 ξA
where V r is the volume of the reaction mixture,
m the total mass of the system (kg), mJ the mass where ν A and ν P are the stoichiometric coeffi-
of component J in the system (kg), ξ J the de- cients of reactant A and product P, respectively.
gree of conversion of J, M J the molar mass of
component J (kg/kmol), and RJ the molar rate
of production of J per unit volume of the re- 2.1.2. Nonisothermal Reactors
action phase (kmol m−3 s−1 ). In the isothermal
case, RJ is only a function of the reactants for All chemical reactions are accompanied by evo-
an irreversible reaction or a function of reactants lution or absorption of heat. The most impor-
and products for a reversible reaction. In terms tant considerations which determine the choice
of the density of the reaction mixture, = m/V r , of temperature in the reactor are:
the material balance can be written in integral
1) Chemical equilibrium and the conversion hav

rate of the desired reaction; the maximum h= (2.9)
1 + 2 ΦhavcA
conversion of a reversible exothermic reac- m pm
tion is reduced when the temperature is in-

creased, but the kinetic rate increases, there- Example. In a batch reactor with a volume of
fore an optimum temperature exists. 5 m3 , an exothermic reaction A → P is carried
2) Undesirable side reactions (which also de- out in the liquid phase. The density of the mix-
pend on temperature and their role in the ture does not change during the reaction. The
overall equilibrium) can influence the maxi- rate of reaction is given by
mum yield of product.
3) Phase transformations of reactants or prod- RA = − kcA
ucts; there are examples where it is better to with k = 4×106 exp (− 7500/T ) s−1 . The heat of
carry out the reaction in the liquid instead reaction is (− ∆H r )A = 1.67×106 J/kg, the ini-
of the gaseous phase to achieve maximum tial concentration of A is cA0 = 1 kmol/m3 , M A =
conversion and mass transfer. An example is 100 kg/kmol and Cp = 4.2×106 J m−3 K−1 .
the formation of methyl tert-butyl ether from The initial temperature of the reaction mixture is
isobutene and methanol. 298 K. The reactor is fitted with a heat-exchange
4) Cost implications of heating reactants to the coil with a surface area of 3.3 m2 . The heat
reacting temperature; energy cost must be exchanger is operated with steam (T H = 393 K,
compared with the gain in yield at increased h = 1000 W m−2 K−1 ) and with cooling water
temperature as maximum yield and maxi- (T c = 290 K, h = 1400 W m−2 K−1 ). Filling and
mum profitability will not always be at the emptying of the reactor take 600 s and 900 s, re-
same temperature [2]. spectively.
For a required conversion ξ A ≥ 0.95, the tem-
Constant Pressure. At constant pressure, perature profile over one reaction cycle and
the energy balance in a well-mixed batch reactor the duration of a reaction cycle shall be de-
is: termined when the following policy of opera-
dT Q̇
tion is followed: heat up to 350 K, the reaction
cp + (∆Hr )J RJ = (2.7) then proceds under isothermal conditions until
dt Vr
ξ A = 0.95, followed by cooling down to 310 K.
where cp denotes the specific heat capacity, Solution. The following equations must be
(∆H r )J the reaction enthalpy for the conversion solved simultaneously for the first part of the
of or to one molar unit of J, and Q̇ denotes the reaction cycle:
rate of heat flow to or from the reactor. In the
case of adiabatic operation, Q̇ = 0. Otherwise, Q̇ dξA
=k (1 −ξA )
can be determined as follows: dt
dT
cp = (− ∆Hr )A cA0 MA k (1 −ξA )
Q̇ =hA T −Tc, H (2.8) dt
hAs
+ [Ts −T ]
where h is the overall heat-transfer coefficient Vr
and A the heat-transfer area. The external tem- Starting from the initial concentration and tem-
perature can be cooler (T c ) or hotter (T H ) than T , perature, a small temperature interval ∆T is se-
depending on whether cooling or heating must lected. Average values for T and k over this inter-
be accomplished. The overall heat-transfer coef- val are then calculated and used together with the
ficient h is calculated from correlations [3] and initial value for ξ in the second equation to solve
it depends on the temperature of the cooling or for ∆t. This value is then used in the first equa-
heating medium. Thus, a heat-transfer coeffi- tion to solve for ξ. An average value for ξ over
cient hav is calculated at the average medium this interval can then be calculated. With the av-
temperature. If Φm is the mass flow rate and erage values of T , k, and ξ, an improved ∆t value
cpm is the specific heat capacity of the cooling or can be calculated from the second equation and
heating medium, then h is corrected according the process is repeated until the required degree
to:
of accuracy is reached. In Figure 1 the temper- Example. A closed tank with an internal vol-
ature profile is shown. Once the conversion is ume of 250 m3 contains a mixture of air with
0.95, cooling commences. The cooling period 4 % butane at 18 ◦ C and a pressure of 100 kPa.
can be calculated by integrating the following The mixture is ignited and the reaction proceeds
energy equation from T = 350 K to T = 310 K: according to:
dT
cp = (− ∆Hr )A cA0 MA k (1 −ξA ) C4 H10 + 6.5 O2 → 4 CO2 + 5 H2 O
dt
hAc
+ [Tc − T ] The heat of combustion at 18 ◦ C and 100 kPa
Vr
is (− ∆H r ) = 2880 kJ/mol. The pressure in the
Integrating the first two equations from the ini- vessel shall be determined after the explosion.
tial conditions until T is 350 K gives a preheat- Solution. Since the reaction proceeds adia-
ing period of 2384 s. The temperature is then batically and at constant volume, the total in-
kept constant and only the first equation is internal energy of the reaction mixture does not
tegrated until the conversion reaches 0.95; this change. The temperature rise is calculated from:
period takes 1000 s. For the cooling-off period
the third equation is integrated and this gives T ξB
(∆Ur )B
5426 s. Adding 1500 s for filling and emptying cv dT + dξB = 0
gives a total period of one cycle of 10 310 s. MB
T0 ξB0
LIVE GRAPH where the index B denotes butane.

Click here to view
To calculate (∆U r )B , the relationship bet-
ween U and H and the ideal gas law will be
used:
∆Hr = ∆Ur +R T ∆n
The total change in number of moles is

(4 + 5 − 7.5 = 1.5), hence:
RT ∆n = 1.5 × 8.314 J mol−1 K−1 ×291 K

= 3.63 × 103 J/mol
Since O2 is the limiting reactant (i.e., O2 is

present in substoichiometric amounts), not all
butane will react. The composition of the final
mixture can then be calculated. In Table 1 the
initial and final compositions are given. The spe-
Figure 1. Temperature profile over a reaction cycle cific heat capacity at constant volume (cv ) of the
product mixture is a function of temperature and
can be found in thermodynamic tables. In this
Constant Volume. The energy balance for
example the average value of cv is 1.06 kJ/kg.
a constant volume process is
The mole fractions of butane before and after
cv
dT
+ (∆Ur )J RJ =
Q̇
(2.10)
the reaction were 0.04 and 0.0089, respectively.
dt Vr These values can be converted to mass fractions
Since ∆U r is the change of internal energy at by multiplying the mole fraction of each compo-
constant volume and temperature, for the case nent in Table 1 by its molecular mass and nor-
of an ideal gas ∆H r and ∆U r are related as fol- malizing. The mass fractions of butane before
lows: and after reaction are 0.077 and 0.017, respec-
tively.
∆Hr = ∆Ur +RT ∆n (2.11)
This relation will be different for reaction mix-
tures with another equation of state.
Table 1. Initial and final gas compositions

Example. A batch reactor must be designed
for the production of 1×105 kg/day fats con-
Compound Mole fraction before Mole fraction taining monounsaturated fatty acids by hydro-
reaction after reaction genation of cottonseed oil. The reaction is car-
Butane 0.04 0.0089 ried out on a nickel catalyst that is dispersed in
Nitrogen 0.758 0.708
Oxygen 0.2028
hard stearin. Hydrogen is bubbled through the
Carbon dioxide 0.182 oil, thus two phases are present. The following
Water 0.093 equations describe the conversion and forma-
tion of acid moieties with diunsaturated (B), cis-
The temperature rise can now be determined: monounsaturated (R1 ), trans-monounsaturated
(R2 ), and saturated (S) aliphatic chains:
(− ∆Hr )B − RT ∆n
cv × (T − T0 ) + × (∆ξB ) = 0 dcB
MB = − (k1 +k2 ) c0.5 Hs cB
so: dt
dcR1
H s c B − k 3 c Hs c R 1
=k1 c0.5 0.5
1.06 kJ/kg× (T −291 K) dt

−2880 kJ/mol − 3.63 kJ/mol Hs c R 2 − k 5 c H s c R 1
+k4 c0.5
+
58 g/mol dcR2
=k2 c0.5 0.5
Hs cB +k3 cHs cR1
× (0.077 − 0.017) = 0 dt
T = 3103 K = 2830 ◦ C − k4 c0.5
H s c R 2 − k 6 c H s cR 2
dcs
Applying the ideal gas law, the pressure can be =k5 cHs cR1 +k6 cHs cR2
dt
determined:
The hydrogen concentration in the gas phase
P ×250 m3 = 1.046×n0 ×8.314 J mol−1 K−1 (cHi ) is in equilibrium with the hydrogen on the
× (3103 K) = 1115.4 kPa catalyst surface, cHs . Since the gas is essentially
where 1.046×n0 is the total number of moles pure hydrogen, cHi is constant. Furthermore it
present after the explosion. The last column in is assumed that the rate of consumption of ad-
Table 1 is the mole fraction based on kmol/kmol sorbed hydrogen on the catalyst surface is bal-
original mixture and adding this column will anced by the rate of mass transfer from the gas
give the relative change in the number of moles phase. Let K D = cHs /cHi denote the ratio bet-
in the mixture. ween the two concentrations, then the following
relation exists:
. /
2.2. Nonhomogeneous Systems − 1 + s1 [1 −ξB ]
2
0.5
KD = YR YR
+
2 γ1 + s 1 + s 2
Batch systems are spatially homogeneous when 5 6
2 0.5
the reactant mixture is well-mixed during the YR YR
1 + s1 (1 −ξB )2 + γ4 γ1 + s 1 + s 2
course of the reaction. Nonideal mixing can 2 5 6

cause settling or separation of phases in liquid – YR YR
2 γ1 + s 1 + s 2
5 6
gas mixtures, mixtures of nonmiscible liquids or
liquid – solid mixtures. However, even reactants where Y R1 = cR1 /cB0 , Y R2 = cR2 /cB0 ,
which are well-mixed, do not necessarily react γ = k 1 cB0 /K L av c0.5Hi , s2 = k 1 /k 2 , s3 = k 1 /k 3 ,
in a homogeneous way. Even if a single phase is s4 = k 1 /k 4 , s5 = k 1 /k 5 c0.5 0.5
Hi , s6 = k 1 /k 6 cHi . The
present, the system can still be spatially nonho- product of the mass-transfer coefficient and the
mogeneous. bubble area av was determined experimentally
as K L av = 0.022 s−1 . Whereas the si values de-
note the ratios of reaction rate constants, γ is a
2.2.1. Gas – Liquid Reactions
ratio between kinetic and mass transfer rates.
In the following example, the design of a batch
reactor, where both a liquid and a gas phase are
present, will be demonstrated.
Experiments on the hydrogenation of cot- density of cottonseed oil. Using a height to diam-
tonseed oil using a Rufert nickel catalyst gave eter ratio of two, the specification of the vessel
the following values for the reaction rate con- is 2.92×5.84 m.
stants [4]: k1 = 0.254 L/mol/min, s2 = 2.89, LIVE GRAPH
Click here to view
s3 = 5.05, s4 = 15.1, s5 = 3.38, s6 = 3.38. The hy-
drogen concentration in the gas phase is
cHi = 0.0129 mol/L. The feedstock composition
(wt %) consists of 25.6 % S, 27 % R1 , 0.4 % R2
and 47 % B. The molar concentration of B, cB
is 1.45 mol/L. The value for γ can now be cal-
culated:
-
0.254 L/mol/min × 1.45 mol/L
γ= -
(60 × 0.022) min−1 ×0.1136 mol/L/min
= 2.45
The reactions are irreversible, hence cs does not

appear in the rate expressions for components B,
R1 , and R2 and they can be integrated indepen-
dently from the balancing equation for S. Time
can be substituted in terms of the conversion of
B:
YR YR YR
dYR1 (1 −ξB ) − s3 + s4 − s5 KD
1 2 1 0.5
=
dξB 1+ s (1 −ξB )
1
2
YR1 YR YR
1 −ξB
dYR2 s2
− s + s 2 − s 1 KD 0.5
= 3
4 5
dξB 1+ 1 (1 −ξB )
s2
These two equations, together with the algebraic

equation for K D can now be integrated, using
the initial conditions Y R1 = 27/47, Y R2 = 0.4/47,
and ξ B = 0. In Figure 2 A, the total yield of mo-
nounsaturates is shown as a function of ξ B . A
maximum is obtained at ξ B = 0.84 and the time it
takes to obtain 84 % conversion of B is 115 min
(see Fig. 2 B). The processing time, excluding
the reaction time, is best ascerted from plant
studies; for this example 2.5 h are taken. Hence
the total time (conversion plus processing) is
4.42 h. Thus, five batches can be processed per
Figure 2. Total yield of monounsaturates in the hydrogena-
day, each batch producing 20×103 kg. At 84 % tion of cottonseed oil (A) and conversion time of diunsatu-
conversion the product mixture consists of 67 kg rates (B)
monounsaturates per 100 kg of mixture, hence
the reactor volume is:
Vr = 1.05×
100 kg
×20 000 kg×
1 2.2.2. Solid – Solid Reactions
67 kg 800 kg/m3
= 39.2 m3 Even when only one phase is present, the re-
action can progress in a nonhomogeneous way.
where the factor 1.05 is introduced because 5 % Reactions with large activation energies require
was added for head space and 800 kg/m3 is the a certain amount of preheating before they be-
gin. If the temperature profile in a batch system ∂T

cp = ∇ ·λ ∇T + (− ∆Hr )J RJ (2.13)
is not uniform, the reaction rate will also be spa- ∂t
tially distributed and if the heat of reaction is
large, it will further contribute to the concentra- where λ denotes the thermal conductivity. Note
tion of high temperatures in local areas inside that diffusion of the solid reactant is negligible.
the reactor. The geometry of the system is determined by the
Solid – solid reactions that are associated shape of the reactant mixture. A popular prac-
with large activation energies and large heats tice is to press the reactant mixture into a cylin-
of reaction often take place in the combustion drical preform. For this case, Equation (2.13)
mode. The combustion mode is associated with must be consistent with a cylindrical geometry,
strong spatial gradients and modeling these type the dimensions of which are determined by the
of reactions requires special techniques. Exam- preform. The temperature at the reaction front
ples of solid – solid reactions which occur in the can be very high and Equation (2.13) must be
combustion mode are those between Ti and C, amended to take phase transformations into ac-
Mo and Si, and Ta and C. The well-mixed reac- count. In the following section some aspects of
tants are usually prepared as a preform that is ig- the maximum temperature rise are discussed.
nited at one end of the sample (see Fig. 3). Once
the combustion wave has traversed the length of Maximum Temperature Rise. For T ad <
the sample, the reaction is complete. Conversion T fus the adiabatic temperature T ad rise of a sys-
is high in these combustion reactions and under tem where reactant A is transformed to product
ideal conditions complete conversion can be ac- P, is given by:
complished. Two factors determine the degree of (− ∆Hr ) cA
conversion. If the system loses a lot of heat dur- Tad =T0 + (2.14)
cp
ing the reaction, the degree of conversion drops.
Thus, the closer the system can be operated to When T ad > T fus and
adiabatic conditions, the higher will be the de-
Tfus
gree of conversion. The second factor is incom-
(−∆Hr ) < cp dT + (−∆Hfus ) the fol-
plete mixing of the reactants. In these type of T0
reactions it is important to have intimate contact lowing equation holds:
between the different species on the micro-level.
Therefore, mixing of the reactants is one of the Tad =T0 +
(− ∆Hr ) cA ν (− ∆Hfus )
− (2.15)
most time- consuming and expensive steps in the cp cp
process.
Otherwise:
(− ∆Hr ) cA (− ∆Hfus )
Tad =Tfus + −
cpl cpl
cp
− [Tfus − T0 ] (2.16)
cpl
where cp1 denotes the specific heat capacity of

the liquid. Average properties over the tempera-
ture range must be used and the densities of the
solid and liquid phases are assumed to be the
same. The final temperature can be decreased
by adding product to the reactant mixture to de-
crease cA . There is a bound on the degree of
Figure 3. Typical configuration of solid – solid batch reac-
tions
dilution; if the system is too dilute, it will not
ignite and self-propagation of the combustion
The mass and energy balances are front is not possible [5].
∂cJ Equations (2.14) – (2.16) are derived on the
= − RJ (2.12) basis of thermodynamic arguments, but the
∂t
batch process is transient and the maximum tem- ture at the center of the Ti – C cylinder is shown
peratures in the transient process can be differ- in Figure 4. The adiabatic temperature for this
ent from those obtained from Equations (2.14) – reaction is obtained from Equation (2.14):
(2.16). Unfortunately no rigorous bounds on the
maximum temperature of a transient process are 1.8 × 108 J/kmol
Tad = 298 K +
known and they must be determined by numeri- 60 kg/kmol × 1113.48 J kg−1 K−1
cal methods. Furthermore, these transient max- = 3052 K
ima can exceed the adiabatic temperature and
Equations (2.14) – (2.16) cannot be relied upon
to give upper estimates of the reaction tempera- The maximum transient temperature is
ture. 5100 K. The temperature overshoot is 2000 K.
Since the melting point of TiC is 3420 K, the
transient maximum temperature will exceed the
melting point.
Reaction Wave Propagation. When the

sample is ignited at one point by an external
heat source, the reaction front can traverse the
sample in a number of ways. The ideal propaga-
tion mode, from a processing point of view, is a
stable front that propagates at a constant speed.
If this front velocity is denoted by vF , a simi-
larity transformation can be made between time
t and the direction of propagation x to render
Equations (2.12), (2.13) time independent:
z =x + vF t (2.17)
The integrity of this planar front is not pre-

served when external heat losses are present.
Figure 4. Temperature at the center of the cylindrical TiC Heat losses also reduce vF . If heat losses are
sample large enough, the system is quenched.
Example. Determine the maximum tempera- Other modes of front propagation also ex-
ture of the following reaction: ist [6]. The planar front can, for example, be-
come unstable and collapse into hot spots which
Ti + C → TiC are seated at different positions from the center-
A stoichiometric mixture of the reactants is line. These hot spots propagate in a helical way
pressed into a cylinder and simultaneously ig- around the centerline, leaving behind regions of
nited at both ends. The cylinder is 2 cm long and incomplete conversion.
perfectly insulated. The necessary properties of
the system are listed below:
2.2.3. Solid – Gas Reactions
Density 3240 kg/m3
Heat capacity 1113.48 J kg−1 K−1
In solid – gas systems, combustion takes place
Thermal conductivity 8.37 W m−1 K−1
Heat of formation at 25 ◦ C 1.84×105 J/mol between a solid and a gaseous component. A
Activation energy of very important factor is the flow of gas through
formation reaction 8.29×105 J/mol the porous solid by means of filtration or perme-
Frequency factor in
expression for rate constant
ation. Hence this type of reaction is often termed
of formation reaction 1.05×105 s−1 filtration combustion. In Figure 5 various config-
urations for filtration combustion are shown.
Solution. Equations (2.12), (2.13) are inte-
grated numerically and the maximum tempera-
of the second configuration. The sample shown

in Figure 5 C is free standing and gas can pen-
etrate from all sides into the sample. However,
the reactant powder must be compressed to give
the sample the necessary strength, therefore the
powder’s permeability will decrease. The con-
figuration depicted in Figure 5 D is the most
practical, because both counter- and crossflow
of reactant gases towards the reaction front can
be maintained without limiting the flow of the
gaseous reactant through the solid medium. The
filtration combustion model is described by the
following set of equations:
∂εg
= − ∇ (εg v) −νg Rs (2.18)
∂t
∂ [εg cpg + (1 −ε) s cps ]

∂t
= ∇ ·∇ (λT ) − ∇ (εg vT ) + (− ∆H)s Rs (2.19)
g RT
p= (2.20)
Mg
v = − P ∇p (2.21)
Rg = −0B pn f (cs ) k (2.22)
where ε is the porosity of the bed, P the perme-

ability in the bed, 0B the initial bulk density of
the solid, and f (cs ) the dependence of the reac-
tion on the concentration of the solid phase. The
Figure 5. Different configurations of batch solid – gas reac- porosity and permeability of the bed change as
tions
A) Reaction initiated at top of container; B) Reaction ini-
the reaction progresses, mainly because of sin-
tiated from bottom of container; C) Free-standing sample tering and melting; this affects the flow of gas
with gas penetrating from all sides; D) Design with both to the front. The effects of sintering and melting
counter- and crossflow of reactant gases towards reaction can be incorporated into the model.
front
The first two configurations are similar. In Example. A rectangular container is filled
Figure 5 A, the reaction was initiated at the top with titanium powder and placed in a chamber
of the container and the front propagates away filled with nitrogen. The reaction is ignited at the
from the open end. In Figure 5 B the reaction was top right of the container and the pressure in the
initiated at the bottom of the container and the chamber is kept constant. Low and high chamber
front propagates countercurrently to the flow of pressures affect the conversion and in Figure 6
gas. An advantage of the second option is that the results for both cases at different times (time
the diffusion length for the gas decreases with increases from top to bottom) are shown.
increasing degree of conversion. Product mate- The front propagates faster when the over-
rials also tend to sinter partially during the re- head pressure is higher and penetrates to the bot-
action, which makes them less permeable than tom of the container. When the overhead pres-
the fresh material, which is another advantage sure is lower, conversion is incomplete and the
Figure 6. Conversion contours at different reaction times (time increases in the direction a – c) for A) low and B) high chamber
pressures
reaction time is also much longer. When the 1) Temperature and heat transfer can be rela-
depth of the container is increased, the chamber tively easily controlled
pressure must be further increased, but the exact 2) Fine catalyst particles can be effectively sus-
values required can only be established through pended in a liquid reacting system
a numerical simulation. 3) In a system with parallel reactions, a reaction
with lower order is favored
4) In polymerization reactions, wider molecu-
3. Continuous Stirred-Tank Reactors lar mass distributions are expected
5) Very economical when long residence time
(CSTR) is required
6) Recommended for liquid rather than gaseous
3.1. Isothermal Homogeneous System reacting systems
The continuous, ideally mixed, stirred-tank re- Material Balance. The overall material bal-
actor (CISTR) is a flow reactor in which all ele- ance for a CISTR which is schematically shown
ments of the fluid have the same composition as in Figure 7 reads:
the outlet stream of the reactor.
The continuous stirred-tank reactor is nor- d (mξJ )
= − ∆Φm ξJ +MJ |R|J Vr (3.1)
mally run at steady state, and is usually oper- dt
ated such that it is well-mixed. As a result, the
CISTR is generally modeled as having no spa- where m is the total mass in the system; − ∆Φm
tial variations in concentration, temperature, or the net inflow of mass by convection and diffu-
reaction rate throughout the vessel. In systems sion; ξ J the degree of conversion of component
where mixing is highly nonideal, the well-mixed J; M J | R |J the mass rate of production of com-
model is inadequate and other techniques, such ponent J per unit volume; and V r the volume of
as residence-time distributions, have to be used the reaction mixture.
to obtain meaningful results.
The CISTR has the following unique charac-
teristics:
the mode of adding and removing reactants

and products, and the cooling or heating rates
are all essential concerns. For more details, see
→ Stirring, [7], [8].
Mixing. For a processing vessel to be effec-

tive, the volume of fluid or slurry that is circu-
lated by the impeller must be sufficient to sweep
out the entire vessel in a reasonable time. Also,
the velocity of the stream leaving the impeller
must be high enough to carry the currents to the
remotest parts of the tank. In addition, an ade-
quate level of turbulence is required in order to
Figure 7. CISTR reactor
For explanation of symbols see text
maintain the high effectiveness of the process.
The proper selection of an impeller, its speed,
and the geometrical dimensions of the reactor
When a CISTR is operated in a steady state,
are very important design parameters.
the required reactor volume is
In practice, for moderately fast reactions, a
ξJ tank reactor may be approximately considered
Vr =Φm (3.2)
MJ |R|J as ideally mixed if the discharge rate of the im-
peller Φc (the circulation rate) is at least five to
or in the case of constant density ten times the feed rate Φm i.e.,
c J 0 ζJ Φc
Vr =Φv (3.3) > 5 − 10 (3.4)
RJ Φm
where Φv is the volumetric flow rate; ζ J the rel- The impeller discharge rate depends on the type
ative degree of conversion; cJ0 the molar con- of impeller, the tank geometry, and operating
centration of species J; and RJ the molar rate of conditions. This discharge rate can be estimated
production of J per unit volume of the reaction from:
phase. The mass balance equations for various
reaction orders are listed in Table 2. Φc
=NQI (3.5)
N d3I
Table 2. Ratio of outlet to inlet concentrations in a CISTR for reac- where d I is the impeller diameter, N the number
tions of different order of impeller revolutions per unit time, and N QI is
Reaction Reaction Concentration a dimensionless constant. The value of this con-
order, n rate equation, RA ratio, cA /cA0 stant depends on the axial blade width of the im-
 "  peller, the number of blades, curvature or pitch,
#
#
−1 k c−1 1 
1+ $ 1− 4k τ  and the ratio of impeller velocity to fluid rota-
A 2 c2
A0
tional velocity [8]. The following values are rec-
0 k 1 − ck τ
' A0 ommended for agitators in baffled tanks which
√ k2 τ 2 are commonly used in industry:
1
2 k cA 1+ 4cA − 2√
kτ
c
0 A0
1
Marine-Type Impeller:
1 k cA 1 +k τ ( ) (
( (
2 k c2A 1
2k cA τ ( 1 + 4k cA0 −1(
0 NQI = 0.5
Turbine (with six blades and width-to-diameter

ratio of 1 : 5):
Most important in designing a homogeneous
CISTR system is to select equipment and stir- NQI = 0.93D/dI for Reimp > 104
ring procedures that will assure essentially per-
fect mixing. Choice of a suitable type of impeller where Reimp = N d 2I /µ is the impeller Reynolds
and reactor arrangement, the required power, number, and D the diameter of the reactor.
Many reactions require rapid dispersal of re- CISTR. When segregated flow takes place, the
actants in order to avoid even momentary build- situation is different. Each aggregate in the out-
up of high concentrations in the system. In ho- let stream can be considered as a batch reactor
mogeneous reacting systems, the most rapid dis- with a reaction time equal to its residence time.
persal can be accomplished by discharging the The fraction of aggregates having a residence
feed as close as possible to the center of the time between t and t + ∆t is E ∆t. If the remain-
impeller. Discharge ports for product removal ing reactant concentration after conversion in a
should be located at the opposite end of the flow batch reactor with residence time t is cBatch
A (t),
pattern from the inlet nozzle. In general, the flow the average concentration at the outlet of the seg-
of a reacting fluid through a reactor is a very regated continuous flow reactor CSSTR can be
complex process. The interaction of flow pat- calculated:
tern and chemical reaction cannot be analyzed
∞
rigorously even in the simple case of a single c̄A 1
= cBatch (t) Edt (3.7)
isothermal reaction. Therefore simplified and/or c A0 c A 0 A
0
idealized models are necessary.
or
Residence-Time Distribution (RTD). The
∞
frequency function often used in statistics c̄A 1 1 −t/τ
= cBatch
A (t) e dt (3.8)
(called the E diagram in RTD description) can c A0 c A 0 τ
0
be derived for a continuous stirred-tank reac-
tor from a mass balance of the reactor with an The average outlet concentrations for different
ideal pulse perturbation at the inlet stream. The reaction kinetic expressions for both ideal mi-
pulse is immediately distributed over the reac- cromixing and segregated flow are listed in Ta-
tor, moreover the product concentration remains ble 3 [9]. Outlet concentrations are identical for
the same everywhere and equals the outlet con- both cases if a first-order reaction takes place.
centration. The E (t) diagram reads: Example [9]. Reactant A (M A = 104 kg/kmol)
is to be polymerized in the dispersed phase in a
1
E (t) = e−t/τ (3.6) continuous stirred-tank reactor. Based on batch-
τ
scale experiments, the following reaction rate
For a continuously operated mixing vessel expression was found:
which shows a RTD of an ideal mixer (Eq. 3.6),
the different states of micromixing are: RA = − k c1.5
A
with k = 2.5 × 10−4 s−1 kmol−0.5 m1.5
1) CISTR: the ideal mixer (mixing on molecu-
lar level) The required size of the tank reactor shall be
2) CSSTR: the completely segregated mixer calculated for a production of 10 t/d of polymer
where the fluid consists of lumps which with a relative degree of conversion ζ̄ A = 0.9,
move through the reactor without exchange under the assumption that coalescence between
of matter with their surroundings the liquid drops does not occur. The feed of the
3) CSTR: the partially segregated mixer dispersed phase consists of pure A, and the den-
sity of this phase remains constant at a value
A detailed description of the amount of mi- of 832 kg/m3 during the reaction. The volume
cromixing with one parameter is generally not fraction of the dispersed phase in the reactor is
possible. For non-first-order reactions, apart 0.165.
from the reaction rate not only the intensity of Solution. The average conversion ζ̄ A at the
mass exchange between fluid elements is impor- outlet of the CSSTR is obtained by rearrange-
tant, but also the residence time of a molecule in ment of Equation (3.8):
the reactor.
In the case of maximum micromixing and ∞
Batch 1 −t/τ
constant density of the reacting system, the con- ζ̄A = ζA (t) e dt (3.8a)
τ
version is identical to that calculated for the 0
By integrating Equation (3.8 a) a value of

Table 3. Design equations for ideally mixed CISTR and for com- √
pletely segregated fluids CSSTR kτ cA0 = 15.4 is found for ζ̄ A = 0.9. The cal-
culated residence time τ is 6 h and the required
volume of the dispersed liquid Φm τ /0.9 A is
equal to 3.34 m3 . The total required volume in
the reactor is 3.34 m3 /0.165 = 20.2 m3 .
Start-Up of a CISTR. For non-steady-state

operations, the accumulation term in Equation
(3.1) cannot be neglected. Two different periods
of non-steady-state operations in a CISTR can
be distinguished:
1) Filling a reactor with reactants (variable re-
actor volume)
2) Non-steady-state operation at a constant re-
actor volume
In the case of an irreversible liquid reaction
(A → B) which takes place in a CISTR under
isothermal and constant density conditions, the
instant concentration in the reactor can be calcu-
lated as follows: For t ≤ τ , no liquid leaves the
reactor and the material balance leads to:
− d (cA V )
= −Φv cA0 +kcA V (3.9)
dt
in which the reaction volume is V = Φv t. Inte-
gration of Equation (3.9) gives:
c A0 V
cA = 1 − e−kt for t ≤ (3.10)
kt Φv
For t > τ the reaction volume V is constant and
equals V r and the product flow out of the reactor
equals the feed rate Φv . The material balance for
reactant A now becomes:
− d (cA Vr ) dcA
= − Vr
dt dt

= −Φv cA0 −cA +kcA Vr (3.11)
Integration yields:
cA0 − (1 +kτ ) cA
= e−(1+kτ )(t−τ )/τ
cA0 − (1 +kτ ) cAτ
for t >τ (3.12)
cA0
−kτ

where cA = kτ 1−e
After a long time (t → ∞) the right-hand
side of Equation (3.12) approaches zero, so that
ultimately the concentration cA in the reactor
The material balance for a batch system together reaches the value cA∞ . A conservative estimate
with the rate expression yields: for the time required to reach steady state can
2
2 be made by substituting cAτ = cA0 in Equation
ζ̄ Batch
A = 1− √ (3.12) for the required degree of conversion.
2 +k t cA0
3.2. Isothermal Heterogeneous Reactors a is the interfacial area per unit volume of both
phases (m2 /m3 ), cAI is the concentration of re-
Contrary to reactions in a single phase where actant A in phase I, K A is the distribution coef-
mixing takes place on a molecular scale, in a ficient of A between both phases, and c0AII is the
multiphase system not all reactive molecules steady-state concentration of A in phase II.
present may be available for chemical reaction The value of the product of mass-transfer co-
due to mass transfer limitations. For a reacting efficient and interfacial area strongly depends
system consisting of two phases L and G, with a on the reactor arrangement and empirical corre-
reaction taking place in phase L only, the mass lations must be used to scale-up such reacting
balance equations are: systems [10], [11].
dmJL
= − ∆ (ΦmL wJL )
dt
+JJL MJ a Vr +RJ MJ (1 −ε) Vr (3.13) 3.3. Nonisothermal Continuous
and: Stirred-Tank Reactors
dmJG
= − ∆ (ΦmG wJG ) +JJG MJ aVr (3.14) All chemical reactions are in principle accom-
dt
panied by evolution or absorption of heat and
The term RJ M J (1 − ε) V r is the production rate these effects often have to be taken into account.
of J by a homogeneous chemical reaction in For flow processes, the energy balance equation
phase L where (1 − ε) is the volume fraction of is
the reaction phase per unit volume of a reactor. 9 :
The terms (−∆Φm wJ ) and (J J M J a) represent d u m
= − ∆ (hΦm ) +Q̇ −Ẇ (3.16)
the net supply of component J by convection and dt
the mass flow of J from the interface to the bulk
where h is the enthalpy per unit mass of the re-
of the phase, respectively.
action mixture and u is the average internal
When a reaction takes place in a system
energy over the reactor volume. For the steady-
of two immiscible or partially miscible liquid
state operation of a continuous tank reactor pro-
phases, the overall process can be controlled by
vided with a heat exchange area A, the energy
chemical reaction and/or mass transfer between
balance becomes:
both phases. In the case of a chemically con-
trolled process, the overall rate expression in Φm (h1 −h0 ) = U A (Tc −T1 ) (3.17)
Equation (3.1) is the sum of the reaction rates
in the individual phases. where the subscripts 1 and 0 refer to the condi-
When mass transfer is the rate-determining tions at the outlet and inlet, respectively; T c is the
step, phase equilibrium cannot be achieved and temperature of the cooling or heating medium.
the reaction rate is fast compared to the rate of The difference in enthalpy (h1 − h0 ) can be cal-
mass transfer. Thus, the reaction proceeds as the culated from:
reactants diffuse through the interface into the
bulk of the other phase. If reactant A is a major
T1 ξJ,1

component of phase I while phase II consists of h1 −h0 = cp dT + (∆hr )J dξJ (3.18)
reactant B and if equilibrium is attained at the T0,O
interface, the rate of mass transfer of A from
phase I to phase II would be equal to the rate where cp is the specific heat capacity at constant
of disappearance of A by chemical reaction in pressure and (∆hr ) the enthalpy of reaction at
phase II. For an irreversible, second-order reac- constant pressure per unit mass of J converted.
tion between A and B, mass transfer of A from If the density and heat capacity of the system
phase I to phase II can be described as: are constant, the energy balance for reactant A
gives:
cAI
JAII =kII a −c0AII (VI +VII ) (3.15)
KA − (∆Hr )A cA0 −cA1
where k II is the mass-transfer coefficient in UA
= cp (T1 −T0 ) + (T1 −Tc ) (3.19)
phase II per unit volume of both phases (m/s), Φv
where (∆H r )A is the heat of reaction per mole is higher than that generated in the system. The
of A converted. In the case of a first-order irre- intermediate intersection point is unstable. Since
versible reaction Equations (3.1) and (3.19) can the slope of the heat production curve at the in-
be rewritten to: termediate point is greater than that of the heat
removal line, any positive temperature perturba-
kτ
− (∆Hr )A cA0 tion will be amplified until the reactor reaches
1 +kτ
the upper stable operating point, and negative
UA
= cp (T1 −T0 ) + (T1 −Tc ) (3.20) temperature deviation leads to extinction (lower
Φv
stable operating point). If the feed temperature
In order to find the maximum temperature T 1 , T 0 and the cooling capacity are such that the heat
Equation (3.20) must be solved by trial and er- removal line 3 prevails (see Fig. 8), the reactor
ror, either numerically or graphically, because k operates in an upper stable state and no special
is an exponential function of temperature. The measures need be taken to start up a process.
left-hand side of Equation (3.20) represents the
heat produced per unit volume of a reaction mix-
ture. The right-hand side represents the heat re-
moved per unit volume of the reaction mixture
as a result of the heat absorbed by the cold feed
and the heat transferred to the cooling medium.
The maximum temperature rise can be reached
when the system is adiabatic (no heat transfer
to the surroundings) and complete conversion is
achieved:
− (∆Hr )A cA0
∆Tad = (3.21)
cp
Figure 8. Heat production (—-) and heat removal (– – –)

Autothermal Reactor Operation. The heat in a nonisothermal CISTR for an irreversible exothermic
released during an exothermic reaction is often reaction A → R
used for preheating inlet reactant streams. A re-
actor system, in which such a feedback of reac-
tion heat to the incoming reactant stream takes LIVE GRAPH
place is said to operate under autothermal con- Click here to view
ditions. The theory of steady-state behavior of
autothermal reactors is described in [12], [13].
Multiplicity. In Figure 8 both right- (heat re-
moval) and left-hand sides (heat production) are
plotted for different inlet and operating condi-
tions. At the intersection of the heat produc-
tion (solid line) and heat removal curves (dashed
lines), Equation (3.20) is obeyed. For a certain
range of inlet parameters several solutions may
exist (multiplicity of steady states). If the heat
removal is represented by line 1 in Figure 8, the
reactor is cooled so effectively that steady-state
operation is possible only at a low temperature
and a very low degree of conversion. If the cool-
ing rate is lowered (line 2), three points of in-
tersection occur with the heat generation curve.
The two intersection points, the lowest and high-
Figure 9. Regions of multiplicity in a CISTR [5]
est reaction temperature, represent stable condi- T = Trifurcation point; ——– τ = l s; – – – τ = 0.5 s
tions due to the fact that the rate of heat removal
In Figure 9 a multiplicity region is presented Stability of Autothermal CISTR. The tran-

as a function of the maximum
temperature in- sient behavior of strongly exothermic react-
∆Tad
crease in the reactor, 1 +St . In the area ening systems may lead to unexpected, undesired
changes in a reactor. This is a result of cou-
veloped by the curves multiplicity will occur. pling between the material and energy balances
Outside, only one (stable) operating point is pos- (Eqs. 3.1 and 3.16). Detailed information on dy-
sible. Operating points located above the multi- namic behavior of autothermal systems can be
plicity region are distinguished by a high degree found in [15–17].
of conversion, those below the multiplicity re- The mass and energy balance equations
gion by a low degree of conversion. The point Equations (3.1) and (3.16) can be rewritten to:
with the lowest value of 1∆T
+St where multiplic-
ad
ity occurs is often called the trifurcation point, dζ τ RA

= −ζ + (3.22)
and the curves departing from it, the bifurcation dΘ c A0
lines.
Hlavacek et al. derived the criteria for ex- and:
istence of multiplicity of steady states for first- dT RA τ
order reactions [14]. Multiplicity occurs when =T0 −T − ∆Tad +St (Tc −T ) (3.23)
dΘ c A0
the dimensionless adiabatic temperature rise
(− ∆H ) c E where τ = V r /Φm is the average residence time,
B = cp Tr 0 A0 RT exceeds a critical value of
∗
0
Θ = t/τ is a dimensionless time, and St a modi-
B :
fied Stanton number (St = UA/cp Φv ).
1) Adiabatic case ( β̄ = 0) In the case of a first-order reaction Equations
(3.22) and (3.23) can be rewritten to:
4γ̄
B∗ = dζ
γ̄ − 4 = −ζ +ks τ (1 −ζ) e∆ϑ (3.24)
dΘ
2) Adiabatic case ( β̄ = 0); γ̄ → ∞
B∗ = 4 dϑ
= − 1 +St ∆ϑ + ∆ϑad ks τ (1 −ζ) e∆ϑ
dΘ
3) Nonadiabatic case; γ̄ → ∞ + ∆ϑ0 +St ∆ϑc (3.25)
B ∗ = 4δ̄ where:
4) Nonadiabatic case ∆ϑ0 = (T0 −Ts )
E
RT 2s
2
4 ε̄ +δ̄γ̄ E
B∗ = ∆ϑc = (Tc −Ts )
γ̄ δ̄ (γ̄ − 4) − 4ε̄ RT 2s
E
∆ϑad = ∆Tad
RT 2s
where γ̄ = E/RT 0 is a dimensionless acti-
vation energy, β̄ = UA/Φv cp is a dimen- and k s is the reaction rate constant at temperature
sionless heattransfer coefficient, δ̄ = 1 + β̄, T s.
2 (Tc −T0 ) is a di-
E When a small perturbation is imposed on a
ε̄ = β̄ Θ̄c , and Θc = RT
0
mensionless cooling temperature. steady state, Equations (3.24) and (3.25) can be
linearized as follows:
Hysteresis in Autothermal Systems. If the
feed temperature T 0 is increased at a constant d ∆ζ 1
= − ∆ζ +ζs ∆ϑ≡a11 ∆ζ +a12 ∆ϑ (3.26)
feed rate, the reaction will be ignited at a certain dΘ 1 −ζs
feed temperature (T 0 )ign and the reactor will op- and:
erate at the upper stable steady state. If T 0 is then
lowered again, the reactor continues operating d ∆ϑ ∆ϑad ζs
= ∆ζ + ∆ϑad ζs − 1 +St ∆ϑ
at a high conversion level until extinction takes dΘ 1 −ζs
place at a feed temperature (T 0 )ext . ≡ a21 ∆ζ + a22 ∆ϑ (3.27)
where ∆ζ = ζ − ζ s and ∆ϑ = ϑ − ϑs ; ζ s and ϑs 3.4. Cascade of Tank Reactors [21]

are the conversion and the dimensionless tem-
perature at steady state. Continuous stirred-tank reactors in series
The solution of Equation (3.26) and (3.27) (Fig. 11) are used when the required residence
has the form: time is long and more than one vessel is neces-
sary for efficient, economical mixing. Conver-
∆ζ =b11 ep1 Θ +b12 ep2 Θ (3.28)
sions, yields, and residence times of the indi-
p1 Θ p2 Θ
∆ϑ =b21 e +b22 e (3.29) vidual stirred-tank reactors are calculated anal-
where: ogously to those for a single CISTR. The steady-
state material balance over the nth reactor for a
(a11 +a22 ) component J reads:
p1, 2 =
2
!
4 (a11 a22 −a12 a21 ) Vrn

1± 1− ξJn −ξJ (n−1) = MJ RJn (3.32)
(a11 +a22 )2 Φm
The chemical process is stable when: In most cases, the set of equations describing
the degree of conversion in a cascade cannot be
1 + St
>ζs (1 −ζs ) (3.30) solved analytically. For a system consisting of n
∆ϑad
equal-sized CISTRs in series an analytical solu-
and: tion can be obtained for first-order irreversible
1 reactions [19]:
− ∆ϑad ζs + 1 +St > 0 (3.31)
1 − ζs
where ζ s = k τ /(1 + k τ ) in the case of first-order cAn =cA0 (1 +kτ )−n (3.33)
reaction. and for second-order reaction: cAn = 14 k τi
If the second condition (Eq. 3.31) is met, the
reactor is dynamically stable and operates at its 1
cAn = −2 + 2·
steady state (ζ s , T s ). However, if this condition 4kτi
is not satisfied the reactor is dynamically unsta- ! 
1 2
ble and operates in a fixed limit cycle around the n
steady-state point (ζ s , T s ) (Fig. 10). −1...+ − 1 + 2 1 + 4k cA0 τi · s (3.34)
LIVE GRAPH In other cases a solution has to be found by an al-

Click here to view
gebraic stepwise method or by a graphical tech-
nique [9], [20].
Example. The second-order, reversible reac-
tion 2 A C + D is carried out in a single
CISTR with total volume of 2.665 m3 . The
volumetric flow rate of reactant A is 7.866×
10−4 m3 /s, and its inlet and outlet concentra-
tions are 24.03 and 6.94 kmol/m3 , respectively.
The forward rate constant at the reaction tem-
perature is 1.156 × 10−4 m3 kmol−1 s−1 and the
equilibrium constant K is 16.0.
It now becomes necessary to replace the
working reactor with a series of identical
CISTRs. The volume of each reactor in a new
reactor arrangement should be one-tenth of the
current one. How many CISTRs are required?
Figure 10. The limit cycle in CSTR [18]

Figure 11. Continuous stirred-tank reactors in series (cascade)
Solution. The reaction rate can be expressed

as follows:
2
cA0 −cA
RA =k1 c2A −
4K
The relation between RA and cA described by

the above equation is shown in Figure 12. In ad-
dition, the balance equation
Φv
RA = cAn − cA(n−1)
Vr
is also valid for each reactor in a series.

The slope Φv /V r in the case of a new ar-
rangement is 2.95 × 10−3 s−1 . A straight line
through cA0 = 24.03 kmol/m3 with this slope
can be drawn to the intersection with the re-
action rate curve. This process has to be re-
peated until cAn = 6.94 kmol/mol is reached.
From Figure 12, the number of stages required
is 3.8. Hence four CSTRs should be used in this
case.
Figure 13. Different configurations for packed-bed reactors

A) Multitube heat exchanger; B) Multistage adiabatic reac-
tor
According to “Chemical Reactor Analysis and Design”
G. F. Froment, K. B. Bischoff, John Wiley & Sons, New
Figure 12. Graphical estimation of required number of York 1990.
CSTRs in series
4. Packed-Bed Reactors
The packed-bed reactor constitutes the keystone
in the production of several important chemicals.
Several reactor configurations are encountered
in practice (e.g., Fig. 13). The heat-exchanger
type of reactor (Fig. 13 A) is used to carry out
highly exothermic reactions. The adiabatic mul-
tistage reactor (Fig. 13 B) with cooling between
stages is used to carry out exothermic equilib-
rium reactions. The autothermal configuration,
an interesting alternative, is a heat-exchanger
type of reactor in which the reactants circulate al-
ternatively through shell and tube arrangements
with the double purpose of being preheated and
keeping the reactor operating within a prespec-
ified thermal regime by cooling it down.
The analysis of transport phenomena for sys-
tems with chemical reaction is usually based on
the transport equations resulting from the dif-
ferential balance laws. To predict global effects,
detailed information about the velocity profiles,
and temperature and concentration fields is re-
quired. This information is extracted from the
solution of the associated transport equations,
subject to pertinent boundary conditions. When
flow through a complex structure such as a Figure 14. Energy transport mechanisms in packed beds
porous medium is involved, these governing
equations are valid even inside the pores. How-
ever, the geometric complexity of a randomly
ordered particulate system prevents any general
4.1. Mass and Energy Balances
solution of detailed concentration, temperature, Mathematical models for adiabatic and nonadia-
and flow fields. Instead, some form of macro- batic packed-bed reactors have been system-
scopic balances based on the average over a atically listed in reviews by Froment [22],
small volumetric element must be employed. A Hlavacek [23], and Hofmann [24]. In these
common practice is, with the help of some em- reviews an attempt is made to classify the mod-
pirical relations, to replace the microscopic mo- els according to their complexity. Basically, the
mentum, mass, and energy balances with corre- mathematical modeling of fixed-bed reactors
sponding macroscopic equations. can be performed either through the finite-stage
Due to the distributed nature of the sys- or the continuum approach [25]. The continuum
tem, a dynamic model contains two or more approach leads to a system of partial differen-
independent variables (time and spatial coordi- tial equations in which mixing effects are ac-
nates). Simultaneously, it is important in prin- counted for in the form of mass diffusion and
ciple to include all relevant transport resistance heat conduction terms. This approach is being
(see Fig. 14) to avoid unrealistic results. Since increasingly favored, mainly due to the contin-
a very complex model may be too difficult to uous progress in computer software and numer-
solve, a number of simplifying assumptions are ical modeling.
often adopted in practice. However, care must In general, for the mathematical treatment of
be taken when choosing the adequate degree of the heat and mass transfer processes in packed
complexity for the reactor model, so as to guar- beds, with or without chemical reaction, three
antee sufficient accuracy for a given practical types of continuous models have been devel-
application. oped:
1) The single-particle model, where intra parti- particularly if it is desired to trace the dynamic
cle phenomena are accounted for separately behavior of the concentration and temperature
2) The two-phase (heterogeneous) model in fields inside the catalyst pellets, the temperature
which both phases, solid and fluid, exchange and concentration in the boundary layer must be
heat and/or mass, and such transport pro- obtained by solving the corresponding mass and
cesses are accounted for energy balances. The first step in solving these
3) The one-phase (pseudohomogeneous) fields is to determine the extent of the bound-
model in which the reactor is approximated ary layer. This can be accomplished by perform-
as a quasi- continuum model ing overall energy and mass balances across the
boundary layer. Once the thickness of the bound-
ary layer has been found (e.g., ∆r), the govern-
ing equations and their boundary conditions will
4.1.1. The Single-Particle Model be defined by:
Mass balance:
Basically the single-particle model is also a het-
erogeneous model. However, it differs from the ∂Cf
=Df ∇2 Cf (4.1)
two-phase model in that the solid phase is not ∂t
regarded as a continuum since the concentra- Energy balance:
tion and temperature distribution inside the sin-
gle pellet are accounted for. ∂Tf
g Cp, f =λf ∇2 Tf (4.2)
Consider a catalyst pellet positioned in a ∂t
flowing stream (Fig. 15). Three different regions
subject to:
can be distinguished: the bulk fluid phase, the
boundary layer surrounding the particle, and the
particle itself.
where η is the effectiveness fac-

Figure 15. Schematic of a single particle in a flowing stream tor, the subscript f denotes fluid, and
R (C s , T s ) = k ∗0 C s exp (− E a /RT ) stands for the
equation for the reaction rate [26].
Bulk Fluid Phase. The bulk fluid phase can
be modeled as a constant temperature and con- Catalyst Pellet. Similar to the analysis of the
stant concentration field. Perturbations at the in- boundary layer, the pellet itself is modeled in
let of the reactor propagate through the fluid and terms of mass and energy transport. The pellet
the conditions at the outer edge of the boundary can be either porous or nonporous; in the latter
layer change accordingly; this dynamic evolu- case there is no mass diffusion of species into the
tion of the boundary condition can be solved by pellet and only an energy balance is necessary.
using a heterogeneous model (see Section 4.1.2). For certain classes of reactions, the assumption
of nonporous catalyst is justifiable, e.g., for reac-
Boundary Layer. Temperature and concen- tions whose high exothermicity prevents the re-
tration conditions in the boundary layer are fre- action front from penetrating deep into the pellet
quently assumed to be identical to those of the even if it were porous. Under these assumptions
bulk fluid phase. This is not always the case and, the energy balance for the catalyst pellet gives:
pseudohomogeneous model, additional transfer

∂Ts mechanisms are superimposed on the contribu-
s Cp, s =λs ∇2 Ts (4.5) tions that originate from the global movement
∂t
of the fluid. These additional mechanisms are
subject to: based upon the observation that the fluid trav-
∂Ts eling between two points of the packed bed un-
= 0 at r =0 dergoes a tortuous journey that is composed of a
∂τ
∂Ts ∂Tf large number of random steps. It is assumed that
ks − λf
∂r r→R− ∂r r→R+ the transfer mechanisms resulting from this pro-
=η (− ∆Hr ) R (Cs ,Ts ) at r = R (4.6) cess can be treated as diffusion- and conduction-
like phenomena. The fact that the modeled sys-
tem is actually heterogeneous is accounted for
4.1.2. The Two-Phase Model by defining transport coefficients where both
contributions due to the solid and fluid phases
Of the two remaining models, the two-phase are considered.
model is not only more realistic but it also con- Although the two-phase models fulfill the ob-
stitutes the basis on which the derivation of the vious physical requirements of considering a
pseudohomogeneous approximation relies. system where two phases exchange mass and/or
The most important feature of this model is energy, they also contain a number of approxi-
that temperature and concentration differences mations. For instance, separation of thermal dis-
are considered between solid and fluid phases. persion effects, which in fact are interconnected,
The mass and energy transport processes are is very difficult. An even more difficult problem
governed by the following equations: arises when heat losses must be accounted for; in
Fluid phase: this case the wall heat transfer coefficient has to
be resolved into its solid- and fluid-phase com-

∂ Ci, f ponents. Ramkrishna and Arce discussed the
ε = − ε ∇ · uCi, f +ε ∇ · Df ·∇Ci, f
∂t validity of the pseudohomogeneous model to re-

+av λf, s Ci, s − Ci, f (4.7) present the heterogeneous nature of packed-beds
[28], [29].
The simplest, most obvious pseudohomoge-
∂Tf neous model was derived by Yagi et al. [30].
εf Cp, f = − εf Cp, f u ·∇Tf +ε ∇ · λf ·∇Tf These authors made use of the fact that, at low
∂t
+av hf, s (Ts −Tf ) (4.8) Reynolds number, temperature differences bet-
ween the solid and fluid phases are negligible
Solid phase: and both phases can be assumed to have the same
temperature. This approach has been general-
∂ Ci,s
(1 − ε) εp = ized, and the one-phase model is adopted, even
∂t
for high Reynolds number, based on the assump-
− η (1 −ε) s R C1,s , . . . ,Ci,s , . . . ,CS,s ,Ts
tion of equal temperatures in both phases (e.g.,
+av λf,s Ci,f −Ci,s (4.9) [31]).
∂Ts
The idea of equivalence was extended by
(1 − ε) s Cp,s = Vortmeyer et al. [32], [33] for arbitrary
∂t
Reynolds numbers. These authors combined the
η (1 −ε) s (−∆Hr ) R C1,s , . . . ,Ci,s , . . . ,CS,s , Ts
energy balances for the fluid and solid phases
+ (1 − ε) ∇ · λs ·∇Ts +av hf,s (Tf −Ts ) (4.10)
(Eqs. 4.8 and 4.10) by assuming that the driv-
ing forces for heat conduction were similar in
both phases. The main difference to the approach
4.1.3. The One-Phase Model followed by Yagi and coworkers is that Vort-
meyer and coworkers derived a dispersion term
By introduction of the effective transport con- which reflects the exchange of energy between
cept heterogeneous fluid – solid systems can be both phases; this term is added to the thermal
treated as quasi- continuum media [27]. In the
Next Page
conductivity of the solid phase to form a quan- This was proven for isothermal [39] and non-
tity which is known as the effective thermal con- isothermal [40] systems. These boundary con-
ductivity. ditions have also been shown to be adequate for
An additional assumption concerns the mass systems with a multiplicity of steady states [41].
transport between the solid and fluid phases. The They also predict the behavior of nonadiabatic
resistance to mass transfer of the film adjacent to systems satisfactorily [42] even though the num-
the solid particles can often be considered neg- ber of possible steady states in these systems
ligible; thus, the surface reactant concentration could change if the Wehner and Wilhelm ap-
can be considered similar to that in the bulk of proach is followed [43].
the fluid phase. Even though the formulation of the boundary
Under these assumptions and by combining conditions as suggested by Wehner and Wil-
both energy balances (Eqs. 4.8 and 4.10), the helm [38] appears more logical from a phys-
transport processes in the packed-bed reactor ical point of view, their correspondence with
can be considered as governed by the following Danckwerts’ suggestion for steady-state oper-
set of equations: ation of adiabatic systems has been proven [44].
Mass balance: Modifications have been proposed when radial
dispersion is also taken into account [45], and the
∂ (Ci )
ε = −ε∇ · (uCi ) +ε∇ · D e ·∇Ci boundary conditions have also been modified to
∂t
−η (1 −ε) s R (C1 , . . . ,Ci , . . . ,CS ,T ) (4.11)
treat the transient situation [46], [47].
For selection of the proper boundary and ini-
Energy balance: tial conditions for flow systems see [48][49][50].
∂T
A simple pseudohomogeneous model without
Cp = − ε f Cp,f u ·∇T +∇ · λe ·∇T (4.12) radial dispersion is now considered. The reactor
∂t
+η (1 −e) s (−∆Hr ) R (C1 , . . . ,Ci , . . . ,CS ,T ) is visualized as a tube with three distinguishable
sections (see Fig. 16): the reaction zone packed
where: with the catalyst (0 ≤ z ≤ L ), and a fore (z < 0)
and aft (z > L ) sections of inert packing. A gen-
Cp =εf Cp, f + (1−ε) s Cp,s
eral formulation of the inlet and exit boundary
An alternative two-phase model was proposed conditions can be written as:
by Carberry and White [34]. This model com- Inlet (z = 0):
bines the pseudohomogeneous and heteroge-
∂Ci ∂Ci
neous models; it is based on the catalyst par- De,z − uz Ci = De,z − uz Ci
∂z 0− ∂z 0+
ticle but uses effective transport properties. As a
hybrid between the two previous models it has (4.13)
been termed the “pseudoheterogeneous” model.
By considering the solid phase to be discontinu- λe,z
∂T
− uz f Cp, f T =
ous, this model appears to perform better when ∂z 0−

matching models. A thorough analysis of this ∂T
λe,z − uz f Cp, f T (4.14)
model is given in [35]. ∂z 0+
Exit (z = L ):
4.1.4. Boundary Conditions

∂Ci ∂Ci
Since the classical works by Hulburt [36], De,z = De,z (4.15)
∂z L− ∂z L+
Danckwerts [37], and Wehner and Wilhelm
∂T ∂T
[38] appeared, boundary conditions in packed- λe,z = λe,z (4.16)
∂z L− ∂z L+
bed reactors have received much attention. The
formulation of the boundary conditions pro- where a given approach is followed by select-
posed by Danckwerts is the most often fol- ing the diffusivities/conductivities as indicated
lowed. This formulation meets the limiting mix- in Table 4 (“yes” means parameter is included
ing conditions of the continuous stirred-tank rein the model, “no” means not included).
actor (CSTR) and the plug-flow reactor (PFR).
Previous Page
Table 4. Dispersion coefficients for different boundary conditions

nonuniform distribution of the porosity causes
the flow to be nonuniformly distributed, particu-
Parameter Hulburt Danckwerts Wehner and larly near the reactor walls [58], [59]. The inclu-
Wilhelm sion of radial porosity and velocity profiles im-
D/λe, z | 0− no no yes proves the agreement between experimental and
D/λe, z | 0+ no yes yes
D/λe, z | L − yes yes yes
theoretical results [60], [61]. It has been found
D/λe, z | L + no no yes [62], however, that the predictions obtained by
assuming constant average porosity and main-
flow velocity for the entire packed bed will be
The conditions for the mass balance at the qualitatively correct in most cases.
lateral walls are such that it is assumed that no
mass flux occurs because the lateral walls are of-
ten impermeable (radial reactors are an excep-
tion). The boundary conditions for the energy
balance, however, vary depending on whether
the reactor is operated adiabatically or nonadia-
batically. For a pseudohomogeneous model with
radial dispersion these boundary conditions are:
Reactor wall (r=R):
∂Ci
= 0 (4.17)
∂r
∂T
λe,r =hw (Tw −T ) (4.18)
∂r
Reactor centerline (r=0):
∂Ci
= 0 (4.19)
∂r
∂T
= 0 (4.20)
∂r Figure 16. Schematic of the flow system in a packed-bed
reactor
In order to use a constant average porosity,

4.2. Values of the Parameters the following integral relation must be fulfilled:
Various steps have been taken towards the R

1
derivation of an integral model for the packed- ε=
πR2
ε (r) r dr
bed reactor by considering the individual steps 0
involved in the transport of a given property in
There is no unique functional relation between
a packed bed. In this section only few correla-
the radius and the porosity, but many function-
tions for typical applications will be mentioned,
alities have been proposed in the literature. To
for more details, see [25], [51–54].
find a realistic value for the average porosity,
the approach suggested by Martin can be fol-
lowed [63]. The bed is considered to be formed
4.2.1. Average Bed Porosity
by two concentric rings with their own prop-
erties; a central core with an average porosity
The existence of oscillatory radial variations of
ε0 and a one-particle-diameter-thick concentric
the void fraction in packed beds has been recog-
shell with porosity εw . The average porosity, as
nized since the early work of Roblee et al. [55]
defined above, must satisfy the relation:
and Benenati and Brosilow [56], [57]. This
A more heuristic approach is to assume a con-

stant value for the axial and radial Bodenstein (or
ε0 A0 +εw Aw =εA
mass Péclet) numbers, i.e.,
Then, from geometric considerations, the fol- 9 :
u zd
lowing equation results: P em,z/r =
De,z/r
= constant
ε =εw − (εw −ε0 ) (1−d/D)2 where z/r denotes that the expression is valid for
both axial and radial transport.
where the porosity for the outer shell (εw ) is es- Experimental evidence has shown that axial
timated as [63]: dispersion in packed beds is typically character-
2

D/d−7/8
ized by Pem, z ≈ 2. In other words, CSTR con-
εw = 1− (1−εmin ) ditions (small Pem, z ) are reached in the void
3 D/d−1/2
within each void cell, and the packed-bed reac-
where εmin is the minimum value observed for tor can be viewed as (L /d) CSTRs in series [65].
the void fraction (εmin = 0.23 and ε0 = 0.39 are Therefore, axial mass diffusion can be neglected
taken from [56]). for ratios L /d > 50. This criterion applies to sys-
tems with particle Reynolds number larger than
unity (i.e., Rep = f uz d/µf > 1).
4.2.2. Effective Transport Coefficients Radial mass dispersion is characterized by a
constant radial mass Péclet number:
Since the effective transport coefficients are 9 :
mainly determined by the flow characteristics, u zd
P em,r = ≈ 8 − 10
in general, packed beds are anisotropic for effec- De,r
tive transport, so that the radial transport com-
ponent is different from its analogue in the axial
direction. For the sake of simplicity, effective Energy Transport. Energy transport is sup-
transport coefficients are often considered to be plemented by radiation and conduction in the
unaffected by secondary flow and dependent on solid phase. Therefore, it is more difficult to de-
the mainflow (forced) only. fine constant values for the heat Péclet numbers.
The problem of equivalence between the hetero-
Mass Transport. A correlation for the mass geneous and pseudohomogeneous models has
transport in both spatial directions is [64]: been addressed in [51], [66].
 
In general the effective thermal conductivity
9 : 0.7 C1 λe(r , z ) is formed by two contributions: the qui-
De(r,z) = u z d ×  + 
Re Sc 1 + C2 escent bed conductivity λ0s and a contribution
Re Sc
due to the flow, i.e.,
where the constants C 1 and C 2 depend on the
λe(r,z) =λ0s +Cλf ReP r
geometry of the packing and the fluid flowing
through the packed bed as listed in Table 5. where the conductivity for the quiescent bed λ0s
Table 5. Constants for the effective mass-transport coefficients [64]
is obtained from the correlation proposed by
Zehner and Schlünder [67], while the con-
Constant Liquids Gases tribution due to the flow can be found from
Spherical Irregular Spherical Irregular the analysis by Vortmeyer and Berninger
packing packing packing packing [66]. The constant in the above equation is cho-
C1 2.5 2.5 0.7 4 sen as C = 0.1 for the radial (r) direction and
(longitudinal) C = 0.1 – 0.2 for the axial (z) direction.
C 1 (radial) 0.08 0.08 0.12 0.12
C2 8.8 7.7 5.8 5.1
The equivalence between the heterogeneous
(longitudinal) and pseudohomogeneous models has been
C 2 (radial) 78 ± 20 proved for nonreactive conditions [51]. For fur-
ther information on energy transport in packed
beds see [51], [52], [68–71].
Effect of Radiation. Transport by radiation the radial temperature profiles predicted for the
is frequently ignored when estimating heat trans- solid and fluid phases. Based on the physical re-
fer coefficients. This transport mechanism de- striction that both profiles can never cross, most
pends on the temperature range for the reactor of them were discarded and only a few could be
operation; for a temperature of 600 K at the reac- considered reliable [53].
tor wall, radiation has been found to contribute The most often accepted correlation has been
up to 20 % to the overall radial heat flux [72]. presented by Dixon et al. [74]. A thorough anal-
The contribution of radiation to effective en- ysis of the estimation of this coefficient has been
ergy transport in packed beds has been analyzed presented [75]. The recommended correlation
[72], [73]. In the model presented the heat trans- has the form:
fer is considered to be controlled by two paral-
lel mechanisms and the overall effective thermal αf, w d
N uf, w =
conductivity is assumed as kf
. /
= 1 − 1.5 (D/d)−1.5 P r1/3 Re0.6 (4.21)
λe,r =λ0e,r +λr a de,r
where αf, w is the fluid-to-wall heat transfer co-
where the contribution due to radiation λr ad e, r efficient.
is
λr ade,r = 4ψσ dT 3
4.3. Further Simplifications
8
= σ dT 3 =Cr T 3
2/e−0.264
Despite its simplicity, the pseudohomogeneous
where σ is the Stefan – Boltzmann constant model has proven to be a very reliable re-
(5.67 × 10−8 J m−2 K−4 s−1 ), ψ is a shape fac- presentation for transport processes in packed
tor, and e is the particle emissivity. The treatment beds [66]. If care is taken when evaluating
of this contribution is carried out by adding an the transport coefficients, predictions obtained
additional term to the conduction term in the en- from a one-phase model will not differ signif-
ergy balance, i.e., icantly from those yielded by a two-phase re-
presentation. Every model has its deficiencies,
1 ∂ ∂T
∇ ·λe · ∇T = r λ0e,r + thus, the heterogeneous model cannot capture
r ∂r ∂r
the radial temperature and concentration gradi-
ents present in the pellets under reactive condi-
∂T
r Cr T 3 +... tions, and the pseudohomogeneous model lacks
∂r
an adequate representation of the solid phase.
1 ∂ ∂T ∂T 2
=λe,r r + 3Cr T 2 +... Windes et al. [54] have suggested an approach
r ∂r ∂r ∂r
to achieve equivalence between the pseudoho-
It is apparent that this contribution can be- mogeneous and heterogeneous models.
come important with increasing particle emis- The questions concerning equivalence stem
sivity and its omission would lead to conserva- from the fact that packed beds behave differ-
tive temperature predictions. ently under reactive and nonreactive conditions.
This was initially interpreted as a change in the
heat transport coefficients under reactive condi-
4.2.3. Wall Heat-Transfer Coefficient tions [76]. Wijngaarden and Westerterp [77]
have addressed the subject in detail and provided
The wall heat-transfer coefficient can be esti- a comprehensive explanation for the difference
mated from many correlations. The correlations between reactive and nonreactive situations. For
available, however, predict heat transfer coeffi- the mixing coefficients independence of chem-
cients which are largely scattered. For instance, ical reaction was demonstrated by Gunn and
for a particle Reynolds number Re = 100, the Vortmeyer [78].
heat transfer coefficient can differ by almost one
order of magnitude [53]. Odendaal et al. ana-
lyzed the available correlations and compared
One-Dimensional Models versus Two- Example. The above analysis is illustrated by

Dimensional Models Although radial temper- solving for the steady-state temperature and con-
ature profiles can be minimized in the design centration profiles in a typical industrial reactor
of the reactor, it is not necessary to suppress with the partial oxidation of o-xylene to phthalic
radial dependence of temperature to obtain re- anhydride as an example. This highly exother-
liable predictions with one-dimensional mod- mic process is carried out in heat-exchanger-
els. In general, the sophistication of the model type reactors. The reactor consists of a bundle of
should never exceed that of the experimental tubes with a cooling fluid circulating around the
data. For this reason, one-dimensional models tube arrangement. The process (of German ori-
have become increasingly useful. gin, but used worldwide) employs V2 O5 on sil-
Beek and Singer [79] addressed this point ica gel pellets as catalyst. The geometric descrip-
by assuming a weak parabolic radial depen- tion and kinetic information have been taken
dence of the temperature profiles on the radial from [82].
dimension. Then it can be shown that predictions If the pseudohomogeneous, two-dimensional
from a one-dimensional model equal the average model is lumped radially, i.e., if the equations
radial temperature T for a two-dimensional are integrated across the cross-sectional area, the
model [25]. The radial temperature distribution following steady-state, one-dimensional model
is then obtained as [25]: results:
T (r/R) ≈ ∂ ∂ 2 CX

0 = − (uz CX ) +De,z
∂z ∂z 2
1− (r/R)2 + (2/Bi ) 9 : 9 :
Tw + 2 T − Tw − (1−ε) s R CX , T (4.22)
1 + (4/Bi )
The equivalence between the one-dimensional

model and the radial average temperature for a ∂ 9 :
0 = − f Cp, f uz T
two-dimensional model is obtained by a proper ∂z
9 :
computation of the overall heat-transfer coeffi- ∂2 T 4U 9 :
+λe,z − T −Tw
cient. For a parabolic temperature profile: ∂z 2 D
9 :
+ (−∆Hr ) (1−ε) s R CX , T (4.23)
1 1 D
= +
U hw 8ke,r where R (C X , T ) = k 0 pO pX exp (−E a /Ru T )
represents the rate of reaction, and pX and
A more refined approach was followed by
pO represent the partial pressures of o-
Crider and Foss [80], who solved the heat
xylene and oxygen, respectively. The reac-
transfer problem analytically under nonreac-
tion is performed in excess oxygen (i.e.,
tive conditions. The equivalence of one/two-
pO /ptot = 0.21 ≈ constant). Although the reac-
dimensional models was achieved by combining
tion mechanism for this process is completed
the radial heat-transfer parameters as follows:
by parallel and consecutive reactions, only the
1 1 D main reaction is addressed here.
= +
U hw 6.133λe,r The results obtained with the one-
dimensional (Eqs. 4.22 and 4.23) and two-
This was later confirmed by Hlavacek et al. [81] dimensional models are presented in Figure 17
who solved the linearized problem and found for two different operating conditions. The one-
identical results. An important theoretical con- dimensional model predicts reactor behavior
clusion can be drawn from this last observation; satisfactorily for the conditions of Figure 17 A
as long as only small radial temperature gradi- (Tw = 630 K). For the conditions of Figure 17 B
ents exist, the chemical reaction only seems to (T w = 645 K), however, the differences between
have a significant effect on the axial temperature this model and the two-dimensional models are
dependence. Under these circumstances, the ra- significant. This can be better understood by
dial temperature dependence can be described analyzing the results presented in Figure 18
via a radially lumped model. where the radial temperature profile is shown
as a function of radial position r/R at different
axial locations. The high-temperature situation tion, the temperature rises sharply in the catalytic
(Fig. 18 B) shows the nonlinear effect of the bed towards a maximum or hot spot (usually lo-
reaction rate and the temperature profile devi- cated near the reactor inlet). These sharp axial
ates markedly from a parabolic dependence(as temperature gradients can cause poor reaction
shown Fig. 18 A). These results show that, for selectivity and extreme temperatures can be re-
mild radial dependence of the temperature dis- sponsible for rapid deactivation or even deteri-
tribution, one-dimensional models can be used oration of the catalyst. Therefore, the hot spot
as a reliable design tool. must be kept within permissible bounds. Fur-
thermore, the attainable conversion frequently
LIVE GRAPH
Click here to view has an upper safety limit at levels where the
temperature profile becomes extremely sensitive
to changes in operational and/or physicochem-
ical parameters. Bilous and Amundson [83]
termed such a reactor condition as “parametric
sensitivity”. Many studies have been reported on
the prediction of this phenomenon, which in turn
can lead the reactor to runaway operation [23],
[84]. The danger inherent in running such sys-
tems is widely recognized, and the final reactor
design must guarantee a safe mode of operation.
Most studies on parametric sensitivity have
assumed constant temperature for the cooling
medium [85–91]. This is a suitable approach for
perfectly mixed coolant, or reactors employing a
LIVE GRAPH
Click here to view boiling liquid or a fluid of abnormally large heat
capacity as cooling medium. However, in the
more common case of molten salt circulation,
the thermal gradients in the shell side cannot be
neglected in the reactor model. Few papers have
studied the nonisothermal situation. For more
information; see [92–106].
Example. Consider again, the production of

phthalic anhydride via partial oxidation of o-
xylene in a multitube heat-exchanger-type re-
actor. The steady-state operation will be de-
scribed by the one-dimensional pseudohomoge-
Figure 17. Comparison between one- and two-dimensional neous model (Eqs. 4.22 and 4.23). Parametric
models sensitivity can be estimated as originally pro-
A) Tw = 630 K, x x, 0 = 0.00924; B) Tw = 645 K, x x, 0 = posed by Bilous and Amundson [83]. It is com-
0.00924
a) Two-dimensional model; b) Crider and Foss model (one- puted as the derivative of the variable to be ana-
dimensional; c) Beek and Singer model (one-dimensional) lyzed with respect to one of the physicochemical
Open circles in Figures 17 A and 17 B denote axial locations parameters of the process. Thus, the parametric
for curves shown in Figures 18 A and 18 B, respectively. sensitivity (Sij ) of the variable χi with respect
to the parameter πj is defined as:
∂χi
4.4. Parametric Sensitivity Sij =
∂πj
Since the 1960s, great improvements have been In what follows the effect of the reactor wall
made in the design and operation of catalytic temperature on the reactor thermal condition is
reactors. In industrial conditions, however, due analyzed, i.e., π = Tw and χ = T . This is a typ-
to the high exothermicity of the chemical reac- ical problem found in industrial practice where

Figure 18. Radial temperature profiles

A) Tw = 630 K, x x, 0 = 0.00924; B) T w = 645 K, x x, 0 = 0.00924
the thermal state of the reactor is monitored (i.e.,

the observed variable would be the readouts of ∂
the reactor thermocouples) and the operator acts 0 = − f Cp,f uz ST
∂z
on the cooling fluid (i.e., the manipulated vari- ∂ 2 ST 4U
able would be the temperature or coolant flow +ke,z − (ST −1)
∂z 2 D
rate) to keep the reactor operating near the de- ∂R
sired state. + (−∆Hr ) (1−ε) s (4.25)
∂Tw
In order to obtain numerical values for the
parametric sensitivity of the reactant concentra- where:
tion (SC ) and the bed temperature (ST ), the gov-
∂R Ea
erning equations are differentiated with respect =k0 pO SC +pX 9 :2 ST
∂Tω Ru T
to the wall temperature, i.e., 9 :
exp −Ea /Ru T
∂ ∂ 2 SC
0 = − (uz SC ) +De,z
∂z ∂z 2 If Equations (4.24) and (4.25) are integrated
∂R simultaneously with the reactor model (i.e.,
− (1−ε) s (4.24)
∂Tw Eqs. 4.22 and 4.23), the sensitivity of the reactant
conversion and bed temperature to changes in
the coolant temperature is obtained at any point parametric sensitivity; a 1 K rise in the inlet tem-
of the reactor length. Of these two sensitivity perature is sufficient to drive the reactor away
profiles, only ST (z) guarantees a safe mode of from a safe operation regime. Figure 19 A, on the
operation. other hand, only shows a small difference in the
The four additional boundary conditions reactor thermal state after a change of 5 K in the
needed are derived from the original boundary inlet temperature. Indeed the 5 K temperature
conditions, i.e., increase is transmitted almost linearly along the
Inlet, z = 0: reactor. These two situations can be better under-
stood by inspecting the normalized temperature
∂SC sensitivity associated with the lower inlet tem-
0 = uz SC −De,z (4.26)
∂z perature operating condition. In Figure 19 A the
f Cp, f uz =f Cp, f uz ST −ke,z
∂ST
(4.27)
temperature sensitivity remains almost constant
∂z along the reactor, i.e., the temperature profile
Exit, z = L: should experience an almost constant increase
for a temperature rise at the inlet of the reactor.
∂SC ∂ST In Figure 19 B, on the other hand, the temper-
0 = = (4.28)
∂z ∂z ature is predicted to grow dramatically in the
vicinity of the hot spot. Furthermore, the sen-
sitivity crosses to negative values after the hot
LIVE GRAPH
Click here to view spot axial location; this suggests a temperature
overshoot promoting a high degree of conversion
and mostly cooling afterwards. Indeed, the tem-
perature profiles corresponding to the higher in-
let temperature confirm the predictions extracted
from analyzing the temperature sensitivity.
4.5. Flow Field Description

Usually the flow distribution in unbounded
porous media is assumed to be well represented
by a linear relation between the pressure drop
LIVE GRAPH
Click here to view and the fluid velocity ( Darcy’s law). When us-
ing such an approximation, however, two main
points are disregarded:
1) Effect of the boundaries on the flow field
2) Increasing importance of the inertial effects
as the flow speed increases
If the fluid obeys the Boussinesq approxima-
tion, the flow field will be governed by [110]:
∂u µf
f = −∇p − u
∂t κ
Figure 19. Parametric sensitivity in packed-bed reactors for
1
different inlet temperatures and x x, 0 = 0.019 −f β1 (T − T0 ) +β2 (C0 −C) g (4.29)
C0
A) T w = 620 K and 615 K; B) T w = 626 K and 625 K
In Figure 19 the axial temperature profiles for the

previous example are shown for two different in- ∇·u= 0 (4.30)
let temperatures and the normalized temperature which is known as the Darcy – Oberbeck –
sensitivity associated with the lower inlet tem- Boussinesq model for flow through a porous
perature. Figure 19 B illustrates the concept of medium [111].
As the flow speed increases, the inertial terms u = [0,uz ] (4.34)

become important and the results of Darcy’s
model are inefficient in describing the momen- Inlet (z = 0):
tum transfer in packed beds. The flow through u = [0,uz (r)] (4.35)
porous media is now said to be described by a
“modified” Darcy’s law: Exit (z = L):
u = [0,uz (r)] (4.36)
∂u 1 µf
f + u · ∇u = −∇p − u
∂t e κ

1
−f β1 (T −T0 ) +β2 (C0 −C) g (4.31)
C0
4.5.2. Permeability and Inertia Coefficient
where the inertial forces are represented by the
term u · ∇u. Even though this term arises from a The pressure drop in a porous medium can be
formal volume averaging in the point field equa- approximated by the Ergun correlation, a lin-
tions [112], its inclusion may lead to inconsisten- ear combination of the Carman – Kozeny and
cies between boundary conditions and govern- Burke – Plummer equations [117]:
ing equations [113]. Forchheimer [114] first
∆p 150 (1−ε)2 1.75 (1−ε) 2
proposed addition of higher order inertial terms = µuz + uz
H ε3 d2 ε3 d
to the relation between pressure drop and fluid
velocity and modified Darcy’s equation to: However, for a certain range of fluid veloci-
ties, a linear dependence of the pressure drop on
dp the fluid velocity (namely, the Carman – Kozeny
+a1 uz +a2 (uz )2 = 0
dz term) provides a reliable representation descrip-
Later he added a third-order term to fit exper- tion. Thus, as Darcy’s law proposes a linear de-
imental data. Forchheimer’s modification for pendence between pressure drop and fluid veloc-
the one-dimensional flow can be formalized for ity, the above equation can be used to estimate
two and three dimensions as [115], [116]: the packing permeability κ and the Forchheimer
correction term b as:
µf f
∇p − f g + u + bu |u| = 0
κ κ d2 ε3
κ=
150 (1−ε)2
where b can be considered a structure property
associated with inertia effects in the porous ma- 1.75d
b=
trix. Then the momentum equation becomes: 150 (1−ε)
∂u µf f
f = −∇p − u − bu |u|
∂t κ κ 4.5.3. Thermal-Expansion Coefficient

1
−f β1 (T − T0 ) +β2 (C0 −C) g (4.32) The thermal-expansion coefficients are tabu-
C0
lated for most of the fluids of interest. When not
available, a satisfactory estimation can be ob-
tained for gaseous fluids by resorting to the ideal
4.5.1. Boundary Conditions gas law. For instance, the expansion coefficient
for temperature variations can be approximated
Only two boundary conditions are necessary to as:
solve the momentum equations. The classical pM
=
nonslip boundary conditions are imposed on the RT
solid walls and a given velocity profile is im- ∂
posed at the entrance and exit of the reactor, i.e., =
∂T T
Reactor wall (r = R):
then:
u = [0, 0] (4.33) 1
β1 ≈ ≈ 10−3
T0
Reactor centerline (r = 0):
4.5.4. Mass-Expansion Coefficient phenomena. All these temperature excursions

may disappear or be too small to drive the sys-
The expansion coefficient for concentration tem out of control. However, the development of
changes is not as readily obtained as its tempera- thermal stresses during these temperature excur-
ture analogue. A satisfactory estimation can still sions adds a new factor to the reactor design and
be obtained by assuming ideal gas behavior. For operation. The mechanical behavior of the cat-
instance, for a binary mixture A + B where the alyst pellet can be analyzed following the basic
reaction A → B takes place, the fluid density can theory of elastic behavior of solids (see [118]).
be written as: For a general situation the equations can be writ-
ten as:
1
=0
1 +cCA y
Energy balance:
where c stands for a combination of the initial ∂T

s Cp, s =ks ∇2 T
and final molar masses: ∂t
∂
Mi −Mf − (3λ + 2µ) αT0 (∇ · u) (4.37)
c= ∂t
Mf
Thermomechanical equations:
If c < 0, then a lower molar mass product is
formed in the chemical reaction (for instance, a ∂2 δ
s =µ∇2 δ + (λ +µ) ∇ (∇ · δ)
decomposition reaction). In contrast c > 0 would ∂t2
indicate the formation of a product with a higher − (3λ + 2µ) α∇T (4.38)
molar mass (for instance, a polymerization reac-
tion). subject to:
If a perturbation is considered in a situation
δr = 0 at r = 0
where no conversion has been achieved (i.e.,
ξ → 0), the gas density can be represented in a σrr = 0 at r = R (4.39)
linear approximation as:
where λ and µ are the Lamé constants, α is the
=0 (1−β2 CA ξ) coefficient of linear expansion, T 0 the tempera-
ture of stressless condition, δ is the displacement
Taking into account that c < 1 and ξ < 1, the de- vector, and σrr are the radial stresses.
pendence of the density on the conversion can Thus, the energy balance has been augmented
be written as: from its previous form (i.e., Eq. 4.5 in Section
4.1.1), by an additional term. This term repre-
≈0 (1−cCA ξ) sents what is known as thermoelastic dissipa-
then: tion. Nevertheless, the temperature fluctuations
due to deformations are usually small and, for
β2 ≈ c most situations, they can be neglected. A more
systematic criterion is to neglect the thermoe-
In the case of a reaction in the liquid phase, the lastic dissipation term whenever the inequality
density must be determined from an appropriate below holds:
equation of state, and the expansion coefficients
should be found experimentally. (3λ + 2µ)2 α2 T0
<< 1
(λ + 2µ) s Cp , s
4.6. Thermomechanical Effects in the Another noticeable feature of the above equa-
Reaction System tions is the hyperbolic nature of the thermoelas-
tic equations. There is a close connection bet-
Several phenomena can be observed when an- ween the coupling discussed previously and ne-
alyzing the dynamic behavior of catalytic and glection of the inertia term in the equation of
noncatalytic packed-bed reactors, e.g., “para- motion. Indeed, the possibility of omitting the
metric sensitivity”, “wrong-way” behavior, trav- coupling terms does not depend only on satisfy-
elling reaction fronts, and ignition and extinction ing the previous indicated inequality, but also on
the fact that the strain rates must be of the same cal connectivity exists between the grid points;
order as the cooling or heating rates. This implies thus, in a two-dimensional situation each grid
that the temporal behavior of the displacement point is surrounded by eight neighbors. Because
vector closely follows the dynamic behavior of of this structure, a duality exists. Instead of look-
the temperature field. In other words, no pro- ing at grid points, every four-point group could
nounced lag or vibrations in the motion of the be seen as a quadrilateral cell. Discretization of
body must arise. Under these circumstances, the the physical domain will thus be seen as con-
inertia term can be neglected and the equations structing a collection of cells covering the entire
become decoupled [119]. domain.
This model is completed by the compability However, efficiency in distributing these ob-
and equilibrium equations (see Chap. 8 in [118]). servers should be the guiding principle; a lim-
ited, fixed number of grid points or grid cells
should be arranged in such a way that the largest
4.7. Numerical Simulation possible amount of information can be extracted
from their use. First, the geometry of the physical
Due to the strongly nonlinear nature of the equa- domain should be approximated in an accurate
tions describing reactive flows, up to now ana- way and, second, the grid points should be able
lytical techniques have failed to produce solu- to monitor all essential features of the evolving
tions for the full form of the governing equations. solution without leaving gaps in any region of
Nevertheless, considerable progress in under- importance.
standing reaction systems has been made pos-
sible through the application of analytical tech-
niques to some limiting situations. For instance, 4.7.1. Discretization of the Physical Domain
since 1980 a wealth of information has been ac-
cumulated that shows results based on the use of In recent years the method of Orthogonal Col-
large activation energy asymptotics. Although location (OC) [120] has been used successfully
credit should be given to similar approaches for in cases of moderate values of the Damköhler
providing physical insight into many reaction number [31] even when the system is highly
problems, the models described are simplified sensitive to changes in the operating conditions
and limitations on the techniques clearly exist. [62]. However, this approach gives inappropri-
To overcome these limitations the systems of ate results at large values of the Péclet and/or
governing equations, together with the appro- Damköhler numbers when boundary layers as-
priate boundary conditions, must normally be sociated with the flow and/or chemical reaction
solved by numerical techniques. exist.
For the application of numerical methods, a Certainly, in combustion-type problems most
number of grid points are distributed over the of the important physics is often restricted
physical domain or the domain is cut up into to small parts (or “boundary layers”) inside
small pieces (cells). The discretization of the the domain. For problems of this type Finite-
governing equations yields a system of algebraic Difference (FD) methods are superior to OC
equations expressing relationships between val- methods because a large number of grid points
ues of the different variables at neighboring grid can be used and computations can still be ef-
points. fectively performed through tri-, penta-, and/or
Because of finite computer resources, it is not nano-diagonal matrix calculations.
possible to monitor the solution at every point of By combining the low truncation error prop-
the region in the space on which the problem has erties of OC methods and the ability of FD to
been defined. A finite number of grid points is locate grid points where needed, Carey and
therefore distributed over the field. Each of these Finlayson [121] proposed a piecewise repre-
points acts as an observer, monitoring the solu- sentation of the profiles. This method known
tion locally and relaying information about it to as Orthogonal Collocation on Finite Elements
its neighbors. In most situations a regular, logi- (OCFE) divides the domain into elements where
the properties are expanded locally in terms of The second approach is known as the Control
orthogonal polynomials. The OCFE method is Volume Formation (CVF). It takes into account
very efficient when dealing with single boundary the fact that the governing equations frequently
layers [121], [122] and one-dimensional propa- represent the conservation of a transported quan-
gation phenomena [123]. Although the OCFE tity for an infinitesimally small control volume;
methods possess several advantages, they have thus, the conservation equations can easily be
some undesirable features such as the drastic in- written for any arbitrary control volume of fi-
crease of the bandwidth with the consequence nite size. The approach consists of dividing the
of high memory and computer time require- physical domain into smaller “cells” and rewrit-
ments for some two-dimensional problems. In ting the governing equations for these finite-size
particular, this method is clearly outclassed by control volumes. In what follows, compressibil-
FD methods when multiple two-dimensional ity effects are neglected and the fluid and solid
boundary layers displace and deform in time. In heat capacities are assumed to be constant.
such situations, a generalized mesh is usually the The conservation law (the energy balance, for
proper domain discretization. To discretize the instance) applied to a control volume V is
governing equations on generalized meshes, FD
∂
schemes have proven simpler and exhibit several Cp T dV = − ∇ · f Cp,f uT
advantages for efficient programming. ∂t
V V
−λe ·∇T ] dV

4.7.2. Discretization of the Governing
+ (−∆Hr ) R (C1 , . . . , Ci , . . . Cs , T ) dV (4.40)
Equations
V
Once the physical domain has been discretized The convective and conductive transport terms
appropriately and a way has been chosen to can be rewritten by using the Gauss divergence
change the grid points locations in response to theorem as:
the evolving solution, the governing equations . /
can be approximated on the so constructed gen- − ∇ · f Cp,f uT − λe ·∇T dV
eralized mesh. The use of a generalized mesh V
makes approximation of the governing partial 0

differential equations more complicated than it = n · f Cp,f uT − λe ·∇T dS (4.41)
would be on an orthogonal cartesian or polar s
grid. Two different approaches have been fol- where S is the surface enclosing the control vol-
lowed to discretize the equations in a generalized ume V and n is the outward unit normal vector
coordinate system, each having its own merits on S.
[124]. If the control volume moves and deforms in
The first approach is based on the transforma- time, and a Lagrangian approach is followed, the
tion of the governing equations to the general- integral of the time-dependent term becomes:
ized curvilinear coordinates. Since the transfor-
mation involves additional terms (“cross deriva- ∂
Cp T dV =
d
Cp T dV
tives”) and variable coefficients (“metrics”), the ∂t dt
V V
resulting equations become more complicated. 0

The additional terms appear because of the − n· us Cp T dS (4.42)
nonorthogonality of the curvilinear coordinates s
in the physical space. Depending on the rear-
where us is the velocity at which the enclosing
rangement of the different terms after substitu-
surface S moves and/or deforms.
tion of the transformation relations, the result-
Then, the integral form of the governing
ing transformed equations can be obtained in a
equations for the control volume V can be rewrit-
conservative or nonconservative form. For more
ten as:
information, see [125].
Mass balance: mum temperature in the reactor is given by cat-

0 alyst deactivation (heterogeneous systems) or by
d mechanical properties of the reactor tube (homo-
ε Ci dV − ε n· [(u − us ) Ci ] dS
dt geneous systems); maximum feed in the reactor
V s
0 may be limited by the capacity of downstream
+ε n· De ·∇Ci dS distillation columns, etc. The optimum design
s
of the reactor must maximize the performance
− R (C1 , . . . , Ci , . . . , CS , T ) dV (4.43) and consider the process constraints. The param-
V eters entering into the optimization calculation
can have different effects, some may have only
Energy balance: a marginal effect while others can be critical for
0 the optimization.
d
Cp T dV = − n· (u − us ) ε f Cp,f T dS The selection of the criterion of optimality
dt
V s (also known as objective function or perfor-
 
0 0 mance index) is crucial for design but somewhat
+ n· (us (1 − ε) s Cp,s T ) dS − n· λe ·∇T dS  arbitrary so the decision to select a certain crite-

s S rion will always have a “fuzzy” character.
+ (−∆Hr ) R (C1 , . . . , Ci , . . . , CS , T ) dV (4.44)
V
5.1. The Objective Function for
The discretization of the governing equations Chemical Reactors
now consists of approximating the integral form
on the generalized mesh formed by quadrilateral The objective function of a chemical reactor
cells. These last forms of the equations are ex- can have different forms. A list of functions as
tremely useful since continuity of fluxes through suggested by Edgar and Himmelblau [126] is
the boundaries of neighboring control volumes given below:
can be easily ensured. Conservation of the trans-
ported quantity, even for the discrete numerical 1) Maximum conversion in a given equipment
approximation, will thus be maintained. 2) Maximum production per batch
3) Minimum time of operation for a prescribed
conversion
5. Optimization of Chemical 4) Maximum profit with respect to volume
Reactors 5) Minimum consumption of energy
6) Minimum reactor volume with respect to cer-
Optimization means calculation of the “best tain concentrations
way” of operating a particular unit where a 7) Maximum concentration by adjusting opti-
chemical reaction takes place. A number of pa- mal temperature profile
rameters must be chosen during the design pro- 8) Maximum selectivity for given feed
cess of a chemical reactor; for instance, inlet 9) Minimum operating cost for a running chem-
temperature and concentration of reacting com- ical reactor
ponents, residence time, temperature of the cool- Typical independent variables are: pressure,
ing liquid, size of the catalyst particles, and di- inlet temperature and concentration, flow rate of
mension of the reactor tube. All these parameters the feed, temperature of the cooling system, and
may have a critical effect on a particular design. diameter of the catalyst pellets.
The optimization process usually includes eco- Frequently, the objective function has a com-
nomical factors in a direct or indirect way. In plex character. It may be desirable, for example,
practical calculations there are many physical to maximize profit and minimize pollution of the
or technical constraints. For example, the com- environment. Here two objective functions are
position of the inlet mixture of reacting gases introduced and the problem is called optimiza-
must be outside of explosion limits; the maxi- tion of a vector objective function. To solve this
problem an efficient point is defined [127]. The the reactor problem is sought which only consid-
system is said to be working at an efficient point ers the important parameters. A quasi-optimal
when a particular scalar objective function can- solution can be very close to the optimum one,
not be optimized further without degrading the and has the advantage that the operating parame-
optima reached for the remaining functions. ters can be easily adjusted and safely controlled.
Mathematically, the optimization problem
can be formulated in the following way. A given
objective function must be maximized: 5.2. Elementary Optimization Problems
F (x1 , x2 , . . . , xn ) = 0 5.2.1. Optimization of a Batch System
subject to the following relations:
A mass balance for the consecutive reaction:
gi (x1 ,x2 , . . . ,xn ) = 0 with i = 1, 2, . . . , r < n
and constraints:
can be easily integrated and the solution for
hj (x1 , x2 , . . . , xn ) ≥0 with j = 1, 2, . . . , m the concentration of B, C B is:
Mathematically, the description of the problem k1 . −k1 t /
0
CB = C A e − e−k2 t (5.1)
is represented by algebraic equations (e.g., for k2 −k1
the nonisothermal CSTR), ordinary differential
equations of initial value type (for the non- where C 0A is the initial concentration of A. The
isothermal packed-bed reactor), nonlinear dif- maximum concentration of B, C ∗B , can be cal-
ferential equations of boundary value type (adia- culated by differentiation and solving for:
batic packed-bed reactor with external heat ex- ∂CB k1 . /
changer), or parabolic partial differential equa-
0
= CA k2 e−k2 t −k1 e−k1 t = 0 (5.2)
∂t k2 −k1
tions (packed-bed tubular reactor). Frequently,
in reaction engineering, these descriptions are i.e.,
highly nonlinear because of the complex ki-
1 k2
netic expressions and exponential dependence t∗ = ln (5.3)
k2 −k1 k1
on temperature of kinetic, adsorption, and equi-
librium constants. where t ∗ is the time for the batch operation
The mathematical techniques used to solve resulting in maximum production of B. The
the optimization problems in reactor design most maximum concentration of B achievable under
often reported in the literature are [128]: t ∗ conditions can be calculated by substituting
Equation (5.3) into Equation (5.1), i.e.,
1) Differential calculus
k2 /(k1 −k2 )
2) Nonlinear programming ∗ 0 k2
CB =CA (5.4)
3) Variational methods and maximum principle k1
4) Dynamic programming
5) Optimization via repeated simulations If the activation energies of both reactions are
different, the maximum selectivity is also a func-
An important aspect in optimum design of tion of the temperature T . The maximum con-
chemical reactors is the parametric sensitivity centration of B can then be calculated from the
of the solution. The multiparametric problems condition:
are often so complex that direct optimization can
∂CB ∂CB
be an unaffordable, time- consuming task. How- = = 0 (5.5)
∂t ∂T
ever, qualitative analysis of the problem could
indicate that only few independent variables sig- This problem cannot be solved analytically and
nificantly affect the solution and that the opti- Equation (5.5) must be solved numerically by
mum solution is rather insensitive towards some a suitable method (e.g., Newton – Raphson) to
of the other variables. Very frequently, in the obtain t ∗ and T ∗ (where T ∗ is the reaction tem-
industrial environment, a quasi-optimization of perature which results in a maximum production
of B). The maximum concentration C ∗B can then The optimization problem consists of finding
be calculated from Equation (5.1) after insert- the optimal residence time and operation tem-
ing t ∗ and T ∗ . The procedure described above perature to maximize the production of C, C ∗C .
can be followed for any arbitrary sequence of An analytical expression for C C can be found
first-order equations that can be integrated ana- as:
lytically. For a complex nonlinear reaction rate
scheme, a simple search approach can be fol- k1 k4
CC = ·
lowed; for a given temperature the problem is in- kA −k4

tegrated numerically as an initial value problem 1 − e−(k4 −k5 )t 1 − e−(kA −k5 )t

− e−k5 t (5.8)
and t ∗ is determined for ∂CB /∂t = 0. Repeating k4 −k5 kA −k5
the calculation for different values of T, a one-
dimensional search for the optimum condition where k A = k 1 + k 2 + k 3 . The problem can be
in T will result in the values of t ∗ , T ∗ , and C ∗B . solved by a search method via, for instance, the
gradient method (→ Mathematics in Chemical
Engineering, Chap. 10.). The results have been
5.2.2. Optimization of a Continuous System summarized in Table 7.
(CSTR) As can be seen from Table 7, the gradient
method converges slowly and the maximum is
If the consecutive reactions described in Section rather flat in t and T . Evidently, t = 0.40 s, and
5.2.1 are carried out in a CSTR, in a similar way T = 773 K can be chosen as reaction conditions.
it can be found that: In this case only 0.014 is lost in selectivity; the
t∗ = √
1
(5.6)
reaction, however, can be carried out at a tem-
k1 k2 perature that is 200 K lower than the optimum
1
temperature. This represents a major energy sav-
∗ 0
CB = CA - 2 (5.7) ing. On the other hand, the residence time is five
k2 /k1 + 1 times higher than at optimum temperature which
represents higher investment cost.
5.2.3. Optimization of Complex Systems:
Illustrative Example
5.3. Optimization of Reactors by the
Consider the following reaction scheme: Search Method
The optimization of a multiparametric reac-

tion system can be accomplished by the search
method. For more information, see [126].
The simplest gradient method is sufficient to
illustrate the principle of the search technique.
All reactions are first order with the rate con- A new approximation is always selected in the
stants ki given in the form: gradient direction ∇F (x), i.e.,

Ei 1 1
ki = k0,i exp − − xk+1 = xk +hk ∇F xk (5.9)
Ru T 658 K
The preexponential factors and activation ener- where the value of hk is selected in such a way
gies are given in Table 6. that:
Table 6. Values of preexponential factors and activation energies
F xk+1 < F xk (5.10)
Kinetic values Reaction
1 2 3 4 5
This method can be easily used for problems
where the gradient of the function can be calcu-
k 0, i , s−1 1.02 0.93 0.39 3.28 0.08
lated analytically. Otherwise, the gradient must
E i , kJ/mol 67.00 58.70 62.80 41.90 62.80
be calculated numerically by finite differences.
Table 7. Course of iterations using the gradient method
Iteration no. T, K t, s C C , kmol/m3 T, K t, s C C , kmol/m3
0 1073 0.50 0.019 773 0.5 0.406

1 909 0.10 0.414 773 0.45 0.409
5 915 0.12 0.422 773 0.4 0.409
16 983 0.076 0.423 858 0.19 0.419
29 983 0.076 0.423 983 0.076 0.423
33 983 0.076 0.423 983 0.076 0.423
The rate of convergence of the gradient require a volume 500 times larger. A disadvan-
method is good if the initial point is far from tage of activated coke is that there is the possi-
the optimum; close to the optimum, however, bility of combustion in the presence of NO. This
the rate of convergence becomes very slow. The can be prevented by careful reactor temperature
search by gradient method can be used easily control, i.e., the adiabatic temperature increase
for parameters with continuous values, compli- in the reactor must be kept low.
cations arise for integer-value parameters (e.g., Feed Temperature. The reaction rate is de-
number of adiabatic reactor stages). The sim- scribed by a Langmuir – Hinshelwood kinetic
plest way to overcome this problem is to perform expression, thus the reaction rate is not very de-
a gradient search for a sequence of fixed integer pendent on temperature. The rate of the surface
value parameters and compare the results. reaction increases with the temperature; how-
ever, the surface concentration is then lowered
Illustrative Example [129]. Optimum oper- because of desorption. The rate of the reverse
ating conditions are to be found for a reactor in reaction:
which nitrogen monoxide is oxidized to nitrogen
dioxide. A dilute mixture of nitrogen monoxide 2 NO −→ N2 + O2
(1.5 vol % NO) in air is fed into the reactor at
a rate of 50 t NO/d. The following parameters can be neglected at temperatures below 200 ◦ C.
should be optimized: catalyst type, feed com- The exit temperature from the high-temperature
position, dew point of the inlet mixture, feed reactor is 250 ◦ C, the outlet gas is cooled by wa-
temperature, temperature control in the reactor, ter to 20 – 30 ◦ C. Cooling the inlet gas to the
pressure, recirculation ratio, pressure drop, de- reactor below 20 ◦ C would require new cooling
gree of conversion, mass velocity, diameter of equipment which would increase the investment
the catalyst pellets, number of catalytic stages, costs.
and length and diameter of the catalyst bed. Dew Point of Feed. Water is a catalyst poison
A number of parameters listed here can be for the oxidation of nitrogen monoxide both on
chosen a priori based on the information about silica gel and activated coke. For a reaction gas
the process. having a dew point 0 ◦ C the amount of catalyst
Initial Concentration. The initial concentra- must be doubled compared with dry gas feed.
tion is 1.5 vol % NO. This is an equilibrium For a dew point of − 30 ◦ C the amount of cata-
concentration which results from synthesis of lyst required increases only by 10 %. Water can
NO from N2 and O2 at ca. 2200 ◦ C. The con- be removed from the inlet gas by drying it in
centration of NO in the inlet gas can be in- an adsorption drying column packed with silica
creased by liquefaction and subsequent distilla- gel.
tion. This modification would increase the pro- Temperature Control in the Reactor. The
cessing costs. adiabatic temperature increase for 98 % conver-
Catalyst Type. Experimental results indicate sion of 1.5 vol % NO in the feed is only 28 ◦ C.
that activated coke is a very good catalyst be- Part of the reaction already occurs in the dry-
cause it significantly increases the reaction rate. ing column (50 % conversion). The temperature
Silica gel is also a suitable catalyst, however, the increase involved (14 ◦ C) does not promote un-
reactor volume must then be 21 times larger. The desirable catalyst oxidation. An adiabatic mul-
homogeneous reactor (without catalyst) would tistage reactor can thus be used for the reaction.
Recirculation. A simple calculation indicates To estimate the catalyst cost (C C ), the life of the
that the reaction is completed after one pass so catalyst is assumed to be five years. Therefore,
recirculation is not necessary. for $ 0.2 per kilogram of catalyst the cost is
Reactor Pressure. Doubling the pressure ap-
proximately doubles the reaction rate and halves CC = 0.018W
the amount of catalyst required. However, since
the mixture is strongly diluted, compression will where W is the mass of the catalyst.
be more expensive than the saving due to a The loss C N that is due to unconverted NO
smaller reaction volume. Therefore, the inlet ($ 2.40/100 kg NO) is
pressure is chosen such that it only compensates
CN = 3.59 × 105 (1 −ξ)
for the pressure drop in the reactor.
Data for Calculation. The rate of oxidation where ξ is the degree of NO conversion in the
of NO is described by Langmuir – Hinshelwood feed.
kinetics as: The overall cost is
p2NO pO2
R= Y =CR +CV +CT +CS +CC +CN
a +bp2NO +cpNO2 +ωpH2 O
The governing equations are described by the The optimization calculation performed here
one-phase model (see Section 4.1.3) and the was based on repetitive calculations of the re-
pressure drop by the Ergun correlation (Section actor using the Box – Wilson method [130] in
4.5.2). which the base point of the first set of trials
The reactor costs C R are given by: should be arbitrarily chosen. The range of the
first set of trial points in the factorial design
0.648
CR = 0.99 128.5tsw DHt + 77.2tdh D2 should be quite narrow. Preliminary calculations
made by varying one factor at a time indicate
where t sw is the thickness of the cylindrical side certain ranges within which the optimum point
wall, D the internal diameter of the reactor, H t probably lies. These ranges are used directly as
the total length of the reactor, and t dh the thick- the upper and lower levels in a two-level facto-
ness of the dished reactor head. The reactor is rial experiment (see Table 8). The half-replicate
designed to withstand 140 kPa overpressure. experiments, the radial line trials, and the factor
The ventilator costs C V are: levels are given in Tables 9, 10, 11, respectively.
∆Pr
CV = 22 900 Table 8. Two-level factorial experimental design
(∆Pr + Pe − 0.579)0.915
Standarized Natural Factor level
where ∆Pr is the pressure drop across the reac-
tor and Pe is the total pressure in the bulk stream variable variable −1 +1
at the reactor exit. x1 y 0.97 0.99
The turbine costs C T are: x2 Ga 200 400
x3 D pb 0.025 0.050

∆Pr x4 Zc 6 8
CT = 122p0.6
H
∆Pr +Pe − 0.579 a
G = mass velocity.
b
Dp = diameter of catalyst particle.
where: c
Z = number of catalyst layers.
. /
pH = 22 900 (∆Pr +Pe + 0.421)0.283 − 1
The average value of trials 101 – 108 is
To estimate the steam costs (C S ) it is assumed 20 488. Since the value at the center of the re-
that the turbine uses steam with 2.76 MPa pres- sponse surface is much less than the average of
sure. The effectiveness of the turbine is 0.68; the the circumferential points, the existence of cur-
turbine works 8000 h/a and steam is generated vature in the explored region is obvious. The
for $ 1.10/1000 kg (1966). Then: results of trials 109 – 112 along the radial line
indicate the occurrence of a minimum in trial
∆Pr
CS = 54pH
∆Pr +Pe − 0.579
110. The results of the optimum design are as 5.4. Optimum Temperature Profile and
follows: Optimization of Multistage Reactors
Table 9. Half-replicate experiments
For reversible exothermic catalytic reactions
Trial x1 x2 x3 x4 Y (e.g., water – gas shift synthesis, oxidation of
101 −1 −1 −1 −1 20 692 SO2 to SO3 , synthesis of methanol and ammo-
102 +1 −1 −1 +1 17 081 nia), the optimum temperature profile plays an
103 −1 +1 −1 +1 21 019 important role in optimum design.
104 +1 +1 −1 −1 22 862
105 −1 −1 +1 +1 21 147 Reaction rate isolines in the ξ – T phase plane
106 +1 −1 +1 −1 18 453 are presented in Figure 20. Three generic lines
107 −1 +1 +1 −1 20 636 (a – c) representing three different reaction rate
108 +1 +1 +1 +1 22 018
Improved trial
values (for an exothermic reversible reaction) in
109 0 0 0 17 733 decreasing order are shown. The locus of opti-
0 mum conditions (d) connects the points of maxi-
mum conversion for a given value of the reaction
rate, the equilibrium line (e) represents the locus
Table 10. Radial line trials of reaction rate R (C, T ) = 0, and the adiabatic
line (f) represents the history of the reaction rate
Trial x1 x2 x3 x4 Y
for a reaction under adiabatic conditions.
110 + 1/2 − 1/2 − 1/2 + 1/2 16 509
111 + 1/4 − 1/4 − 1/4 + 1/4 17 077
112 + 3/4 − 3/4 − 3/4 + 3/4 17 173
Table 11. Factor levels
−2 −1 0 +1 +2
x1 0.98 0.9825 0.985 0.9875 0.99

x2 200.0 225.0 250.0 275.0 300.0
x3 0.025 0.028125 0.03125 0.034375 0.375
Catalyst activated coke

Size of catalyst ≈ 0.01 m
Composition of gas entering bed 1.50 vol % NO
Number of layers
8
Thickness of each layer ≈ 0.80 m
Mass velocity ≈ 0.34 kg m−2 s−1
Diameter of bed ≈ 4.0 m
Temperature of entering gas 293 K
Temperature of leaving gas ≈ 331.50 K
Pressure of entering gas ≈ 11.69 kPa
Pressure of leaving gas ≈ 11.0 kPa
Fraction conversion
0.986
Dew point, entering gas 243 K
Weight of catalyst ≈ 37 850 kg
Annual costs (1966) Figure 20. Reaction rate in exothermic reversible systems
Reactor $ 8230 a) – c) Loci of constant reaction rate; d) Optimum tempera-
Blower $ 180 ture profile; e) Equilibrium curve; f) Adiabatic line
Turbine $ 120
Steam $ 1330 For an equilibrium reaction:
Catalyst $ 1500
Nitrogen monoxide loss $ 5210
Total $ 16 570 ν1A + ν2B ν3P + ν4Q
the reaction rate is given by:

configuration is cooling between adiabatic lay-

ν1 ν2 ν3 ν4 ers. This strategy of approximation the optimum
R =k1 CA CB −k2 CP CQ (5.11)
temperature profile is shown in Figure 21.
and for the optimum temperature where the max-
imum rate can be achieved, the following rela-
tion holds:
∂r ν1 ν2 ∂k1 ν3 ν4 ∂k2
=CA CB −CP CQ = 0 (5.12)
∂T ∂T ∂T
If k 1 and k 2 show an Arrhenius dependence on
temperature then:
ν3 ν4
CP CQ k1 E1
ν1 ν2 = (5.13)
CA CB k2 E2 T∗
where T ∗ is the optimum reaction temperature.

For equilibrium conditions the following ex-
pression holds:
ν3 ν4 Figure 21. Approximation to the optimum temperature pro-
CP CQ k1
ν1 ν2 = (5.14) file
CA CB k2 Te a) Optimum profile; b) Equilibrium curve; c) Adiabatic op-
e eration; d) Intermediate cooling
where T is the equilibrium temperature.
Combining Equations (5.13) and (5.14),
gives:
5.5. Optimization of a Multibed
T∗ 1
= (5.15) Adiabatic Reactor with Heat Exchange
Te Rn T e
1 + E −E ln E2
2E 1 1 Between Catalytic Stages
The mass of catalyst W required for process-
ing a given molar flow rate F of reactants in an A schematic for optimization of a n stage
adiabatic packed bed can be calculated from: adiabatic packed-bed reactor is shown in Fig-
ure 22. The mass of the catalyst W is a function
y of the inlet temperatures of the individual stages
W dy
=Z = (5.16) and the degrees of conversion obtained in the
F R
0 different stages:
For the optimum temperature profile in the reac-
W = W T 1 , T 2 , . . . , T n , ξ1 , ξ2 , . . . , ξn

tor the integral in Equation (5.16) is minimum,
i.e., Assume that the degree of conversion in the nth

stage is given. It is necessary to calculate 2 n −1
y
∂Z
=
∂r dy
= 0 (5.17)
variables in such a way so that the mass of the
∂T ∂T r2 catalyst is minimal. These parameters can be cal-
0
culated by differential calculus, i.e.,
The optimum temperature profile is presented in
Figure 20 (curve d). ∂Z
= 0 for i, j = 1, 2, . . . , n (5.18)
For adiabatic tubular reactors the optimum ∂Tj
ξi ,Ti (i=j)
temperature profile cannot be easily adjusted.
∂Z
Figure 20 reveals that optimum reaction rate is a = 0 for i, j = 1, 2, . . . , n(5.19)
∂ζj T i ,ξi (i=j)
decreasing function in the ξ vs. T diagram while
the adiabatic line is an increasing function. To where ξ and T denote inlet conversion and tem-
reconcile the different trends of optimum temperature to a tray and ξ and T denote outlet
perature profile and adiabatic line, heat must be conversion and temperature. After differentia-
withdrawn in the axial direction. The simplest tion:

∂Z ∂ 1
ζj = =f (ζ) (5.24)
∂Z ∂ 1 ∂ζ ∂T R
= dζ = 0 for i, j =1, 2, . . . , n
∂Tj ∂T R
ζj subject to the initial condition:

 Z = 0 for ζ = 0 (5.25)
ζj+1
ζj
∂Z ∂  dζ dζ  Equation (5.24) is integrated with Equation
= = 
 + 

∂ζj ∂ζj R T j
R Tj+1 (5.25) until Z = 0. The calculated exit degree of
ζj
ζj+1
conversion and exit temperature provide a value
(5.21) of reaction rate R. The inlet temperature in the
second stage is calculated from Equation (5.23).
The process is repeated for the remaining n − 1
1 1 stages. In a similar way adiabatic reactors can
= − = 0 (5.22)
R Tj ,ζj
R Tj+1 ,ζj+1 be optimized with “cold shot”, i.e., cooling bet-
ween stages with fresh gas [131].
i.e.,

R Tj ,ζj =R Tj+1
,ζj+1 for i, j = 1, 2, . . . , n
(5.23)
6. References
1. R. Shinnar, “Chemical Reaction
Modeling – The Desirable and the Achievable,”
in: Chemical Reaction Engineering – Houston,
ACS, Washington, D.C., 1978, p. 1.
2. K. R. Westerterp, W. P. M. van Swaaij, A. A. C.
M. Beenackers: Chemical Reactor Desgin and
Operation, J. Wiley & Sons, New York 1982.
Transport Phenomena, J. Wiley & Sons, New
York 1960.
4. H. F. Rase: Chemical Reactor Design for
Process Plants, J. Wiley & Sons, New York
1977.
5. V. V. Aleksandrov, A. A. Davydenko, Y. A.
Kovalenko, N. P. Poddudnyi: “Influence of
Two-Dimensionality of the Front with Heat
Losses on the Limits of Stationary Gasless
Combustion,” Fiz. Goreniya Vzryva 23 (1987)
2 – 14.
6. J. Puszynski, J. Degreve, V. Hlavacek,
“Modeling of Exothermic Non-Catalytic
Reactions,” Ind. Eng. Chem. Prod. Res. Dev.
26 (1987) 1424 – 1434.
7. F. A. Holland, F. S. Chapman: Liquid Mixing
and Processing in Stirred Tanks, Reinhold,
Figure 22. Schematic of a multibed adiabatic reactor with New York 1966.
intermediate cooling 8. V. W. Uhl, J. B. Gray (eds.): Mixing Theory
ξ and T denote inlet, ξ and T denote outlet conditions
and Practice, vols. I and II, Academic Press,
There are 2 n −1 equations (Eqs. 5.20 and New York 1966.
5.23) to calculate the values of the optimum pa- 9. K. R. Westerterp, W. P. M. Van Swaaij, A. A. C.
rameters. Numerically, Equation (5.20) can be M. Beenackers: Chemical Reactor Design and
solved easily by transforming it to a differential Operation, J. Wiley & Sons, New York 1984.
equation:
10. G. Astarita: Mass Transfer with Chemical 26. S. S. E. Elnashaie, D. L. Cresswell: “Dynamic
Reaction, Elsevier, Amsterdam 1967. Behaviour and Stability of Non-Porous
11. R. H. : Perry’s Engineering Handbook, 6th ed. Catalyst Particles,” Chem. Eng. Sci. 28 (1973)
McGraw Hill, New York 1984. 1387 – 1399.
12. C. van Heerden: “Autothermic Processes; 27. G. F. Froment, K. B. Bischoff: Chemical
Properties and Reactor Design”, Ind. Eng. Reactor Analysis and Design, J. Wiley &
Chem. 45 (1953) 1242. Sons, New York 1979.
13. C. van Heerden: “The Character of the 28. D. Ramkrishna, P. Arce: “Can
Stationary State of Exothermic Processes,” Pseudohomogeneous Reactor Models be
Chem. Eng. Sci. 8 (1958) 133. Valid?,” Chem. Eng. Sci. 44 (1989)
14. V. Hlavacek, M. Kubicek, J. Jelinek: 1949 – 1966.
“Modeling of Chemical Reactors – XVIII, 29. P. Arce, D. Ramkrishna: “Pattern Formation in
Stability and Oscillatory Behavior of the Catalytic Systems: The Role of Fluid Mixing,”
CSTR,” Chem. Eng. Sci. 25 (1970) 1441. AIChE J. 37 (1991) no. 1, 98 – 110.
15. R. Aris, N. R. Amundson: “An Analysis of 30. S. Yagi, D. Kunii, N. Wakao: “Studies on Axial
Chemical Reactor Stability and Control,” Effective Thermal Conductivities in Packed
Chem. Eng. Sci. 7 (1958) 121. Beds,” AIChE J. 6 (1960) no. 4, 543 – 546.
16. D. D. Perlmutter: Stability of Chemical 31. A. Jutan et. al.: “Multivariable Computer
Reactors, Prentice Hall, Englewood Cliffs, Control of a Butane Hydrogenolysis Reactor:
NJ, 1972. Part I. State Space Reactor Modeling,” AIChE
17. R. A. Schmitz: “Multiplicity, Stability and J. 23 (1977) no. 5, 732 – 742.
Sensitivity of States in Chemically Reacting 32. D. Vortmeyer, K. J. Dietrich, K. O. Ring:
Systems,” Chem. React. Eng. Rev. 148 (1975) “Comparison of One- and Two-Phase Model
156. Predictions for Adiabatic Packed-Bed
18. A. H. Heemskerk, W. R. Dammers, J. M. H. Chemical Reactors,” Adv. Chem. Ser. 133
Fortuin: “Limit Cycles Measured in a (1974) 588 – 599.
Liquid-Phase Reaction System,” Chem. Eng. 33. D. Vortmeyer, R. J. Schaefer: “Equivalence of
Sci. 35 (1980) 439. One- and Two-Phase Models for Heat Transfer
19. O. Levenspiel: Chemical Reaction Processes in Packed Beds: One Dimensional
Engineering, 2nd ed., J. Wiley & Sons, New Theory,” Chem. Eng. Sci. 29 (1974) 485 – 491.
York 1972. 34. J. J. Carberry, D. White: “On the Role of
20. J. M. Eldridge, E. L. Piret: “Continuous Flow Transport Phenomena in Catalytic Reactor
Stirred-Tank Reactor Systems,” Chem. Eng. Behavior,” Ind. Eng. Chem. 61 (1969) 27 – 31.
Prog. 46 (1950) 290. 35. S. Feyo de Azevedo, M. A. Romero-Ogawa,
21. N. H. Chen: Process Reactor Design, Allyn A. P. Wardle: “Modelling of Tubular
and Bacon, Newton, Mass. 1983. Fixed-Bed Catalytic Reactors: A Brief
22. G. F. Froment: “Packed Bed Reactors. Steady
Review,” Chem. Eng. Res. Des. 68 (A) (1990)
State Conditions,” Review A 5 in Chemical
483 – 502.
Reactor Engineering, Proceedings of the Fifth
36. H. M. Hulburt: “Chemical Processes in
European/Second International Symposium on
Continuous-Flow Systems. Reaction
Chemical Reaction Engineering, Amsterdam,
Kinetics,” Ind. Eng. Chem. 36 (1944) no. 11,
Elsevier, Amsterdam 1972.
1012 – 1017.
23. V. Hlavacek: “Aspects in Design of Packed
37. P. V. Danckwerts: “Continuous Flow Systems.
Catalytic Reactors,” Ind. Eng. Chem. 62
Distribution of Residence Times,” Chem. Eng.
(1970) no. 7, 8 – 26.
Sci. 2 (1953) no. 1, 1 – 18.
24. H. Hofmann: “Probleme bei der
38. J. F. Wehner, R. H. Wilhelm: “Boundary
mathematischen Modellierung von
Conditions of Flow Reactor,” Chem. Eng. Sci.
Schüttschicht-Reaktoren,” Chem.-Ing-Tech.
6 (1956) 89 – 93.
46 (1974) no. 6, 236 – 242.
39. L. T. Fan, Y. K. Ahn: “Critical Evaluation of
25. V. Hlavacek, J. Votruba: “Steady-State
Boundary Conditions for Tubular Flow
Operation of Fixed-Bed Reactors and
Reactors,” Ind. Eng. Chem. Process Des. Dev.
Monolithic Structures,” in L. Lapidus, N. R.
3 (1962) no. 1, 190 – 195.
Amundson (eds.): Chemical Reactor Theory. A
Review, Chap. 6, Prentice Hall, Englewood
Cliffs, N.J., 1977.
40. V. Hlavacek, M. Marek: “Axialer Stoff- und Transfer Parameters in Packed Beds,” AIChE
Wärmetransport im adiabatischen J. 28 (1982) no. 3, 508 – 510.
Rohrreaktor – II. Numerische 53. W. Odendaal, W. Gobie, J. J. Carberry:
Untersuchung – Ablauf einer einfachen “Thermal Parameter Sensitivity in the
Reaktion bzw. einer Folgereaktion,” Chem. Simulation of the Nonisothermal,
Eng. Sci. 21 (1966) 501 – 514. Nonadiabatic Fixed Bed Reactor – The
41. V. Hlavacek, H. Hofmann: “Modeling of Two-Dimensional Heterogeneous Model,”
Chemical Reactors – XVII. Steady State Axial Chem. Eng. Commun. 58 (1987) 37 – 62.
Heat and Mass Transfer in Tubular Reactors. 54. L. C. Windes, M. J. Schwedock, W. H. Ray:
Numerical Investigations of Multiplicity,” “Steady State and Dynamic Modeling of a
Chem. Eng. Sci. 25 (1970) 187 – 199. Packed Bed Reactor for the Partial Oxidation
42. V. Hlavacek et. al.: “Boundary Conditions for a of Methanol to Formaldehyde. I. Model
Tubular Nonisothermal Nonadiabatic Packed Development,” Chem. Eng. Commun. 78
Bed Reactor with Wall Heat Transfer in the (1989) 1 – 43.
Fore and Aft Sections,” Chem. Eng. Commun. 55. L. H. S. Roblee, R. M. Baird, J. W. Tierney:
3 (1979) 451 –460. “Radial Porosity Variations in Packed Beds,”
43. J. Puszynski: “Experimental and Numerical AIChE J. 4 (1958) 460 – 464.
Studies of Catalytic Nonadiabatic Reactors” 56. R. F. Benenati, C. B. Brosilow: “Void Fraction
Ph. D. Thesis, Institute for Chemical Distribution in Beds of Spheres,” AIChE J. 8
Technology, Prague, Czechoslovakia 1980. (1962) no. 3, 359 – 361.
44. K. B. Bischoff: “A Note on Boundary 57. V. M. H. Govindarao, G. F. Froment: “Voidage
Conditions for Flow Reactors,” Chem. Eng. Profiles in Packed Beds of Spheres,” Chem.
Sci. 16 (1961) no. 1, 131 – 133. Eng. Sci. 41 (1986) no. 3, 533 – 539.
45. L. C. Young, B. A. Finlayson: “Axial 58. B. C. Chandrasekhara, D. Vortmeyer: “Flow
Dispersion in Nonisothermal Packed Bed Model for Velocity Distribution in Fixed Beds
Chemical Reactors,” Ind. Eng. Chem. Fundam. Under Isothermal Conditions, ” Wärme
12 (1973) no. 4, 412 – 422. Stoffübertrag. 12 (1979) 105 – 111.
46. A. Rasmuson: “Exact Solution of a Model for 59. D. Vortmeyer, J. Schuster: “Evaluation of
Diffusion in Particles and Longitudinal Steady Flow Profiles in Rectangular and
Dispersion in Packed Beds: Numerical Circular Packed Beds by a Variational
Evaluation,” AIChE J. 31 (1985) 518, 519. Method,” Chem. Eng. Sci. 38 (1983) no. 10,
47. A. Rasmuson: “ Exact Solution of Some 1691 – 1699.
Models for the Dynamics of Fixed Beds using 60. O. Kalthoff, D. Vortmeyer:
Danckwerts’ Inlet Condition,” Chem. Eng. Sci. “Ignition/Extinction Phenomena in a Wall
41 (1986) no. 3, 599, 600. Cooled Fixed Bed Reactor. Experiments and
48. R. A. Novy, H. T. Davis, L. E. Scriven: Model Calculations Including Radial Porosity
“Upstream and Downstream Boundary and Velocity Distributions,” Chem. Eng. Sci.
Conditions for Continuous-Flow Systems,” 35 (1980) 1637 – 1643.
Chem. Eng. Sci. 45 (1990) no. 6, 1515 – 1524. 61. D. Vortmeyer, R. P. Winter: “Improvements in
49. R. A. Novy, H. T. Davis, L. E. Scriven: “A Reactor Analysis Incorporating Porosity and
Comparison of Synthetic Boundary Velocity Profiles,” Ger. Chem. Eng. (Engl.
Conditions for Continuous-Flow Systems,” Transl.) 7 (1984) 19 – 25.
Chem. Eng. Sci. 46 (1991) 57 – 68. 62. J. E. Gatica et. al.: “Steady and Non-Steady
50. R. A. Novy, H. T. Davis, L. E. Scriven: “A State Modeling of Tubular Fixed Bed
Comparison of Initial Conditions for Reactors,” Chem. Eng. Commun. 78 (1989)
Continuous-Flow Systems,” Chem. Eng. Sci. 73 – 96.
46 (1991) no. 7, 1725 –1737. 63. H. Martin: “Low Péclet Number
51. A. G. Dixon, D. L. Cresswell: “Theoretical Particle-to-Fluid Heat and Mass Transfer in
Prediction of Effective Transfer Parameters in Packed Beds,” Chem. Eng. Sci. 33 (1978)
Packed Beds,” AIChE J. 25 (1979) no. 4, 913 – 919.
663 – 676. 64. C. L. de Ligny: “Coupling between Diffusion
52. D. Vortmeyer, R. Berninger in A. G. Dixon, and Convection in Radial Dispersion of Matter
D. L. Cresswell (eds.): “Comments on the by Fluid Flow through Packed Beds,” Chem.
Paper, Theoretical Prediction of Effective Heat Eng. Sci. 25 (1970) 1177 – 1181.
65. J. J. Carberry: Chemical and Catalytic 80. J. E. Crider, A. S. Foss: “Effective Wall Heat
Reaction Engineering, McGraw-Hill, New Transfer Coefficients and Thermal Resistances
York 1976. in Mathematical Models of Packed Beds,”
66. D. Vortmeyer, R. Berninger: “Comparison of AIChE J. 11 (1965) no. 6, 1012 – 1018.
Dispersion Models for Calculation of 81. V. Hlavacek, M. Marek, T. M. John: “Tubular
Temperature Profiles in Packed Beds,” Ger. Non-Isothermal Nonadiabatic Packed Bed
Chem. Eng. (Engl. Transl.) 6 (1983) 9 – 14. Reactor. An Analysis of the One-Dimensional
67. P. Zehner, E. P. Schlunder: Case,” Collect. Czech. Chem. Commun. 34
“Wärmeleitfähigkeit von Schüttungen bei (1969) 3664 –3675.
mäßigen Temperaturen,” Chem. Ing. Tech. 42 82. G. F. Froment: “Fixed Bed Catalytic Reactors.
(1970) 933 – 940. Current Design Status,” Ind. Eng. Chem. 59
68. A. G. Dixon: “Thermal Resistance Models of (1967) no. 2, 18 – 27.
Packed-Bed Effective Heat Transfer 83. O. Bilous, N. R. Amundson: “Chemical
Parameters,” AIChE J. 31 (1985) no. 5, Reactor Stability and Sensitivity: II. Effects of
826 – 834. Parameters on Sensitivity of Empty Tubular
69. A. G. Dixon: “Wall and Particle-Shape Effects Reactors,” AIChE J. 2 (1956) no. 1, 117 – 126.
on Heat Transfer in Packed Beds,” Chem. Eng. 84. G. F. Froment: “Progress in the Fundamental
Commun. 71 (1988) 217 – 237. Design of Fixed Bed Reactors,” in L. K.
70. D. L. Cresswell, A. G. Dixon: in [52]511 – 513. Doraiswamy, R. A. Mashelkar (eds.): Frontiers
71. A. G. Dixon, D. L. Cresswell: “Effective Heat in Chemical Reaction Engineering 1, Wiley
Transfer Parameters for Transient PackedBed Eastern, New Delhi 1984, p. 12.
Models, ” AIChE J. 32 (1986) no. 5, 809 –819. 85. P. L. Chambré: “On the Characteristics of a
72. D. Vortmeyer: “Radiation in Packed Solids,” Nonisothermal Chemical Reactor,” Chem.
Ger. Chem. Eng. (Engl. Transl.) 3 (1980) Eng. Sci. 5 (1956) 209 – 216.
124 – 138. 86. C. H. Barkelew: “Stability of Chemical
73. C. L. Tien: “Thermal Radiation in Packed and Reactors,” Chem. Eng. Prog. Symp. Ser. 55
Fluidized Beds,” J. Heat Transfer 110 (1988) (1959) no. 25, 37 –46.
1230 –1242. 87. R. J. van Welsenaere, G. F. Froment:
74. A. G. Dixon, M. A. DiConstanzo, B. A. Soucy: “Parametric Sensitivity and Runaway in Fixed
“Fluid-Phase Radial Transport in Packed Beds Bed Catalytic Reactors,” Chem. Eng. Sci. 25
of Low Tube-to-Particle Diameter Ratio,” Int. (1970) 1503 – 1516.
J. Heat Mass Transfer 27 (1984) no. 10, 88. C. McGreavy, C. I. Adderley: “Parametric
1701 – 1713. Sensitivity and Temperature Runaway in
75. E. Tsotsas, E.-U. Schlünder: “Heat Transfer in
Heterogeneous Fixed Bed Reactors,” Adv.
Packed Beds with Fluid Flow: Remarks on the
Chem. Ser. 133 (1974) 519 – 531.
Meaning and the Calculation of a Heat
89. R. A. Rajadhyaksha, K. Vasudeva, L. K.
Transfer Coefficient at the Wall,” Chem. Eng.
Doraiswamy: “Parametric Sensitivity in Fixed
Sci. 45 (1989) no. 4, 819 – 837.
Bed Reactors,” Chem. Eng. Sci. 30 (1975)
76. R. E. Chao, R. A. Caban, M. M. Irizarry: “Wall
1399 – 1408.
Heat Transfer to Chemical Reactors,” Can. J.
90. A. Oroskar, S. A. Stern: “ Stability in
Chem. Eng. 51 (1973) 67 – 70.
Chemical Reactors,” AIChE J. 25 (1979)
77. R. J. Wijngaarden, K. R. Westerterp: “Do the
no. 5, 903 – 905.
Effective Heat Conductivity and the Heat
91. M. Morbidelli, A. Varma: “Parametric
Transfer Coefficient at the Wall Inside a
Sensitivity and Runaway in Tubular Reactors,”
Packed Bed Depend on a Chemical Reaction?
AIChE J. 28 (1982) no. 5, 705 – 713.
Weakness and Applicability of Current
92. T. F. Degnan, J. Wei: “The Cocurrent Reactor
Models,” Chem. Eng. Sci. 44 (1989)
Heat Exchanger: I. Theory,” AIChE J. 25
no. 8, 1653 – 1663.
(1979) no. 2, 338 – 344.
78. D. J. Gunn, D. Vortmeyer: “The
93. L. M. Akella, H. H. Lee: “A Design Approach
Reaction-Independence of Mixing Coefficients
Based on Phase Plane Analysis:
in Fixed-Bed Reactors,” AIChE J. 36 (1990)
Countercurrent Reactor/Heat Exchanger with
no. 9, 1449 – 1451.
79. J. Beek, E. Singer: “A Procedure for Parametric Sensitivity,” AIChE J. 29 (1983)
Scaling-up a Catalytic Reactor,” Chem. Eng. no. 1, 87 – 94.
Prog. 47 (1951) 534 – 540.
94. A. Soria Lopez, H. I. DeLasa, J. A. Porras: 106. V. Balakotahia: “Simple Runaway Criteria for
“Parametric Sensitivity of a Fixed Bed Cooled Reactors,” AIChE J. 35 (1989) no. 6,
Catalytic Reactor: Cooling Fluid Flow 1039 –1043.
Influence,” Chem. Eng. Sci. 36 (1981) 107. H. C. Brinkman: “A Calculation of the Viscous
285 – 291. Force Exerted by a Flowing Fluid on a Dense
95. H. I. DeLasa: “Application of the Swarm of Particles,” Appl. Sci. Res. Lect. A: 1
Pseudoadiabatic Operation to Catalytic Fixed (1947) 27 – 34.
Bed Reactors,” Can. J. Chem. Eng. 61 (1983) 108. D. A. Nield: “The Boundary Correction for the
710 – 718. Rayleigh-Darcy Problem: Limitations of the
96. G. P. Henning, G. A. Pérez: “Parametric Brinkman Equation,” J. Fluid Mech. 128
Sensitivity in Fixed-Bed Catalytic Reactors,” (1983) 37 – 46.
Chem. Eng. Sci. 41 (1986) no. 1, 83 – 88. 109. K. Vafai, C. L. Tien: “Boundary and Inertia
97. G. P. Henning, G. A. Pérez: “A Generalization Effects on Flow and Heat Transfer in Porous
of Two Intrinsic Criteria for Runaway in Fixed Media,” Int. J. Heat Mass Transfer 24 (1981)
Bed Catalytic Reactors: Part I. Development of 195 – 203.
the Criteria,” Chem. Eng. Commun. 59 (1987) 110. D. D. Gray, A. Giorgini: “The Validity of the
107 – 125. Boussinesq Approximation for Liquid and
98. E. Bauman et al.: “Parametric Sensitivity in Gases,” Int. J. Heat Mass Transfer 19 (1976)
Tubular Reactors with Co-Current External 545 – 551.
Cooling,” Chem. Eng. Sci. 45 (1990) no. 5, 111. D. D. Joseph: Stability of Fluid Motions, vol. 2,
1301 – 1307. chap. X and XII, Springer Verlag, Berlin 1976.
99. G. P. Henning, G. A. Pérez: “A Generalization 112. D. Drew, L. Segel: “Averaged Equations for
of Two Intrinsic Criteria for Runaway in Fixed Two-Phase Flow,” Stud. Appl. Math. 50
Bed Catalytic Reactors: Part II. Criteria (1971) no. 3, 205 – 231.
Performance Analysis of Co-Current vs. 113. J. L. Beck: “Convection in a Box of Porous
Counter-Current Operation,” Chem. Eng. Material; Saturated with Fluid,” Phys. Fluids
Commun. 59 (1987) 127 – 136. 15 (1972) no. 8, 1377 – 1383.
100. D. O. Borio, J. E. Gatica, J. A. Porras: 114. Ph. Forchheimer: “Wasserbewegung durch
“Wall-Cooled Fixed-Bed Reactors: Parametric Boden,” VDJZ 45 (1901) no. 50, 1781 – 1788.
Sensitivity as a Design Criterion,” AIChE J. 115. M. Choudhary, M. Propster, J. Szekely: “On
35 (1989) no. 2, 287 – 292. the Importance of the Inertial Terms in the
101. D. O. Borio et. al. “Cocurrently-Cooled Modeling of Flow Maldistribution in Packed
Fixed-Bed Reactors: A Simple Approach to Beds,” AIChE J. 22 (1976) no. 3, 600 – 603.
Optimal Cooling Design,” AIChE J. 35 (1989) 116. M. Choudhary, J. Szekely, S. W. Weller: “The
no. 11, 1899 – 1902. Effect of Flow Maldistribution on Conversion
102. M. Morbidelli, A. Varma: “Parametric in a Catalytic Packed-Bed Reactor: Part I.
Sensitivity and Runaway in Fixed-Bed Analysis,” AIChE J. 22 (1976) no. 6,
Catalytic Reactors,” Chem. Eng. Sci. 41 1021 – 1027.
(1986) 1063 – 1071. 117. S. Ergun: “Fluid Flow through Packed
103. M. Morbidelli, A. Varma: “On Parametric Columns,” Chem. Eng. Prog. 48 (1952)
Sensitivity and Runaway Criteria of 89 – 94.
Pseudohomogeneous Tubular Reactors,” 118. B. A. Boley, J. H. Weiner: Theory of Thermal
Chem. Eng. Sci. 40 (1985) no. 11, Stresses, J. Wiley & Sons, New York 1960.
2165 – 2168. 119. B. A. Boley, I. S. Tollins: “Transient Coupled
104. M. Morbidelli, A. Varma: “A Generalized Thermoelastic Boundary Value Problems in
Criterion for Parametric Sensitvity: the Half Space,” J. Appl. Mech. 29 (1962)
Application to Thermal Explosion Theory,” no. 4, 637 – 646.
Chem. Eng. Sci. 43 (1988) 91 – 102. 120. J. V. Villadsen, W. E. Stewart: “Solution of
105. M. Morbidelli, A. Varma: “A Generalized Boundary-Value Problems by Orthogonal
Criterion for Parametric Sensitivity: Collocation,” Chem. Eng. Sci. 22 (1967)
Application to a Pseudohomogeneous Tubular 1483 – 1495.
Reactor with Consecutive or Parallel 121. C. G. Carey, B. A. Finlayson: “Orthogonal
Reactions,” Chem. Eng. Sci. 44 (1989) no. 8, Collocation on Finite Elements,” Chem. Eng.
1675 – 1696. Sci. 30 (1975) 587 – 596.
122. K. F. Jensen, W. H. Ray: “The Bifurcation 127. J. H. Seinfeld, W. L. McBride: “Optimization

Behavior of Tubular Reactors,” Chem. Eng. with Multiple Performance Criteria,” Ind. Eng.
Sci. 37 (1982) 199 – 222. Chem. Process Des. Dev. 9 (1970) 53.
123. J. E. Gatica, J. Puszynski, V. Hlavacek: 128. D. J. Wilde: Optimum Seeking Methods,
“Reaction Front Propagation in Nonadiabatic Prentice Hall, Englewood Cliffs, NJ, 1964.
Exothermic Reaction Flow Systems,” AIChE 129. C. Chu, O. A. Hougen: “Optimum Design of a
J. 33 (1987) no. 5, 819 – 833. Catalytic Nitric Oxide Reactor,” Chem. Eng.
124. D. A. Anderson, J. C. Tannehill, R. H. Pletcher: Prog. 57 (1961) no. 6, 51.
Computational Fluid Mechanics and Heat 130. H. H. Rosenbrock, C. Storey: Computational
Transfer, McGraw-Hill, New York 1984. Techniques for Chemical Engineers,
125. R. G. Hindman: “Generalized Coordinate Pergamon Press, New York 1966.
Forms of Governing Fluid Equations and 131. J. Caha, V. Hlavacek, M. Kubicek: “Study of
Associated Geometrically Induced Errors,” the Optimization of Chemical Engineering
AIAA J. 16 (1982) 1359 – 1367. Equipment. Numerical Solution of the
126. T. F. Edgar, D. M. Himmelblau: Optimization Optimization of an Adiabatic Reactor,” Int.
of Chemical Processes, McGraw-Hill, New Chem. Eng. 13 (1973) 466.
York 1988.
Fundamentals of Chemical Engineering
Estimation of Physical Properties 537
Estimation of Physical Properties

Ulfert Onken, Fachbereich Chemietechnik, Universität Dortmund, Dortmund, Federal Republic of Germany
Kai Fischer, Fachbereich Technische Chemie, Universität Oldenburg, Oldenburg, Federal Republic of
Germany
Jürgen Rarey, Fachbereich Technische Chemie, Universität Oldenburg, Oldenburg, Federal Republic of
Germany
1. Introduction . . . . . . . . . . . . . . 539 4.2.2.3. Prediction of Vapor-Liquid and Gas-

1.1. Scope . . . . . . . . . . . . . . . . . . . 539 Liquid Equilibria . . . . . . . . . . . . 567
1.2. Data Sources . . . . . . . . . . . . . . 539 4.2.3. Liquid – Liquid Equilibria . . . . . . 567
1.3. Theoretical and Empirical 4.2.4. Solid – Liquid Equilibria . . . . . . . 568
Methods . . . . . . . . . . . . . . . . . 540 5. Thermodynamic Data of
2. Molecular and Macroscopic Chemical Reactions . . . . . . . . . 569
Properties . . . . . . . . . . . . . . . . 541 5.1. Definitions . . . . . . . . . . . . . . . 569
2.1. Intermolecular Forces . . . . . . . 541 5.1.1. Reaction Enthalpy . . . . . . . . . . . 569
2.2. Theorem of Corresponding States 543 5.1.2. Gibbs Energy of Reaction and
2.3. Estimation of Critical Properties 544 Chemical Equilibrium . . . . . . . . 569
2.4. Other Characteristic Constants of 5.2. Group Contribution Methods for
Pure Compounds . . . . . . . . . . . 546 the Estimation of Enthalpies and
3. Thermal and Caloric Properties of Gibbs Energies of Formation . . . 571
Single-Phase Systems . . . . . . . . 547 5.3. Applications . . . . . . . . . . . . . . 573
3.1. Pressure – Volume – Temperature 5.3.1. Reaction Enthalpy . . . . . . . . . . . 573
Behavior of Gases and Liquids . . 547 5.3.2. Chemical Equilibrium . . . . . . . . 574
3.1.1. Pure Gases . . . . . . . . . . . . . . . 547 6. Transport Properties of Pure
3.1.2. Pure Liquids . . . . . . . . . . . . . . 549 Compounds and Mixtures . . . . . 576
3.1.3. Mixtures . . . . . . . . . . . . . . . . . 551 6.1. Viscosity . . . . . . . . . . . . . . . . . 576
3.1.3.1. Gas Mixtures . . . . . . . . . . . . . . 551 6.1.1. Viscosity of Pure Gases . . . . . . . 576
3.1.3.2. Liquid Mixtures . . . . . . . . . . . . 553 6.1.2. Viscosity of Gas Mixtures . . . . . . 578
3.2. Caloric Properties . . . . . . . . . . 553 6.1.3. Viscosity of Pure Liquids . . . . . . 578
3.2.1. Heat Capacity of Ideal Gases . . . . 554 6.1.4. Viscosity of Liquid Mixtures . . . . 579
3.2.2. Heat Capacity of Pure Liquids . . . 554 6.2. Thermal Conductivity . . . . . . . 581
3.2.3. Heat Capacities of Liquid Mixtures 556 6.2.1. Thermal Conductivity of Gases at
4. Phase Equilibria . . . . . . . . . . . 556 Low Pressure . . . . . . . . . . . . . . 582
4.1. Pure Compounds . . . . . . . . . . . 556 6.2.2. Thermal Conductivity of Gases at
4.1.1. Vapor Pressure, Boiling Point, and High Pressure . . . . . . . . . . . . . . 583
Melting Point . . . . . . . . . . . . . . 556 6.2.3. Thermal Conductivity of Gas
4.1.2. Enthalpy of Vaporization . . . . . . . 558 Mixtures . . . . . . . . . . . . . . . . . 585
4.2. Mixtures . . . . . . . . . . . . . . . . 560 6.2.4. Thermal Conductivity of Liquids . . 585
4.2.1. Vapor – Liquid Equilibria with 6.2.5. Thermal Conductivity of Liquid
Liquid-Phase Activity Coefficients 561 Mixtures . . . . . . . . . . . . . . . . . 587
4.2.1.1. Basic Considerations . . . . . . . . . 561 6.3. Diffusion Coefficients . . . . . . . . 587
4.2.1.2. Data Correlation: Binary and Mul- 6.3.1. Diffusion Coefficients of Gases at
ticomponent Mixtures of Nonelec- Low and Moderate Pressures . . . . 588
trolytes . . . . . . . . . . . . . . . . . . 561 6.3.2. Diffusion Coefficients of Liquids . 589
4.2.1.3. Prediction of Equilibrium Data . . . 562 7. Surface Tension of Liquids . . . . 592
4.2.2. Vapor – Liquid and Gas – Liquid 7.1. Surface Tension of Pure Liquids . 592
Equilibria with Equations of State . 566 7.2. Surface Tension of Liquid
4.2.2.1. Basic Considerations . . . . . . . . . 566 Mixtures . . . . . . . . . . . . . . . . 594
4.2.2.2. Data Correlation . . . . . . . . . . . . 566 8. References . . . . . . . . . . . . . . . 595
538 Estimation of Physical Properties
Symbols µ chemical potential, J/mol; dipole mo-

ment, Debye
a activity
ν kinematic viscosity, m2 /s; number of
B, B second virial coefficient, m3 /mol or Pa
groups in a molecule; stoichiometric co-
c molar heat capacity, J mol−1 K−1
efficient
C, C third virial coefficient, (m3 /kmol)2 or Pa2
density, kg/m3
D diffusion coefficient, m2 /s
σ Lennard – Jones length, 10−10 m; surface
E energy, J; Eucken factor
tension, N/m
f fugacity, Pa or atm
ω acentric factor
G molar Gibbs energy (free enthalpy), J/mol
∆ difference
∆G f Gibbs energy of formation, J/mol
χ Stiel polar factor
∆G 0f Gibbs energy of formation at standard
Γ group activity coefficient
pressure, J/mol
ϕ fugacity coefficient
∆G r Gibbs energy of reaction, J/mol
Π Poynting correction
H molar enthalpy, J/mol
Ω collision integral
∆H f enthalpy of formation, J/mol
∆H 0f enthalpy of formation at standard pres-
sure, J/mol Subscripts
∆H r enthalpy of reaction, J/mol
∆H lv enthalpy of vaporization, J/mol b at normal boiling point (101.325 kPa)
∆H lv c critical property
T b enthalpy of vaporization at boiling tem-
perature, J/mol D diffusion
∆H sv enthalpy of sublimation, J/mol id ideal state (gas, mixture)
∆H trs enthalpy of phase transition, J/mol i, j, k components
I increment m mixture; at melting point
k Boltzmann constant, J/K p constant pressure
K equilibrium constant r reduced quantity; reaction
K p equilibrium constant expressed in partial sat state of saturation
pressure T constant temperature
M molecular mass, g/mol v constant volume
n number of moles 0 pure component
p pressure, Pa (or bar)
P parachor, m3 kg0.25 s−0.5 mol−1 Superscripts
Q group interaction parameter
r distance, m; number of components of a C combinatorial
mixture E excess
R universal gas constant, J mol−1 K−1 g gas
S entropy, J/K int internal
T temperature, K, ◦ C l liquid
V molar volume, m3 /mol s solid
w weight fraction ref reference
x mole fraction in liquid phase R residual
y mole fraction in gas phase trans translational
z compressibility factor; coordination trs transition
number v vapor
α relative volatility vap vaporization
β compressibility, Pa−1 0 reference-state value, atmospheric pres-
ε Lennard – Jones energy, J sure
γ activity coefficient ∞ infinite dilution
η dynamic viscosity, Pa · s cal calculated value
λ thermal conductivity, W m−1 K−1 exp measured value
1. Introduction Before estimating data, data tables and other

sources should be consulted for measured values
1.1. Scope (see Section 1.2). If no such data can be found (as
is often the case), experimental determination
The design of chemical processes requires a of missing data can be considered. For several
knowledge of the values of the properties of the properties (e.g., density or vapor pressure) such
individual chemical compounds and mixtures to experiments can be performed without much ex-
be handled, as well as data on the chemical reac- pense. However, for those physical properties
tion systems involved in the process. Important whose measurement requires appreciable exper-
types of relevant data are given in Table 1; other imental effort (e.g., phase equilibria), informa-
data may, however, also be required (e.g., for tion from data sources is rather scarce.
optical or electrical properties). Another, even more crucial problem in data
retrieval is the fact that multicomponent mix-
Table 1. Data for chemical processes tures have to be handled in most chemical pro-
Type of compounds, Type of data
cesses. Since the concentrations in these mix-
material, system tures are important variables that may vary both
Individual chemical physical properties a locally and with time, it is practically impossible
compounds (starting and to provide all experimental data for the required
end products,
intermediates)
concentration ranges.
1) thermal state properties a , e.g., These considerations show that methods for
density, vapor pressure data estimation and prediction are necessary
2) caloric properties a , e.g., heat
capacity, latent heats
tools for the design of chemical processes. This
3) transport properties a , chemical is true not only for planning production plants,
properties b (safety, toxicity, but also for process development. Many prop-
environmental hazards)
Mixtures, nonreacting physical properties a
erty data are not available, especially in pro-
phase equilibria a cesses for new products. Experimental determi-
Mixtures, reacting chemical equilibrium a nation is often impossible due to shortage of
reaction enthalpy a time. In these cases qualified data estimation is
reaction velocity a, b
catalytic activity a, b
necessary. Other areas in which data estimation
Materials of construction mechanical properties b and prediction are widely used are feasibility
corrosion b and comparative process studies. These activi-
a
Data required for basic design of processes.
ties must often be performed within a short time
b
Data estimation not possible. and with a limited financial budget.
Although all the classes of data listed in Ta-

ble 1 are relevant for the design and operation 1.2. Data Sources
of chemical processes, only some of them are
The first step in obtaining the data needed for
essential. Thus basic design of a process unit
a design problem is a search for experimental
for liquid – liquid extraction requires data on
data; such data can generally be considered to
both the selectivity and capacity of the solvent,
be more reliable than predicted data. Moreover,
whereas data on toxicity and inflammability are
most methods of data estimation require knowl-
not necessary, although they are important for
edge of certain property data for the respective
plant operation. The present review of estima-
compounds (e.g., boiling point, density, critical
tion methods covers only those groups of data
temperature, and critical pressure). Besides, pre-
that are essential for process design. Reaction
diction of mixture properties is more reliable
velocity data cannot, however, be included, de-
when it is based on qualified experimental data
spite the fact that they are very important. On the
for the pure components.
basis of present knowledge reaction velocities
Available data sources range from handbooks
cannot be predicted with an acceptable degree
for everyday work (D’Ans – Lax [73], Hand-
of reliability and this situation is not expected to
book of Chemistry and Physics [74]) to the com-
change in the near future.
prehensive tables of Landolt – Börnstein [75]

and the numerous specialized data collections, plv V v =RT 1+B plv (1.3)
e.g., the Dechema Data Series [76] and other
data books (see General References [10] to [71]). Substituting this into Equation (1.2) gives:
An efficient and rapidly developing way of
obtaining data for physical and chemical proper- dlnplv ∆H lv
=− (1.4)
ties and equlibria is data retrieval with computer- d (1/T ) R 1+B plv
ized data banks (e.g., [77–79]). Prediction meth-
ods for several types of data (e.g., phase equi- In contrast to this exact procedure, enthalpies
libria) have been incorporated into these data of vaporization ∆H lv T b at the boiling point T b
banks. can be estimated roughly with the simple rule of
Pictet and Trouton which states that the ratio of
∆H lvT b to T b should have the same value for all
liquids. As can be seen from Table 2, this simple
1.3. Theoretical and Empirical Methods
rule is true for many compounds:
Methods for estimating property data [1–9] may
∆HTlvb /Tb = const. ≈ 88JK−1 mol−1 (1.5)
differ in nature. They may be based on laws of
physics and physical chemistry, or they may em- This behavior is presumably related to inter-
ploy purely empirical rules; most methods can molecular forces. A possible explanation is that
be classified somewhere between these two ex- the energy necessary for vaporizing a liquid is
tremes. mainly used to separate the liquid molecules
The enthalpy of vaporization, for example, from each other. The strength of intermolecular
can be determined with a thermodynamic equa- forces should thus be more or less independent
tion, i.e., the Clausius – Clapeyron equation for of the type of compound and molecular struc-
the dependence of vapor pressure plv on the ab- ture.
solute temperature T
Table 2. Rule of Pictet and Trouton
dplv ∆H lv
= v (1.1)
dT T V −Vl Substance ∆H lv ∆H lv
Tb , T b, K T /Tb ,
b
kJ/mol J mol−1 K−1
where ∆H lv is the enthalpy of vaporization, V v
He 0.8 4.2 19.8
is the volume of the vapor phase, and V l the Ne 1.8 27.1 65.0
volume of the liquid phase. Equation (1.1) is a Ar 6.5 87.3 74.5
rigorous relation; when it is used to determine H2 9.0 20.4 44.3
the vaporization enthalpy, vapor pressure data at N2 5.6 77.4 72.1
CH4 8.2 111.6 73.3
several temperatures must be known as well as HCl 16.2 188.1 85.8
the densities of the vapor and liquid phases at CS2 26.8 319.3 83.8
the saturated vapor pressure plv . At low vapor CCl4 30.0 349.9 85.8
n-C6 H14 29.0 341.9 84.7
pressures (≤ ca. 0.1 MPa) V l is small compared
n-C8 H18 34.6 398.5 86.8
to V v and may therefore be neglected. Further- C6 H6 30.8 353.3 87.2
more, the vapor phase may be assumed to show C2 H5 OC2 H5 26.6 307.8 86.4
ideal behavior. With these simplifications Equa- C2 H5 Cl 24.6 285.3 86.2
NH3 23.4 239.7 97.4
tion (1.1) can be expressed as: H2 O 40.7 373.2 109.0
C2 H5 OH 38.7 351.6 110.1
dlnplv ∆H lv C6 H5 NH2 45.1 457.5 98.6
=− (1.2)
d (1/T ) R CH3 COOH 23.7 391.7 60.5
Hg 59.1 629.8 93.9
where R is the gas constant. For vaporization at Na 89.0 1163.0 76.6
0.1 MPa the deviations in ∆H lv caused by ne- Zn 114.7 1180.0 97.2
Pb 179.5 2025.0 88.6
glecting V l are usually < 1 % and ≤ ca. 5 % Ni 374.3 2915.0 113.8
by assuming ideal gas behavior for the vapor
phase. Real gas behavior may be accounted for
by the second virial coefficient B (see Section Associating liquids obviously do not obey the
3.1, Eq. 3.13): rule of Pictet and Trouton. The carboxylic acids
(formic and acetic acid) show negative devia- was only possible by the input of additional data.
tions for Trouton’s constant and form dimers in Such data are often not available, and a sub-
both the liquid and the vapor phases. This means optimum result has to suffice. As with the rule
that in the vaporization process the effective mo- of Pictet and Trouton, pitfalls may often be en-
lar mass is higher than that of the monomeric countered when many other empirical and semi-
acid, resulting in a higher value of ∆H lv T b and empirical methods are applied to compounds
consequently of Trouton’s constant. For the as- with special or extreme molecular properties, for
sociating liquids in Table 2 showing positive de- example, those that form hydrogen bonds (e.g.,
viations from Equation (1.5) (i.e., ammonia, wa- water, hydrogen fluoride, trichloromethane, al-
ter, methanol, ethanol) association is limited to cohols, carboxylic acids) or that have a very low
the liquid phase; additional energy is required molecular mass (hydrogen, helium).
to vaporize these liquids because the bonds re-
sponsible for association have to be broken.
For liquified gases with very low boil- 2. Molecular and Macroscopic
ing points (e.g., helium, hydrogen) Trouton’s
constant is much lower than 88 J mol−1 K−1 ,
Properties
whereas some of the higher boiling metals show
a tendency towards higher values for this param- 2.1. Intermolecular Forces
eter. Evidently at the reference temperature T b
of Equation (1.5) conditions are not really com- Physical macroscopic properties of substances
parable. Several modifications of Equation (1.5) are determined by molecular properties and in-
have therefore been proposed of which only that teractions. Molecular properties may be classi-
proposed by Kistiakowsky is mentioned here, fied as internal or external. Internal properties
because it does not require additional data [80]: (e.g., spectroscopic properties and chemical re-
activity) are directly determined by the chemical
∆HTlv structure of the molecule, i.e., composition, type
b
= 36.6+R lnTb Jkmol−1 K−1 (1.6) of chemical bond, and steric structure. External
Tb
properties are mainly relevant to molecular in-
Example. Vaporization enthalpy of diethyl ether teraction (e.g., molecular cross section, dipole
moment, polarizability) and are of more gen-
Boiling point [81]: T b = 34.60 ◦ C (307.75 K)
Vapor pressure [81] at 30.00 ◦ C (303.15 K): eral character although they are also related to
plv = 0.08629 MPa chemical structure. A strict distinction between
at 40.00 ◦ C (313.15 K): internal and external molecular properties can-
plv = 0.12280 MPa
not be made. For example, optical spectra with
distinct narrow lines in the gas phase may show
Enthalpy of vaporization at boiling point line broadening when the spectrum is recorded
(∆H lv
T b , kJ/mol): from the liquid phase. This is obviously due to
Calculated value
molecular interaction.
Clausius – Clapeyron equation: Thermal behavior of matter (i.e., the depen-
simplified version (Eq. 1.2) 27.86 dence of density on temperature and pressure,
with second virial coefficient phase equilibria etc.) has its origin in interaction
(B = − 0.43 MPa−1 [82]), (Eq. 1.4) 26.65
Pictet – Trouton rule (Eq. 1.5) 27.10
between molecules, caused by forces of attrac-
Equation (1.6) 25.90 tion and repulsion.
Experimental value [83] 26.70 Intermolecular forces include:
1) Electrostatic forces between ions, permanent
The above example demonstrates that results
dipoles and multipoles (e.g., quadrupoles),
from theoretical equations will be more reliable
as well as ions and dipoles
than estimations based on empirical rules pro-
2) Induction forces, e.g., dipoles caused by the
vided that the theoretical relationships have not
influence of the electric field of permanent
been grossly simplified. The increase in accu-
dipoles on the electronic cloud of nonpolar
racy obtained by using the more exact Equa-
molecules (displacement of electrons)
tion (1.4) instead of the simplified Equation (1.2)
3) Dispersion forces (so-called Van der Waals r 0 . The LJ length σ determines the distance bet-
forces), i.e., forces caused by the interactions ween two molecules at which E is zero. The two
of fluctuating dipoles of nonpolar molecules characteristic parameters of the LJ potential and
4) Chemical forces leading to the formation of other two-parameter models can, in principle,
associates and complexes be related not only to molecular data, but also
to macroscopic properties (e.g., critical temper-
Molecular interactions are functions of the ature and critical pressure). Hence it should be
spatial positions of molecules relative to each possible to determine the molecular parameters
other. These positions are determined by the po- ε and σ from macroscopic quantities. However,
tential energy E of the particles, which is the in practice such calculations using statistical me-
sum of the repulsive and attractive forces, E rep chanics are rather cumbersome. Therefore em-
and E att , respectively. E rep affects E positively pirical relations have been proposed, for exam-
while E att contributes negatively: ple by Stiel and Thodos [84]:
E =Erep −Eatt (2.1) 18/5
ε=65.3kTc zc (2.5)
In the simple case of the interaction between two
1/3 −6/5
spherically symmetric molecules, E is a function σ= 1.866 × 10−3 Vc zc 10−10 m (2.6)
of the distance r between the molecules only. For
the general case of nonspherical molecules E is where k is the Boltzmann constant, T c the crit-
dependent on the distance and the orientation of ical temperature, zc the critical compressibility
the molecules. The contribution of the attractive factor, and V c the critical molar volume.
forces E att to the potential energy is in general
a function of the reciprocal of the sixth power of
the intermolecular distance r (except in the case
of ions and chemical forces):
1
Eatt ∼ (2.2)
r6
Consequently, Equation (2.2) is valid for all
types of “normal” nonpolar and polar species,
but not for compounds or mixtures showing as-
sociation or dissociation.
Little is known about the characteristics of
repulsive forces. They are, however, obviously
of stronger influence at very small distances than
attractive forces. A commonly used relation bet-
ween E rep and the distance r is
1
E ∼ (2.3) Figure 1. The Lennard – Jones 12-6 potential energy of
r12 spherical molecules
The Lennard – Jones (LJ) 12 – 6 potential is Equations (2.5) and (2.6) demonstrate the
obtained from Equations (2.1) – (2.3) and de- analogy between the intermolecular potential
scribes the dependence of E(r) on the inter- and the theorem of corresponding states as a
molecular distance general concept for the p V T behavior of fluid

phases (see Section 2.2). As a consequence this
σ 12 σ 6 molecular approach using a two-parameter po-
E (r) = 4ε − (2.4)
r r tential function is also called the microscopic
where ε is the LJ energy and σ the LJ length; corresponding states theorem. The application
these parameters are characteristic for a given of both concepts is not limited to spherical
species of molecules. As shown in Figure 1, ε is molecules; they may also be used for aspheri-
the minimum of the potential energy at a distance cal molecules with low to moderate polarity.
Among the various two-parameter potential Hence the following universal function is ob-
functions [85] the LJ potential is preferred be- tained:
cause of its simplicity. Thus Equation (2.4) is
used for the estimation of virial coefficients and z =f (Tr ,pr ) (2.10)
transport properties (e.g., viscosity, diffusion co-
efficients). In order to account for effects of po- Equation (2.10) implicitly contains the charac-
lar structures, a third parameter may be intro- teristics of the respective chemical compound
duced, as in the Stockmayer potential [86]. The because T r and pr are defined by the critical
Stockmayer potential is an extension of the LJ parameters T c and pc . This approach employs
potential and takes the dipole moment into con- only two characteristic parameters to describe
sideration. the pVT behavior of a compound. Hence satis-
factory agreement between theory and experi-
ment cannot be expected for all types of sub-
stances. However, for a large number of “nor-
2.2. Theorem of Corresponding States
mal” compounds (e.g., weakly polar, nonasso-
ciating substances, see Section 1.3) reasonable
Van der Waals was the first to successfully
quantitative representation of pVT behavior can
quantify the finding that the pressure volume
be achieved by applying methods based upon the
temperature (pV T ) behavior in the gas and liq-
corresponding states principle with two param-
uid states of many compounds is similar. He
eters [87]. Calculations of gas-phase properties
proposed an equation of state containing two
are generally more reliable than those of the liq-
parameters a and b specific for the compound
uid state. The region close to the critical point
considered:
cannot be represented with sufficient accuracy.
a For compounds with a very low boiling point
p+ 2 (V − b) =RT (2.7)
V (e.g., hydrogen, nitrogen), modified critical pa-
where p is the pressure, V the molar volume, R rameters must be used for the definitions of the
the gas constant, and T the absolute temperature. reduced variables [88]. In order to apply corre-
This equation (which is discussed in more detail sponding states methods to polar compounds a
in Section 3.1) describes not only the nonideal third characteristic parameter is necessary, e.g.,
gas phase, but also the liquid-phase compress- the acentric factor or the polar factor of Stiel
ibility and the region of coexisting liquid and (Section 2.4).
LIVE GRAPH
vapor phases including the critical point. Since Click here to view
the van der Waals constants a and b are related
to the critical properties (denoted here by the
subscript c), the introduction of dimensionless
reduced variables T r , pr , and V r defined by
T p V
Tr = ; pr = ; Vr = (2.8)
Tc pc Vc
yields a universal “reduced” equation of state

which is in principle valid for all substances.
This procedure is justified when all com-
pounds show the same pVT behavior described
in reduced variables. Figure 2 shows a pres-
sure – density – temperature diagram in reduced
variables. This theorem of corresponding states
for fluid phases is conveniently expressed using
the compressibility factor z defined by (cf. Sec-
tion 3.1.1)
Figure 2. Pressure – density diagram of a pure substance
pV
z= (2.9)
RT
2.3. Estimation of Critical Properties molecule and the increments I p c for the func-
tional groups (Table 3):
In view of the benefits of the principle of corre-
sponding states much attention has been devoted 0.1
pc = [MPa] (2.14)
to the critical properties of pure substances. (0.113 + 0.0032N − si Ipc )2
Knowledge of these properties is important for
many methods of estimating pure component
properties. Critical Volume. The difficulties encoun-
Since measurement of critical volume, pres- tered in the experimental determination of the
sure, and temperature is difficult and tedious, es- critical molar volume V c lead to difficulties
timation methods are useful tools for providing in the accurate prediction of this quantity too.
information about the critical constants. Most When Joback’s method is used [91], [92], only
estimation techniques employ the principle of increments are needed:
additivity which assumes that a physical prop-
erty can be obtained from the sum of the contri- Vc = 17.5+ si IVc (2.15)
butions of the atoms, functional atomic groups,
and bonds of the molecule considered. These where V c is the critical volume [cm3 /mol] and
group contribution or incremental methods are I V c are Joback’s increments (Table 3).
widely used for the prediction of physical prop- Example. Calculation of critical properties of
erties. chlorobenzene, C6 H5 Cl, with Joback’s method
and for comparison the results obtained with Ly-
Critical Temperature. According to the dersen’s method.
empirical Guldberg rule the ratio of the normal Functional groups: 5 =C− (ring), 1 =C<
boiling point T b to the critical temperature T c is (ring), 1 −Cl; T b = 404.9 K [93]; superscripts:
equal to 2/3: exp = experimental value, cal = calculated value
Critical temperature: Deviation
Tb /Tc = 2/3 (2.11)
T cexp = 632.4 K T ccal − T cexp

Joback (Eq. 2.13): si I T c = 0.0658

Based on the more general form of this rule − 2.9 K
T ccal = 404.9/(0.584 + 0.0635 − 0.00433) = 629.5 K
Tc = const.Tb (2.12) Lydersen T ccal = 629.6 K − 2.8 K
Critical pressure:
various methods have been proposed for pre- pexp
c = 4.52 MPa

c − pc
(pcal exp
)/pexp
c
dicting critical temperatures [88], [89], e.g., the Joback (Eq. 2.14): si I p c = 0.0014
widely used procedure of Lydersen [90] (for − 1.7 %
c = 0.1/[0.113 + (0.032×12) − 0.0014] = 4.44 MPa
pcal
equations and increments, see [89]). With effi- Lydersen pcal
c = 4.55 MPa + 0.6 %
cient statistical methods and new experimental Critical volume:
data, Joback [91], [92] developed an improved
exp
V c = 308 cm /mol3
(V ccal − V cexp )/V cexp

Joback (Eq. 2.15): si I V c = 295.0

version of Lydersen’s method, which is given V ccal = 17.5 + 295.0 = 312.5 cm3 /mol + 1.5 %
by: Lydersen V ccal = 310.0 cm3 /mol + 0.6 %
Tb
Tc = (2.13)
0.584 + 0.965 si ITc − ( si ITc )2
Discussion. Table 4 gives an overview of sev-
where si is the number of structural groups of
eral methods for the estimation of critical prop-
type i and I T c the Joback increment of func-
erties together with average uncertainties of the
tional groups as given in Table 3. The informa-
predicted values. The uncertainty in the pre-
tion needed for the estimation of the critical tem-
diction of the critical pressure is considerably
perature comprises the normal boiling point and
higher than that for the prediction of critical
the tabulated group increments.
temperature; for the critical volume it is often
still greater. Higher errors are also observed for
Critical Pressure. For the prediction of crit-
molecules of larger size or complex structure be-
ical pressure pc Joback [91], [92] used an equa-
cause relevant experimental data are scarce.
tion containing the number of atoms N in the
Table 3. Increments used in the estimation of critical temperature Tc , pressure pc , volume Vc , normal boiling point Tb , and melting point
Tm (Joback’s method [91], [92])
Type of increment ITc I pc IV c ITb ITm
Nonring increments
−CH3 0.0141 −0.0012 65 23.58 −5.10
>CH2 0.0189 0 56 22.88 11.27
>CH− 0.0164 0.0020 41 21.74 12.64
>C< 0.0067 0.0043 27 18.25 46.43
=CH2 0.0113 −0.0028 56 18.18 −4.32
=CH− 0.0129 −0.0006 46 24.96 8.73
=C< 0.0117 0.0011 38 24.14 11.14
=C= 0.0026 0.0028 36 26.15 17.78
≡CH 0.0027 −0.0008 46 9.20 −11.18
≡C− 0.0020 0.0016 37 27.38 64.32
Ring increments
−CH2 − 0.0100 0.0025 48 27.15 7.75
>CH− 0.0122 0.0004 38 21.78 19.88
>C< 0.0042 0.0061 27 21.32 60.15
=CH− 0.0082 0.0011 41 26.73 8.13
=C< 0.0143 0.0008 32 31.01 37.02
Halogen increments
−F 0.0111 −0.0057 27 −0.03 −15.78
−Cl 0.0105 −0.0049 58 38.13 13.55
−Br 0.0133 0.0057 71 66.86 43.43
−I 0.0068 −0.0034 97 93.84 41.69
Oxygen increments
−OH (alcohol) 0.0741 0.0112 28 92.88 44.45
−OH (phenol) 0.0240 0.0184 −25 76.34 82.83
−O− (nonring) 0.0168 0.0015 18 22.42 22.23
−O− (ring) 0.0098 0.0048 13 31.22 23.05
>C=O (nonring) 0.0380 0.0031 62 76.75 61.20
>C=O (ring) 0.0284 0.0028 55 94.97 75.97
O=CH− (aldehyde) 0.0379 0.0030 82 72.24 36.90
−COOH (acid) 0.0791 0.0077 89 169.09 155.50
−COO− (ester) 0.0481 0.0005 82 81.10 53.60
=O (except as above) 0.0143 0.0101 36 −10.50 2.08
Nitrogen increments
−NH2 0.0243 0.0109 38 73.23 66.89
>NH (nonring) 0.0295 0.0077 35 50.17 52.66
>NH (ring) 0.0130 0.0114 29 52.82 101.51
>N− (nonring) 0.0169 0.0074 9 11.74 48.84
−N= (nonring) 0.0255 −0.0099 74.60
−N= (ring) 0.0085 0.0076 34 57.55 68.40
−CN 0.0496 −0.0101 91 125.66 59.89
−NO2 0.0437 0.0064 91 152.54 127.24
Sulfur increments
−SH 0.0031 0.0084 63 63.56 20.09
−S− (nonring) 0.0119 0.0049 54 68.78 34.40
−S− (ring) 0.0019 0.0051 38 52.10 79.93
Comparison of the methods listed in Table 4 When the properties of molecules with
shows the considerable improvement of Ly- strongly interacting groups are estimated, the
dersen’s method by Joback. Somewhat more application of classical group contribution meth-
accurate but more complicated than Joback’s ods leads to systematic errors. Moreover, these
method is the method of Ambrose [94], [95]. methods cannot distinguish between certain iso-
With Fedor’s method [96] only critical tempera- mers, e.g., o-, m-, and p-derivatives of ben-
tures can be predicted. Normal boiling point data zene. To avoid these shortcomings Constanti-
are not needed, but the results are less reliable nou and Gani [97] proposed a new incremental
than those obtained by the methods of Joback method which does not require any information
and Ambrose. other than the molecular structure of the com-
Table 4. Selected methods for the prediction of critical data of organic compounds
Method Applicability Information required Error
Lydersen T c , pc , V c with increments for 41 functional groups; >Si< T b for T c T c : 1.5 %

increments for T c and pc ; –B< increment for T c
1955 [90] M for pc pc : 10 %
V c: 4 %
Joback T c , pc , V c with increments for 40 functional groups T b for T c T c : 0.8 %
1984 [91] pc : 6 %
V c : 2.5 %
Ambrose T c (52), pc (52), V c (35) with increments for functional groups T b for T c T c : 0.7 %
(number of functional groups given in parentheses)
1978 [94] M for pc pc : 5 %
1979 [95] V c: 3 %
Fedors T c with increments for 48 functional groups T b not required T c: 5 %
1982 [96]
Constantinou, Gani T c , pc , V c with increments for 78 functional groups and for T b not required T c : 0.9 %
structural effects (e.g., proximity, isomerism, ring structure)
1994 [97] pc : 3 %
V c: 2 %
pound. To allow for secondary structural effects, Compound ω Compound ω

so-called second-order groups are introduced in Methane 0.008 Water 0.344
addition to the 78 first-order groups. Including Nonane 0.445 Ammonia 0.250
the increments of second-order groups reduces Cyclohexane 0.212 Hydrogen − 0.216
Benzene 0.212 Phenol 0.438
the error in estimated critical data by a factor of Methanol 0.556 Aniline 0.384
about 1.5 on average. 1-Octanol 0.587
Comprehensive compilations of critical data
have been published for organic compounds Knowing the critical temperature and pres-
[98], [99] and inorganic compounds [100]. sure of a substance and its vapor pressure plv
(i.e., with the Antoine coefficients A, B, and C,
Eq. 4.5), the acentric factor can be calculated as
2.4. Other Characteristic Constants of follows:
Pure Compounds  
pc
ω=log   −1 (2.17)
The Acentric Factor ω. In order to extend exp A − B
0.7Tc +C
corresponding states methods to compounds and
If only the normal boiling point T b is known the
mixtures consisting of nonspherical and polar
Equation of Edmister [101] gives a reasonable
molecules, the Pitzer acentric factor ω was de-
estimate (pc in atmospheres):
fined as a third parameter:
3 log pc
lv ω= −1 (2.18)
p 7 Tc /Tb −1
ω=−log −1 (2.16)
pc Tr =0.7 The average uncertainty of this approximation
lv is 5 % [102].
where p is the vapor pressure of the pure com- Example. Calculation of the acentric factor
ponent. The Pitzer acentric factor is intended to for benzoic acid
give a measure of nonspherity or acentricity of T c = 752 K; pc = 45.6 bar; T b = 523 K; ω exp =
a molecule’s potential force field. For an ideal 0.620 [88]; Antoine constants [89] A = 10.5432,
spherical molecule it should be zero. Acentric B = 4190.70, C = −125.2
factors for some compounds are given below Substituting into Equation (2.17)
[89]:  
pc
ω cal
= log   − 1
exp 10.5432 − 4190.7
(0.7×752)−125.2
= 0.617
Relative deviation = 0.6 %. principles and easy-to-handle methods. More

With Equation (2.18) detailed information is given in [104–106].
For n moles of an ideal gas consisting of rigid
3 1 45.6
ω cal = log −1 = 0.618 molecules of zero volume and zero interaction
7 (752/523) −1 1.013 potential energy the following equation holds
Relative deviation = 0.3 %.
An incremental method for the estimation pV =RT (3.1)
of the acentric factor has been developed by
where V is the molar volume.
Constantinou et al. [103]. It is based on the
The ideal gas law is a universal limiting law
same structural groups as the procedure of Con-
valid for all substances when the density ap-
stantinou and Gani [97] for the prediction
proaches 0. Equation (3.1) can usually be used
of critical properties. No experimental data are
with sufficient accuracy for gases at low pres-
needed for this method. The average error is 3 %;
sure p << pc . The deviation of the behavior of
however, for 31 of the 78 structural groups (e.g.,
real substances with respect to Equation (3.1) is
nitrogen and sulfur groups), increments are not
usually expressed by the compressibility factor
available.
z
The Stiel Polar Factor χ. This factor relates pV
z= (3.2)
the actual reduced vapor pressure to the value RT
calculated by the Pitzer equation (Eq. 2.16) at
The dependence of z on pressure is plotted in
the reduced temperature T r = 0.6:
Figure 3 for a real fluid which obeys the prin-

plv(exp) ciple of corresponding states. Below the critical
χ=log (2.19) pressure z is less than unity, i.e., the attractive
plv(Pitzer)
Tr =0.6 forces are dominant. Above T c and pc , z exceeds
It is therefore also a measure of polarity and is unity due to increasing influence of the repulsive
related to the acentric factor by forces.
LIVE GRAPH
Click here to view
plv
χ=log +1.7ω+1.552 (2.20)
pc Tr =0.6
Example. Calculation of the Stiel polar factor

for benzoic acid plv (T r = 0.6) = 0.099 bar (An-
toine Eq. 4.5 [88])
Substituting into Equation (2.20):

0.099
χ=log +1.7 × 0.620 + 1.552 = −0.0573
45.6
3. Thermal and Caloric Properties of

Single-Phase Systems Figure 3. Generalized compressibility chart [107]
3.1. Pressure – Volume – Temperature In order to describe real fluid behavior an ex-
Behavior of Gases and Liquids pression must be found of the form
3.1.1. Pure Gases z =f (T ,p) or z =f (T ,V ) (3.3)
that is capable of describing pVT behavior for

The pressure – volume – temperature (pVT ) be-
a wide variety of substances over a wide range
havior can be calculated with equations of state.
of pressure and temperature. The two following
In this review emphasis is placed upon basic
fundamental boundary conditions must be satis- The pVT behavior can be predicted with a
fied: generalized equation when information on the
critical properties and the acentric factor ω is
∂p
=0 (3.4) available. These equations are particularly use-
∂V

T
c ful for hydrocarbons. According to [110] the av-
∂2p erage error for this class of substances is 1 – 2 %.
=0 (3.5)
∂V 2 Tc Deviations increase in the vicinity of the critical
point and for polar substances.
Cubic Equations of State. In his pioneer- Virial Equation of State. Statistical me-
ing work of 1873 Van der Waals introduced chanics yield an equation of state in which the
his famous equation of state which is the basic compressibility factor z is given as a polynomial
form for many other cubic (in volume) expres- in reciprocal molar volume:
sions:
pV B C
a =z =1+ + 2 +... (3.11)
p+ (V − b) =RT (3.6) RT V V
V2
The substance-specific constants a and b can be In this so-called virial equation the virial coef-
determined using conditions (3.4) and (3.5): ficients B, C, . . . are functions of temperature
only and can be related to molecular interaction
27 (RTc )2 parameters. Another form of the virial equation
a= (3.7)
64 pc uses pressure as the independent parameter:
1 RTc
b= (3.8) pV
8 pc =z =1+B p+C p2 +... (3.12)
RT
One of the most widely used two-parameter The two forms of the virial Equations (3.11) and
equations was suggested in 1949 by Redlich (3.12) can be truncated after the second term if
and Kwong (RK): they are applied at low pressure, i.e., at reduced
RT a densities < 0.5. Then the coefficients B and B
p= − 1/2 (3.9)
V −b T V (V +b) are related by:
Since the parameters a and b are substance- B
B= (3.13)
specific constants, the equation is completely RT
determined by the critical properties. The RK
Use of the virial equation is very convenient be-
equation and its subsequent modifications are
cause of its simple form. Experimental data on
more accurate than the Van der Waals equation.
second and, in part, third virial coefficients of
One very succesful modification of the attractive
pure gases and mixtures are given in [111].
term in the RK equation was recommended by
Soave (RKS) [108]:
Calculation of Second Virial Coefficients.
. /2 Many calculation schemes for the prediction of
1/2
RT ac 1+M (ω) 1−Tr
p= − (3.10) second virial coefficients have been published,
V −b V (V + b) e.g., [112–114]. The frequently used method
where of Tsonopoulos [113] will be described here
briefly. The equations can be used for most non-

M (ω) = 0.48 + 1.574ω−0.176ω 2 (3.10a) polar or slightly polar substances. Real fluid be-
havior is calculated using Pitzer’s approach
ac = 0.42748 (RTc )2 /pc (3.10b)
pc pr
z = 1+B =z (0) +ωz (1) (3.14)
b= 0.08664 (RTc ) /pc (3.10c) RTc Tr
pc
B =b(0) +ωb(1) (3.15)
Another widely accepted modification of the RTc
RK equation was proposed by Peng and Robin-
son (PR) [109]. with

0.33 0.1385 RT C0 1 (bRT − a)
b(0) = 0.1445− − p= + B0 RT − A0 − 2 +
Tr Tr2 V T V2 V3
0.0121 6.07 × 10−4 aα c
− − (3.15a) + 6 + 2 3 1+β/V 2 exp −β/V 2 (3.19)
Tr3 Tr8 V T V
0.331 0.423 0.008 where A0 , B0 , C 0 , a, b, c, α, and β are substance-
b(1) = 0.0637+ − − (3.15b)
Tr2 Tr3 Tr8 specific constants. An advantageous modifica-
For strongly polar compounds Tsonopoulos tion is the generalized form suggested by Lee
suggested the following modification of Equa- and Kesler [115] and its extension by Plöcker
tion (3.15) et al. [116] (LKP equation). For this type of
equation of state the compressibility factor of
B
pc c d
=b(0) +ωb(1) + 6 − 8 (3.16)
a real fluid is related to the properties of a sim-
RTc Tr Tr ple fluid (ω = 0), e.g., to those of n-octane as a
For several substances (e.g., ketones, aldehydes, reference fluid [105].
ethers, nitriles) Tsonopoulos gives recommen- A BWR extension with 20 substance-specific
dations for the calculation of the parameter c parameters and remarkable accuracy was sug-
gested in the 1970s by Bender [117]. In 1987
c= −2.113 × 10−4 µr −3.885 × 10−21 µ8r (3.17) Polt reported these constants for 51 substances
[118]. Figure 4 shows the p T behavior of
where toluene calculated with the Bender equation.
106 µ2p pc
µr = (3.18)
Tc2
3.1.2. Pure Liquids
(pc in MPa, T in K, and the dipole moment µp
in Debye). The parameter d vanishes for sub- Because of their importance in industrial pro-
stances that do not exhibit hydrogen bonding. cesses, density data are available for most or-
For other compounds it has to be determined by ganic liquids. Usually at least one experimen-
experiment. tal value for ambient conditions can be found.
Example. Calculation of the second virial It is therefore more important to gain informa-
coefficient of acetone, C3 H6 O, at 310 K with tion about the temperature dependence of liquid
Tsonopoulos’s method densities rather than to estimate liquid densities
M = 58.08 g/mol, T c = 508.1 K, pc = 4.7 MPa, µ = from other properties. Nevertheless, some meth-
2.9 Debye, ω = 0.304 ods have been published for the estimation of
With T r = 0.610 substitution into Equations liquid densities, e.g., [119].
(3.15 a) and (3.15 b) gives b (0) = − 0.8537,
b (1) = − 1.3276. Liquid Density at Normal Boiling Temper-
Substituting into Equation (3.16) and neglecting ature. Schroeder suggested a very simple and
the third and fourth terms yields: convenient method for the estimation of liquid
Bnonpolar = − 1.1303 m3 /kmol molar volumes at the normal boiling point [120]
With µr = 153.107 from Equation (3.18), (see also [106, p. 52]). He proposed an addi-
c = − 33.525 ×10−3 from Equation (3.17), and tive rule for the prediction of molar volumes.
substituting into Equation (3.16): The number of atoms of each type of element
Bpolar = − 1.715 m3 /kmol in the molecule (i.e., carbon, hydrogen, oxygen,
Experimental: B = − 1.730 m3 /kmol [111] and nitrogen, etc.) must be counted, multiplied
Relative deviation = 0.9 % by a weighting factor, and summed up. Addi-
tional increments are then added to account for
Other Equations of State. The repre- the molecular structure (i.e., double bonds) as
sentation of pVT behavior of polar gases and shown in Table 5.
liquids with two-parameter cubic equations of The method gives surprisingly good esti-
state is usually unsatisfactory. Accuracy can be mates of molar volume with an average error of
improved significantly by applying equations of ca. 3 %. Exceptions are substances that exhibit
the Benedict – Webb – Rubin (BWR) type:
LIVE GRAPH
Click here to view
Figure 4. Pressure – density behavior of toluene calculated with the Bender equation of state [118]
Table 5. Increments for the prediction of molar volumes of pure liquids at the normal boiling point according to Schroeder’s method [120]
Element Increment, m3 /kmol Bond Increment, m3 /kmol
Carbon 0.007 double bond (C=C) 0.007

Hydrogen 0.007 triple bond (C≡C) 0.014
Oxygen 0.007 ring systems 0.007
Nitrogen 0.007 (including naphthalene, anthracene)
Bromine 0.0315
Chlorine 0.0245
Fluorine 0.0105
Iodine 0.0385
Sulfur 0.0210
hydrogen bonding or a high degree of associa- nou et al. [122]. The procedure is the same as
tion. for the authors’ method for estimating the acen-
Example. Calculation of liquid molar vol- tric factor (see Section 2.4, [103]). For 17 of the
ume V lb of ethyl acetate, CH3 COOCH2 CH3 , 78 structural groups the values of the increments
at the normal boiling point (101.325 kPa) using are not given. The average error in the results is
Schroeder’s method 0.9 %.
Groups: 4C+2O+8H
Calculated: V lb = 4×0.007 + 2×0.007 + More Sophisticated Estimation Methods.
8×0.007 = 0.098 m3 /kmol Many analytical methods have been published,
Experimental [121]: V lb = 0.0978 m3 /kmol they are mostly based upon the principle of cor-
Relative deviation = 0.2 %
responding states. Consequently, standard den-
sity values are necessary for which the critical
More reliable results for the molar volume at density can be used. A single experimental value
normal boiling temperature can be obtained with can often be used for very accurate extrapola-
the group contribution method of Constanti- tions with respect to temperature.
The Gunn – Yamada expression is convenient The more recently published method of Han-
and very accurate (without any additional ad- kinson and Thomson achieves higher accuracy
justed parameters) for predicting liquid molar for liquid density [124]. This technique employs
volumes V l at the state of saturation [123]: specific constants for various groups of sub-
(0) stances as well as three substance-specific pa-
V l /Vsc =Vr (1−ωI) (3.20)
rameters that have been tabulated for more than
(0) 400 compounds (e.g., in [106], [124]) or can be
where I and Vr are generalized functions and
V sc is a scaling parameter. estimated. An overview of estimation methods
For 0.2 < T r < 1.0: is given in Table 6.
I = 0.29607 − 0.09045Tr −0.04842Tr2 (3.21) Pressure Dependence of Liquid Density.

For 0.2 < T r < 0.8: With the isothermal compressibility β T
(0)
Vr = 0.33593 − 0.33953Tr +1.51941Tr2 1 ∂V
βT = − (3.27)
−2.02512Tr3 +1.11422Tr4 (3.22) V ∂p T
For 0.8 < T r < 1.0 and the relation [127]

(0) 1/2 1/7
Vr = 1.0 + 1.3 (1−Tr ) log (1−Tr ) β 1/7 βsat
2 = (3.28)
−0.50879 (1−Tr ) −0.91534 (1−Tr ) (3.23) V Vsat
In terms of V 0.6 (the saturated liquid molar vol- the following approximation holds:
ume at the reduced temperature T r = 0.6), V sc is
defined as V l /Vsat
l
= [1 + 9βsat (p−p0 )]−1/9 (3.29)
V0.6
Vsc = (3.24) where β sat is estimated by the relation
(0.3862 − 0.0866ω)
If V 0.6 is not available, V sc can be estimated as Vc
βsat = · 1 − 0.89ω 1/2
follows ( pc in MPa): RTc

0.10132 ·exp 6.9547 − 76.2853Tr +191.3060Tr2
Vsc =RTc (0.2920 − 0.0967ω) (3.25)
pc −203.5472Tr3 +82.7631Tr4 (3.30)
Usually, one experimental value of V l under This method holds for the range of reduced tem-
ambient conditions (T r ≈ 0.6) is available and perature 0.35 < T r < 0.98 and for reduced pres-
can be applied as a reference value V ref at T ref
r . sure of pr < 10 with an average uncertainty of
In these cases the following form of the method 3 %.
of Gunn and Yamada is useful:
(0)
Vl Vr (Tr ) [1−ωI (Tr )]
= · (3.26) 3.1.3. Mixtures
V ref Vr(0) T ref 1−ωI Trref
r
Example. Calculation of the saturated liq- 3.1.3.1. Gas Mixtures

uid molar volume V l of n-propylamine,
CH3 CH2 CH2 NH2 , at 293.15 K using the The constants used in the methods for the cal-
method of Gunn and Yamada. culation of pVT behavior in gas mixtures must
M = 59.112 g/mol, T c = 497 K, ω = 0.303, be related to the relevant parameters of the pure
pc = 4.81 MPa [121] components and to the composition of the mix-
ture. Additional correlation parameters may be
Calculated:
From Equation (3.22) V (0)
necessary. The objective of this section is to pro-
r = 0.3839
From Equation (3.25) V sc = 0.2287 m3 /kmol vide some information on mixing rules.
With Equation (3.21) I = 0.2259
Substituting in Equation (3.20) V l = 0.08178 m3 /kmol
Experimental [121]: V l = 0.0824 m3 /kmol
Relative deviation: 0.75 %
Table 6. Selected methods for the determination of saturated liquid molar volumes of pure organic compounds
Method Range of application Information required Error, %
Substances Temperature
Yen, Woods [125] nonpolar and polar 0.3 < T r < 1 c , T c , zc , z 1

Gunn, Yamada [123] nonpolar and weakly polar 0.3 < T r < 0.99 T c , ω, ref (T − T ref )/100
Hankinson, Thomson [124] 0.25 < T r < 1.0 T c b , V c b , ω cb , <2
increments
Bhirud [126] nonpolar (polar) T c , ω, ref a 1
a
Not absolutely necessary.
b
Tabulated in [106], [124]; can also be calculated.
Virial Equation. Statistical thermodynam- Cubic Equations of State. For cubic equa-
ics yield the following rigorous relation for the tions of state with two parameters (e.g., Eqs. 3.6,
second virial coefficient Bm of a mixture of r 3.9, 3.10), the quadratic mixing rule is usually
components with a quadratic dependency on the applied for the constant a. Analogous to Equa-
molar fractions yi and yj : tion (3.31) one obtains for a mixture of r com-
ponents:

r
r
Bm = yi yj Bij (3.31)
r
r
i j am = yi yj aij (3.37)
i j
The virial coefficient Bii ≡ Bi of the pure com-
ponent i can be calculated as described in Sec- where the cross coefficients aij are given by the
tion 3.1.1. For the cross virial coefficients of the geometric mean of the pure component parame-
mixture Bij similar methods can be employed ters aii and ajj corrected by a binary parameter
if the critical properties of the mixture and the k ij :
acentric factor ωij are known.
Prausnitz discusses simple rules that yield aij = (aii ajj )0.5 (1−kij ) (3.38)
sufficiently accurate results for practical appli-
cations [128]: For the parameter b, a linear dependence on
composition is generally assumed:
Tcij = (Tci Tcj )0.5 (1−kij ) (3.32)

r
bm = yi bi (3.39)
where kij is a specific parameter that has to be i
adjusted to experimental data.
 3
1/3 1/3
Vci +Vcj Pseudocritical Properties. Since many
Vcij =   (3.33)
2 methods take advantage of the principle of
corresponding states using reduced quantities
for temperature, pressure, volume, and critical
zci +zcj compressibility, knowledge of these properties
zcij = (3.34)
2 in mixtures is important. If a mixture with a fixed
The following relations can also be readily decomposition is assumed to behave like a pure
rived: fluid, so-called pseudocritical constants can be
introduced that serve as scaling factors.
pcij =
zcij RTcij
(3.35)
Many attempts to calculate pseudocritical
Vcij properties have been published. Some basic
methods are given below (the subscript m de-
notes mixture):
ωi +ωj
ωij = (3.36)
2
1) Kay’s rule for T cm [129] where cp is the molar heat capacity at constant
pressure. Since heat capacity data for high pres-
sures are scarce and the variation in H between
Tcm = yi Tci (3.40)
two states is independent of the path of integra-
Deviations from results obtained by using tion, the difference in H is preferably determined
more complicated methods are less than 2 % via
[110].
2) pcm according to Prausnitz and Gunn [130] H2 −H1 = H T1 ,p0 −H (T1 ,p1 )
T2

(yi zci ) + c0p (T ) dT
pcm =RTcm (3.41)
yi Vig T1

3) Joffe’s rule for the acentric factor ω m of the − H T2 ,p0 −H (T2 ,p2 ) (3.45)
mixture [131]
where the superscript 0 indicates the reference
state shown by an arrow in Figure 5. As a conse-
ωm = yi ωi (3.42) quence, the temperature dependence of enthalpy
is calculated at zero pressure, i.e., in the ideal gas
Algebraic expressions of varying complex- state. The dependence on pressure is given by
ity have been suggested for the mixing rules for the so-called departure functions (e.g., H – H 0 ,
each equation of state applicable to mixtures. S – S 0 ) that can be determined with an appropri-
They are summarized and discussed extensively ate equation of state. For the heat capacity the
in [106]. rigorous thermodynamic equation is
p
∂2V
3.1.3.2. Liquid Mixtures cp −c0p = −T dp (3.46)
∂T 2
p0
Molar volumes V lm of mixtures comprising non-
reacting components which do not differ greatly Expressions for many equations of state as well
in structure can be calculated for low and mod- as extensive tabulations are given in [106], [110],
erate pressure ( p < pc ) by Amagat’s rule: [127].

l l
Vm = xi V0i (3.43)
where x i is the mole fraction of component i.

Deviations for real mixtures do not generally ex-
ceed ± 1 % of V lm .
3.2. Caloric Properties

Enthalpy is the basic thermodynamic quantity
used in energy balances for chemical processes.
According to rigorous thermodynamics, the dif-
ference in molar enthalpy (H) between two
states (denoted by subscripts 1 and 2) can be
calculated via
T2 Figure 5. Integration paths for enthalpy calculation between
H (T2 ,p2 ) −H (T1 ,p1 ) = cp (T ,p) dT states 1 (T 1 , p1 ) and 2 (T 2 , p2 )
Arrow denotes the reference value referred to in the text
T1
p2
∂H
+ dp (3.44)
∂p
p1
3.2.1. Heat Capacity of Ideal Gases Example. Heat capacity c0p of di-
isopropyl ether, (CH3 )2 CHOCH(CH3 )2 ,
Classical kinetic theory leads to the simple re- M = 102.177 g/mol.
lation c0p = 1/2 R for each translational degree of
freedom, a contribution of 1/2 R for each axis Group sj Ia Ib Ic Id
of rotation, and of R for each vibrational degree
−CH3 4 19.5 −8.08 1.53 −9.67
of freedom. Neglecting vibrational degrees of ×10−3 ×10−4 ×10−8
freedom, a primitive estimate for c0p applicable >CH− 2 −23.0 0.204 −2.65 1.20
to small molecules can be obtained from the re- ×10−4 ×10−7
lation −O− 1 25.5 −6.32 1.11 −5.48
×10−2 ×10−4 ×10−8
c0p =R (1+f /2) (3.47)
where f is the sum of translational and rotational Substitution into Equation (3.48):
degrees of freedom of the molecule. c0p (800 K) = 313.1 J mol−1 K−1
Example. Consider molecular nitrogen Experimental value:
N2 with five degrees of freedom (three c0p = 311.5 J mol−1 K−1 at 800 K [106]
translational, two rotational). At moder- Relative deviation: 0.5 %
ate temperatures (ca. 300 K) Equation (3.47)
yields cp = 29.1 J mol−1 K−1 whereas the Benson’s method [135] yields accurate val-
IUPAC compilation [132] for N2 reports ues not only for c0p but also for ∆H 0f298 and S 0298 .
cp = 29.2 J mol−1 K−1 at 300 K and 0.1 MPa. Many functional groups have been incorporated
This approximation is not of sufficient ac- into this method. Its strength lies in the fact that
curacy for practical engineering purposes over a the neighborhood of each group is considered.
wide range of temperatures. Hence empirical es- For special classes of molecules and isomers
timation methods are commonly accepted for the additional corrections may be applied (e.g., for
calculation of the heat capacity of ideal gases. rings with heteroatoms).
Other methods for the estimation of molar
Group Contribution Methods. Joback’s heat capacities are listed in Table 7.
method [133], [134] is a simple additive group
contribution method based on a polynomial in Heat Capacities of Ideal Gas Mixtures.
temperature using the same structural groups The heat capacity of a mixture cp 0m in the ideal
as in his method for the estimation of critical gas state is given by the simple mixing rule
properties (Section 2.3). For a molecule with r
different types of groups, c0p can be calculated c0pm = xi c0pi (3.49)
by
r

r
c0p = sj Ia − 37.93 + sj Ib +0.210 T
r 3.2.2. Heat Capacity of Pure Liquids

+ sj Ic −3.91 × 10−4 T2

Several approaches have been proposed for de-

r
termining the heat capacity of liquids, i.e., theo-
−7
+ sj Id +2.06 × 10 T 3
(3.48)
retical methods, corresponding states, Watson’s
thermodynamic cycles, or group contribution
where sj is the number of the group j and the methods. These methods are discussed exten-
increments I a , I b , I c , and I d , are component- sively in [106].
specific parameters and are tabulated for various A successful group contribution method was
groups not only for the ideal-gas heat capacity proposed by Chueh and Swanson [141]. It can
but also for the enthalpy of formation ∆H 0f298 be used to calculate the heat capacities of liq-
and the Gibbs enthalpy of formation ∆G 0f298 uids at room temperature (293.15 K) for many
(see Chap. 5, Table 14). The average error in c0p organic compounds. The average uncertainty is
is usually less than 2 % [106]. 2 – 3 %.
Next Page

Table 7. Selected incremental methods for the calculation of ideal gas heat capacities
Method Range of application Error, %
Substances T, K
Dobratz 1941 [136] no triple bonds

Rihani, Doraiswamy 1965 [137] no triple bonds 2–3
Benson 1968, 1969 [135] 280 – 1100 1
Thinh 1976 [138] hydrocarbons only 200 – 1500 1–2
Yoneda 1979 [139] hydrocarbons only 280 – 1100 <2
Joback 1984 [133], [134] 280 – 1100 1–2
Harrison, Seaton 1988 [140] 280 – 1500 3
Table 8. Increments of structural groups for the prediction of liquid where si is the the number of group i and Ii the
heat capacities (Missenard’s method) [142]
increment of group i (values are given in Ta-
ble 8).
A more refined incremental method for the
estimation of heat capacities of organic liquids
has been developed by Ruzicka and Domal-
ski [143]. With a detailed definition of 29 hy-
drocarbon and 85 heteroatomic groups and 36
structural corrections, this method predicts heat
capacities as a function of temperature from the
melting point up to the normal boiling point. The
average error in results from these temperature
functions is 2 – 6 %; above the boiling point, er-
rors may be 1 – 2 % higher.
Several estimation methods based upon the
principle of corresponding states have been dis-
cussed by Bondi [144]. Particularly at higher
temperatures these methods are superior to the
group contribution methods. They require, how-
ever, additional information (see also Table 9).
Bondi [144] (see also [106]) proposed a modi-
fication of Rowlinson’s method:

0.45
clp −c0p =R· 1.45+
1−Tr

(1−Tr )1/3 1.742

+R·0.25ω 17.11 + 25.2 + (3.51)
Tr 1−Tr
where c0p is the heat capacity in the ideal gas

state.
Missenard published an incremental
Example. Calculation of heat capacity of liq-
method for the prediction of liquid heat ca-
uid nitrobenzene, C6 H5 NO2 , at 303.2 K using
pacities in the temperature range 250 – 373 K
the method of Missenard [142]
[142]. This method is limited, however, to re-
M = 123.112 g/mol
duced temperatures T r < 0.75. It employs the
Calculated:
equation
I C6 H5 I NO2

clp (T ) = si Ii (3.50) 298 K 117.2 65.7
323 K 123.4 66.9
303 K 118.4 65.9
Previous Page

Table 9. Selected methods for the prediction of heat capacities of liquids
Method Range of application Information Error, % Type of method

required
Bondi – Rowlinson not recommended for 0.4 < T r < 0.96 c0p , T c , ω 5 corresponding states
polar substances
1966 [144]
Chueh, Swanson 293 K <3 group contribution
1973 [141]
Missenard no double bonds 248 < T < 373 K, 5 group contribution
1965 [142] but T r < 0.75
Ruzicka, Domalski Tm < T < Tb 2–6 group contribution
1993 [143]
Substitution into Equation (3.50): clp and vapor phase, respectively. With ∆H lv ≈
=184.3 J mol−1 K−1 const., V v = R T /p, and V v >> V l (see Section
Experimental: clp = 177.4 J mol−1 K−1 [121] 1.3), integration yields
plv ∆H lv 1 1
ln 1
lv
= − (4.2)
p2 R T2 T1
3.2.3. Heat Capacities of Liquid Mixtures where R is the gas constant. This relation leads to
the simple August equation with two adjustable
The heat capacity of liquid mixtures can usually constants
be calculated as the arithmetic mean value of the
individual components because deviations from B
lnplv =A+ (4.3)
observed values do not exceed 5 % if the compo- T
nents are similar in structure and do not exhibit
Integrating Equation (4.1) using a linear func-
hydrogen bonding:
tion in temperature for the enthalpy of vaporiza-
tion gives the Rankine – Kirchhoff equation
clpm = xi clpi (3.52)
B
A comprehensive study of the heat capacity be- log plv =A+ +C log T (4.4)
T
havior of liquid mixtures is given in [146].
Figure 6 shows a typical vapor pressure versus
temperature curve exhibiting an inflection point.
4. Phase Equilibria Two-parameter equations such as Equation (4.3)
are only able to represent a linear relationship
between ln plv and 1/T . Three-parameter equa-
4.1. Pure Compounds
tions, such as the frequently used Antoine equa-
tion,
4.1.1. Vapor Pressure, Boiling Point, and
Melting Point B
log plv =A − (4.5)
T +C
Vapor Pressure Correlation Functions.
Many correlation functions have been published can also describe positive or negative curvatures.
which are related to the Clausius – Clapeyron The description of the vapor pressure of a pure
equation: component, within or close to the experimental
uncertainty over a wide range of temperature,
dplv ∆H lv is possible using the so-called Frost – Kalkwarf
= v (4.1)
dT T V −V l equation:
where ∆H lv is the enthalpy of vaporization, and lnplv =A+

B Dplv
+C lnT + 2 (4.6)
V l and V v are the molar volumes of the liquid T T
which is implicit in pressure. This relation, along 1) Nonpolar organic and inorganic substances
with a number of other correlation forms (e.g.,
Wagner, Riedel, and Riedel – Plank – Miller 221.79
equations), achieves the best performance for β = − 4.267−
h2.5 exp (0.0384h2.5 )
practical purposes [147] (not considering poly- 3.8126
nomial functions such as the Chebyshev polyno- + +H (4.8)
exp (2272.44h−3 )
mial series proposed by Ambrose [148]). Exper-
imental vapor pressure data are given in [149]. where H = 0 with exceptions for H2
(H = 0.19904), He (H = 0.41815), and Ne
(H = 0.02319).
m=0.78425exp (0.089315h)
−8.5217exp (−0.74826h) (4.9)

−m
−ln (pc /1.01325) + 1−Tbr β
δ= 7 −1
(4.10)
Tbr
h in Equations (4.8) and (4.9) is defined as
ln (pc /1.01325)
h= (4.11)
(1/Tbr ) −1
2) Polar compounds (except alcohols and wa-

Figure 6. Vapor pressure curve of a pure liquid ter)

Estimation Methods. Methods for estimat- δ= 0.08594exp 7.462 × 10−4 Tc (4.12)
ing the vapor pressures of pure substances are
of low accuracy compared to the quality of mea-
surement. For several homologous series (e.g.,
straight-chain alkanes) plv can, however, be pre- m= 0.466Tc0.166 (4.13)
dicted with considerable accuracy.
For reasonable predictions of vapor pres-
sure over a wider range of temperature the nor-
mal boiling point must be known from experi-
7 +ln (p /1.01325)
δ 1−Tbr c
ments. Equation (4.3) provides a rough estimate β= (4.14)
−m
if plv data for two temperatures, e.g., the boiling 1−Tbr
point T b and the critical point (pc and T c ), are
3) Alcohols and water
known. From critical temperatures and pressures
(which can be estimated with the methods dis-
cussed in Chap. 2), generalized functions such 2.464
δ= (4.15)
as the Lee – Kesler method [150] or the Gomez- M exp 9.8 × 10−6 M Tc
Nieto – Thodos equation [151] yield vapor pres-
sures with uncertainties of a few percent. The
latter method is based upon the following equa- m= 0.0052M 0.29 Tc0.72 (4.16)
tion:
−m β from Equation (4.14)
lnplv
r =β Tr −1 +δ Tr7 −1 (4.7)
with relations for the parameters β, m, and δ as

follows:
Example. Calculation of vapor pressure of Boiling points of 438 organic compounds cal-
benzene, C6 H6 , with the Gomez method culated with this method showed an average er-
T b = 353.2 K, T c = 562.2 K, pc = 4.89 MPa [152] ror of 12.9 K [152]. This appears to be rather
Substituting into Equations (4.8) – (4.11): large, but considering that no experimental in-
h = 6.5513, m = 1.3446, δ = 0.1530, β = − 4.2955 formation is required, the T b data are accept-
Experimental vapor pressure from [153] able as approximate values (cf. example below).
This is not, however, true for the estimation of
T, K plv , kPa Rel. deviation, melting points. Here a test of Joback’s method
on 388 organic compounds yielded an average
exp. cal. cal − exp, %
error of 23 K; moreover, deviations of more than
288 7.784 8.01 3.0 100 K may occur, e.g., for benzene 171 K (calc)
330 46.63 46.92 0.6
400 352.4 351.7 − 0.2
and 279 K (exp), for cyclohexane 168.5 K (calc)
and 280 K (exp).
The reason for these discrepancies is the large
Vapor pressures of pure liquids can also be variety of intermolecular structures in the crys-
predicted with the aid of a cubic equation of talline solid state. In fact, almost all compounds
state via an iterative calculation. The method of- form an individual crystalline solid state (and
fers the advantage that other properties such as often more than one such state) as a separate
densities at saturation and heats of vaporization phase. This means that specific information is re-
can also be obtained. quired for describing solid phases whereas more
general relations are sufficient for the treatment
Boiling Point and Melting Point. Several of liquid or gas phases. Consequently for reli-
methods have been developed for the prediction able prediction of the temperature of solid – liq-
of the normal boiling point T b , i.e., the boiling uid phase changes specific information for the
temperature at a pressure of 101.325 kPa. Some solid concerned is needed.
are discussed in [147]. A convenient method Example. Calculation of normal boiling
for organic compounds proposed by Ogata and point of ethyl acrylate, CH2 =CHCOOCH2 CH3 .
Tsuchida [154] is based on the simple equation Experimental: T b = 373.0 K [152]
Tb =py+q+273.15 [K] (4.17) 1) Ogata – Tsuchida method (Eq. 4.17)

y p q
CH2 =CH−COOR 0.918 29.0
The parameter y is related to the alkyl groups, CH3 CH2 77.1
and p and q are characteristic constants for other T b = 372.9 K
functional groups. This method is limited to Deviation: − 0.07 K
compounds with one functional group besides
the alkyl group. The authors report an accuracy
of 2 to 3 K for 91 % of more than 600 substances 2) Joback’s method (Eq. 4.18)
investigated. −CH3 >CH2 =CH− =CH2 −COO−
23.58 22.88 24.96 18.18 81.10
For the estimation of both boiling and melt- T b = 368.7 K
ing temperatures of pure compounds Joback Deviation: − 4.3 K
[155], [156] developed an incremental method
in which he employs the same structural groups A new and more highly refined incremental
as in his method for critical data estimation: method for predicting T b and T m has been de-
normal boiling point veloped by Constantinou and Gani [157] (see
also Section 2.4) with average errors of 5.4 K for
Tb = 198.0+ ITb [K] (4.18)
T b and 14 K for T m .
melting point
4.1.2. Enthalpy of Vaporization
Tm = 122.0+ ITm [K] (4.19)
Increments IT b and IT m are given in Table 3. Determination from Vapor Pressure Data.
As has been shown in Section 1.3 the vaporiza-
tion enthalpy of a pure liquid can be determined Other Methods. Vapor pressure data are of-
from vapor pressure data with the rigorous equa- ten unavailable or of insufficient accuracy for the
tion of Clausius and Clapeyron (Eq. 1.1). Its ap- application of the Clausius – Clapeyron equa-
proximate version (Eq. 1.2) yields tion. Other estimation methods then have to be
dlnplv used for the estimation of the vaporization en-
∆H lv =RT 2 (4.20) thalpies. Two of these are described in Section
dT
With the Antoine Equation (4.5) for the differ- 1.3 (Eqs. 1.5 and 1.6). Vetere [159] suggested
ential quotient d ln plv /d T the following relation the following set of correlations (∆H lv , J/mol;
is obtained: M, g/mol; T b , K) [147]:
B 1) Hydrocarbons
∆H lv =RT (4.21)
(T +C)2
Equation (4.21) can be readily used to calcu- ∆HTlv
late ∆H lv with the aid of tabulated Antoine RTb
b
=7.0054 + 1.647log M
constants [149]. For moderate to high pressures . /−1.037
( plv > 0.1 MPa) the simplifying assumptions 0.7806 Tb − (263M )0.581
+ (4.24)
leading to Equation (1.2) are not justified. This M
means that the molar volumes of the liquid and
the vapor must be taken into account. In Equa- 2) Alcohols, organic acids, methylamine
tion (1.4) this has been done only for the vapor
phase. ∆HTlv
b
=9.7643 + 1.5748log
A convenient way to consider both vapor and RTb
liquid molar volume is described by Haggen- 3.1018Tb 0.0176375Tb2
macher [158]. He employs the difference in the Tb − +
M M
compressibility factors of the vapor and the liq- 2.57131 × 10−5 Tb3
uid: − (4.25)
M
p v
∆z lv =z v −zl = V −V l (4.22) 3) Esters
RT
which can be approximated by the relation
1/2 ∆HTlv
plv b
=5.501 + 1.901log
∆z =lv
1− r3 (4.23) RTb
Tr
0.04852Tb 0.53689 × 10−3 Tb2
Use of Equations (4.22) and (4.23) allows deter- Tb + +
M M
mination of V v − V l . Introduction of this term −6
0.6977 × 10 Tb3
into Equation (4.1) improves the calculation of − (4.26)
M
the enthalpy of vaporization except in the region
close to the critical point. Correction factors for 4) Other polar compounds
acetone and trichloromethane are shown in Fig-
ure 7. ∆HTlv
b
LIVE GRAPH =5.3405 + 1.8453log
Click here to view
RTb
0.047109Tb 0.52125 × 10−3 Tb2
Tb + +
M M
0.67738 × 10−6 Tb3
− (4.27)
M
Corresponding states methods (e.g., Pitzer’s
correlation) should also be mentioned. These
methods are discussed in [160].
Figure 7. Influence of the Haggenmacher correction on the

prediction of the heats of vaporization
Table 10. Selected methods for the prediction of the enthalpy of vaporization ∆ H lv of pure substances
Method Range of application Information Error, %

required ∗
Riedel 1954 [162] T = Tb T b , T c , pc 2

Chen 1965 [163] T = Tb T b , T c , pc 2
Vetere 1973 [159] T = Tb plv (T ), T c , pc 2 ∗∗
Antoine equation, 0.4 < T r < 0.8 plv (T ), T c , pc , l for T r > 0.5 with
(Haggenmacher 1946 [158]) inclusion of Eq. (4.23)
Wagner 1973 [164] T vls < T < 0.95 T c plv (T ), (T c , pc ) 1 ∗∗
Kobayashi 1984 [165] nonpolar, weakly polar T r < 0.98 T c, ω 1.5
Watson 1943 [166] nonpolar, weakly polar 0.5 < T r < 0.75 T c , ∆H lvref 0.05 (T − T ref )
Lee – Kesler – Pitzer 1975 [150] nonpolar, weakly polar 0.5 < T r < 0.98 T c , pc , ω 1.5
∗ In addition to the corresponding parameters and increments.

∗∗ Depends on the accuracy of vapor pressure data.
A summary of estimation methods for ∆H lv Temperature Dependence. The tempera-

appears in Table 10. Figure 8 shows a compari- ture dependence of the vapor pressure can be
son of different estimation methods. Experimen- represented satisfactorily using Watson’s equa-
tal data can be found in [161]. tion [166]:
LIVE GRAPH n
Click here to view
1−Tr
∆HTlv = ∆HTlvb (4.28)
1−Tbr
A value of 0.38 is recommended for the exponent

n, but if other values of ∆H lv are available this
equation can be used efficiently for the correla-
tion of the temperature dependence of ∆ H lv by
adjusting the exponent n.
4.2. Mixtures
Calculation of phase equilibria is based on the
thermodynamic conditions for equilibrium, i.e.,
equality of temperature T , pressure p, and fu-
gacities f i of each component i in the coexisting
phases. This means that for the mathematical de-
scription of phase equilibria, expressions repre-
senting fugacities as a function of composition
are required. Two types of formulations are used
which differ in the state of reference. With the
ideal gas as state of reference, the fugacity fi of
component i in a mixture is given by
fi =xi ϕi P (4.29)
Figure 8. Comparison of estimation methods for the pre-
diction of heat of vaporization of chloromethanes where xi is the concentration of i (usually as
a) Dichloromethane; b) Trichloromethane; c) Tetrachloro-
methane mole fraction) and ϕi the fugacity coefficient
Open symbols denote experimental data, lines denote pre- (with ϕi = 1 for ideal gases).
dicted values With an arbitrary state of reference, which
is very often the pure component i at its vapor
pressure, the following relation is defined:
This means that a simplified version of Equation

fi =xi γi fi0 (4.30) (4.33) can be used for the majority of vapor – liq-
with γi as activity coefficient of i in the mixture uid equilibria without much loss in accuracy:
and f 0i as fugacity of i at the state of reference.
yi p=xi γi plv
0i (4.34)
With Equation (4.34) the vapor phase is con-

4.2.1. Vapor – Liquid Equilibria with sidered ideal and all nonideality effects are at-
Liquid-Phase Activity Coefficients tributed to the liquid-phase activity coefficient
γi . For γi = 1, Equation (4.34) transforms into
4.2.1.1. Basic Considerations Raoult’s law for the partial pressure pi in ideal
mixtures:
For the correlation and prediction of vapor – liq-
uid equilibria at low to moderate pressure (< ca. pi =yi p=xi plv (4.35)
0i
1.0 MPa) Equation (4.30) is usually applied to
the liquid phase. The vapor phase is either con- The activity coefficients γi in liquid mixtures
sidered to be ideal or a correction for real gas are directly related to an important thermody-
behavior is applied (e.g., by estimated second namic quantity characterizing nonideal mixing
virial coefficients). The reference state in the liq- behavior, i.e., the molar excess Gibbs energy of
uid phase for each component i in the mixture mixing ∆GE which is defined as the difference
is the pure liquid i with a vapor pressure plv 0i at in the molar Gibbs energy of mixing between
temperature T . With this reference state Equa- real and ideal mixtures:
tion (4.30) for component i in a liquid mixture
is given by ∆GE = ∆G−∆Gid (4.36)
 
p This quantity is related to the activity coeffi-
 1 
fil =xi γi plv
0i ϕ0i exp 
l
V0i dp (4.31) cients γi of all components i in a mixture by
RT
p0i the following equation:

which includes two corrections, i.e., the fugac- ∆GE =RT xi lnγi (4.37)
ity coefficient ϕ0i for the pure liquid at pressure
p0i and the exponential term called the Poynt- Conversely, the activity coefficients γi in a mix-
ing factor which corrects for the difference of ture can be obtained from ∆ G E when this quan-
fugacity between plv0i and system pressure p. If tity is known as a function of composition (i.e.,
the liquid volume V l0i is assumed to be constant of all xi ) according to:
(independent of pressure), the Poynting factor
Πi is simply given by ∂n·∆GE
RT lnγi = (4.38)
∂ni T ,p,nj
l
V0i p − plv
0i
Πi =exp (4.32)
RT where n is the total number of moles and ni the
number of moles of component i.
Equality of fugacities in the vapor and liquid
phases yields with Equations (4.29) and (4.31)
the following general relation for vapor – liquid 4.2.1.2. Data Correlation: Binary and
equilibria: Multicomponent Mixtures of
Nonelectrolytes
yi ϕi p=xi γi plv
0i ϕ0i Πi (4.33)
Numerous correlation methods have been pub-
with yi and xi as the mole fractions of i in the
lished. They include flexible polynomials (e.g.,
vapor and liquid, respectively.
Margules, van Laar, Redlich – Kister series)
At pressures up to several hundred kilopas-
and other more sophisticated semitheoretical
cal (several bar) the fugacity coefficients ϕi and
models, especially those based on the concept
ϕ0i and the Poynting factor Πi are usually not
of local composition [Wilson, Non-Random
significantly different (< 2.3×10−3 ) from unity.
Table 11. Model equations for calculating the molar excess Gibbs energy of mixing ∆GE in liquid mixtures
Model Parameter Equation
Margules-3 A ln γ 1 = x 22 [A + 2 (B − A) x 1 ]
(binary systems) B ln γ 2 = x 21 [B + 2 (A − B) xr2 ]
∆GE

r
Wilson [167] Λij , Λji (Λii = Λjj = 1) RT = − x i ln xj Λij

i i

r
r
x Λ
lnγi = − ln xj Λij +1−
k ki
xj Λkj
i k j
V l0j λ −λ
with Λij = exp − ijRT ii
Vl
0i

r
τji Gji xj
∆GE

r
j
NRTL [168] τij , τji , αij = αji RT =− xi
r
i Gki xk
k  

r
τji Gji xj xk τkj Gkj

r xj Gij  
τij −
i k
lnγi =
r +
r 
Gki xk j Gkj xk Gkj xk
k k k
with τij = g −giiij
RT and
Gij = exp {− αij τij }
E

A

UNIQUAC [169] τij , τji ∆G

RT = xi lnSi + z2 qi xi ln S i − qi xi ln xj Aj τji
i i i i i
ln γi = ln γ C R
i + ln γ i
S S
lnγiC = 1−Si +lnSi − z2 qi 1+ Ai +ln Ai

qj xj τji
i i
j
qj xj τij
lnγiR =qi 1 − ln
q x −
q x τ j j j k k kj
j k
−∆u
with τij =exp T ij , ∆uii =∆ujj =0,
z = 10
Si , Ai , see Equations (4.42) and (4.43)
Two-Liquid ( NRTL), and UNIversal QUAsi- tion concept was introduced by Wilson [167];
Chemical ( UNIQUAC) equations]. the essential feature of this idea is that it consid-
Relations for some of these model equations ers only binary interactions between neighbor-
are given in Table 11. If reliable experimen- ing molecules in the liquid mixture.
tal data are available, equations with two pa- Other models using the local composition
rameters per binary system are usually suitable concept are the NRTL [168] and UNIQUAC
for correlating and extrapolating available data [169] equations. In contrast to the Wilson equa-
with respect to composition and, to a limited tion these models are able to describe the coex-
degree, to temperature. Numerous papers have istence of two liquid phases, i.e., liquid – liquid
been published comparing different ∆G E mod- phase splitting.
els. But no essential advantages for any of these
correlation methods could be found with respect
to their ability to fit data. 4.2.1.3. Prediction of Equilibrium Data
Another important aspect has to be consid- Solution-of-Groups Concept. Measure-
ered. The majority of published vapor – liquid ment of vapor – liquid equilibria is difficult,
equilibrium data are concerned with binary sys- time-consuming, and costly. Thus reliable and
tems, only a few with ternary systems, and very widely applicable estimation methods are of
few with systems of four and more compo- utmost interest. Numerous attempts to derive
nents. In practical chemical engineering prob- methods for the prediction of the properties of
lems, however, systems with at least five or more nonelectrolyte liquid mixtures using only pure
components often have to be treated. Here the component information (e.g., dipole moment
models based on the concept of local compo- or parachor) have failed. In contrast, methods
sition show the advantage that only binary pa- based on structural groups have turned out to
rameters are required for the representation of be quite successful. The starting point for these
multicomponent systems. The local composi- concepts is the assumption that a mixture is com-
posed of structural groups and not of molecules. only and is the Staverman expression taken from
Consequently interactions between structural the UNIQUAC model:
groups are considered instead of interactions
z Si Si
between molecules. The large variety of molec- lnγiC = 1−Si +lnSi + qi 1− +ln (4.41)
ular mixtures resulting from the huge number 2 Ai Ai
of compounds is reduced to a limited number of where xi is the mole fraction. The volume frac-
combinations of structural groups (e.g., −CH3 , tion Si and surface fraction Ai are defined as
> CH2 , −OH, −CHO, > C=O). This “solution- follows:
of-groups” concept was originally introduced to
ri
phase equilibrium calculations by Redlich et Si = (4.42)
r j xj
al. [167] and Wilson and Deal [171]. The first j
method of practical importance based on this Ai =
qi
(4.43)
concept was the Analytical Solution Of Groups q j xj
j
(ASOG) method of Derr and Deal [172].
where the parameters ri and qi represent the rela-
ASOG Method. This method employs an tive volume and relative surface area of the com-
athermal Flory – Huggins term to consider size ponent i; z is the coordination number and is usu-
effects and the Wilson equation for the inter- ally fixed as z = 10. These size parameters have
actions of the structural groups. Therefore the been tabulated for many groups [175] or can be
activity coefficient γi is split into two parts: calculated [176].
The residual part considers group – group in-
lnγi = lnγiC +lnγiR (4.39) teractions via the group activity coefficient Γi
following the UNIQUAC model for the main
where the combinatorial part ln γ C i considers groups m and n:
size effects and the residual part ln γ R
i the group
interactions. Equation (4.39) is the basic rela- lnΓk =
tionship of the solution-of-groups concept. The  
Θm Ψkm
residual part ln γ R
i is related to the pure liquid i Qk 1 − ln Θm Ψmk − 
(4.44)
according to m
Θn Ψnm
n
. /
lnγiR =
(i)
νki lnΓk − lnΓk (4.40) with the area fraction Θm of group m defined by
k
Qm Xm
Θm = (4.45)
where νki is the number of groups of type k in Qn Xn
(
component i; Γk and Γ k i) are the correspond- where Xm is the group mole fraction and Qm <
ing group activity coefficients in the mixture and the group surface area. The group energy term
in the pure liquid, respectively. They are calcu- Ψnm for the interaction between the groups m
lated from interaction parameters that have been and n is defined by
determined from reliable vapor – liquid equilib-
rium data. The latest version of ASOG gives −amn
Ψnm =exp (4.46)
interaction parameters for 43 structural groups T
[173]. At present, interaction parameters amn are
known for 50 main groups, some of which com-
UNIFAC Method. More recently Fre- prise subgroups (e.g., main group CH2 with
denslund et al. [174] derived the UNIversal subgroups C, CH, CH2 , and CH3 ). Several
Functional group Activity Coefficients (UNI- smaller molecules (e.g., water, methanol) and
FAC) method. This group contribution model some molecules with special structures (e.g.,
applies the UNIQUAC equation [169] to the pyridine, N-methylpyrrolidone) have been de-
solution-of-groups concept (Eq. 4.39). Since fined as main groups.
this model is most widely accepted and applied, The interaction parameters have been deter-
it is described here in more detail. The combina- mined from reliable, thermodynamically con-
torial part contains pure component parameters sistent experimental vapor – liquid equilibrium
Figure 9. Status (1991) of the UNIFAC parameter matrix [178]

Abbreviations: A = aromatic; (C)3 N = tertiary amine; DMF = dimethylformamide; DMSO = dimethyl sulfoxide; DOH = 1,2-
ethanediol; NMP = N-methylpyrrolidone
data [175], [177], [178]. The present state can 3) Neighboring effects (i.e., interaction bet-
be seen in Figure 9. ween “strong” functional groups within the
The predictive ability of the UNIFAC method same molecule) are not considered.
is quite remarkable. Provided accurate pure-
component vapor pressures are known, errors in Much effort has been and still is devoted
vapor phase composition are usually ca. 1 mol%. to overcoming these shortcomings, e.g., [179].
Typical results of UNIFAC predictions are dis- Gmehling et al. [180], [181] have included ex-
played in Figure 10, which demonstrates the pre- perimental data for both heats of mixing and ac-
dictive power of the UNIFAC method. In cases tivity coefficients at infinite dilution into their
where only little or unreliable primary data are data base from which they determined tem-
available for the determination of group inter- perature-dependent group interaction parame-
action parameters (e.g., for combinations with ters. They showed that this modified UNIFAC
aldehydes) serious deviations may be expected. method can be used to predict temperature-
dependent activity coefficients at both bulk com-
This original UNIFAC method has additional position and high dilution and also mixing en-
limitations: thalpies with satisfactory accuracy.
A different approach in applying group con-
1) Limited temperature dependence leading to tributions for the prediction of activity coeffi-
unsatisfactory prediction of heat of mixing cients was proposed by Kehaian et al. [182].
data Their method is based on Barker’s lattice theory;
2) In many cases isomers cannot be distin- interaction parameters have only been published
guished from one another for a limited number of group combinations.
Figure 10. Results of UNIFAC predictions (curves) compared with experimental data (dots) for 16 ketone – alkane mixtures
x 1 = mole fraction of underlined component in the liquid phase; y = mole fraction of underlined component in the vapor phase
Only two interaction parameters (aCH2 , CH2 CO = 476.4 K, aCH2 CO, CH2 = 26.76 K) have been used for all diagrams [177].
For practical purposes the classical UNIFAC mer solutions Oishi and Prausnitz proposed
method with its large interaction parameter ma- the inclusion of a free volume term ln γ FV
i in
trix provides a useful tool for the prediction Equation (4.39) [184]:
of vapor – liquid equilibria of unknown systems
lnγi = lnγiC +lnγiR +lnγiFV (4.47)
and also for the selection of solvents in extrac-
tive and azeotropic distillation [183]. The ma- For gas – liquid equilibria the activity coeffi-
trix of UNIFAC interaction parameters is given cient approach (Eq. 4.30) employing the pure
in [178]. liquid as reference state cannot apparently be ap-
plied when the system temperature exceeds the
Extensions of the UNIFAC Method for critical temperature of one of the components,
Polymer Solutions and for Gas Solubilities. as is the case with solubilities of so-called per-
In order to apply the UNIFAC method to poly- manent gases (e.g., nitrogen, oxygen, methane,
ethylene) in liquids at ambient temperature. A a consequence, the molecular methods have not
hypothetical liquid state of the gaseous compo- yet become established for engineering calcula-
nent i may then be defined by extrapolating the tions.
standard fugacity f 0i beyond the critical tempera-
ture. Using this hypothetical liquid state Nocon
et al. [185], [186] obtained satisfactory predic- 4.2.2.2. Data Correlation
tions of solubilities of nitrogen, oxygen, carbon
dioxide, methane, and ethylene in hydrocarbons An extensive compilation of high-pressure
and alcohols with a UNIFAC method based on vapor – liquid equilibria and gas – liquid equi-
Equation (4.47) (i.e., by including a free volume libria data has been presented by Knapp et al.
term). [189]. They tested the capability of four com-
mon equations of state (Lee – Kesler – Plöcker,
LKP; Benedict – Webb – Rubin – Starling,
4.2.2. Vapor – Liquid and Gas – Liquid BWRS; Redlich – Kwong – Soave, RKS;
Equilibria with Equations of State Peng – Robinson, PR; see Section 3.1.1) in re-
presenting experimental data for a large number
4.2.2.1. Basic Considerations of binary systems. The calculations of Knapp et
al. show that there is no principal advantage of
Taking the ideal gas as standard state for the fu- any of these equations. They yield satisfactory
gacities (Eq. 4.29), the equilibrium condition of results when the components involved are not
equal fugacities in the vapor and liquid phases highly polar or do not differ too much in size.
yields for component i: More generally applicable are the so called
∆G E mixing rules. Huron and Vidal [190]
yi ϕvi =xi ϕli (4.48) proposed using the following definition of the
excess Gibbs energy:
With this relation the same thermodynamic

model can be used for both phases. The fugacity ∆GE = RT lnϕ − xi lnϕi0 (4.50)
coefficient can be calculated from the rigorous
relation where the fugacity coefficient ϕ accounts for the
real behavior of the mixture:
p
1 ∂V RT
lnϕi = − dp (4.49) p
RT ∂ni p 1 RT
0
T ,p,nj=i lnϕi = V − dp (4.51)
RT p
0
employing an equation of state for V . The ad-
vantage of this approach is that no standard-state The fugacity coefficients ϕi0 of the pure com-
fugacity is necessary. This is particularly useful ponents are given by Equation (4.49). Substi-
when the mixture consists of both sub- and su- tution of ∆G E in Equation (4.50) by Equation
percritical components. A further advantage is (4.37) leads to an expression from which mix-
the possibility of calculating other mixture prop- ing rules for the parameter a of cubic equations
erties such as densities, enthalpies, and entropies of state (Section 3.1.1) can be derived. When in-
of the two phases. Numerous equations of state finite pressure (p → ∞) is chosen as reference
have been published but accurate prediction of state, it can be assumed that the parameter b is
phase equilibria of mixtures is not yet possi- equal to the molar volume V . With this assump-
ble from pure-component data only. Hence, bition and the linear mixing rule for bm (Eq. 3.39)
nary interaction parameters (see Section 3.1.3.1) the Huron – Vidal (HV) mixing rule for the RKS
must be obtained from experimental data for equation of state (Eq. 3.11) can be derived:
mixtures.
ai xi lnγi
Modern statistical mechanics have achieved am = bm RT xi · − (4.52)
bi RT 0.6931
remarkable progress in the last two decades
[187], [188]. Nevertheless, computation time is Other reference states may be chosen. For ex-
still considerable. Adequate force models are ample with p = 0 the modified Huron – Vidal
available only for rather simple molecules. As (MHV) mixing rules have been derived [191].
With a constant value for the ratio V /b the MHV1 (Eq. 4.54) of several hydrocarbon gases (1) in
mixing rule [192] for the RKS equation of state the liquid solvent (2) eicosane.
is obtained:
f1
H12 = lim (4.54)
xi →0 x1
am = (4.53)
 
ai xi lnγi + xi ln bbm where f 1 is the fugacity of gaseous component
bm RT  xi · + i 
(1) and x 1 the mole fraction of gaseous compo-
bi RT A
nent (1) in the liquid. LIVE GRAPH
Depending on the value of V /b different val- Click here to view
ues for A will result. In the PSRK method (pre-

dictive Soave – Redlich – Kwong [193], Sec-
tion 4.2.2.3) with V /b = 1.1 the value of A
is − 0.64663. Equation (4.53) allows any G E
model for the liquid phase to be incorporated
(see Section 4.2.1.2) into the RKS equation of
state.
Based on the ∆G E mixing rules several other
models have been proposed; they differ mainly
in the reference pressure and in the V /b ratio.
They are all well suited for the representation of
vapor – liquid and gas – liquid equilibria, also at
high pressures and for strongly polar systems.
For the latter systems they should be preferred
to equations of state combined with density-
dependent mixing rules (e.g., [194]) or with as-
sociation models (e.g., [195], [196]).
4.2.2.3. Prediction of Vapor-Liquid and

Gas-Liquid Equilibria
Since any type of GE model can be introduced

into Equation (4.53), group contribution meth-
ods can be applied, too. The PSRK group con-
tribution equation of state [193] combines the
UNIFAC method (Section 4.2.1.3) with the RKS
equation of state. Thus all group interaction pa-
rameters tabulated for UNIFAC can be used. Figure 11. Results of PSRK predictions (lines) compared
Moreover new groups for gaseous components with experimental data (•) from the Dortmund Data Bank)
have been included: NH3 , CO2 , CH4 , O2 , Ar, for Henry coefficients of hydrocarbon gases in eicosane (n-
N2 , H2 S, H2 , CO, SO2 , NO, N2 O, SF6 , He, Ne, C20 H42 )
Kr, Xe, HCl, HBr [193], [197].
Compared to other group contribution equa-
tions of state proposed for estimating vapor – liq- 4.2.3. Liquid – Liquid Equilibria
uid equilibria up to the critical region [198],
[199], [200] the PSRK method can be applied Phase splitting of a liquid mixture into two liq-
over a wider range of temperature and pressure. uid phases occurs when a single liquid phase is
In addition, many more groups and their param- thermodynamically unstable. For the computa-
eters have been defined for the PSRK method. tion of liquid – liquid equilibria, equality of fu-
As an example of its predictive power, a com- gacities for each component in the two phases
parison of predicted gas solubilities is given in is usually applied. Since this equilibrium condi-
Figure 11. It shows the Henry coefficients H 12 tion is only necessary, but not sufficient, it should
be combined with an analysis of thermodynamic Octanol – Water Distribution Coefficients.

stability in order to find the true equilibrium. Us- The distribution coefficient of toxic substances
ing Equation (4.30) for the fugacities fi and fi between octanol and water is an important prop-
in phases I and II with the same reference state erty in toxicology and environmental science
for f 0i yields the following relation: since it correlates with the distribution of sub-
stances between a lipid and an aqueous phase.
xi γi =x
i γi (4.55) For the estimation of octanol – water distribution
coefficients, Hansch and Leo [204] developed a
The products xi γi and x i γ i are the so-called much used group contribution method. Another
activities. Since Equation (4.55) holds for each such method has been proposed by Wienke and
component of a liquid – liquid system, it should Gmehling [205]. It is based on the UNIFAC
be possible to predict liquid – liquid equilibria method and has the advantage that other equi-
when the ∆G E function (Eq. 4.37) and conse- librium constants relevant to the distribution of
quently the activity coefficients of the individ- chemicals in the environment, i.e., Henry con-
ual components in the multicomponent system stants and water solubilities, can be predicted
are known (e.g., from vapor – liquid equilibria with the same parameters.
or from prediction methods developed for these
phase equilibria, such as UNIFAC). This proce-
dure entails several problems, however: 4.2.4. Solid – Liquid Equilibria
1) Whereas in vapor – liquid equilibrium calcu-
Solid – liquid equilibria may be roughly classi-
lations activity coefficients serve as a correc-
fied into systems without miscibility of the com-
tion of Raoult’s law (cf. Eqs. 4.34 and 4.35),
ponents in their solid states (eutectic systems)
they are the sole numerical input into cal-
and systems that form mixed crystals. With non-
culations of liquid – liquid equilibria. There-
electrolytes the first type of behavior is much
fore, the accuracy of activity coefficients γi
more frequent. For these systems the following
for modeling and predicting liquid – liquid
relation between the solubility of pure solid i
equilibria has to be considerably higher than
(expressed as liquid mole fraction x li ) and tem-
for vapor – liquid equilibria.
perature T holds:
2) Systems with phase splitting often show
rather high temperature dependence of activ-
∆Hisl T
ity coefficients, which is in general predicted ln xli γil = − 1− (4.56)
RT Tm,0i
less reliably.
3) The majority of vapor – liquid equilibrium where ∆H sl i is the enthalpy of melting and T m, 0i
data and the associated activity coefficient the melting point of pure component i (terms of
data have been determined at other, usually higher order have been neglected in Eq. 4.56).
higher temperatures than are of interest for The liquid-phase activity coefficient γ li can be
liquid – liquid equilibria. estimated with group contribution methods such
as UNIFAC [206], [207]. At high concentra-
Modifications of the UNIFAC method, ei- tions of i the equilibrium temperature T (i.e.,
ther by creating a separate UNIFAC parameter the freezing point of a liquid solution or melt)
matrix for liquid – liquid equilibrium prediction can be predicted quite reliably without know-
[201] or by including experimental liquid – liq- ing the value of the liquid-phase activity coeffi-
uid equilibria data into the determination of in- cient γ li , because γ li generally approaches unity
teraction parameters [181], [202], have achieved at these concentrations. With this assumption,
limited success. rearrangement of Equation (4.56) (with some
The use of equations of state has been tested simplifications) yields the well-known Raoult
with promising results for the calculation of liq- equation for the lowering of the freezing point
uid – liquid equilibria, for example, extrapola- of solutions at low solute concentrations:
tion of liquid – liquid equilibria to higher pres-
sures and representation of vapor – liquid – liq- RTm,0i
Tm,i − T = (1−xi ) (4.57)
uid equilibria [203]. ∆Hisl
5. Thermodynamic Data of Chemical is still in use. Generally the standard forma-

Reactions tion enthalpy ∆H 0f298 of a compound is given
for its most stable state at standard pressure
5.1. Definitions (1.01325 bar at 298.15 K) . For the elements
∆H 0f298 is zero by definition in their most stable
Thermodynamic data of chemical reactions are state under standard conditions (for gases: the
highly important in process design for two rea- ideal gas state).
sons: The standard reaction enthalpy ∆H 0r298 for
Equation (5.1) is thus given by
1) Molar reaction enthalpies (heats of reaction) 0 0 0
∆H r are required in the design of chemical ∆Hr298 =γ ∆Hf298,C +δ∆Hf298,D
reactors, since the heat effect connected with −α∆Hf298,A
0
−β ∆Hf298,B
0
(5.4)
the reaction must be known to control the re-
action temperature. or in general
2) The molar Gibbs energy ∆G r (also called
0
∆Hr298 = νi ·∆Hf298,i
0
(5.5)
the free enthalpy) of a chemical reaction is
directly related to the reaction equilibrium; At temperature T the heat of reaction ∆H 0rT
knowledge of ∆G r allows prediction of equi- is calculated from ∆H 0r298 with the aid of the
librium concentrations. molar heat capacities (ideal gas state) c0pi of the
reactants:
T
5.1.1. Reaction Enthalpy 0 0
∆HrT =∆Hr298 + ∆cpr dT (5.6)
298.15
Reaction enthalpies can be determined from the
with ∆cpr = νi cpi . This is in fact a heat bal-
enthalpies of formation ∆Hf of the compounds
ance. Therefore in the case of phase changes
taking part in the reaction. Thus, for the reaction
between standard-state and reaction conditions
αA + βBγc + δD (5.1)
(T, p) for one or several reactants the respective
phase change enthalpies ∆H trs also have to be
the reaction enthalpy ∆H r is given by included yielding the following general expres-
sion:
∆Hr =γ ∆HfC +δ∆HfD −α∆HfA −β ∆HfB (5.2)
T
0 0
or by the general form ∆HrT = ∆Hr298 + ∆cpr dT
298.15

∆Hr = νi ∆Hfi (5.3) + νi ∆Hitrs (5.7)
where ν i is the stoichiometric coefficient of

compound i (according to the rules of chemical
thermodynamics, ν i is positive for products and
negative for educts) and ∆H fi is the enthalpy of 5.1.2. Gibbs Energy of Reaction and
formation of compound i. Chemical Equilibrium
For the calculation of reaction enthalpies
the formation enthalpies of many compounds Gibbs energies of reaction are calculated analo-
have been tabulated for a standard state gously to reaction enthalpies. For the reaction of
of 1.01325 bar = 1 atm at 298.15 K [208–215]. Equation (5.1) the Gibbs energy ∆Gr is equal to
They are designated as ∆H 0f298 (with super- the sum of the Gibbs energies of formation ∆G f
script 0 for standard pressure and subscript 298 of the reactants multiplied by their stoichiomet-
for standard temperature, 298 K). Since 1982 ric coefficients:
0.1 MPa = 1 bar has been recommended as stan- ∆Gr =γ ∆GfC +δ∆GfD −α∆GfA −β ∆GfB (5.8)
dard pressure, but in chemical thermodynam-
ics and relevant data compilations 1.01325 bar The general form of Equation (5.8) is
For all those reactions for which values of ei-

∆Gr = νi ∆Gfi (5.9) ther ∆G 0f298 or ∆H 0f298 and S 0298 are available for
each reactant the value of K at 25 ◦ C (298.15 K)
In order to determine the standard Gibbs en- can easily be determined:
ergy of reaction ∆G 0r298 with Equation (5.8) or
(5.9) the relevant standard quantities of forma- ∆G0r298
tion ∆G 0f298 have to be used. lnK298.15 = − (5.12b)
298.15R
Another way of calculating ∆G 0r298 uses the
definition The dependence of K on temperature is given
by the Van’t Hoff Equation:
∆Gr = ∆Hr −T ∆Sr (5.10)
0
dlnK ∆HrT
Application of Equation (5.10) requires ∆H 0r298 dT
=
RT 2
(5.15)
from Equation (5.5) and ∆S 0r298 obtained from
standard entropies S 0298 according to Equation Integration of Equation (5.15) with ∆H 0rT as a
(5.11): function of temperature according to Equation

(5.6) yields a general relation for calculating K
0
∆Sr298 = 0
νi S298 (5.11) at temperature T when it is known at temperature
T 0 (e.g., 298.15 K):
Data for ∆G 0f298 and S 0298 can be found for many
0
∆HrT
compounds in data collections, e.g., in [208], 1 1
lnK (T ) = lnKT0 − 0
−
[211], [213], [214]. R T T0
Conditions for equilibrium at constant pres- T
1
sure and temperature yield the following − ∆cpr dT
RT
relation between the Gibbs energy of re- T0
action ∆G0rT (ideal gas at standard pres- T
sure = 1.01325 bar = 101.325 kPa) and equilib- 1 ∆cpr
+ dT (5.16)
rium constant K: R T
T0
∆G0rT = −RT lnK (T ) (5.12a) For a first approximation the integrals in Equa-
tion (5.16) can be neglected which means that
For the chemical reaction of Equation (5.1) K is the reaction enthalpy ∆H r is considered to be
defined as independent of temperature. With K known at
γ δ
T 0 = 298.15 K this first approximation is
fC 0α f 0β
fD f A
K= β
· 0γ B (5.13) 0
αf
fA fC fD 0δ ∆Hr298 1 1
B lnK (T ) = lnK298.15 + − (5.17)
R 298.15 T
with the standard fugacity f 0i of the reactants
A, B, C, D (equal to the standard pressure of In a second approximation the sum of the molar
1 atm). K is a function of temperature only, but heat capacities ∆cpr is considered to be constant
not of pressure. At low pressure where real gases [∆cpr (T ) = ∆cpr ]:
do not show much difference from ideal gas 0
∆Hr298 1 1
phase behavior, the fugacities fi can be consid- lnK (T ) = lnK298.15 + −
R 298.15 T
ered as ideal gas partial pressures. The “ther-
∆cpr T 298.15
modynamic” (true) equilibrium constant K is + ln + −1 (5.18)
R 298.15 T
then practically equal to the numerical value of
the equilibrium constant K p expressed in par- For approximate estimations Equations (5.17)
tial pressures pi = yi p ( yi is the mole fraction and (5.18) are sufficient; accurate predictions,
of component i in the gas phase) of the reactants especially at high temperatures, require evalua-
as: tion of the integrals in Equation (5.16).
Concerning the effect of pressure on equi-
pγC pδD
Kp = ≈ K· (1atm) νi
(5.14) librium concentrations the influence of real
β
pα
A pB gas behavior on K p has to be considered. At
low to moderate pressures (up to several hun- molecules can be used as the basis for estimating
dred kilopascal)

K p is approximately equal to thermodynamic reaction quantities, in particular

vi of organic substances.
K(1 atm) (Eq. 5.14). But with higher pres-
sure the difference between the numerical values Various such group contribution methods
of K and K p increases and cannot be neglected have been proposed for the estimation of stan-
at pressures > ca. 1 MPa. This effect can be pre- dard enthalpies, Gibbs energies of formation,
dicted when the pVT behavior of the reaction and standard entropies (Table 13). The method
mixture is known. Using the relation of Joback [216], [217] is explained in more de-
tail.
fi =ϕi yi p=ϕi pi (5.19) In the Joback method ∆H 0f298 , ∆G 0f298 , and
the molar heat capacities c0p are calculated via
where ϕi is the fugacity coefficient for compo- Equation (5.21), (5.21a), and (3.46):
nent i, Equation (5.13) is transformed as follows:

νi 0
∆Hf298 = 68.29+ si IHi [kJ/mol] (5.21)
pγ pδ ϕγC ϕδD 1
K= C D · ·
pα β α β
A pB ϕA ϕB
atm

νi ∆G0f298 = 53.88+ si IGi [kJ/mol] (5.21a)
1
=Kp Kϕ · (5.20)
atm where si is the number of structural groups of
The parameter Kϕ represents the effect of real type i and IHi and IGi are the increments of struc-
gas behavior on chemical equilibrium. The mag- tural groups i for enthalpy and Gibbs energy of
nitude of this effect on high-pressure equilibria formation, respectively.
can be seen from Table 12, where data for the The structural groups are the same as in the
methanol synthesis equilibrium are given. Joback method for the estimation of critical data
(Chap. 2). The values of the group contributions
Table 12. Effect of pressure on equilibrium of methanol synthesis IHi for ∆H 0f298 ; IGi for ∆G 0f298 ; and I a , I b , I c ,
at 300 ◦ C (CO + 2 H2 CH3 OH) K = 2.316×10−4 and I d for the coefficients of the polynomial for
p, bar (MPa) Kϕ K p , atm−2 c0p are given in Table 14.
10 (1) 0.96 2.41×10−4
As is evident from Equations (5.21) and
25 (2.5) 0.90 2.57×10−4 (5.21a), standard formation enthalpies ∆H 0f and
50 (5) 0.80 2.90×10−4 standard Gibbs energy of formation ∆G 0f can
100 (10) 0.61 3.80×10−4 be obtained directly for 298.15 K only. In order
200 (20) 0.38 6.09×10−4
300 (30) 0.27 8.58×10−4
to calculate these quantities and the equilibrium
constant K for other temperatures, the molar heat
capacities c0p have to be evaluated as a function
of temperature with Equation (3.46); ∆H 0f and
K can be then determined with Equations (5.6)
5.2. Group Contribution Methods for and (5.16), respectively.
the Estimation of Enthalpies and Gibbs Deviations of ∆H 0f298 and ∆G 0f298 calculated
Energies of Formation with the Joback method from literature data are
mostly below 10 kJ/mol; in a few cases, however,
Especially in processes for new products, ther- differences of more than 20 kJ/mol were found
modynamic data (∆H 0f , ∆G 0f ) are often not [218]. With the methods of Benson [219], [220]
available for all compounds and their estimation and of Yoneda [221] errors are somewhat smaller
is extremely helpful. because they use larger numbers of groups which
Chemical reactions can be considered as pro- allow higher differentiation in structure. Appli-
cesses in which molecular bonds are broken and cation of these methods is, however, rather te-
others are formed. The thermodynamic func- dious. In both methods ∆G 0f298 is obtained via
tions for a chemical reaction can therefore be Equation (5.10), formulated for the reaction of
considered as the sum of the contributions of formation for which ∆H 0f298 and the standard
those chemical bonds which are altered (i.e., entropy S 0298 are estimated with group contribu-
broken or formed) by the reaction. In a simi- tions. In the same way, molar heat capacities c0p
lar approach the structural groups of the reacting
Table 13. Group contribution methods for the estimation of ∆H 0f , ∆G 0f , and S 0
Authors Estimated Form in which contributions are Average error, Secondary sources for
parameters given kJ/mol increments; remarks
Benson [219], [220] ∆H 0f , S 0 IH (298), IS (298); Ic (T ) 10 [218]
Constantinou and Gani [225] ∆H 0f , ∆G 0f IH (298); IG (298) 10 ∆H 0f and ∆G 0f at 298 K only
Franklin [222] ∆H 0f IH (T ) 15 [227]; in kcal/mol
Joback [216], [217] ∆H 0f , ∆G 0f IH (298); IG (298); Ic = f (T ) 15 this article (Table 14); [218]
van Krevelen and Chermin ∆G0f IG = A + B T 15 [226], [227]; in kcal/mol
[224]
Verma and Doraiswamy [223] ∆H 0f IH = A + B T 15 [227]; in kcal/mol
Yoneda [221] ∆H 0f , S 0 IH (298), IS (298); Ic = f (T ) 10 [218]
Table 14. Increments for the calculation of enthalpies and Gibbs energies of formation by Joback’s method [216], [217]
Type of increment IH , kJ/mol IG , kJ/mol Molar heat capacities ∗, J mol−1 K−1
∆a ∆b ∆c ∆d
Nonring increments
−CH3 −76.45 −43.96 1.95 E + 1 −8.08 E −3 1.53 E −4 −9.67 E −8
>CH2 −20.64 8.42 −9.09 E −1 9.50 E −2 −5.44 E −5 1.19 E −8
>CH− 29.89 58.36 −2.30 E + 1 2.04 E −1 −2.65 E −4 1.20 E −7
>C< 82.23 116.02 −6.62 E + 1 4.27 E −1 −6.41 E −4 3.01 E −7
=CH2 −9.63 3.77 2.36 E + 1 −3.81 E −2 1.72 E −4 −1.03 E −7
=CH− 37.97 48.53 −8.00 1.05 E −1 −9.63 E −5 3.56 E −8
=C< 83.99 92.36 −2.81 E + 1 2.08 E −1 −3.06 E −4 1.46 E −7
=C= 142.14 136.70 2.74 E + 1 −5.57 E −2 1.01 E −4 −5.02 E −8
≡CH 79.30 77.71 2.45 E + 1 −2.71 E −2 1.11 E −4 −6.78 E −8
≡C− 115.51 109.82 7.87 2.01 E −2 −8.33 E −6 1.39 E −9
Ring increments
−CH2 − −26.80 −3.68 −6.03 8.54 E −2 −8.00 E −6 −1.80 E −8
>CH− 8.67 40.99 −2.05 E + 1 1.62 E −1 −1.60 E −4 6.24 E −8
>C< 79.72 87.88 −9.09 E + 1 5.57 E −1 −9.00 E −4 4.69 E −7
=CH− 2.09 11.30 −2.14 5.74 E −2 −1.64 E −6 −1.59 E −8
=C< 46.43 54.05 −8.25 1.01 E −1 −1.42 E −4 6.78 E −8
Halogen increments
−F −251.92 −247.19 2.65 E + 1 −9.13 E −2 1.91 E −4 −1.03 E −7
−Cl −71.55 −64.31 3.33 E + 1 −9.63 E −2 1.87 E −4 −9.96 E −8
−Br −29.48 −38.06 2.86 E + 1 −6.49 E −2 1.36 E −4 −7.45 E −8
−I 21.06 5.74 3.21 E + 1 −6.41 E −2 1.26 E −4 −6.87 E −8
Oxygen increments
−OH (alcohol) −208.04 −189.20 2.57 E + 1 −6.91 E −2 1.77 E −4 −9.88 E −9
−OH (phenol) −221.65 −197.37 −2.81 1.11 E −1 −1.16 E −4 4.94 E −8
−O− (nonring) −132.22 −105.00 2.55 E + 1 −6.32 E −2 1.11 E −4 −5.48 E −8
−O− (ring) −138.16 −98.22 1.22 E + 1 −1.26 E −2 6.03 E −5 −3.86 E −8
>C=O (nonring) −133.22 −120.50 6.45 6.70 E −2 −3.57 E −5 2.86 E −9
>C=O (ring) −164.50 −126.27 3.04 E + 1 −8.29 E −2 2.36 E −4 −1.31 E −7
O=CH− (aldehyde) −162.03 −143.48 3.09 E + 1 −3.36 E −2 1.60 E −4 −9.88 E −8
−COOH (acid) −426.72 −387.87 2.41 E + 1 4.27 E −2 8.04 E −5 −6.87 E −8
−COO− (ester) −337.92 −301.95 2.45 E + 1 4.02 E −2 4.02 E −5 −4.52 E −8
=O (except as above) −247.61 −250.83 6.82 1.96 E −2 1.27 E −5 −1.78 E −8
Nitrogen increments
−NH2 −22.02 14.07 2.69 E + 1 −4.12 E −2 1.64 E −4 −9.76 E − 8
>NH (nonring) 53.47 89.39 −1.21 7.62 E −2 −4.86 E −5 1.05 E −8
>NH (ring) 31.65 75.61 1.18 E + 1 −2.30 E −2 1.07 E −4 −6.28 E −8
>N− (nonring) 123.34 163.16 −3.11 E + 1 2.27 E −1 −3.20 E −4 1.46 E −7
−N= (nonring) 23.61
−N= (ring) 55.52 79.93 8.83 −3.84 E −3 4.35 E −5 −2.60 E −8
=NH 93.70 119.66 5.69 −4.12 E −3 1.28 E −4 −8.88 E −8
−CN 88.43 89.22 3.65 E + 1 −7.33 E −2 1.84 E −4 −1.03 E −7
−NO2 −66.57 −16.83 2.59 E + 1 −3.74 E −3 1.29 E −4 −8.88 E −8
Sulfur increments
−SH −17.33 −22.99 3.53 E + 1 −7.58 E −2 1.85 E −4 −1.03 E −7
−S− (nonring) 41.87 33.12 1.96 E + 1 −5.61 E −3 4.02 E −5 −2.76 E −8
−S− (ring 39.10 27.76 1.67 E + 1 4.81 E −3 2.77 E −5 −2.11 E −8
∗ E = exponent of 10: E + 1 = 101 , E − 2 = 10−2 etc.

are determined when Equations (5.6) and (5.16)

are applied for ∆H 0r and K at other temperatures. Group i si IHi si IHi
Straightforward estimation of ∆H 0f and ∆G 0f −CH3 1 − 76.45 − 76.45
at different temperatures is also possible [222– −CH2 − 5 − 20.64 −103.20
224]. Application of these older methods is con- −OH 1 −208.04 −208.04
−O− 1 −132.22 −132.22
venient because they do not require estimation of

heat capacity data. Results from these methods si IHi = − 519.91 kJ/mol
are, however, in kilocalories per mole.
Equation (5.21): ∆H 0f298 = 68.29 − 519.91 =
− 451.62 kJ/mol
5.3. Applications
Equation (5.5): ∆H 0r298 =
5.3.1. Reaction Enthalpy − 451.62 + 274.9 + 52.67 = − 124.05 kJ/mol
Step 2. ∆H 0r390 with Equation (5.6)
In the determination of reaction enthalpies with Sum of molar heat capacities:
Equation (5.3) the enthalpy of formation is of-
ten not known for all reactants. The following
procedure can then be adopted:
νi a b c d
Example. Calculation of reaction enthalpy
for ethoxylation of n-butanol at 390 K. n-Butanol −1 4.1782 −2.242 4.62
4.543 ×10−1 ×10−4 ×10−8
Monoethers of ethylene glycol (e.g., n- Ethylene −1 −37.79 3.682 −3.467 20.86
butoxyethanol) are produced by ethoxylation of oxide ×10−1 ×10−4 ×10−8
alcohols, i.e., by addition of ethylene oxide: n- 5.4462 − 2.220 1.52
Butoxyetha- 1 28.255 ×10−1 ×10−4 ×10−8
nol
−2.414 3.489 − 23.96
61.502 ×10−1 ×10−4 ×10−8
= ∆a = ∆b = ∆c = ∆d
The design of the reactor for the ethoxylation

of n-butanol at 390 K is dependent on the en- T
thalpy of this reaction (∆H r390 ). Determination ∆cpr dT
of ∆H r390 consists of three steps: T0
T

1) Calculation of ∆H 0r298 from the standard = a+bT +cT 2 +dT 3 dT
formation enthalpies ∆H 0f298 with Equation T0
(5.5) ∆b 2
2) Calculation of ∆H 0r390 with Equation (5.6) =∆a (T − T0 ) + T −T02
2
3) Calculation of the ∆H r390 with n-butanol ∆c 3 ∆d 4
and n-butoxyethanol as liquids and ethylene + T −T03 + T −T04
2 4
oxide in the gaseous state, using Equation

390
(5.7)
∆cpr dT =924.0Jmol−1
Step 1. ∆H 0r298 with Equation (5.5). 298.15
0
∆Hr390 = −124.05 + 0.924 = −123.13kJ/mol
∆H 0f298 n-butanol − 274.9 kJ/mol
∆H 0f298 ethylene oxide − 52.67 kJ/mol Step 3. ∆H r390 with Equation (5.7)
∆H 0f298 n-butoxyethanol: no data available

νi ∆Hitrs = ∆Hn−butoxyethanol
lv
−∆Hn−butanol
lv
Estimation with Joback’s method [216], [217] = 48.517 − 43.781 = 4.736kJ/mol

∆Hr390 = −123.13 + 4.74 = −118.4kJ/mol
5.3.2. Chemical Equilibrium librium reaction may be so fast that product re-
covery becomes practically impossible.
With Equation (5.12 a) the equilibrium constant The application of ∆G 0r for the selection of
K of a chemical reaction can be determined. processes and process conditions will now be
The necessary thermodynamic data have been demonstrated for hydrocarbon pyrolysis. Fig-
tabulated for many inorganic and organic com- ure 12 shows the temperature dependence of the
pounds. However, in using results of such cal- Gibbs energy of formation for several hydrocar-
culations, inaccuracies in the original data must bons. All of the hydrocarbons apart from acety-
be considered. Thus enthalpies and Gibbs ener- lene show increasing instability with higher tem-
gies of formation are derived from calorimetric peratures, i.e., increasing decomposition into
measurements: formation enthalpies of some or- the elements carbon (as graphite) and hydro-
ganic compounds are usually determined from gen. The much lower temperature dependence
measured heats of combustion. With combustion of ethylene and benzene means that these com-
enthalpies of ca. ≥ 1000 kJ/mol, inaccuracies of pounds are less stable than paraffinic hydrocar-
about ± 1 kJ/mol in the final values of ∆G 0r and bons (e.g., C6 H14 and C20 H42 ) at low tempera-
∆H 0r have to be expected independent of the ture and more stable at high temperature. There-
absolute value of the resulting quantities. If the fore, in pyrolysis of naphtha (C5 – C10 paraffins)
Gibbs energy of formation has to be estimated for the production of ethylene (steam cracking),
for one or more of the reactants (cf. Section 5.2), temperatures of 500 – 900 ◦ C are employed. Ap-
the error in ∆G 0r is ≥ 10 kJ/mol. parently it is pointless to try to develop a cat-
In Table 15 an example of the effect of errors alyst for the synthesis of ethylene from naph-
in ∆G 0r on K and on equilibrium concentrations tha at lower temperatures (e.g., 300 – 400 ◦ C).
is given. Obviously, K values obtained in this On the other hand naphtha pyrolysis yielding
way are too inaccurate to be used for exact pro- acetylene requires higher temperatures, prefer-
cess calculations without experimental verifica- ably > 1150 ◦ C; with methane as raw material
tion. even higher temperatures are necessary.
Table 15. Deviations of equilibrium constant K caused by errors in
∆G0r (∆G0r = 0.0 kJ/mol at 500 K) LIVE GRAPH
Click here to view
Error in ∆G 0r , kJ/mol K
+ 1.0 (max.) 0.786

− 1.0 (min.) 1.272
+ 10.0 (max.) 0.090
− 10.0 (min.) 11.08
For preliminary investigations and for feasi-

bility studies, however, predicted Gibbs energies
of reaction with limited accuracy are helpful.
For | ∆G 0r | values > 40 kJ/mol, the equilibrium
is either highly favorable for the reaction (for
negative ∆G 0r ) or the reaction is practically im-
possible (for positive ∆G 0r ).
With knowledge of ∆G 0r it is possible to pre-
dict whether a reaction is impossible or thermo-
dynamically feasible, i.e., whether the reaction
equilibrium may yield the desired products if
equilibrium can be achieved. Equilibrium may
not, however, be reached in practice. For exam-
ple, the velocity of the equilibrium reaction may
be so low that no detectable conversion occurs.
Figure 12. Temperature dependence of the Gibbs energy of
In other cases consecutive reactions of the equi- formation for selected hydrocarbons
a) Methane; b) Ethane; c) Hexane; d) Eicosane (n-C20 H42 );
e) Acetylene; f ) Ethylene; g) Benzene
Due to increasing instability at higher tem-

perature, reaction time has to be kept short to T , ◦C ln K (T ) K (T )
prevent decomposition; fast cooling of the re- 0 1.9246 6.852
action mixture after leaving the reactor is also 25 1.3353 3.801
necessary. 50 0.8372 2.310
100 0.0412 1.042
Example. Calculation of equilibrium con- 150 −0.5667 0.567
stant for the reaction of 2-propanol to diisopro- 200 −1.0461 0.351
pyl ether 250 −1.4338 0.238
2-Propanol is produced by reacting propene
with water. In a subsequent reaction diisopropyl Step 3. Higher accuracy for ln K = f (T ) with
ether is formed at ca. 150 – 250 ◦ C: Equation (5.18)
Example: Reaction temperature T = 473.15 K
(= 200 ◦ C), calculate ∆cpr = νi cpi (385.65K)
with Joback’s method [216], [217].
The loss in 2-propanol due to this reaction might νi cpi 0

385 , J mol−1 K−1
be reduced by altering the reaction temperature. 2-Propanol −2 106.79
The temperature dependency of the equilibrium Diisopropyl ether 1 191.71
constant must therefore be determined. This can Water 1 34.35
be done in three steps: ∆cpr = 12.48
1) Determination of ∆G 0r298 (with Eq. 5.8) Evaluation of the last term of the sum in Equa-
and of the equilibrium constant K 298 (with tion (5.18):
Eq. 5.12 b)
2) First approximation for K T at temperature
∆cpr T 298.15
T (Eq. 5.17) with ∆H 0r298 by using Equation ln + −1
R 298.15 T
(5.5).
12.48 473.15 298.15
3) Second approximation for K T with Equation = ln + −1 = 0.138
8.314 298.15 473.15
(5.18)
exp (0.138) = 1.148; K (473.15 K ) = 1.148 0.351
Step 1. ∆G 0r298 with Equation (5.8) and K298 = 0.403
with Equation (5.12 b)
Sum of the standard Gibbs energies and standard Comparison with the result from Step 2
enthalpies of formation; data from [214]. (K = 0.351) shows that the contribution of the
last term of Equation (5.18) is only minor.
νi ∆G 0f298 , ∆H 0f298 ,
Although formation of diisopropyl ether is
kJ/mol kJ/mol less favored at higher temperature (250 ◦ C), the
2-Propanol − 2 − 173.71 − 272.77 equilibrium concentration of this product is still
Diisopropyl ether 1 − 121.96 − 319.03 considerable. Moreover, the velocity of the se-
Water 1 − 228.77 − 242.00 quential reaction increases with temperature.
∆G0r298 = ∆H 0r298 =
− 3.31 − 15.96
Therefore, a decrease in diisopropyl ether for-
mation is not to be expected when the reaction
temperature is increased.
−3310 In the above calculation tabulated data of
lnK298 = − = 1.3353
8.314 × 298.15 ∆G 0f298 are used, in the following K 298 is de-
K298 = 3.80 termined from ∆G 0f298 estimated with Joback’s
method.
Step 2. First approximation of ln K = f (T ) with Calculation of K 298 in Step 1 using ∆G 0r298 de-
Equation (5.17). termined with Joback’s method

−15960 1 1
lnK (T ) =1.3353+ −
8.314 298.15 T
The kinematic viscosity ν [m2 /s] is defined by

νi ∆G 0f298 , kJ/mol η
ν= (6.1)
2-Propanol −2 − 164.88
Diisopropyl ether 1 − 110.24
Water 1 − 228.56 and is still often expressed in Stokes [cm2 /s].
∆G0r298 = − 9.04 A review on methods for predicting and cor-
relating viscosity data has been given by Mon-
nery et al. [228]. The following discussion is
−9040
lnK =− = 3.6469 restricted to Newtonian fluids and thus includes
8.314 × 298.15
most organic liquids and solvents but excludes
K298 = 38.4
many polymer solutions, melts, and slurries.
The value of K obtained with Joback’s method Typical viscosity behavior of a pure substance
is ten times higher than that determined with ( ethanol) is shown in Figure 13.
tabulated ∆G0f298 data.
LIVE GRAPH
Click here to view
6. Transport Properties of Pure

Compounds and Mixtures
Transport properties largely determine the type
and dimensions of equipment in the process
industries. They are therefore of great im-
portance in the engineering design of many
processes – not just those involved in the chemi-
cal industry. Although transport properties are
macroscopic nonequilibrium quantities, they Figure 13. Viscosity behavior of ethanol [232]
may, to a certain extent, be related to static equi-
librium quantities. In particular, kinetic theory
has been very useful in explaining the mecha- 6.1.1. Viscosity of Pure Gases
nisms of heat, mass, and momentum transport in
dilute gases. For a detailed description of trans- Gases at Low Pressure (< 1 MPa). Kinetic
port phenomena, see → Transport Phenomena. theory yields the following relation for gases
From the ratios of the transport coefficients consisting of rigid, noninteracting, elastic spher-
of the liquid to the gas phase given below it is ev- ical molecules with a Maxwellian velocity dis-
ident that transport processes in the two phases tribution:
differ considerably:
M 1/2 1/2
η=C T (6.2)
Density ratio l
/ g 3
ca. 10 σ2
Viscosity ratio η l /η g 10 – 100 where η is expressed in µPa · s and σ is the colli-
λl /λg
Thermal conductivity ratio
Diffusion coefficient ratio Dl /Dg
10 – 100
ca. 10−4
sion diameter in 10−10 m [Å]; M is the molecular
mass in g/mol and C a constant (C = 2.6693).
Chapman and Enskog described the effect of
intermolecular forces by considering the poten-
tial energy of atoms and molecules [229]. They
6.1. Viscosity found that viscosity can be expressed in the gen-
eral form
The dynamic viscosity η of a fluid is defined
as the ratio of the shear stress to velocity M 1/2 1/2
η=C T (6.3)
gradient. The SI unit of dynamic viscosity is σ 2 Ωv
Pa · s = N · s/m2 but poise is also still in use where where Ωv , the collision integral, can be calcu-
1 P = 1 g s−1 cm−1 = 10−1 N · s/m2 and lated from an appropriate potential energy func-
1 cP = 1 mPa · s tion, such as that of Lennard – Jones (see Section
2.1). Despite the simplifying assumptions used LIVE GRAPH

Click here to view
when deriving Equation (6.3), the accuracy of
the viscosity of nonpolar gases is quite accept-
able (ca. 1 %).
Information on the potential energy function
and the molecular parameters for more com-
plex molecules is, however, scarce. Values for
the molecular parameters and solutions for Ωv
for various compounds are tabulated in [230],
[231].
Figure 14 shows viscosity data of some
organic gases and vapors. In polar gases
dipole – dipole interactions must be taken into
account. Consequently the collision integral is
calculated employing suitable potential func-
tions, e.g., the Stockmayer potential [233]. The
accuracy in the estimation of viscosity of polar
gases by Equation (6.3) is usually better than
2 %.
Figure 15. Generalized reduced viscosities as a function of

reduced temperature [235]
Values on the curve denote the reduced pressure pr = p/pc .
1/6
M 3 p4c
η = C (6.4)
Tc
Figure 15 shows the generalized reduced vis-

cosities as a function of reduced temperature. In
the accurate method proposed by Lucas [236],
[238] the basic relation for the reduced viscosity
η r is
η
ηr =
ηc
FP0 FQ
0
·

= 0.807T 0.618
r −0.357exp (−0.449Tr )
+0.34exp (−4.058Tr ) +0.018] · (6.5)
where
1 1/6
Figure 14. Viscosity data of some gases and vapors [232] = 1.76 10−4 Tc M −3 p−4
c (6.6)
ηc
a) Helium; b) Carbon dioxide; c) Nitrogen; d) Hydro-
gen chloride; e) Hydrogen sulfide; f ) Water; g) Ammonia; η is in µPa · s and pc is in MPa. The correc-
h) Methane; i) Hydrogen cyanide tion factors F 0P and F 0Q account for polarity and
quantum effects, respectively, and can be ob-
tained from critical data. In terms of the reduced
Corresponding States Methods. Several
dipole moment µr
methods employ the principle of correspond-
ing states by defining a critical viscosity η c . pc 2
µr = 524.6 µ (6.7)
1/3 Tc2
With the relation σ = const. × V c , Equation
(6.3) transforms into: three different equations have been formulated
for F 0P :
Next Page

FP0 = 1 yi ηi
ηm = (6.8)
0 ≤µr <0.022 (6.7a) yi Φij
FP0 = 1 + 30.55 (0.292−zc )1.72 Wilke [239] and more recently Brokaw [240],
0.022 ≤µr <0.075 (6.7b) [241] and Reichenberg [242] have published
methods for calculating the binary interaction
FP0 = 1 + 30.55 (0.292−zc )1.72 parameter Φij . Deviations with respect to ex-
[0.96 + 0.1 (Tr −0.79)] perimental data are usually < 5 % [230]. Lucas
0.075 ≤µr (6.7c) has developed a calculation scheme that may be
The factor F 0Qcan be set equal to unity except used if no pure component viscosity data are
in the case of quantum gases (He, H2 , D2 ). The available [236], [237]. These methods are de-
errors in predicting gas viscosities are usually scribed in more detail, e.g., in [234].
< 3 % for nonpolar compounds and somewhat
higher for polar substances. Table 16 gives an
overview on important estimation methods. 6.1.3. Viscosity of Pure Liquids
Effect of Pressure on Gas Viscosity. Above Many methods have been published for estimat-
ca. 1 MPa, pressure has an increasing influence ing liquid viscosities. These methods can be ap-
on gas viscosity particularly in the vicinity of the plied in the temperature range slightly above the
critical point. triple point up to reduced temperatures of about
Lucas has suggested an efficient method 0.75 – 0.8 at moderate pressures. A method for
for the prediction of the viscosity of dense the prediction of viscosities at the melting point
gases with errors usually < 5 % [236], [237]. is given in [247].
The method correlates a reduced viscosity η/η 0 No single method is clearly superior to the
(where η 0 is the low-pressure viscosity) with others. Since the method of Van Velzen et al.
pressure. The Lucas technique offers the advan- [248] is well established it is presented here.
tage that the viscosity is expressed in terms of This group contribution method is based upon
temperature and pressure, whereas other meth- the following empirical relation (η in mPa · s):
ods employ density as a variable and require an
1 − 1

B T
additional equation of state. Finally, if no exper- η=10 T 0 (6.9)
imental data are available, the low-pressure vis-
cosity η 0 can be estimated with the same model where T 0 is a fictive temperature and B is a pa-
(according to Eq. 6.5). rameter characteristic for the molecular struc-
Example. Calculation of viscosity of gaseous ture of the substance concerned. It is determined
carbon monoxide with the Lucas method using an equivalent chain length N +
M = 28.01 g/mol, T c = 132.9 K, µ = 0.1 Debye,
N + =N + ni IN (6.10)
pc = 3.5 MPa [233].
From Equation (6.6) 1/η c = 7.02×10−2 (µPa · s)−1 where N is the total number of carbon atoms, I N
Since µr = 1.04×10−3 (Eq. 6.7) it follows that the increment, and ni the number of increment
F 0P = 1. I N . The parameter B is given by
Hence using Equation (6.5) η g = 15.1 µPa · s
Experimental value η g = 15.4 µPa · s at 250 K
B =Ba + IB (6.11)
[238]
Relative deviation: − 2.0 % For molecules with N + ≤ 20 and N + > 20:
N + ≤ 20 :
6.1.2. Viscosity of Gas Mixtures 2
T0 = 28.86 + 37.439N + −1.3547 N +
3
Extending the kinetic theory of Chapman and +0.02076 N + (6.12a)
Enskog, viscosities of multicomponent gas mix-
tures can be approximated by
Previous Page

Table 16. Selected methods for estimating low-pressure viscosity of gases
Method Range of application Information required a Error, %
Kinetic theory polar and nonpolar σ, µ, Ωv , ε0 /k ca. 2

Chung 1984 [243], 1988 [244] not quantum gases T c , V c , µ, σ 2
Bromley, Wilke 1951 [245] polar compounds T c, V c ca. 5
Reichenberg 1975 [246] T r< 3 T c , pc , µ 1 b, 3 c
Lucas 1980 [237], [238] not highly associated gases T c , pc , z c , µ 1 b, 3 c
a
In addition to the corresponding parameters and increments.
b
Nonpolar.
c
Polar.
properties as well as the acentric factor must be

+
N > 20 :
known.
An overview of selected estimation methods
To = 8.164N + +238.59 (6.12b)
for the viscosity of liquids is given in Table 18. In
and addition, viscosities of some liquids are pre-
sented as a function of temperature in Figure 16.
N + ≤ 20 :
2
Ba = 24.79 + 66.885N + −1.3173 N + LIVE GRAPH
3 Click here to view
−0.00377 N + (6.13a)
N + > 20 :
Ba = 530.59 + 13.740N + (6.13b)
The structure parameters are given in Ta-

ble 17. Since the method is only fairly accurate
(errors 10 – 15 %) it cannot easily be applied to
complex molecules [234]. Moreover, the predic-
tions of viscosity for the first members of homol-
ogous series often yield higher errors.
Example. Calculation of viscosity of liquid
diethylamine (CH3 CH2 )2 NH, using the method
of Van Velzen et al. [248].
With N = 4: N + = 4 + 1.390 + 0.461×4
= 7.234
For secondary amines: I B = 25.39 + 8.744 N+
= 88.64
From Equation (6.13 a): Ba = 438.27
From Equation (6.12 a): T 0 = 236.66 K Figure 16. Dynamic viscosity η l of some liquids [232]
a) Hydrogen chloride; b) Acetone; c) Trichloromethane;
d) Methanol; e) Benzene; f ) Water; g) Decane; h) Formic
At 283.2 K η lcal = 0.4306 mPa · s, η lexp = acid; i) Aniline
0.3878 mPa · s [249]; rel. deviation: 11.0 %
At 310.8 K η lcal = 0.2944 mPa · s, η lexp =
0.2732 mPa · s [249]; rel. deviation: 7.8 % 6.1.4. Viscosity of Liquid Mixtures
At higher temperatures (T r > 0.75) the
method of Letsou and Stiel [254] should be The viscosity of a liquid mixture is not usually
used. Their method is based upon the princi- a linear function of composition and is very dif-
ple of corresponding states and valid in the ficult to predict. A first estimate of the viscosity
range 0.76 < T r < 0.98. Only liquids at satura- of liquid mixtures can be obtained by
tion pressure can be considered. The critical
Table 17. Parameters of structural groups in the method of Van Velzen et al. [248] for estimating viscosities of liquids
Group IN IB
n-Alkanes 0 0
Isoalkanes 1.389 – 0.238 N 15.51
Saturated hydrocarbons with two methyl 2.319 – 0.238 N 15.51
groups in iso position
n-Alkenes −0.152 – 0.042 N −44.94 + 5.410 N +
n-Alkadienes −0.304 – 0.084 N −44.94 + 5.410 N +
Isoalkenes 1.237 – 0.280 N −36.01 + 5.410 N +
Isoalkadienes 1.085 – 0.322 N −36.01 + 5.410 N +
Hydrocarbon with one double bond and two 2.626 – 0.518 N −36.01 + 5.410 N +
methyl groups in iso position
Hydrocarbon with two double bonds and two 2.474 – 0.560 N −36.01 + 5.410 N +
methyl groups in iso position
Cyclopentanes N < 16 0.205 + 0.069 N −45.96 + 2.224 N +
N ≥ 16 3.971 – 0.172 N −339.67 + 23.135 N +
Cyclohexanes N < 17 1.48 −272.85 + 25.041 N +
N ≥ 17 6.517 – 0.311 N −272.85 + 25.041 N +
Alkyl benzenes N < 16 0.60 −140.04 + 13.869 N +
N ≥ 16 3.055 – 0.161 N −140.04 + 13.869 N +
Polyphenyls −5.340 + 0.815 N −188.40 + 9.558 N +
Alcohols:
Primary 10.606 – 0.276 N −589.44 + 70.519 N +
Secondary 11.200 – 0.605 N 497.58
Tertiary 11.200 – 0.605 N 928.83
Diols (correction) 557.77
Phenols (correction) 16.17 – N 213.68
−OH on side chain to aromatic ring −0.16 213.68
(correction)
Acids 3 ≤ N < 11 6.795 + 0.365 N −249.12 + 22.449 N +
N ≥ 11 10.71 −249.12 + 22.449 N +
Iso acids 3 ≤ N < 11 6.795 + 0.365 N − 0.24 nic −249.12 + 22.449 N +
N ≥ 11 10.71 − 0.24 nic −249.12 + 22.449 N +
(nic = number of methyl groups in iso position)
Acids with aromatic nucleus in structure 4.81 −188.40 + 9.558 N +
(correction)
Esters 4.337 – 0.230 N −149.13 + 18.695 N +
Esters with aromatic nucleus in structure −1.174 + 0.376 N −140.04 + 13.869 N +
(correction)
Ketones 3.265 – 0.122 N −117.21 + 15.781 N +
Ketones with aromatic nucleus in structure 2.70 −760.65 + 50.478 N +
(correction)
Ethers 0.298 + 0.209 N −9.39 + 2.848 N +
Aromatic ethers 11.5 – N −140.04 + 13.869 N +
Halogenated compounds:
Fluoride 1.43 5.75
Chloride 3.21 −17.03
Bromide 4.39 −101.97 + 5.954 N +
Iodide 5.76 −85.32
Special configurations (corrections):
C(Cl)x 1.91 – 1.459x −26.38
−CCl−CCl− 0.96 0
−C(Br)x − 0.50 81.34 – 86.850x
−CBr−CBr− 1.60 −57.73
CF3 , in alcohols −3.93 341.68
CF3 , in other compounds −3.93 25.55
Aldehydes 3.38 146.45 – 25.11 N +
Aldehydes with an aromatic nucleus in 2.70 −760.65 + 50.478 N +
structure (correction)
Anhydrides 7.97 – 0.50 N −33.50
Anhydrides with an aromatic nucleus in 2.70 −760.65 + 50.478 N +
structure (correction)
Amides 13.12 + 1.49 N 524.63 – 20.72 N +
Amides with an aromatic nucleus in structure 2.70 −760.65 + 50.478 N +
(correction)
Group IN IB
Amines:
Primary 3.581 + 0.325 N 25.39 + 8.744 N +
Primary amine in side chain of aromatic −0.16 0
compound (correction)
Secondary 1.390 + 0.461 N 25.39 + 8.744 N +
Tertiary 3.27 25.39 + 8.744 N +
Primary amines with NH2 group on aromatic 15.04 – N 0
nucleus
Nitro compounds:
1-nitro 7.812 – 0.236 N −213.14 + 18.330 N +
2-nitro 5.84 −213.14 + 18.330 N +
3-nitro 5.56 −338.01 + 25.086 N +
4-nitro; 5-nitro 5.36 −338.01 + 25.086 N +
Aromatic nitro-compounds 7.812 – 0.236 N −213.14 + 18.330 N +
Table 18. Selected methods for estimating the viscosity of pure liquids
Method Range of application Information Error,

required ∗ % ∗∗
Thomas 1946 [250] T > T m+ 5 K T c , l 20

no strongly polar and naphthenic compounds
T < Tb
but sulfur-containing substances
T r < 0.75
Morris 1964 [251] no sulfur-containing compounds, no highly T > T m+ 5 K Tc 14
branched substances T r < 0.75
Van Velzen et al. 1972 [248] no sulfur-containing compounds, not for the T r < 0.75 10 – 15
first members of homologous series
l
Orrick – Erbar 1974 [252] no sulfur- or nitrogen-containing compounds T r < 0.75 T c , M, 15
Przezdziecki – Sridhar 1985 no sulfur- or nitrogen-containing T r < 0.75 T c , pc , V c , M, ω, l 15
[253] compounds, no alcohols
Letsou – Stiel 1973 [254] nonpolar, weakly polar compounds at 0.76 < T r < 0.98 T c , pc , M, ω 10
saturation
hydrocarbons T > T m+ 5 K 10
Joback – Reid 1987 [255]
T r < 0.75
no sulfur-, nitrogen-, or fluorine-containing T > T m+ 5 K 18
Tatevskii et al. 1987 [256]
compounds T r < 0.75
∗ In addition to the corresponding increments.

∗∗ In some cases errors may be considerably higher.
cosity for 50 pure fluids together with a compre-

lnη= xi lnηi (6.14) hensive discussion of theories for dense fluids
are given in [260].
Methods to date do not allow confident predic-
tions, particularly when dealing with highly po-
lar compounds or components differing greatly
in size. 6.2. Thermal Conductivity
On the basis of Eyring’s theory, McAllister
published a relation for the kinematic viscosity The thermal conductivity λ is defined as the pro-
of binary and ternary mixtures which allows esti- portionality constant between heat flux and tem-
mations for chemically similar compounds with perature gradient. It is usually expressed in terms
average errors of 15 % [257]. For details and rec- of W m−1 K−1 .
ommendations see [258].
Viscosity data can be found, e.g., in [259].
The pressure – temperature dependence of vis-
6.2.1. Thermal Conductivity of Gases at diction methods (e.g., the Eucken model and the
Low Pressure Mason and Moschick approach) have been pro-
posed based on the dimensionless Eucken factor
This chapter discusses methods for the predic- E
tion of thermal conductivities at pressures up to
1 MPa. The lower boundary is the region of ex- E=
λM
(6.16)
tremely low pressures (< 10−2 kPa) where the ηcv
mean free path of molecules becomes large com- where cv is the molar heat capacity at constant
pared to the macroscopic dimensions of the ap- volume. For further details see, e.g., [234].
paratus (Knudsen domain). Thermal conductivi-
ties of some organic gases and vapors are shown Table 19. Coefficients A, B, and C for the Roy and Thodos method
as a function of temperature in Figure 17. In the for predicting thermal conductivities of liquids (Eq. 6.20) [234]
limiting case of noninteracting monatomic hard Substance A T r + B T 2r + C T 3r

spheres, kinetic theory leads to the basic relation Saturated hydrocarbons ∗ − 0.152 T r + 1.191 T 2r − 0.039 T 3r
T 1/2 Olefins − 0.255 T r + 1.065 T 2r + 0.190 T 3r
λg = 2.63 × 10−23 (6.15) Acetylenes − 0.068 T r + 1.251 T 2r − 0.183 T 3r
M 1/2 σ 2 Ωv Naphthalenes and − 0.354 T r + 1.501 T 2r − 0.147 T 3r
where T is the absolute temperature, M the aromatics
Alcohols 1.000 T 2r
molecular mass, σ the characteristic dimension Aldehydes, ketones, − 0.082 T r + 1.045 T 2r + 0.037 T 3r
of the molecule, and Ωv the collison integral. ethers, esters
Equation (6.15) gives the temperature depen- Amines and nitriles 0.633 T 2r + 0.367 T 3r
Halides − 0.107 T r + 1.330 T 2r − 0.223 T 3r
dence of λg at low pressure. Cyclic compounds (e.g., − 0.354 T r + 1.501 T 2r − 0.147 T 3r
pyridine, thiophene,
ethylene oxide, dioxane,
piperidine)
∗ Not recommended for methane.
For the estimation of the thermal conductiv-

ity of gases, Roy and Thodos [262] used an
approach based upon the reduced thermal con-
ductivity λr
λr
λ= . / (6.17)
210 (M 3 Tc /p4c )1/6
with the pressure pc expressed in bar. As pro-

posed by Eucken, the reduced thermal conduc-
tivity is separated into two terms
λr =λtrans
r +λint
r (6.18)
LIVE GRAPH The term λtrans

r considers the translational en-
Click here to view ergy of the molecules and is determined by cor-
relating dilute gas properties with temperature.
The second term λintr takes internal (i.e., rota-
tional and vibrational) energy contributions into
account and employs specific polynomial coef-
Figure 17. Thermal conductivities λg of some organic gases
and vapors (data from [261]) ficients for different classes of compounds.
a) Methane; b) Ethane; c) Dimethylamine; d) Water;
e) Ethanol; f ) Dimethyl ether; g) Chloromethane; h) Tri- λtrans
r =
chloromethane
8.757 [exp (0.0464Tr ) −exp (−0.2412Tr )] (6.19)
The thermal conductivity λ and the viscosity
η of a gas are closely related. Successful pre- λint 2 3
r =β ATr +B Tr +C Tr (6.20)
The coefficients A, B, and C are tabulated for extended their equation for low-pressure thermal
nine classes of organic compounds (e.g., paraf- conductivity data:
fins, olefins, alcohols). The additional parameter
β is determined by employing group increments 31.2θη 0 1 1/2
λg = +B6 y +qB7 y 2 T r G2 (6.22)
Ii M G2
with λ expressed in terms of the reduced density
β= Ii (6.21)
function y (V , V c in cm3 /mol)
The method of Roy and Thodos yields estimates Vc
for both polar and nonpolar organic substances at y= (6.23)
6V
ambient pressure. The constants for this method
are given in Tables 19 and 20. The only spe- and the parameters
cific data required are the molecular mass and
(Tc /M )1/2
the critical temperature. The average error is ca. q= 3.586 × 10−3 2/3
5 %. Vc
Example. Estimation of the thermal conduc-
tivity of 2-butanol, CH3 CH2 CH(OH)CH3 , at η0 viscosity at low pressure, Pa · s
480 K by the method of Roy and Thodos. G1 , G2 generalized functions of reduced density
M = 74.122 g/mol, T b = 372.66 K, T c = 535.95 K, B1 – B7 parameters which are functions of the acentric factor
ω, the reduced dipole moment µ (Eq. 6.31), and the
pc = 41.95 bar [249]. association factor k (Eq. 6.24)
θ function of T r , cv /R, and ω (Eq. 6.27)
β = (–CH3 ) + (–CH2 –) + (–CH2 –) + (–CH2 ) + (–OH)
= 0.73 + 2.0 + 3.18 + 3.68 + 4.62 = 14.21 Additional equations:
with A = 0, B = 1, C = 0 from Table 19
Bi =ai +bi ω+ci µr +di k (6.24)
From Equation (6.19): λtrans = 2.073
From Equation (6.20): λint = 11.398 The parameters ai , bi , ci and d i are listed in Ta-
From Equation (6.21): λ = 0.0316 W m−1 K−1 ble 21.
Experimental: λ = 0.0324 W m−1 K−1 [263]
Relative deviation: − 0.8 % 1 − 0.5y
G1 = (6.25)
(1−y)3
Other more sophisticated methods have been G2 = (6.26)
suggested based upon the principle of corre- B1 [1 − exp (−B4 y)] +B2 G1 exp (B5 y) +B3 G1
sponding states, e.g., [264]. These methods em- y (B1 B4 +B2 +B3 )
ploy the Eucken factor and require much more
information on the properties of the substances θ=

(6.27)

considered, i.e., the critical properties (T c , pc , 0.215 + 0.28288α − 1.061β +0.26665Z
1+α
and V c ), the heat capacity at constant volume 0.6366+β Z +1.061αβ
cv , and the viscosity. α=cv /R − 1.5 (6.28)
β =0.7862 − 0.7109ω+1.3168ω 2 (6.29)

6.2.2. Thermal Conductivity of Gases at
High Pressure
Z =2.0 + 10.5Tr (6.30)
Typical p λ behavior of fluids is displayed in 131.3µ
Figure 18. Some methods used for gases at low µr = (6.31)
(Tc Vc )1/2
pressures, particularly the corresponding states
methods using the Eucken factor, have been ex- Data for the associaton factor k are given, e.g.,
tended to correlate high-pressure thermal con- in [234, p. 396].
ductivity data. For the region close to the critical Since no appropriate correlation for the polar
point, however, other methods must be chosen. factor is available, the application of the Chung
The method of Chung et al. [266] is typical method is limited to nonpolar and a few polar
and will be briefly described here. These authors substances. Errors are usually < 8 % [234].
Table 20. Parameters for the Roy and Thodos method for predicting thermal conductivities of gases [234]
Table 21. Constants (Eq. 6.24) for Chung’s method , p. 522 [234] ∗
i ai bi ci di
1 2.4166 E + 0 7.4824 E − 1 −9.1858 E − 1 1.2172 E + 2

2 −5.0924 E − 1 −1.5094 E + 0 −4.9991 E + 1 6.9983 E + 1
3 6.6107 E + 0 5.6207 E + 0 6.4760 E + 1 2.7039 E + 1
4 1.4543 E + 1 −8.9139 E + 0 −5.6379 E + 0 7.4344 E + 1
5 7.9274 E − 1 8.2019 E − 1 −6.9369 E − 1 6.3173 E + 0
6 −5.8634 E + 0 1.2801 E + 1 9.5893 E + 0 6.5529 E + 1
7 9.1089 E + 1 1.2811 E + 2 −5.4217 E + 1 5.2381 E + 2
∗ E = exponent of 10: E + 1 = 101 , E + 2 = 102 etc.
LIVE GRAPH
Click here to view
erties, the acentric factor, the constant-volume
heat capacity cv at low pressure, and low-pres-
sure viscosity data are required for the predic-
tion. The accuracy of estimation methods is usu-
ally < 10 % [234]. An overview of estimation
methods is given in Table 22.
6.2.3. Thermal Conductivity of Gas

Mixtures
As a first approximation the thermal conductiv-

ity of a gas mixture can be described as a lin-
ear function of composition. Deviations increase
with increasing polarity of the components and
increasing difference in size and structure.
Methods for the prediction of mixture data
are based upon the theoretically derived Wassil-
jewa equation:

yi λi
Figure 18. Isotherms of the thermal conductivity of carbon λm = (6.32)
yj Aij
tetrachloride [265]
The binary interaction parameters Aij can
Example. Calculation of thermal conductiv- be determined employing the methods of
ity of carbon dioxide at 473.15 K and 30 MPa Mason – Saxena or Lindsay [234]. Errors are
M = 44.01 g/mol, ω = 0.239, T c = 304.1 K, usually < 8 % according to [234], but greater de-
V c = 93.9 cm3 / mol [234], µ = 0 De- viations are possible for components differing
bye; hence from Equation (6.31): µr = 0, greatly in size and polarity. Nevertheless, rea-
V = 112.95 cm3 /mol, = 8.8537×10−3 mol/cm3 , sonable estimates of thermal conductivities of
cv = 39.5 J mol−1 K−1 [267], η 0 = 23.04×10−6 mixtures can be obtained from pure component
(at 473.15 K, 0.1 MPa). data using a linear combination of λi in mole
Calculation: G 1 = 1.4560, G2 = 0.6489, α = 3.251, fraction.
β = 0.692, θ = 1.8687, z = 18.34
λ = 0.04968 W m−1 K−1
Experimental: λ = 0.05181 W m−1 K−1 [238]
Relative deviation = − 4.1 %
6.2.4. Thermal Conductivity of Liquids
Thermal conductivities of liquids are signif-

The reliable estimation of thermal conductiv- icantly higher than those of gases due to
ities in dense gases is only possible for nonpolar their much higher density. Liquid thermal
substances; information about the critical prop- conductivities λl are usually in the range
Table 22. Selected methods for estimating the thermal conductivity of gases at low pressure
Method Range of application Information required ∗ Error,

%
Substances Temperature and pressure
Eucken and modifications polar and nonpolar compounds, M, cv , η 10 – 15

no associating gases
Stiel – Thodos 1964 [270] no associating gases T r < 10 11
M, T c , pc , cv , η
10−4 < pr < 0.2
Misic – Thodos 1961 [268] hydrocarbons only M, T c , pc , cp 8
Roy – Thodos 1968, 1970 [262], preferably for polar compounds M, T c , pc 8
[269]
Ely – Hanley 1983 [264] low- and high-pressure M, T c , V c , zc , ω, cv 5–7
version
Chung et al. 1980 [266] weakly polar but preferably T r< 5 M, T c , ω, cv (η) 5–7
nonpolar compounds
∗ In addition to the corresponding increments.
0.1 – 0.17 W m−1 K−1 (Fig. 19) and are, like liq- LIVE GRAPH
Click here to view
uid densities, only a weak function of pressure.
Comprehensive compilations of thermal con-
ductivity data are given in [271], [272]. Since the
numerical variation of λl values is small, estima-
tion is comparatively easy, except for strongly
polar or associating substances. Empirical meth-
ods usually provide estimates of considerable
accuracy, often comparable to experimental un-
certainty.
Sato’s Method. Sato found that a simple

empirical relationship exits between λl at the
normal boiling point T b and the molecular mass
M [273]:
1.11
λl (Tb ) = (6.33)
M 1/2
In order to extend this relation the equation [274]
can be employed to give
. /
λl =B 3 + 20 (1−Tr )2/3 (6.34)
where B is a substance-specific parameter [279]. Figure 19. Thermal conductivities λl of some organic liq-
uids (data from [261])
Combination of Equations (6.33) and (6.34) a) Methanol; b) Ethanol; c) 1-Butanol; d) 1-Octanol;
yields e) Trichloromethane; f ) Chlorodifluoromethane; g) Aniline;
h) Pyridine; i) Nitrobenzene
1.11 3 + 20 (1−Tr )2/3
λl = √ · (6.35)
M 3 + 20 (1−Tb /Tc )2/3
Method of Latini and Baroncini [275],
The only information required is the critical tem- [276]. This estimation method is based upon
perature and the normal boiling point. Errors the relation
are usually < 15 %, but are generally higher for A∗ Tbα (1−Tr )0.38
strongly polar substances. λl = (6.36)
M β Tcγ 1/6
Tr
Specific data required for the application of the
method are the normal boiling point T b , the criti-
cal temperature T c , and the molecular mass. For are recommended, preferably with (1 − T r ) as
chlorofluorohydrocarbons the method is appli- an independent variable.
cable up to T r < 0.9. The exponents α, β, γ and
the parameter A∗ are given in Table 23 for vari- Effect of Pressure on Thermal Conductiv-
ous organic compounds. According to [234] the ity. The thermal conductivity increases signifi-
errors in estimating liquid thermal conductivity cantly at pressures above pr > 0.5. Missenard
are usually < 10 %. suggested an empirical approach for the dimen-
sionless thermal conductivity normalized by the
Table 23. Constants for the Latini – Baroncini method (from [234])
thermal conductivity at low pressure (p0 ) [281]:
Compounds A∗ α β γ
λ1 (pr )
Saturated hydrocarbons 0.0035 1.2 0.5 0.167 = 1+C p0.7
r (6.38)
λ1 (p0 )
Olefins 0.0361 1.2 1.0 0.167
Cycloparaffins 0.0310 1.2 1.0 0.167 Values of the generalized parameter
Aromatics 0.0346 1.2 1.0 0.167
Alcohols 0.00339 1.2 0.5 0.167 C = f (T r , pr ) are reported by the author for
Organic acids 0.00319 1.2 0.5 0.167 several compounds.
Ketones 0.00383 1.2 0.5 0.167
Esters 0.0415 1.2 1.0 0.167
Ethers 0.0385 1.2 1.0 0.167
Chlorofluorohydrocarbons: 6.2.5. Thermal Conductivity of Liquid
R 20, R 21, R 23 0.562 0 0.5 −0.167 Mixtures
Others 0.494 0 0.5 −0.167
The thermal conductivity of organic liquid mix-
Both estimation methods can be employed re- tures λm can usually be approximated with suffi-
liably up to T r < 0.65. Numerous other methods cient accuracy by linear combination of the ther-
have been published, but are either of limited mal conductivities of the pure components.
applicability or require much more specific in- For binary systems Jamieson et al. recom-
formation without offering significant improve- mended the following relation in terms of the
ment in reliability and accuracy. weight fraction wi [272]:
An overview of methods for estimating the
λm =w1 λ1 +w2 λ2
thermal conductivities of liquids is given in Ta-
1/2
ble 24. −α (λ2 −λ1 ) 1−w2 w2 (6.39)
Example. Estimation of thermal conductivity
of liquid isopropylbenzene, C9 H12 , at 323 K. which employs an adjustable binary parameter
M = 120.194 kg/kmol, T b = 425.56 K, α. If no experimental mixture data are available,
T c = 631.13 K [249] α is set equal to unity.
For multicomponent mixtures Li suggested
Experimental: λl = 0.1187 W m−1 K−1 [276] an equation with volume fractions [282]:
Calculation:
Sato’s method (Eq. 6.35): λl = 0.125 W m−1 K−1
r
r
1
Relative deviation=5.1 % λm = 2 Φ i Φj (6.40)
Latini’s method (Eq. 6.36): λl = 0.119 W m−1 K−1 i j
(1/λi +1/λj )
Relative deviation=0.2 %
where the volume fraction Φi of component i is
defined by
Effect of Temperature on Thermal Con- xi Vi
ductivity. At low to moderate pressures Φi = (6.41)
( xj Vj )
(< 1 MPa) and over a limited range of tempera-
ture, the thermal conductivity decreases linearly
with temperature
λl =A − B T (6.37) 6.3. Diffusion Coefficients
For more accurate description over wider tem- The diffusion coefficient D is defined as the pro-
perature ranges, higher order polynomial series portionality factor between mass flux and the
Table 24. Selected methods for estimating the thermal conductivities of liquids
Method Range of application Information required Error,

%
Robbins – Kingrea 1962 [277] no nitrogen- or sulfur-containing 0.4 < T r < 0.9 T b , T c , cp , l , ∆H lv
b 5
compounds
Missenard 1965 [278] M, T b , clp , lb 8
Sato – Riedel 1973 [279] no low molecular mass hydrocarbons, 0.5 < T r < 0.75 M, T b , T c 15
no highly polar compounds
Baroncini – Latini 1978, 1984 [275], no nitrogen- or sulfur-containing M, T b , T c 8
[276] compounds, no aldehydes 50 ≤ M ≤ 250
Nagvekar – Daubert 1987 [280] no sulfur-containing compounds 0.3 < T r < 0.8 Tc 6
LIVE GRAPH
concentration gradient; it is usually given in Click here to view
[cm2 /s]. In this discussion only molecular diffu-

sion is considered with concentration gradients
(i.e., primarily gradients in chemical potential)
as driving force in systems which are free of
external force fields and are homogeneous with
respect to temperature and pressure. Diffusion
is treated comprehensively in [233], [283].
6.3.1. Diffusion Coefficients of Gases at Low

and Moderate Pressures
Molecular Theory. Statistical mechanics

lead, via integration of the Boltzmann equa-
tion, to the Chapman and Enskog equation for
the mutual diffusion of the components i and j:
(1/Mi +1/Mj )1/2
Dij =3/16 (2πkT )1/2 2 Ω
fD (6.42)
πN σij D
where k is the Boltzmann constant; Mi , Mj the

molecular masses of components i, j respec-
tively; N the number of molecules per unit vol-
ume; σij a characteristic length; and f D a cor-
rection term. Introducing the ideal gas law into Figure 20. Diffusion coefficients of selected gases in air at
ambient pressure
this equation gives a basic relation that is valid a) Hydrogen; b) Helium; c) Water; d) Ammonia;
for spherical molecules in dilute gases: e) Methane; f ) Methanol; g) Ethanol; h) Benzene; i) Hexane
T 1.5 [1/Mi +1/Mj ]0.5 1 Employing simple combination rules, i.e.,

Dij =0.01333 2 Ω
(6.43)
p σij D
σi +σj
σij = and εij = (εi εj )1/2 (6.44)
This expression ( p in MPa) contains the charac- 2
teristic length σij (in 10−10 m) and the dimen- diffusion coefficients can be determined
sionless collison integral ΩD , which can be de- with reasonable accuracy without consider-
termined from an appropriate intermolecular po- ing concentration effects, even for complicated
tential. For monatomic gases the potential func- molecules. For mixtures containing highly po-
tion of Lennard and Jones may be chosen (values lar compounds more sophisticated intermolec-
of σij and ΩD for the Lennard – Jones potential ular potential functions must be applied. Diffu-
are given for some components, e.g., in [234]). sion coefficients of some components in air are
shown as a function of temperature in Figure 20. Experimental: D12 = 0.236 cm2 /s (at 328.4 K)
[234]
Method of Fuller et al. Fuller and
coworkers suggested an incremental method Temperature Dependence of Binary Diffu-
for Dij [cm2 /s] based on Equation (6.43) [283], sion Coefficients. Molecular theory (Eq. 6.42)
[284]: predicts the following form for the temperature
dependence of binary diffusion coefficients:
1.013 [1/Mi +1/Mj ]1/2
Dij = ·
104 p D ∼ T 1.5 (6.46)
T 1.75
. / (6.45) [neglecting ΩD (T )]. For real systems the expo-
1/3 1/3 2
(ID )i + (ΣID )j nent is often about 1.8.
with p in MPa where (Σ I D )i and (Σ I D )j are
Effect of Pressure on Binary Diffusion Co-
the diffusion volumes of components i and j, re-
efficients of Gases. In general, diffusion coef-
spectively which are given by Fuller et al. for
ficients decrease with increasing pressure ac-
simple molecules such as the noble gases, nitro-
cording to Equation (6.43). At higher pressures
gen, and oxygen [284]. Some values for diffu-
( p >> pc ) the influence of pressure becomes
sion volumes (Σ I D ) follow:
more complex and corresponding states meth-
He 2.67 CO 18.0 ods must be employed [285], [286].
Ne 5.98 CO2 26.9
Ar 16.2 N2 O 35.9
Kr 24.5 NH3 20.7
Effect of Concentration on Diffusion Coef-
Xe 32.7 H2 O 13.1 ficients of Gases. Binary diffusion coefficients
H2 6.12 SF6 71.3 can usually be assumed to be independent of
D2 6.84 Cl2 38.4 composition. A discussion of the theory of dif-
N2 18.5 Br2 69.0
O2 16.3 SO2 41.8 fusion in multicomponent gas mixtures is given,
Air 19.7 e.g., in [233], [283], [287]. A procedure for pre-
dicting multicomponent diffusion phenomena is
For other molecules (Σ I D ) is calculated by given in [288].
summing up the increments I D for the elements
and structural groups in the molecule. Values for
these increments follow [284]: 6.3.2. Diffusion Coefficients of Liquids
C 15.9 F 14.7 The Stokes – Einstein equation provides the ba-

H 2.31 Cl 21.0
O 6.11 Br 21.9
sis for many empirical correlations of diffusion
N 4.54 I 29.8 coefficients in liquids. This relation describes the
Ring, aromatic −18.3 S 22.9 movement of a large hypothetical spherical par-
Ring, heterocyclic −18.3 ticle through a solvent consisting of infinitely
small molecules. With these assumptions binary
The authors claim an average accuracy in the diffusion coefficients are given as a function of
prediction of diffusion coefficients of ca. 4 %. solvent viscosity ηj and the “molecular” radius
Example. Calculation of D12 of ethyl- of the solute ri :
ene – water using Fuller’s method.
kT
Dij = (6.47)
1) C2 H4 : M = 28.05 g/mol; (Σ I D )C2 H4 = 6πηj ri
2 C + 4 H = 2×15.9 + 4×2.31 = 41.04
2) H2 O: M = 18.02 g/mol; (Σ I D )H2 O = The effect of solvent viscosity on binary diffu-
2 H +1 O = 2×2.31 + 1×6.11 = 10.73 sion coefficients is shown in Figure 21.
From Equation (6.45): D12 = 0.242 cm2 /s (at

0.1 MPa, 328.4 K)
In many cases the surface tensions σi and σj

are similar and their ratio can be set equal
to unity, making this expression very conve-
nient.
2) n-Paraffin solutions:
∞ T 1.47 c
Dij = 1.33 × 10−7 ηj (6.50)
V 0.71
0i
where the exponent c = (10.2/V 0i ) − 0.791.

According to the authors errors are < 4 %.
3) Organic solutes in water:

∞ −0.19
Dij = 1.25 × 10−8 V0i −0.292 T 1.52 ηjδ
(6.51)
Figure 21. Diffusivity of carbon tetrachloride in various sol-
vents [289] where the parameter δ = (9.58/V l0i ) − 1.12.
a) Hexane; b) Heptane; c) Isooctane; d) Methanol;
e) Toluene; f ) Benzene; g) Carbon tetrachloride; h) Cy-
According to the authors the errors are usu-
clohexane; i) Ethanol; j) Dioxane; k) Kerosine; l) Decalin ally < 10 %.
Since Equation (6.47) only holds for simple Example. Calculation of infinite dilution dif-
systems, a variety of empirical correlations have fusion coefficients using the Hayduk – Minhas
been published. They are usually applicable to method.
solvent – solute systems with low to moderate
viscosity (< 20 – 40 mPa · s). 1) Acetone in ethyl acetate [249]:
Acetone Ethyl acetate

Diffusion Coefficients at Infinite Dilution.
The diffusion coefficient D∞ ij for solute i at in- M, g/mol 58.08 88.106
finite dilution in solvent j is a useful reference V l 0i , cm3 /mol 73.52 97.83
ηi , mPa · s 0.4508
value for the determination of binary diffusion σi , N/m 0.02332 0.02375
coefficients of liquid mixtures.
The estimation technique of Hayduk and
Minhas comprises several equations for differ- From Equation (6.49): D∞ 12 = 2.59 ×
ent types of solutions [290]: 10−5 cm2 /s
Experimental: D∞ 12 = 3.18×10
−5
cm2 /s at
1) Nonelectrolyte systems: 293 K [235]
Relative deviation: − 18.6 %
Pj0.5 1.55 × 10−8 T 1.29 2) Toluene in n-hexane [249]:
∞
Dij = (6.48)
Pi0.42 0.23 η 0.92
V0j j
Toluene n-Hexane
where V 0j [cm3 /mol] is the liquid molar vol- M, g/mol 92.14 86.177
ume of solvent j at its normal boiling point, V l0i , cm3 /mol 106.9 131.60
η j its viscosity [mPa · s], and P the parachor ηi , mPa · s 0.2942
(see Section 7.1) [cm3 g0.25 s−0.5 mol−1 ].
From the definition of the parachor as Substituting c = − 0.6956 in Equation (6.50):
P ≡ σ 0.25
i V 0i (Eq. 7.2 where σi is the surface D∞
12 = 4.90×10
−5
cm2 /s
tension of component i ), Equation (6.48) can Experimental: D∞ 12 = 4.12×10
−5
cm2 /s at
be rewritten as 298 K [235]
0.420.27
V0j 0.125
∞ T 1.29 σj
Dij = 1.55 × 10−8 (6.49)
V0i ηj0.92 σi0.105
3) Aniline in water [249]:

LIVE GRAPH
Click here to view
Aniline Water
M, g/mol 93.128 18.02

V l0i , cm3 /mol 77.42
ηi , mPa · s 1.002
Substituting δ = − 0.996 in Equation (6.51):

D∞
12 = 1.021×10
−5
cm2 /s LIVE GRAPH
Click here to view
Experimental: D12 = 0.92×10−5 cm2 /s at
∞
293 K [235]
The application of the method of Hayduk
et al. is somewhat more complicated for sys-
tems with associating compounds (e.g., organic LIVE GRAPH
acids). Table 25 gives an overview of estimation Click here to view
methods.
Effect of Composition on Binary Diffu-

sion Coefficients in Liquids. The dependence
of binary diffusion coefficients on concentration
is shown in Figure 22. In mixtures with com-
pounds differing greatly in size and polarity the Figure 22. Effect of composition on binary diffusion
coefficients [294]
effect of concentration on diffusion coefficients A) Benzene – carbon tetrachloride at 298.41 K; B)
cannot be neglected. Even a linear combination Chlorobenzene – bromobenzene at 299.93 K; C)
of diffusion coefficients at infinite dilution does Toluene – chlorobenzene at 300.11 K
not yield accurate results. The thermodynamic
For systems showing ideal mixing behavior
correction term (∂ ln ai / ∂ ln xi ) is common to
the differential quotient ∂ ln ai / ∂ ln xi is equal
many estimation methods as in the Darken equa-
to zero. In view of the fact that Equation (6.53)
tion [291] for a binary mixture of components i
in some cases overcorrects for nonideal behav-
and j
ior, Rathburn and Babb recommended the in-
∞

∞ ∂ lnai
troduction of an exponential constant f for the
Dij = xi Dij +xj Dji (6.52) thermodynamic correction [292]:
∂ lnxi
f
where x is the mole fraction and a the activity; ∞ ∞
∂ lnai
Dij = xi Dij +xj Dji (6.55)
ai (xi ) can be obtained from vapor – liquid equi- ∂ lnxi
librium data. From the Gibbs – Duhem equation
The values for f originally proposed by Rath-
it follows that
burn and Babb (in parentheses) have been
∂ lnai ∂ lnaj reevaluated by Siddiqi and Lucas [293]: f = 0.6
= (6.53) (0.6) for positive deviations from Raoult’s law
∂ lnxi ∂ lnxj
and f = 0.4 (0.3) for negative deviations.
Application of the NRTL equation (Section Another correlation has been proposed by Vi-
4.2.1.2) yields for a binary mixture: gnes [295]:
∂ lna1 . xj ∞ xi / ∂ lnai
= 1 − 2x1 x2 ∞
Dij = Dij Dji (6.56)
∂ lnx1 ∂ lnxi

τ21 G221 τ12 G212
× 3
+ 3
(6.54) Siddiqi and Lucas found that the average error
(x1 +x2 G21 ) (x2 +x1 G12 ) was less than 5 % for the prediction of 79 data
sets. For systems with polar components they
report deviations of 11 %.
Table 25. Selected methods for estimating diffusion coefficients in liquid solutions at infinite dilution
Method Range of applicability Information required ∗ Error, % ∗∗

l
Wilke – Chang 1955 [296] not reliable for water as solute M 2 , η2 , V 1 , (T b ),
association 11 (w), 20 (o)
parameters
l
Scheibel 1954 [297] usually appropriate for aqueous M 2 , η 2 , V 1 , (T b ) 11 (w), 20 (o)
solutions
Othmer – Thakar 1953 [298] preferably for aqueous solutions V l01 , η water 5 (w)
Reddy – Draiswamy 1967 [299] M 2 , V l01 , V l02 η 2 22 (o), 25 (w)
Lusis – Ratcliff 1968 [300] preferably for alkane – alkane V l01 , V l02 , η 2 29 (o)
systems, not for aqueous solutions
Tyn – Calus 1975 [301] different correlations for different M 2 , V l01 , V l02 , P1 , P2 , η 2 9
types of systems
Nakanishi 1978 [302] not for highly viscous solvents V l01 , V l02 , η 2 14
(η < 20 – 30 mPa · s)
Hayduk – Minhas 1982 [290] different correlations for different M 2 , V l02 , V l01 , η 2 , P1 , P2 , (σi ) 10
types of systems
l l
Siddiqi – Lucas 1986 [293] including dissolved gases V 01 , V 02 , η2 13 (o), 20 (w)
∗ Subscripts: 1 = solute; 2 = solvent.

∗∗ w = aqueous solutions; o = organic solutions.
( p >> pc ); experimental data can be found in

LIVE GRAPH
Click here to view the compilation of Jasper [303]. Water ex-
hibits an extraordinarily high surface tension
of 72 mN/m at room temperature. The vari-
ation of surface tension with temperature of
some organic compounds is shown in Fig-
ure 23. Salt melts typically have surface ten-
sions of ca. 100 – 200 mN/m and metal melts of
300 – 1000 mN/m. At low to moderate pressures
( p < pc ) the influence of inert gases can be ne-
glected.
7.1. Surface Tension of Pure Liquids
Two basically empirical categories of methods

are used for the estimation of surface tension.
One type uses the parachor P and the other em-
Figure 23. Variation of surface tension with temperature ploys the principle of corresponding states.
[304]
a) Acetic acid; b) Diethyl ether; c) Ethyl acetate Parachor Methods. The parachor is a char-
acteristic parameter which, according to its def-
inition in Equation (7.1), is a function of surface
tension. It has been defined by Sudgen [305] as
7. Surface Tension of Liquids
1/4 Mi
Pi =σi (7.1)
Surface and interfacial tension influence mass li − vi
and heat transfer processes considerably. In this
chapter only the liquid – vapor interface is dis- where li and vi are the liquid and saturated va-
cussed. por densities of pure compound i, respectively.
Surface tension σ is expressed in units of At temperatures considerably lower than the
[N/m] or preferably in [mN/m] (≡ [dyn/cm]). critical temperature the density of the vapor vi
Surface tensions of organic liquids vary bet- can be neglected compared to the density of the
ween 20 and 50 mN/m at moderate pressure liquid li , thus simplifying Equation (7.1) to
1/4 Mi 1/4 Table 26. Quale’s increments for the estimation of the parachor Pi
Pi =σi =σi V li (7.2)
li [cm3 g0.25 s−0.5 mol−1 ] [306]
Group Increment
The parachor is virtually independent of tem-
perature; it is approximately an additive quantity Carbon – hydrogen
which can be determined by summing up in- C 9.0
H 15.5
crements. Several such methods have been pro- CH3 55.5
posed. The method of Quale [306] is recom- CH2 in −(CH2 )n −
mended (for increments see Table 26). n < 12 40.0
n > 12 40.3
Surface tensions predicted with this method Alkyl groups
usually show errors of less than 5 % for nonpo- 1-Methylethyl 133.3
lar and weakly polar compounds and 5 – 10 % 1-Methylpropyl 171.9
for compounds with hydrogen bounds [307]. 1-Methylbutyl 211.7
2-Methylpropyl 173.3
Example. Calculation of surface tension of 1-Ethylpropyl 209.5
acetamide, CH3 CONH2 , at 378.2 K from para- 1,1-Dimethylethyl 170.4
chor estimated with the method of Quale [306] 1,1-Dimethylpropyl 207.5
Structural groups: 1 (CH3 −), 1 (−CONH2 ) (see 1,2-Dimethylpropyl 207.9
1,1,2-Trimethylpropyl 243.5
Table 26) C6 H5 189.6
P = 55.5 + 91.7 = 147.2 cm3 g0.25 s−0.5 mol−1 Special groups
With M = 59.068 g/mol, l = 977.05 kg/m3 , −COO− 63.8
−COOH 73.8
plv v lv
0i = 12.4 hPa [308] and = p0i M/(RT ) = −OH 29.8
3
0.023 kg/m from Equation (7.1): σ = −NH2 42.5
0.0352 N/m −O− 20.0
Experimental: σ = 0.03696 N/m at 378.2 K [308] −NO2 74
−NO3 (nitrate) 93
Relative deviation: − 4.9 % −CO(NH2 ) 91.7
(Deviation between Eqs. 7.1 and 7.2 = 0.01 %) R−[−CO−]−R (ketone)
Number of C atoms in R + R :
R + R = 2 51.3
Corresponding States Methods. These R + R = 3 49.0
methods are based upon a relation proposed R + R = 4 47.5
by Van der Waals [309]: R + R = 5 46.3
R + R = 6 45.3
σ=kTc
1/3 1/32/3
p (1−Tr )m (7.3) R + R = 7 44.1
−CHO 66
where k and m are constants, T c is the critical O (not noted above) 20
N (not noted above) 17.5
temperature, pc the critical pressure, and T r the S 49.1
reduced temperature. Employing the Stiel po- P 40.5
lar factor χ (see Section 2.4), Hakim et al. [310] F 26.1
Cl 55.2
transformed Equation (7.3) into a relation which Br 68.0
is particularly useful for alcohols ( pc in bar, σ I 90.3
in N/m): Ethylenic bonds
Terminal 19.1
m
1−Tr Qp (χ,ω) 2,3-position 17.7
σ=p1/32/3 T 1/31/3 (7.4) 3,4-position 16.3
0.4 1000
Triple bond 40.6
with the functions Qp and m in terms of the Stiel Ring closure
Three-membered 12
polar factor χ and the acentric factor ω Four-membered 6.0
Five-membered 3.0
Qp = 0.156 + 0.365ω−1.754χ Six-membered 0.8
−13.57χ2 −0.506ω 2 +1.287ωχ (7.5)
m= 1.21 + 0.5385ω−14.61χ−32.07χ2
A simpler relation based on Equation (7.3)
was proposed by Brock and Bird [311]; it
−1.656ω 2 +22.03ωχ (7.6)
should only be used for nonpolar or weakly polar
Errors are usually between 5 and 10 %. liquids.
Example. Calculation of surface tension of LIVE GRAPH

Click here to view
1-butanol, CH3 CH2 CH2 CH2 OH, at 303.2 K ac-
cording to Hakim et al. [310].
M = 74.122 g/mol, pc = 44.13 bar, T c = 563.0 K,
χ = − 0.07, ω = 0.593 [308].
From Equation (7.6): m = 0.8981.
From Equation (7.5): Qp = 0.1974.
From Equation (7.4): σ = 0.02314 N/m.
Experimental: σ = 0.02378 N/m [308].
Relative deviation: − 2.7 %.
7.2. Surface Tension of Liquid Mixtures

Organic Systems. Surface tensions of mix-
tures of organic compounds can be estimated by
the simple mixing rule:

σm = xi σi (7.7)
where xi is the mole fraction of component i or Figure 24. Surface tension of binary organic mixtures at
298 K [311]
by the more general relation a) N itrobenzene – carbon tetrachloride;
b) Acetophenone – benzene;
β
σm = xi σiβ (7.8) c) N itrobenzene – benzene;
d) Diethylether – benzene
with the exponent β. The mole fraction refers to the underlined component.
An exponent β = − 1 is sometimes used: LIVE GRAPH
Click here to view
−1
xi
σm = (7.9)
σi
Equation (7.2) can be extended for nonaqueous

mixtures:
4
lm xi
σm = Pi (7.10)
M
where xi and yi are the mole fractions of com-

pound i in the liquid and vapor phases, respec-
tively, and
1
= xi /i (7.11)
m
Again, the parachor of the pure compounds is Figure 25. Surface tension of aqueous solutions of organic
employed (see Section 7.1). When experimental compounds (data from [312])
surface tension data for the mixture are avail- a) Sucrose; b) Methanol; c) Acetonitrile; d) Ethanol
able, Pi can also be used as a correlation pa- A large number of more sophisticated meth-
rameter. The accuracy of Equation (7.10) is usu- ods have been published based on the principle
ally < 10 %. If the parachor is applied as an ad- of corresponding states or on phenomenologi-
justable parameter using experimental informa- cal or statistical thermodynamics. These meth-
tion, precision is of course much higher. The ods are discussed in detail in [307].
concentration dependence of the surface tension
of some binary organic solutions is shown in Fig-
ure 24.
Aqueous Systems. The surface tension of 2. T. E. Danner, R. P. Daubert (Eds.): Manual for
water is strongly affected by small amounts Predicting Chemical Process Design Data,
of dissolved organic compounds because hy- Pennsylvania State University 1987.
drophobic molecules are repelled by the water 3. G. Hecht et al.: Berechnung
molecules and are therefore enriched at the sur- thermodynamischer Stoffwerte von Gasen und
face. The surface tension of aqueous solutions of Flüssigkeiten, VEB Deutscher Verlag für
organics therefore depends on the hydrophobic- Grundstoffindustrie, Leipzig 1966.
ity of the organic solute with a highly nonlinear 4. C. Jochum, M. G. Hicks, J. Sunkel (eds.):
influence of solute concentration. In general, the Physical Property Prediction in Organic
Chemistry, Springer Verlag, Berlin 1988.
surface tension of water is greatly decreased by
5. R. C. Reid, T. K. Sherwood: The Properties of
hydrophobic solutes (Fig. 25).
Gases and Liquids, 2nd ed., McGraw-Hill,
For estimating the effect of organic solutes New York 1966.
on the surface tension of water Meissner et al. 6. R. C. Reid, J. M. Prausnitz, T. K. Sherwood:
[313] have proposed a method which is based The Properties of Gases and Liquids, 3rd ed.,
on the following equation: McGraw-Hill, New York 1977.
. xi / 7. R. C. Reid, J. M. Prausnitz, B. E. Poling: The
σm =σ0w 1 − 0.411log 1+ (7.12) Properties of Gases and Liquids, 4th ed.,
A
where σ 0w is the surface tension of pure water, 8. Z. Sterbacek, B. Biskup, P. Tausk: Calculation
xi the molar concentration of the organic com- of Properties Using Corresponding-State
ponent, and A is a substance-specific constant. Methods, Elsevier, Amsterdam 1979.
Values of A (×104 ) for a number of organic sub- 9. S. Weiß et al. (eds.): Verfahrenstechnische
stances follow: Berechnungsmethoden, part 7: Stoffwerte,
Propionic acid 26 Ethyl propionate 3.1 VCH Verlagsgesellschaft, Weinheim 1986.
1-Propanol 26 Propyl acetate 3.1
2-Propanol 26 General References
Methyl acetate 26 Valeric acid 1.7 General Data Collections
Isovaleric acid 1.7
Propylamine 19 Pentanol 1.7
10. D. Behrens, R. Eckermann (eds.): Chemistry
Methyl ethyl 19 Isopentanol 1.7 Data Series, Dechema, Frankfurt/Main 1977.
ketone 11. D’Ans-Lax: Taschenbuch für Chemiker und
Butyric acid 7 Propyl propionate 1.0 Physiker, 4th ed., vols. 1 – 3, Springer Verlag,
Isobutyric acid 7 Caproic acid 0.75
Butanol 7 Heptanoic acid 0.17
Berlin 1997.
Isobutanol 7 Octanoic acid 0.034 12. R. P. Daubert, T. E. Danner: Design Institute
Propyl formate 8.5 Decanoic acid 0.0025 for Physical Property Data (DIPPR)/American
Ethyl acetate 8.5 Institute of Chemical Engineers (AIChE):
Methyl propionate 8.5
Data Compilation Tables of Properties of Pure
Diethyl ketone 8.5
Compounds, Pennsylvania State University
1985.
The accuracy of this method is reported to be 13. H. Landolt, R. Börnstein: Zahlenwerte und
better than 15 %. Another more precise but more Funktionen aus Naturwissenschaft und
complicated estimation method was suggested Technik, 6th ed., Springer Verlag, Berlin 1950.
by Tamura et al. [314]. This method is applica- 14. Physical Sciences Data,vols. 1 – 44, Elsevier,
ble to binary mixtures only and is discussed in Amsterdam 1987.
detail in [307]. 15. Thermodynamics Research Centre (TRC):
Selected Values of Properties of Chemical
Compounds, Texas A & M University,
College Station, Texas, 1994.
8. References 16. Y. S. Touloukian, C. Y. Ho (eds.): CINDAS
General References Data Series on Material Properties,
Methods vols. 1 – Hemisphere, Washington 1981.
1. S. Bretsznajder: Prediction of Transport and 17. Y. S. Touloukian, C. Y. Ho: Thermophysical
Other Physical Properties of Fluids, Pergamon Properties of Matter, vols. 1 – 13, IFI/Plenum
Press, Oxford 1971. Press, New York 1970.
18. VDI-Wärmeatlas, 7th ed., VDI-Verlag, 33. Y. S. Touloukian, T. Makita: Specific Heat.
Düsseldorf 1994. Nonmetallic Liquids and Gases, IFI/Plenum
19. D. R. Lide (ed.): Handbook of Chemistry and Press, New York 1970; Suppl. 1976.
Physics, 76th ed., CRC Press, Boca Raton, 34. Y. S. Touloukian, E. H. Buyco: Specific Heat.
Florida, 1995. Nonmetallic Solids, IFI/Plenum Press, New
York 1970.
General References 35. Further reference: [55]
Universal Handbooks
20. Beilsteins Handbuch der Organischen Chemie, General References
4th ed., Springer Verlag, Berlin 1958. Thermodynamic Data of Mixtures
21. Gmelin Handbook of Inorganic and 36. W. Arlt, M. E. A. Macedo, P. Rasmussen, J. M.
Organometallic Chemistry, 8th ed.,VCH Sorensen: Liquid – Liquid Equilibrium Data
Verlagsgesellschaft, Weinheim 1990. Collection,Chemistry Data Series, vol. V,
parts 1 – 4, Dechema, Frankfurt/Main
General References 1979 – 1987.
Thermodynamic Data of Pure Compounds 37. C. Christensen, J. Gmehling, P. Rasmussen, U.
22. O. Knacke, O. Kubaschewski, K. Hesselmann: Weidlich, T. Holderbaum: Heats of Mixing
Thermochemical Properties of Inorganic Data Collection, Chemistry Data Series,
Substances, vol. 1, Springer Verlag, Berlin vol. III, parts 1 – 4, Dechema, Frankfurt/Main
1973, vol. 2, Verlag Stahleisen, Düsseldorf 1984 – 1991.
1977. 38. H. Engels: Phase Equilibria and Enthalpies of
23. T. Barin: Thermochemical Data of Pure Electrolyte Solutions, Chemistry Data Series,
Substances, 3rd ed., VCH Verlagsgesellschaft, vol. XI, Dechema, Frankfurt/Main 1990.
Weinheim 1995. 39. J. Gmehling, U. Onken et al.: Vapor – Liquid
24. M. W. Chase et al.: Joint Army Navy Air Force Equilibrium Data Collection, vol. 1: part 1
(JANAF) Thermochemical Tables, 3rd ed., (1977), part 1 a (1981), part 1 b (1988), part
American Chemical Society, American 2 a (1985, reprint), part 2 b (1987), part 2 c
Institute of Physics, Washington, D.C., 1986. (1982), part 2 d (1982), part 2 e (1988), part
25. J. D. Cox, G. Pilcher: Thermochemistry of 2 f (1990), part 3/4 (1979), part 3 a (1993),
Organic and Organometallic Compounds, part 3 b (1993), part 4 a (1994), part 5
Academic Press, London 1970. (1982), part 5 a (in prep.), part 6 a (1980),
26. J. B. Pedley, R. D. Naylor, S. P. Kirby: part 6 b (1980), part 6 c (1984), part 7
Thermochemical Data of Organic Compounds, (1980), part 8 (1984), Dechema,
2nd ed., Chapman and Hall, New York 1986. Frankfurt/Main 1977 – 1994.
27. F. D. Rossini: Selected Values of Chemical 40. J. Gmehling et al.: Activity Coefficients at
Thermodynamic Properties, National Bureau Infinite Dilution, Chemistry Data Series,
of Standards, Circular 500, Washington 1952. vol. IX, parts 1 – 4, Dechema, Frankfurt/Main
28. D. R. Stull, G. C. Sinke: “Thermodynamic 1986 – 1994.
Properties of the Elements,” in: Advances in 41. J. Gmehling, J. Menke, J. Krafczyk, K.
Chemistry Series, vol. 18, American Chemical Fischer: Azeotropic Data, parts I – II, VCH
Society, Washington, D.C., 1956. Verlagsgesellschaft, Weinheim 1994.
29. D. R. Stull, E. F. Westrum, G. C. Sinke: The 42. IUPAC: Solubility Data Series, Pergamon
Chemical Thermodynamics of Organic Press, Oxford 1979.
Compounds, Krieger, Malabar, Fla. 1987. 43. H. Knapp, R. Döring, L. Öllrich, U. Plöcker,
30. A. L. Suris: Handbook of Thermodynamic J. M. Prausnitz: Vapor – Liquid Equilibria for
High Temperature Process Data, Hemisphere, Mixtures of Low-Boiling Substances,
Washington 1987. Chemistry Data Series, vol. VI, parts 1 – 4,
31. A. Tamir, E. Tamir, K. Stephan: Heats of Dechema, Frankfurt/Main 1982 – 1989.
Phase Change of Pure Components and 44. H. Knapp, M. Teller, R. Langhorst:
Mixtures, Elsevier, Amsterdam 1983. Solid – Liquid Equilibrium Data Collection,
32. Y. S. Touloukian et al.: Thermodynamic and Chemistry Data Series, vol. VIII, Dechema,
Transport Data Properties of Gases, Liquids Frankfurt/Main 1987.
and Solids, McGraw-Hill, New York 1959. 45. A. Seidell, W. F. Linke: Solubilities of
Inorganic and Organic Compounds, 4th ed.,
vols. 1 – 2, Princeton [vol. 1(1958), vol. 2 General References

(1965)]. Transport Data
46. H. Stephen, T. Stephen: Solubilities of 58. K. Stephan, T. Heckenberger: Thermal
Inorganic and Organic Compounds, Conductivity and Viscosity Data of Fluid
Pergamon Press, Oxford 1963, reprinted 1979. Mixtures, Chemistry Data Series, vol. X,
47. N. K. Voskresenskaya (ed.): Handbook of Dechema, Frankfurt/Main 1989.
Solid – Liquid Equilibria in Systems of 59. K. Stephan, K. Lucas: Viscosity of Pure Dense
Anhydrous Inorganic Salts, Keter Press, Fluids, Plenum Press, New York 1979.
Jerusalem 1970. 60. D. S. Viswanath, G. Natarjan: Data Book on
48. J. F. Zemaitis, D. M. Clark, M. Rafal, N. C. the Viscosity of Liquids, Hemisphere, New
Scrivner: Handbook of Aqueous Electrolyte York 1989.
Thermodynamics, AIChE, New York 1986.
49. Further reference: [31] General References
Selected Compounds
General References 61. J. Barthel, R. Neuder: Electrolyte Data
Critical Data Collection: Conductivities, Transference
50. D. Ambrose: “Correlation and Estimation of Numbers, Limiting Ionic Conductivities,
Vapour Liquid Critical Properties, I. Critical Chemistry Data Series, vol. XII, parts 1 – 3,
Temperatures of Organic Compounds,” Dechema, Frankfurt/Main 1992 – 1997.
National Physical Laboratory, Teddington, 62. R. R. Dreisbach: “Physical Properties of
NPL Rep. Chem. 92 (1978) corr. March 1981, Chemical Compounds,” vols. I – III, in:
Teddington, NPL Rep. Chem. 98 (1979). Advances in Chemistry Series, vols. 15, 22, 29,
51. K. H. Simmrock, R. Janowsky, A. Ohnsorge: American Chemical Society, Washington, DC
Critical Data of Pure Substances, Chemistry [vol. I (1955), vol. II (1959), vol. III (1961)].
Data Series, vol. II, parts 1 – 2, Dechema, 63. E. W. Flick: Industrial Solvents Handbook,
Frankfurt/Main 1986. 3rd ed., Noyes Data Corporation, New Jersey
1985.
General References 64. A. L. Horvath: Physical Properties of
Vapor Pressure Inorganic Compounds, Fletcher & Son,
52. T. Boublik, V. Fried, E. Hala: The Vapor Norwich, UK, 1975.
Pressures of Pure Substances, 2nd ed., 65. J. A. Riddick, W. B. Bunger, T. K. Sakano:
Elsevier, Amsterdam 1984. Organic Solvents. Physical Properties and
53. S. Ohe: Computer Aided Data Book of Vapor Methods of Purification, 4th ed. , vol. II,
Pressure, Data Book Publishing, Tokyo 1976. Wiley, New York 1986.
54. I. Wichterle, J. Linek: Antoine Vapour 66. R. M. Stephenson, S. Malanowski: Handbook
Pressure Constants of Pure Compounds, of the Thermodynamics of Organic
Academia, Praha 1971. Compounds, Elsevier, Amsterdam 1987.
55. B. J. Zwolinski, R. C. Wilhoit: Handbook of 67. Thermodynamics Research Centre (TRC):
Vapour Pressures and Heats of Vaporisation of Selected Values of Properties of Hydrocarbons
Hydrocarbon and Related Compounds, and Related Compounds, vol. 1, Texas A & M
Thermodynamic Research Center, Department University, College Station, Texas, 1977.
of Chemistry, Texas 1971. 68. Thermodynamics Research Centre (TRC):
TRC Thermodynamic Tables–Hydrocarbons,
General References vols. 1 – 11, Texas A & M University, College
pVT Behavior Station, Texas, 1942.
56. J. Cholinski, A. Szafranski et al.: Second Virial 69. Thermodynamics Research Centre (TRC):
Coefficients for Organic Compounds, Institute TRC Thermodynamic
of Physical Chemistry, Polish Academy of Tables–Non-Hydrocarbons, vols. 1 – 8, Texas
Sciences, Warszawa 1985. A & M University, College Station, Texas,
57. J. H. Dymond, E. B. Smith: The Virial 1955.
Coefficients of Pure Gases and Mixtures : A 70. J. Timmermanns: The Physico-Chemical
Critical Compilation, Clarendon Press, Oxford Constants of Pure Organic Compounds,
1980. Elsevier, New York [vol. 1 (1950), vol. 2
(1965)].
71. Y. S. Touloukian (ed.): Thermophysical 80. W. Kistiakowsky, Z. Phys. Chem. 107 (1923)
Properties of High Temperature Solid 65.
Materials, vols. 1 – 6, MacMillan, New York 81. J. Timmermanns: The Physico-Chemical
1967. Constants of Pure Organic Compounds,
72. W. Hao, H. S. Elbro, P. Alessi: Polymer Elsevier, New York [vol. 1 (1950), vol. 2
Solution Data Collection, Chemistry Data (1965)].
Series, vol. XIV, parts 1 – 3, Dechema, 82. Thermodynamics Research Centre (TRC):
Frankfurt/Main 1982 – 1992. Selected Values of Properties of Chemical
Compounds, Texas A & M University,
General References College Station, Texas, 1982.
References for Chapter 1 83. J. A. Riddick, W. B. Bunger, T. K. Sakano:
73. D’Ans-Lax: Taschenbuch für Chemiker und Organic Solvents. Physical Properties and
Physiker, 4th ed., vols. 1 – 3, Springer Verlag, Methods of Purification, 4th ed., vol. II, Wiley,
Berlin 1997. New York 1986.
74. D. R. Lide (ed.): Handbook of Chemistry and
Physics, 76th ed., CRC Press, Boca Raton, General References
Florida, 1995. References for Chapter 2
75. H. Landolt, R. Börnstein: a. “ Eigenschaften 84. L. I. Stiel, G. Thodos, Chem. Eng. Data Ser. 7
der Materie in Ihren Aggregatzuständen,” (1962) 234.
Zahlenwerte und Funktionen aus 85. J. S. Rowlinson: Liquids and Liquid Mixtures,
Naturwissenschaft und Technik, 6th ed., vol. II 2nd ed., Butterworth, London 1969.
Springer Verlag, Berlin 1956; b. “ 86. J. O. Hirschfelder, C. F. Curtiss, R. B. Bird:
Makroskopische und technische Eigenschaften Molecular Theory of Gases and Liquids, 4th
der Materie,” Zahlenwerte und Funktionen aus print, Wiley, New York 1967.
Naturwissenschaft und Technik, 6th ed., new 87. L. C. Nelson, E. F. Obert, Trans. ASME 76
series, Group IV Springer Verlag, Berlin 1974. (1954) 1057.
76. D. Behrens, R. Eckermann (eds.): Chemistry 88. R. C. Reid, J. M. Prausnitz, T. K. Sherwood:
Data Series, Dechema, Frankfurt/Main 1977. The Properties of Gases and Liquids, 3rd ed.,
77. U. Onken, J. Rarey-Nies, J. Gmehling: “The McGraw-Hill, New York 1977.
Dortmund Data Bank: A Computerized 89. R. C. Reid, J. M. Prausnitz, B. E. Poling: The
System for Retrieval, Correlation, and Properties of Gases and Liquids, 4th ed.,
Prediction of Thermodynamic Properties of McGraw-Hill, New York 1987.
Mixtures,” Int. J. Thermophys. 10 (1989) 90. A. L. Lydersen: “Estimation of Critical
739 – 747. Properties of Organic Compounds,” Univ.
78. C. Jochum, M. G. Hicks, J. Sunkel (eds.): Wisconsin Coll. Eng., Eng. Exp. Stn. Rept. 3,
Physical Property Prediction in Organic Madison, Wisc., April 1955.
Chemistry, Springer Verlag, Berlin 1988. 91. K. G. Joback, MS Thesis, Massachusetts
79. Fachinformationszentrum (FIZ) Chemie, Institute of Techn., Cambridge, Mass., 1984.
Postfach 12 60 50, D-10583 Berlin, Germany; 92. K. G. Joback, R. C. Reid, Chem. Eng.
http://www.fiz-chemie.de DECHEMA e.V., Commun. 57 (1987) 233.
Informationssysteme und Datenbanken, 93. J. Timmermanns: The Physico-Chemical
Postfach 15 01 04, D-60061 Frankfurt/Main, Constants of Pure Organic Compounds,
Germany; http://www.dechema.de Design Elsevier, New York [vol. 1 (1950), vol. 2
Institute for Physical Property Data (DIPPR), (1965)].
STN International, 2540 Olentangy River 94. D. Ambrose: “Correlation and Estimation of
Road, P.O.Box 2228, Columbus, Ohio, 43202, Vapour Liquid Critical Properties, I. Critical
USA. STN International, Postfach 2465, Temperatures of Organic Compounds,” NPL
D-76012 Karlsruhe, Germany; Rep. Chem. UK Natl. Phys. Lab. Div. Chem.
http://www.fiz-karlsruhe.de STN International, Stand. 92 (1978) (corr. March 1980).
95. D. Ambrose, NPL Rep. Chem. UK Natl. Phys.
Tokyo Headquarters, 5-3 Yonbancho,
Lab. Div. Chem. Stand. 98 (1979).
Chiyoda-ku, Tokyo 102, Japan. Physical
96. R. F. Fedors, Chem. Eng. Commun. 16 (1982)
Properties Data Service (PPDS), Institution of
149.
Chemical Engineers, 165 – 171 Railway
97. L. Constantinou, R. Gani, AIChE J. 40 (1994)
Terrace, Rubgy, CV21 3HQ, England.
1697.
98. A. P. Kudchadkar, G. H. Alani, B. J. Zwolinski, 119. J. Partington: An Advanced Treatise on

Chem. Rev. 68 (1968) 659. Physical Chemistry, vol. I: Fundamental
99. K. H. Simmrock, R. Janowsky, A. Ohnsorge: Principles: The Properties of Gases;
Critical Data of Pure Substances, Chemistry Longmans, Green & Co., New York 1949.
Data Series, vol. II, part I, Dechema, 120. F. Schroeder in [119]
Frankfurt/Main 1986. 121. J. A. Riddick, W. B. Bunger: Organic Solvents,
100. J. F. Mathews, Chem. Rev. 72 (1972) 71. Physical Properties and Methods of
101. W. C. Edmister, Pet. Refin. 37 (1958) no. 4, Purification, 3rd ed., vol. II, 1970; 4th ed.,
173. 1986, J. Wiley, New York.
102. S. Weiß et al. (eds.): Verfahrenstechnische 122. L. Constantinou, R. Gani, J. P. O’Connell,
Berechnungsmethoden, part 7: Stoffwerte, Fluid Phase Equilib. 103 (1995) 11.
VCH Verlagsgesellschaft, Weinheim 1986. 123. R. D. Gunn, T. Yamada, AIChE J. 17 (1971)
103. L. Constantinou, R. Gani, J. P. O’Connell, 1341.
Fluid Phase Equilib. 103 (1995) 11. 124. R. W. Hankinson, G. H. Thomson, AIChE J.
25 (1979) 653.
General References 125. L. C. Yen, S. S. Woods, AIChE J. 16 (1966) 95.
References for Chapter 3 126. V. L. Bhirud, AIChE J. 24 (1978) 880, 1127.
104. J. S. Rowlinson: Liquids and Liquid Mixtures, 127. S. Weiß et al. (eds.): Verfahrenstechnische
2nd ed., Butterworth, London 1969. Berechnungsmethoden, part 7: Stoffwerte,
105. J. M. Prausnitz, R. N. Lichtenthaler, E. Gomes VCH Verlagsgesellschaft, Weinheim 1986.
de Azevedo: Molecular Thermodynamics of 128. J. M. Prausnitz, R. N. Lichtenthaler, E. Gomes
Fluid-Phase Equilibria, Prentice-Hall, de Azevedo: Molecular Thermodynamics of
Englewood Cliffs, N.Y., 1986. Fluid-Phase Equilibria, 2nd ed.,
106. R. C. Reid, J. M. Prausnitz, B. E. Poling: The Prentice-Hall, Englewood Cliffs, N.Y., 1986
Properties of Gases and Liquids, 4th ed., 129. W. B. Kay, Ind. Eng. Chem. Ind. Ed. 28 (1936)
McGraw-Hill, New York 1987. 1014.
107. L. C. Nelson, E. F. Obert, Trans. ASME 76 130. J. M. Prausnitz, R. D. Gunn, AIChE J. 4
(1954) 1057. (1958) 430, 494.
108. G. Soave, Chem. Eng. Sci. 27 (1972) 1197. 131. J. Joffe, Ind. Eng. Chem. Fundam. 10 (1971)
109. D. Y. Peng, D. B. Robinson, Ind. Eng. Chem. 532.
Fundam. 15 (1976) 59. 132. S. Angus et al. (eds.): IUPAC International
110. R. C. Reid, J. M. Prausnitz, T. K. Sherwood: Thermodynamic Tables of the Fluid State:
The Properties of Gases and Liquids, 3rd ed., Carbon Dioxide, Pergamon Press, Oxford
McGraw-Hill, New York 1977. 1973.
111. J. H. Dymond, E. B. Smith: The Virial 133. K. G. Joback, MS thesis, Massachusetts
Coefficients of Pure Gases and Mixtures: A Institute of Techn., Cambridge, Mass., 1984.
Critical Compilation, Clarendon Press, 134. K. G. Joback, R. C. Reid, Chem. Eng.
Oxford 1980. Commun. 57 (1987) 233.
112. K. S. Pitzer, R. F. Curl, J. Am. Chem. Soc. 79 135. S. W. Benson et al.: “Additive Rules for the
(1957) 2369. Estimation of Thermochemical Properties,”
113. C. Tsonopoulos, AIChE J. 20 (1974) Chem. Rev. 69 (1969) 279; J. Phys. Colloid
263 – 272; 21 (1975) 827. Chem. 52 (1948) 1060. S. W. Benson:
114. J. G. Hayden, J. P. O’Connell, Ind. Eng. Chem. Thermochemical Kinetics, Wiley, New York
Process Des. Dev. 14 (1975) no. 3, 209. 1968.
115. B. J. Lee, M. G. Kesler, AIChE J. 21 (1975) 136. C. J. Dobratz, Ind. Eng. Chem. Ind. Ed. 33
510. (1941) 759.
116. U. Plöcker, H. Knapp, J. M. Prausnitz, Ind. 137. D. N. Rihani, L. K. Doraiswamy, Ind. Eng.
Eng. Chem. Process Des. Dev. 17 (1978) 324. Chem. Fundam. 4 (1965) 17.
117. E. Bender: Die Berechnung von 138. T.-P. Thinh, T. K. Trong, Can. J. Chem. Eng.
Phasengleichgewichten mit der thermischen 54 (1976) 344.
Zustandsgleichung, Habilitationsschrift, Ruhr 139. Y. Yoneda, Bull. Chem. Soc. Jpn. 52 (1979)
Universität, Bochum 1971. 1297.
118. A. Polt, Ph. D. thesis, Universität 140. B. K. Harrison, W. H. Seaton, Ind. Eng. Res.
Kaiserslautern 1987. 27 (1988) 1536 – 1540.
141. C. F. Chueh, A. C. Swanson, Chem. Eng. Prog. 165. R. Kobayashi, J. Magee, A. Sivaraman, Fluid
69 (1973) no. 7, 83; Can. J. Chem. Eng. 51 Phase Equilib. 16 (1984) 1.
(1973) 596. 166. K. M. Watson, Ind. Eng. Chem. Ind. Ed. 35
142. A. Missenard, Compte Rendue 260 (1965) (1943) 398.
5521. 167. G. M. Wilson, J. Amer. Chem. Soc. 86 (1964)
143. V. Ruzicka, Jr., E. S. Domalski, J. Phys. Chem. 127.
Ref. Data 22 (1993) 579, 619. 168. H. Renon, J. M. Prausnitz, Ind. Eng. Chem.
144. A. Bondi, Ind. Eng. Chem. Fundam. 5 (1966) Process Des. Dev. 8 (1969) 413; AIChE J. 15
443. (1969) 785.
145. T.-F. Yuan, L. J. Stiel, Ind. Eng. Chem. 169. D. S. Abrams, J. M. Prausnitz, AIChE J. 21
Fundam. 9 (1970) 393. (1975) 116.
146. A. S. Teja, J. Chem. Eng. Data 28 (1983) 83. 170. O. Redlich, E. L. Derr, G. Pierotti, J. Am.
Chem. Soc. 81 (1959) 2283.
General References 171. G. M. Wilson, C. H. Deal, Ind. Eng. Chem.
References for Chapter 4 Fundam. 1 (1962) 20.
147. S. Weiß et al. (eds.): Verfahrenstechnische 172. E. L. Derr, C. H. Deal, Ind. Chem. Eng. Symp.
Berechnungsmethoden, part 7: Stoffwerte, Ser. 3 (1969) 40.
VCH Verlagsgesellschaft, Weinheim 1986. 173. K. Tochigi, D. Tiegs, J. Gmehling, K. Kojima,
148. D. Ambrose, J. F. Counsell, A. J. Davenport, J. J. Chem. Eng. Jpn. 23 (1990) 453.
Chem. Thermodyn. 6 (1974) 693. 174. A. Fredenslund, R. L. Jones, J. M. Prausnitz,
149. T. Boublik, V. Fried, E. Hala: The Vapor AIChE J. 21 (1975) 1086.
Pressures of Pure Substances, 2nd ed., 175. A. Fredenslund, J. Gmehling, P. Rasmussen:
Elsevier, Amsterdam 1984. Vapour Liquid Equilibria Using UNIFAC-A
150. B. J. Lee, M. G. Kesler, AIChE J. 21 (1975) Group-Contribution Method, Elsevier,
510. Amsterdam – New York 1977.
151. M. Gomez-Nieto, G. Thodos, Ind. Eng. Chem. 176. A. Bondi: Physical Properties of Molecular
Fundam. 16 (1977) 254. Liquids, Crystals and Glasses, Wiley, New
152. R. C. Reid, J. M. Prausnitz, B. E. Poling: The York 1968.
Properties of Gases and Liquids, 4th ed., 177. J. Gmehling, P. Rasmussen, A. Fredenslund,
McGraw-Hill, New York 1987. Ind. Eng. Chem. Process Des. Dev. 21 (1982)
153. J. A. Riddick, W. B. Bunger: Organic Solvents, 118.
Physical Properties and Methods of 178. H. Hansen et al., Ind. Eng. Chem. Res. 30
Purification, 3rd ed., vol. II, 1970; 4th ed., (1991) 2352.
1986, J. Wiley, New York. 179. B. Larsen, P. Rasmussen, A. Fredenslund, Ind.
154. Y. Ogata, M. Tsuchida, Ind. Eng. Chem. 49 Eng. Chem. Prod. Res. Dev. 26 (1987) 2274.
(1957) no. 3, 415. 180. U. Weidlich, J. Gmehling, Ind. Eng. Chem.
155. K. G. Joback, MS thesis, Massachusetts Prod. Res. Dev. 26 (1987) 1372.
Institute of Techn., Cambridge, Mass., 1984. 181. J. Gmehling, J. Li, M. Schiller, Ind. Eng.
156. K. G. Joback, R. C. Reid, Chem. Eng. Chem. Res. 32 (1993) 178.
Commun. 57 (1987) 233. 182. H. V. Kehaian, S. I. Sandler, Fluid Phase
157. L. Constantinou, R. Gani, AIChE J. 40 (1994) Equilib. 17 (1984) 139.
1697. 183. B. Kolbe, J. Gmehling, U. Onken, Inst. Chem.
158. J. E. Haggenmacher, J. Am. Chem. Soc. 68
Eng. Symp. Ser. 56 (1979); Ber. Bunsen Ges.
(1946) 1633.
Phys. Chem. 83 (1979) 1133.
159. A. Vetere in [88], p. 209].
184. T. Oishi, J. M. Prausnitz, Ind. Eng. Chem.
160. R. C. Reid, J. M. Prausnitz, T. K. Sherwood:
Process Des. Dev. 17 (1978) no. 3, 333.
The Properties of Gases and Liquids, 3rd ed.,
185. G. Nocon, U. Weidlich, J. Gmehling, U.
Onken, Ber. Bunsen Ges. Phys. Chem. 87
161. A. Tamir, E. Tamir, K. Stephan: Heats of
(1983).
Phase Change of Pure Components and
186. G. Nocon, U. Weidlich, J. Gmehling, J.
Mixtures, Elsevier, Amsterdam 1983.
Menke, U. Onken, Fluid Phase Equilib. 13
162. L. Riedel, Chem. Ing. Tech. 26 (1954) 679.
163. N. H. Chen, J. Chem. Eng. Data 10 (1965) (1983) 381.
207. 187. K. E. Gubbins, Chem. Eng. Prog. 85 (1989)
164. W. Wagner, Cryogenics 13 (1973) 470. 38.
188. M. Luckas, K. Lucas, Fluid Phase Equilib. 45 210. M. W. Chase et al.: Joint Army Navy Air Force
(1989) 7 – 13. (JANAF) Thermochemical Tables, 3rd ed.,
189. H. Knapp et al.: Vapor – Liquid Equilibria for Journal of Physical and Chemical Reference
Mixtures of Low-Boiling Substances, Data, Suppl. 14,1, American Chemical
Chemistry Data Series, vol. VI, Dechema, Society, American Institute of Physics,
Frankfurt/Main 1982. Washington, D.C., 1986.
190. M.-J. Huron, J. Vidal, Fluid Phase Equilib. 3 211. J. D. Cox, G. Pilcher: Thermochemistry of
(1979) 255. Organic and Organometallic Compounds,
191. S. Dahl, M. L. Michelsen, AIChE J. 36 (1990) Academic Press, London 1970.
1829. 212. F. D. Rossini: Selected Values of Chemical
192. M. L. Michelsen, Fluid Phase Equilib. 60 Thermodynamic Properties, National Bureau
(1990) 213. of Standards, Circular 500, Washington 1952.
193. T. Holderbaum, J. Gmehling, Fluid Phase 213. D. R. Stull, G. C. Sinke: “Thermodynamic
Equilib. 70 (1991) 251. Properties of the Elements,” in: Advances in
194. W. B. Whiting, J. M. Prausnitz, Fluid Phase Chemistry Series, vol. 18, American Chemical
Equilib. 9 (1982) 119. D. Luedecke, J. M. Society, Washington, D.C., 1956.
Prausnitz, Fluid Phase Equilib. 22 (1985) 1. 214. D. R. Stull, E. F. Westrum, G. C. Sinke: The
195. A. Anderko, Fluid Phase Equilib. 45 (1991) Chemical Thermodynamics of Organic
39. Compounds, Wiley, New York 1969.
196. W. G. Chapman, K. E. Gubbins, G. Jackson, 215. Thermodynamics Research Centre (TRC):
M. Radosz, Ind. Eng. Chem. Res. 29 (1990) Selected Values of Properties of Chemical
1709. Compounds, Texas A & M University,
197. J. Gmehling, J. Li, K. Fischer, Fluid Phase College Station, Texas, 1982 Selected Values
Equilib. 141 (1997) 113. of Properties of Hydrocarbons and Related
198. S. Skjøld-Jørgensen, Fluid Phase Equilib. 16 Compounds, vols. 1, Texas A & M University,
(1984) 317. College Station, Texas, 1977; TRC
199. S. Skjøld-Jørgensen, Ind. Eng. Chem. Res. 27 Thermodynamic Tables – Non-Hydrocarbons,
(1988) 110. vols. 1 – 8, Texas A & M University, College
200. K. Tochigi, K. Kurihara, K. Kojima, Ind. Eng. Station, Texas, 1955; TRC Thermodynamic
Chem. Res. 29 (1990) 2142. Tables – Hydrocarbons, vols. 1 – 11, Texas A
201. F. Magnussen, P. Rasmussen, A. Fredenslund, & M University, College Station, Texas, 1942.
Ind. Eng. Chem. Process Des. Dev. 20 (1981) 216. K. G. Joback: MS thesis, Massachusetts
331. Institute of Techn., Cambridge, Mass., 1984.
202. J. Gmehling, Fluid Phase Equilib. 107 (1995) 217. K. G. Joback, R. C. Reid, Chem. Eng.
1. Commun. 57 (1987) 233.
203. F. Zielke, D. A. Lempe, Fluid Phase Equilib. 218. R. C. Reid, J. M. Prausnitz, B. E. Poling: The
141 (1997) 63. Properties of Gases and Liquids, 4th ed.,
204. C. Hansch, D. A. Leo, Substituent Constants McGraw-Hill, New York 1987.
for Correlation Analysis in Chemistry and 219. S. W. Benson: Thermochemical Kinetics,
Biology, Wiley, New York 1979. Wiley, New York 1968.
205. G. Wienke, J. Gmehling, Toxicol. Environ. 220. S. W. Benson et al., Chem. Rev. 69 (1969) 279.
Chem. 65 (1998) 57. 221. Y. Yoneda, Bull. Chem. Soc. Jpn. 52 (1979)
206. A. Jakob, R. Joh, C. Rose, J. Gmehling, Fluid 1297.
Phase Equilib. 113 (1995) 117. 222. J. L. Franklin, Ind. Eng. Chem. 41 (1949)
207. J. Gmehling, T. F. Anderson, J. M. Prausnitz, 1070; J. Chem. Phys. 21 (1953) 2029.
Ind. Eng. Chem. Fundam. 17 (1978). 223. K. K. Verma, L. K. Doraiswamy, Ind. Eng.
Chem. Fundam. 4 (1965) 389.
General References 224. D. W. Van Krevelen, H. A. G. Chermin, Chem.
References for Chapter 5 Eng. Sci. 1 (1951) 66; Chem. Eng. Sci. 1
208. H. Landolt, R. Börnstein: Zahlenwerte und (1952) 238.
Funktionen aus Naturwissenschaft und 225. L. Constantinou, R. Gani, AIChE J. 40 (1994)
Technik, 6th ed., Springer Verlag, Berlin 1950. 1697.
209. G. J. Janz: Thermodynamic Properties of 226. R. C. Reid, J. M. Prausnitz, T. K. Sherwood:
Organic Compounds, Academic Press, New The Properties of Gases and Liquids, 3rd ed.,
York 1967. McGraw-Hill, New York 1977.
227. R. C. Reid, T. K. Sherwood: The Properties of 249. J. A. Riddick, W. B. Bunger: Organic Solvents,
Gases and Liquids, 2nd ed., McGraw-Hill, Physical Properties and Methods of
New York 1966. Purification, 3rd ed., vol. II, 1970, 4th ed.,
228. W. D. Monnery, W. Y. Svrcek, A. K. Mehrota, 1986, J. Wiley, New York.
Can. J. Chem. Eng. 73 (1975) 3. 250. L. H. Thomas, J. Chem. Soc. 1946, 573.
251. P. S. Morris, MS thesis, Polytechnic Institute
General References of Brooklyn, Brooklyn, N.Y., 1964.
References for Chapter 6 252. C. Orrick, J. H. Erbar in [234], p. 456.
229. S. Chapman, T. G. Cowling: The Mathematical 253. J. W. Przezdziecki, T. Sridhar, AIChE J. 31
Theory of Nonuniform Gases, Cambridge, (1985) 333.
NY, 1939. 254. A. Letsou, L. I. Stiel, AIChE J. 19 (1973) 409.
230. S. Weiß et al. (eds.): Verfahrenstechnische 255. K. G. Joback, R. C. Reid, Chem. Eng.
Berechnungsmethoden, part 7: Stoffwerte, Commun. 57 (1987) 233.
VCH Verlagsgesellschaft, Weinheim 1986. 256. V. M. Tatevski, A. V. Abramenkov, O. E.
231. R. C. Reid, J. M. Prausnitz, T. K. Sherwood: Grikina, Russ. J. Phys. Chem. 61 (1987) 1454.
The Properties of Gases and Liquids, 3d ed., 257. R. A. McAllister, AIChE J. 6 (1960) 427.
McGraw-Hill, New York 1977. 258. J. B. Irving: “Viscosities of Binary Liquid
232. VDI Wärmeatlas, 7th ed., VDI Verlag, Mixtures: A Survey of Mixture Equations,”
Düsseldorf 1994. NEL Rep. GB 630 (1977); “Viscosities of
233. J. O. Hirschfelder, C. F. Curtiss, R. B. Bird: Binary Liquid Mixtures: The Effectiveness of
Molecular Theory of Gases and Liquids, 4th Mixture Equations,” NEL Rep. GB 631 (1977).
print, Wiley, New York 1967. 259. Y. S. Touloukian, C. Y. Ho: “Viscosity.
234. R. C. Reid, J. M. Prausnitz, B. E. Poling: The Thermophysical Properties of Matter,” The
Properties of Gases and Liquids, 4th ed., TPRC Data Ser., vol. 2, Plenum Press, New
McGraw-Hill, New York 1987. York 1975.
235. O. A. Uyehara, K. M. Watson, Natl. Pet. News 260. K. Stephan, K. Lucas: Viscosity of Pure Dense
36 (1944) R 714. Fluids, Plenum Press, New York 1979.
236. K. Lucas: Phase Equilibria and Fluid 261. W. Blanke (ed.): Thermophysikalische
Properties in the Chemical Industry, Stoffgrößen, Springer Verlag, Berlin 1989.
Dechema, Frankfurt 1980, p. 573. 262. D. Roy, G. Thodos, Ind. Eng. Chem. Fundam.
237. K. Lucas, Chem. Ing. Tech. 53 (1981) 959. 7 (1968) 529.
238. VDI-Wärmeatlas, 7th ed., VDI-Verlag, 263. N. B. Vargaftig: Tables on the Thermophysical
Düsseldorf 1994. Properties of Gases and Liquids, 2nd ed.,
239. C. R. Wilke, J. Chem. Phys. 18 (1950) 517. Hemisphere, Washington 1975.
240. R. S. Brokaw, NASA Tech. Note D-4496, Apr. 264. J. F. Ely, J. M. Hanley, Ind. Eng. Chem.
1968. Fundam. 22 (1983) 90.
241. R. S. Brokaw, Ind. Eng. Chem. Process Des. 265. L. A. Guildner, Proc. Natl. Acad. Sci. USA 44
Dev. 8 (1969) 240. (1958) 1149.
242. D. Reichenberg, Symp. Transp. Prop. Fluids 266. T. H. Chung, L. L. Lee, K. E. Starling, Ind.
and Fluid Mixtures, Natl. Eng. Lab., Glasgow, Eng. Chem. Fundam. 19 (1980) 186.
UK, 1979; see also [234], p. 404. 267. S. Angus et al. (eds.): IUPAC: International
243. T.-H. Chung, L. L. Lee, K. E. Starling, Ind. Thermodynamic Tables of the Fluid State:
Eng. Chem. Fundam. 23 (1984) 8. Carbon Dioxide, Pergamon Press, Oxford
244. T. H. Chung, L. L. Lee, K. E. Starling, Ind. 1973.
Eng. Chem. Res. 27 (1988) 671. 268. D. Misic, G. Thodos, AIChE J. 7 (1961) 264;
245. L. A. Bromley, C. R. Wilke, Ind. Eng. Chem. J. Chem. Eng. Data 9 (1963) 540.
43 (1951) 1641. 269. D. Roy, G. Thodos, Ind. Eng. Chem. Fundam.
246. D. Reichenberg, AIChE J. 16 (1970) 854; 9 (1970) 71.
AIChE J. 21 (1975) 181. 270. L. I. Stiel, G. Thodos, AIChE J. 7 (1961) 611;
247. E. N. da C. Andrade, Endeavour 13 (1954) AIChE J. 10 (1964) 26.
117. 271. Y. S. Touloukian, C. Y. Ho: “Thermal
248. D. Van Velzen, R. L. Cardozo, H. Conductivity. Thermophysical Properties of
Langenkamp, Ind. Eng. Chem. Fundam. 11 Matter,” The TPRC Data Ser., vol. 3, Plenum
(1972) 20. Press, New York 1972.
272. D. T. Jamieson, J. B. Irving, J. S. Tudhope: 294. H. R. Kamal, L. N. Canjar, AIChE J. 8 (1962)

Liquid Thermal Conductivity: A Data Survey no. 3, 329.
to 1973, H. M. Stationery Office, Edinburgh 295. A. Vignes, Ind. Eng. Chem. Fundam. 5 (1966)
1975. 189.
273. T. Maejima in [234], p. 550. 296. C. R. Wilke, P. Chang, AIChE J. 1 (1955) 264.
274. L. Riedel, Chem. Ing. Tech. 21 (1949) 349; 23 297. E. G. Scheibel, Ind. Eng. Chem. 46 (1954)
(1951) 59, 321, 465. 2007.
275. G. Latini, M. Pacetti, Therm. Conduct. 15 298. D. F. Othmer, M. S. Thakar, Ind. Eng. Chem.
(1978) 245. 45 (1953) 589.
276. C. Baroncini, G. Latini, P. Pierpaoli, Int. J. 299. K. A. Reddy, L. K. Draiswamy, Ind. Eng.
Thermophys. 5 (1984) no. 4, 387. Chem. Fundam. 6 (1967) 77.
277. L. A. Robbins, C. L. Kingrea, Hydrocarbon 300. M. A. Lusis, G. A. Ratcliff, Can. J. Chem. Eng.
Process. Pet. Refiner 41 (1962) 133. 46 (1968) 385.
278. A. Missenard, Comptes Rendus 260 (1965) 301. M. T. Tyn, W. F. Calus, J. Chem. Eng. Data 20
5521. (1975) 106.
279. K. Sato in [234], p. 550 302. K. Nakanishi, Ind. Eng. Chem. Fundam. 17
280. M. Nagvekar, T. E. Daubert, Ind. Eng. Chem. (1978) 253.
Res. 26 (1987) 1362.
281. A. Missenard, Rev. Gen. Therm. 5 (1970)
General References
no. 101, 649.
References for Chapter 7
282. C. C. Li, AIChE J. 22 (1976) 927.
303. J. J. Jasper, J. Phys. Chem. Ref. Data 1 (1972)
283. W. Jost: Diffusion in Solids, Liquids, Gases,
841.
Academic Press, New York 1960.
284. E. N. Fuller, J. C. Giddings, J. Gas 304. D. B. Macleod, Trans. Faraday Soc. 19 (1923)
Chromatogr. 3 (1965) 222. E. N. Fuller, K. 38.
Ensley, J. C. Giddings, Ind. Eng. Chem. 58 305. S. Sugden, J. Chem. Soc. 125 (1924) 1177.
(1966) no. 5, 18. 306. Q. R. Quale, Chem. Ref. 53 (1953) 439.
285. L. S. Tee, G. R. Kuether, R. C. Robinson, W. E. 307. R. C. Reid, J. Prausnitz, B. E. Poling: The
Stewart, Am. Pet. Inst. Div. Refin. May 1966. Properties of Gases and Liquids, 4th ed.,
286. S. Takanishi, J. Chem. Eng. Jpn. 7 (1974) 417. McGraw-Hill, New York 1987.
287. E. L. Cussler: Diffusion: Mass Transfer in 308. J. A. Riddick, W. B. Bunger, T. K. Sakano:
Fluid Systems, Cambridge University Press, Organic Solvents. Physical Properties and
Cambridge 1984, Chaps. 3, 7. Methods of Purification, 4th ed., vol. II, Wiley,
288. D. Reinhardt, K. Dialer, Chem. Eng. Sci. 36 New York 1986.
(1981) 1557. 309. J. D. Van der Waals, Z. Phys. Chem. 13 (1894)
289. W. Hayduk, S. C. Cheng, Chem. Eng. Sci. 26 716.
(1971) 635. 310. D. I. Hakim, D. Steinberg, L. I. Stiel, Ind. Eng.
290. W. Hayduk, B. S. Minhas, Can. J. Chem. Eng. Chem. Fundam. 10 (1971) 174.
60 (1982) 295. 311. J. R. Brock, R. B. Bird: AIChE J. 1 (1955) 174.
291. L. S. Darken, Trans. Am. Inst. Min. Metall. 312. W. Blanke (ed.): Thermophysikalische
Eng. 175 (1948) 184. Stoffgrößen, Springer Verlag, Berlin 1989.
292. R. E. Rathburn, A. L. Babb, Ind. Eng. Chem. 313. H. P. Meissner, A. S. Michaelis, Ind. Eng.
Process Des. Dev. 5 (1966) 273. Chem. Ind. Ed. 41 (1949) 2782.
293. M. A. Siddiqi, K. Lucas, Can. J. Chem. Eng. 314. M. Tamura, M. Kurata, H. Odani, Bull. Chem.
64 (1986) 839. Soc. Jpn. 28 (1955) 83.
Construction Materials in Chemical Industry 605
Construction Materials in Chemical Industry

Hubert Gräfen, Bayer AG, Leverkusen, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . 605 5.1.6.3. Development State of Stainless Cr –

2. Material Requirements . . . . . . . 605 Ni Steels . . . . . . . . . . . . . . . . . 627
2.1. Processability and Joining . . . . . 606 5.2. Cast Iron . . . . . . . . . . . . . . . . 628
2.2. Mechanical Stability and its 5.3. Nickel and Nickel Alloys . . . . . . 629
Dependence on Temperature . . . 606 5.3.1. Nickel – Copper Alloys . . . . . . . . 629
2.3. Corrosion Resistance . . . . . . . . 608 5.3.2. Nickel – Chromium Alloys . . . . . . 630
2.4. Resistance to Wear . . . . . . . . . . 609 5.3.3. Nickel – Molybdenum and Nickel –
3. Choice of Materials . . . . . . . . . 609 Molybdenum – Chromium Alloys . 630
4. Quality Assurance through 5.4. Aluminum and Aluminum Alloys 631
Material Tests and Checking 5.5. Copper and Copper Alloys . . . . 634
of Fabrication and Functioning . 611 5.6. Lead and Lead Alloys . . . . . . . . 636
5.7. Zinc and Zinc Alloys . . . . . . . . 637
5. Properties and Applications
5.8. Tin and Tin Alloys . . . . . . . . . . 638
of Materials . . . . . . . . . . . . . . 612
5.9. Titanium, Zirconium, Niobium,
5.1. Steels . . . . . . . . . . . . . . . . . . . 612
and Tantalum . . . . . . . . . . . . . 638
5.1.1. Unalloyed and Low-Alloy Steels for 5.10. Organic Materials . . . . . . . . . . 641
Vessels and Pipelines . . . . . . . . . 612 5.10.1. Selection Criteria . . . . . . . . . . . 642
5.1.2. Steels with High-Temperature 5.10.2. Properties and Application Criteria 642
Strength . . . . . . . . . . . . . . . . . 614 5.10.3. Thermosetting Plastics . . . . . . . . 644
5.1.3. Heat-Resistant Steels . . . . . . . . . 615 5.11. Inorganic Nonmetallic Materials 645
5.1.4. Steels for Low Temperatures . . . . 616 5.11.1. Glass . . . . . . . . . . . . . . . . . . . 645
5.1.5. Steels Resistant to Pressurized Hy- 5.11.2. Graphite . . . . . . . . . . . . . . . . . 646
drogen . . . . . . . . . . . . . . . . . . 616 5.11.3. Refractory and Acid-Resistant
5.1.6. Stainless Steels . . . . . . . . . . . . . 617 Bricks . . . . . . . . . . . . . . . . . . 646
5.1.6.1. Technical Properties . . . . . . . . . . 621 5.11.4. Engineering Ceramics . . . . . . . . 647
5.1.6.2. Chemical Properties . . . . . . . . . . 623 6. References . . . . . . . . . . . . . . . 648
1. Introduction in process plant manufacture are described and

development trends are discussed.
Components of chemical plant are generally
subjected to thermal, chemical, and mechani-
cal stresses. The combination of these stresses 2. Material Requirements
places very heavy demands on plant materials,
especially with regard to corrosion. Thus even In the choice of materials for production plant
unalloyed and low-alloy steels have to meet very in the chemical industry, there are three basic
strict quality requirements. They must have high considerations:
purity, for example, and their nonmetallic inclu-
sions must be finely dispersed, since they af- 1) The processibility of the material in its com-
fect the ability of plant to withstand corrosion mercially available form (sheet, piping, pro-
cracking, such as stress corrosion cracking and files, etc.)
damage by hydrogen. By far the most important 2) The ability of materials to withstand produc-
materials are the highly alloyed stainless steels tion processes. This is a complex property
and nickel-based alloys, though aluminum, cop- that includes mechanical stability and its de-
per and their alloys, and refractory metals, and pendence on temperature, resistance to cor-
organic and inorganic materials are also impor- rosion, and possibly resistance to wear also.
tant. In this article the applications of materials 3) The costs of materials, of their processing,
606 Construction Materials in Chemical Industry
and of the inspections of the chemical appa- 2.2. Mechanical Stability and its
ratus during its useful lifetime. Dependence on Temperature [9]
As so many factors have to be taken into con- Chemical apparatus in use is subjected to widely
sideration, choosing materials is not easy, espe- differing mechanical stresses. The possible vari-
cially if the plant is to be used for a recently ations of mechanical stress with time are shown
developed chemical process. The prospect of a schematically in Figure 1. These stresses may
suitable choice is best where the material scien- be monoaxial, biaxial, or triaxial.
tist, chemical engineer, plant designer, and plant
engineer have worked closely together [1], [2].
2.1. Processability and Joining
Shaping (e.g., bending, rounding, and flang-

ing), separating (e.g., cutting and machining) Figure 1. Forms of the time function of mechanical stress
and joining (e.g., welding, bonding, and pipe
rolling) are particularly important processes in The behavior of materials under polyaxial
the fabrication of chemical plant. Coating and stress – the states of stress in plant components
processes that modify the properties of mate- are almost always of this kind – is seldom known
rials (e.g., quenching, tempering, nitriding, age as such, because strength data are usually avail-
hardening) are also widely used. The choice of able only as yield strength and tensile strength
fabrication processes depends on the properties for loads exerted monoaxially in a tensile test.
of the material concerned, e.g., on its suitability Therefore, where a particular exposure is con-
for cold shaping or welding. Fabrication must cerned, the material’s mechanical stability must
not affect materials so drastically that their re- be assessed by comparing its known mechanical
sistance to the conditions of subsequent use is strength values with a stress calculated accord-
significantly impaired. ing to the appropriate theory of strength [10].
Joint welding is by far the most important In the fabrication of chemical apparatus pref-
joining process in chemical plant fabrication, erence is given to materials that are easily
while build-up welding is used widely both for shaped, since they react to the application of ex-
coating in original plant fabrication, and for re- cessive force by undergoing energy-consuming
pairs [3–5]. The weldability of a component de- changes of shape instead of simply breaking.
pends on the weldability of the material and Temperature has an important influence on the
on the design and fabrication of the part [6]. mechanical stability of materials. As the temper-
Although each factor may be decisive on its ature rises, strength decreases, ease of shaping
own, the interplay of factors must never be over- increases, and creep behavior becomes the main
looked. It is thus pointless to choose a steel with factor determining mechanical stability.
the highest possible yield strength unless one Thus, above a limit temperature, which de-
has checked that dangerous peak stress will not pends on the material, the yield strength or ten-
occur (through deficiencies of design) and that sile strength at the envisaged operating tempera-
welding defects will not be caused by the use of ture can no longer serve as a characteristic value
welding techniques unsuited to the material. for calculating the stress of a chemical apparatus
Bonding is used for materials that cannot be (Fig. 2, see next page) [9].
welded or whose properties are changed exces- The strength of metals increases with de-
sively by welding [7], [8]. As adhesive bonds creasing temperature. Therefore, components
cannot be exposed to elevated temperatures, this intended for use at room temperature might be
method of joining parts has acquired little impor- expected to be more resistant to loads exerted
tance for chemical apparatus. at lower temperatures. That this is only partly
true is explained by the deformation behavior
of materials. The characteristic strain values of
metals tend to drop suddenly as the tempera-
ture decreases, and this is accompanied by an will enable a part to be designed so that it satisfies
increase in the tendency to undergo brittle frac- safety requirements is often difficult, because
ture. The inherent risk of brittle fracture is not the combinations of loads exerted in practical
accounted for directly by strength calculations. use cannot be accounted for fully by measur-
ing the alternating stress endurance limit (e.g.,
by the Wöhler method). The shape and surface
condition of the part must also be considered
(Fig. 4). More realistic criteria can be obtained
by determining the resistance to service condi-
tions of components themselves. The AD (Ar-
beitsgemeinschaft Druckbehälter) leaflets [12]
on calculations for pressure vessels or their com-
ponents are based on the assumption that these
vessels are normally subjected to static loads. If
Figure 2. Dependence of characteristic strength data on the pressure fluctuates, the resultant additional
temperature (schematic) stresses can be taken into account according to
AD leaflet S 1, in which allowance for them
Susceptibility to brittle fracture is represented
is made by reducing the permissible stresses
by values for elongation at rupture and reduction
(Fig. 5). Prediction of useful lifetime is particu-
of area in the tensile test, and also by the tran-
larly difficult when alternating stresses and creep
sition temperature obtained from a plot of the
stresses are superimposed.
notched-bar impact energy versus temperature
(Fig. 3) (see also → Mechanical Properties and LIVE GRAPH
Click here to view
Testing of Metallic Materials). In choosing a ma-
terial to suit a particular set of requirements, ade-
quate safety must be ensured by taking this tran-
sition temperature into consideration, as well as
the influences exerted on the material during its
production and processing. In the case of high-
strength materials, it is also advisable to perform
fracture toughness testing [11].
LIVE GRAPH
Click here to view
Figure 4. Influence of the surface quality on alternating

stress tests on high-presure tubes (nominal bore 6 mm; nom-
inal pressure 250 MPa) made of alloy 30CrMoV9 (mate-
rial no. 1.7707; HB30 ≈ 3000 MPa; tensile strength = 900 –
1100 MPa)
a) Cold-worked; b) Nitrided; c) Electropolished; d) Nitrided;
e) Polished; f) and g) As-delivered
In such cases there is still no accepted method

for prediction of useful life. It would also appear
unrealistic to seek “universally valid” theories
Figure 3. Transition temperature T t of the notched-bar im- and better to simulate typical stress processes in
pact energy test specimens similar to plant components, thus
a) High level, fracture on working; b) Transition range,
mixed fracture; c) Low level, brittle fracture providing the design engineer with useful life
data for particular kinds of materials and prob-
Where alternating stresses occur, determin- lems. According to the available experience it is
ing suitable characteristic material values that best to design plant and components so that they
can withstand the stress that gives the shortest iron-based and nickel-based alloys, this interre-
useful life. lation affects the static load fatigue resistance
LIVE GRAPH of parts exposed to corrosion processes at high
Click here to view
temperatures.
LIVE GRAPH
Click here to view
Figure 5. Admissible number of cycles for pressure vessels

as a function of stress
a) Range of alternating compressive stress = 90 %;
b) Range of alternating compressive stress = 100 %
Figure 6. Creep rupture behavior of copper at 95 ◦ C
a) 0.5 M H2 SO4 (air saturated); b) 0.5 M H2 SO4 (air); c) Air
(precorroded in 0.5 M H2 SO4 ); d) Air
∆m = Mass loss, wt %
2.3. Corrosion Resistance (→ Corrosion)
Basically it may be assumed that the behavior
The longevity of most apparatus depends not of a part exposed to corrosive influences depends
only on mechanical loads but also on the nature largely on the stability of the material, which, in
and spectrum of the corrosive ambient medium. turn, depends mainly on the film which forms at
As a rule the characteristic symptom of corro- the surface. Efforts are therefore being made to
sion damage is not the loss of material but an find alloys that can improve the conditions for
impairment of function and load-bearing capac- surface film formation. It is also necessary to
ity. Uniform corrosion, for example, may cause ensure that the microstructures of alloys remain
a considerable loss of mass before the service- as stable as possible, so that demixing (which,
ability of a part begins to suffer. Localized or for example, could impair the passivation ca-
selective corrosion proceeds rapidly towards the pability of alloys) cannot occur in welding, hot
inside of a part, such that a notching effect is ex- forming, etc. This is particularly important be-
erted on parts that bear mechanical loads. Cor- cause precipitation may strengthen the tendency
rosion of this kind may rapidly cause vessels to towards local activation (local removal of the
leak, or parts to fail through low-ductility frac- passive layer), whereby local corrosion may be
ture. initiated.
If the surface becomes creviced or pitted, Highly localized corrosion that results from
the stress becomes nonuniform, and the opera- simultaneous chemical attack and mechani-
tional stability of the component under alternat- cal stress is particularly serious. The crite-
ing stresses is impaired. This also reduces the rion of failure here is the occurrence of low-
static fatigue resistance under constant load, as ductility fracture. Stress corrosion cracking, fa-
shown by the example in Figure 6 [13]. The static tigue cracking, and water-induced cracking are
fatigue resistance of copper samples exposed si- phenomena of this kind. They are particularly
multaneously to corrosion and mechanical load- important with regard to serviceability, useful
ing is impaired to a much greater extent that of life, and operational reliability.
precorroded samples that have already under- The special danger of anodic stress corrosion
gone a considerably greater loss of mass and cracking and hydrogen-induced cracking is that
are then stressed mechanically. This exemplifies they can rarely be detected while the cracks are
the interaction between corrosion and creep. For spreading and before the apparatus starts to leak
or a part breaks. Although anodic stress corro- The demands made on chemical plant in use
sion cracks outwardly resemble brittle fractures, are becoming increasingly strict, and the vari-
the metal itself retains its ductility. ety of fabrication processes and range of ma-
The initiation of cracking by the various terials available are growing. These factors, to-
stress corrosion cracking mechanisms that result gether with the need to use economical fabrica-
from the action of a given corrodent on a given tion techniques, have given the choice of mate-
material depends very much on the mechanical rials a complexity that calls for systematic con-
stresses involved. sideration. A basic procedure for the selection
In the case of fatigue cracking the loss of fa- of materials for chemical plant is shown in Fig-
tigue strength for finite life and loss of fatigue ure 7 (see next page). Clearly the demands of
strength have caused considerable difficulties in the application and those of the fabrication pro-
the dimensioning of parts. cess must be taken into account as fully as possi-
ble so that the overall requirements are correctly
formulated and properly interpreted in the fix-
2.4. Resistance to Wear (see also ing of verifiable property data. At the same time
→ Abrasion and Erosion) the behavior of materials under operating con-
ditions and those of fabrication must be known
Since all production processes, except chemi- so that one can judge reliably whether or not a
cal reactions, involve physical operations such given material is suitable for a given purpose.
as comminution, conveyence, and separation of Often, these preconditions cannot be met en-
phases, the wear resistance of materials is im- tirely. In many cases, therefore, model experi-
portant for many types of chemical apparatus. ments and serial testing are necessary as em-
Models of the various kinds of wear have been pirical aids to selection. Establishing and then
developed [14]; in practice, however, the con- interpreting the combination of mechanical and
ditions are complex, for not only may severals corrosion-chemical exposures, all of which are
kinds of wear occur simultaneously, but overlap often supplemented by wear, is particularly dif-
and interaction of wear and corrosion processes ficult for chemical plant. Frequently, corrosion
can also arise. behavior is treated in the selection procedure as
Thus, as a rule, only practical trials reveal the the decisive criterion. In fact, experience in the
actual stress conditions involved. Compared to operation of chemical plant has shown that much
corrosion, however, wear is less problematic be- of the damage that occurs to chemical appara-
cause it does not cause cracklike damage, and its tus arises from the use of materials that are in-
effects are more easily repaired, e.g., by build-up sufficiently resistant to corrosion under practical
welding. conditions, and that damage of purely mechan-
ical origin is generally much less frequent [15].
Therefore, technical rules exist for designing
and dimensioning apparatus to meet combined
3. Choice of Materials mechanical and thermal stresses. The standard-
ized calculation procedures based on strength
Designers of chemical apparatus must pay care- and ductility data are intended to provide the
ful attention to materials as well as the purpose designer with a proven basis on which to work.
for which the apparatus is intended. This is im- However, where wear processes (corrosion and
portant at all stages, from initial planning to the abrasion) are concerned, that is not possible;
detailed drawing of the finalized design. For a here, instead, special design criteria must be
selection process, however, not just the function worked out in each individual case.
and properties needed by the components, but A shortlist of materials can be drawn up
also the operations by which the components are from corrosion tables, which give the corrosion
fabricated from the material, must be taken into behavior of specific materials [16], [17]. Nev-
consideration. Not only do these operations call ertheless, the most extensive tables can never
for definite properties on the part of materials, take into consideration all the conditions of a
they may also affect the behavior of components given practical case. Almost always there is
under service conditions. more than one corrosive agent, because chemi-
Figure 7. Basic procedure for the choice of materials for chemical apparatus
cal processes normally involve starting materials In view of this complexity, close coopera-
and end products, intermediates and byproducts, tion between material scientists, chemical engi-
often with unknown properties, and solids that neers, chemists, designers, apparatus manufac-
promote wear. Furthermore, reactions are influ- turers, and – where chemical apparatus subject
enced by pressure and temperature. Thus the cor- to compulsory testing, e.g., pressure vessels, is
rosion behavior of materials cannot be given in concerned – the representatives of the officially
tables with any degree of accuracy, and terms recognized supervisory authorities, is particu-
such as resistant or nonresistant may be inap- larly desirable.
propriate in an actual application. The results of Because corrosion reactions are so complex
laboratory tests are consideraly more useful. and depend on so many factors, an assessment
The most reliable predictions are those based of the corrosion behavior of a given material –
on plant tests performed either in a plant engaged corrodent system will differ greatly according
in practical production or in a pilot plant. Often, to the method of investigation. False interpreta-
however, such tests are very laborious. Even in tions can be avoided and comparison improved
cases where tests have been carried out, corro- if one has a good knowledge of the kinds of in-
sion may still occur, possibly because the stabil- formation provided by the chosen test method
ity of a material has been impaired by excessive as well as knowing its limitations. It is therefore
cold forming or by excessive heat input in weld- understandable that standardized corrosion tests
ing, or because the states of the material in the are few in number or contain more general in-
test plant and in the subsequently constructed structions. Frequently, they cover only the states
chemical apparatus were not identical. of materials that are most favorable from the as-
pect of corrosion chemistry (that is to say the ho-
mogeneous structural states existing at the time welded sheets that have the surface quality of the
of delivery), describing, for example, the testing parts to be used in practice. If stress corrosion
of stainless steels for resistance to intergranular cracking is involved, plastically and elastically
corrosion (DIN 50 914) or the testing of stain- stressed specimens or tuning fork specimens are
less steels in boiling nitric acid (DIN 50 921 and used.
ASTM A 262-70). A comparison of the sensi- Material specimens are generally attached to
tivities of unalloyed and low-alloyed steels to interior parts, such as an agitator or a thermome-
intergranular stress corrosion cracking is given ter protection tube. To prevent polarization of
in DIN 50 915. specimens through contact with plant compo-
A common feature of all investigation meth- nents, and consequent falsification of measure-
ods is that they refer to the material, and not di- ments, the fixing screws are placed in insulating
rectly to the stresses that occur in practice. Sup- sheaths.
plementary chemical or electrochemical tests In addition to the exposure of test specimens,
simulating the conditions that occur in practice the parts of a pilot plant itself should be exam-
are therefore necessary in the selection of ma- ined as a source of further information on cor-
terials. Chemical tests are performed on sam- rosion behavior. For critical plant units such as
ples exposed to gaseous and liquid corrodents at heat exchangers, it has been found advisable to
the operating pressure and temperature, whereas remove a tube from time to time, to cut it open,
in electrochemical corrosion tests, the depen- and to examine the inside and outside surfaces
dence of corrosion on potential is investigated for corrosion symptoms.
and provides information on the effects of vari- If stability tests cannot be performed in pilot
ables which alter the potential. installations, laboratory tests under conditions
The results of chemical corrosion tests and as close as possible to those of practice must be
electrochemical corrosion tests may differ fun- carried out. They should also be carried out as
damentally. The differences arise because in a supplementary measure in cases where plant
chemical tests the corrosion potential may vary tests have not clearly revealed the time depen-
with time. In electrochemical tests the potential dency of the corrosion processes, and severer
is fixed, so that, though they are more informa- conditions of attack may therefore help to com-
tive in some respects, their practical value may plete the picture.
be limited in others. General guidelines on the conduct of corro-
The characteristic stability data needed in the sion tests are given in DIN 50 905. These guide-
choice of materials can be obtained in two ways: lines should be followed as a route to recipro-
1) By inserting suitable material specimens in cally comparable results that can be transferred
pilot plants or in existing, but not yet entirely to the plant component in question.
satisfactory, production plants, For further details on chemical and electro-
2) By performing laboratory corrosion tests. chemical corrosion tests, see → Corrosion.
With regard to the corrosive medium in cor-

rosion tests, careful attention must be paid to 4. Quality Assurance through
a number of important factors, such concentra-
tion, temperature, dissolved gases, impurities, Material Tests and Checking of
solid matter, and rate of flow. As there are so Fabrication and Functioning
many parameters, tests should use suitable spec-
imens in a plant and under conditions as close To ensure that a chemical apparatus will be prop-
as possible to those of practical use. erly fabricated and that its functioning free from
The specimens should be placed at several disturbances, many tests must be carried out be-
representative locations. In a distillation column, fore and during fabrication, before the apparatus
for example, they should be placed in the pit, in is put into operation, and while it is in actual use.
the vicinity of the feed point, and in the head. At the stage of testing of materials when they
The shape of a specimen used depends on leave the factory and arrive at the plant manufac-
the types of corrosion expected. Where general turer’s establishment it is normally fairly easy to
corrosion predominates, it is sufficient to use ascertain whether or not they are of the required
quality, as the required property data will have 5. Properties and Applications of
been agreed on the basis of quality standards or Materials
similar specifications. The same cannot be said
of fabrication checks, which include, in partic- 5.1. Steels
ular, checking the construction for compliance
with the blueprints and examining the welding Steels are still the materials most commonly
work. Here the test engineer has more latitude, used for chemical plant. Their variety of alloy
especially in interpreting the results of nonde- compositions and the range of variation of their
structive tests. It must be emphasized that the properties permit an exceptional degree of adap-
first step in fabrication testing should be a thor- tation to practical requirements.
ough visual inspection; this gives the tester an
overall impression of the care taken by the manu-
facturer. Checking compliance with legislation 5.1.1. Unalloyed and Low-Alloy Steels for
and official regulations is mainly the responsibil- Vessels and Pipelines
ity of the Technical Control Associations and the
plant safety inspection departments of the large Sheet and piping made of unalloyed and low-
chemical firms. Functioning tests check the be- alloyed steels with carbon contents up to ca.
havior of the apparatus under conditions close to 0.25 wt % are used extensively in chemical plant
those of practice. Of exceptional importance are for vessels (pressure vessels, storage vessels,
the regular inspections of plant in use that are in- etc.) and pipelines that are not exposed to partic-
tended to reveal incipient damage early enough ularly severe corrosion. The main standards and
to ensure that plant shut-down can be avoided designations of several typical steels are com-
and any necessary repairs need not be under- piled in Table 1. Comparable steels with com-
taken in haste. Once again, visual inspection parable properties are described in the standard
takes precedence. Much emphasis is also placed specifications of other countries – see, for ex-
on nondestructive methods – thickness measure- ample, SAE, AISI, ASTM (United States), BS
ment, for example, and tests that reveal initial (Great Britain), NF (France), SS (Sweden), UNI
cracking [18]. Testing of plant in service also (Italy) and NBN (Belgium). The steels are nor-
provides knowledge that may be useful in select- mally processed in the normalized state.
ing materials for new chemical apparatus by re- Owing to the introduction of weldable fine-
vealing weaknesses of design, materials, or fab- grained structuralsteels with yield strengths of
rication.
Table 1. Quality standards for unalloyed and low-alloy steels widely used in chemical plant
Standard Short title Typical steels
Short name Material number
DIN 17 100 Steels for general structural purposes RSt 37 – 2 1.0038

St 44 – 2 1.0044
DIN 1629 Seamless unalloyed circular steel tubes for St 37.0 1.0254
special requirements St 44.0 1.0256
St 52.0 1.0421
DIN 17 155 Steel plates and strips for pressure purposes HI 1.0345
H II 1.0425
15 Mo 3 1.5415
DIN 17 102 Weldable, finegrained construction steels StE 285 1.0486
(normalized) StE 355 1.0562
WStE 460 1.8935
DIN 17 175 Seamless tubes of heat-resistant steels St 35.8 1.0305
St 45.8 1.0405
15 Mo 3 1.5415
Stahl-Eisen-Werkstoffblatt 087 – 81 Structural steels resistant to weathering WTSt 37 – 2 1.8960
WTSt 37 – 3 1.8961
LIVE GRAPH
≥ 360 MPa, boiler plate consisting of unal- Click here to view
loyed steels, whose yield strengths are consid-
erably lower, is used on a smaller scale than
it was formerly. The use of high-strength heat-
treated structural steels with yield strengths of
≥ 700 MPa [19–23] will presumably increase.
Pipes consisting of welded steel strip will be
used increasingly instead of seamless pipes [24].
Steels are suitable for fusion welding by all
processes, but the welding filler metals must
Figure 8. Influence of sulfur content on the reduction of area
be suited to the base material. Specific weld- at rupture in the thickness direction of StE 355 steel plates
ing guidelines must be adhered to increasingly a) 40 – 55 mm plate, 0.015 – 0.054 % S; b) 40 mm plate,
as the alloy content and yield strength rise; these ≤ 0.010 % S; c) ≥ 50 mm plate, ≤ 0.006 % S; d) 20 – 50 mm
guidelines can be found by consulting either the plate, TN treated, 0.002 % S
standards or manufacturers of steels and welding
filler materials. Processing guidelines for weld-
able fine-grained structural steels are compiled
in DIN standards.
Normalized fine-grained structural steels are
now very popular. They combine the excellent
strength and toughness imparted by fine-grain
hardening [25] with the advantages offered by
modern ladle metallurgy in respect of purity and
microalloying.
The blast or shot injection of calcium com-
pounds to reduce the sulfide content of steel
(TN process) and the addition of cerium and zir-
conium to produce globular, finely distributed
sulfide inclusions should also be mentioned.
These processes improve purity, block segrega-
tion, weldability, and toughness.
In special cases, these desulfurization meth-
ods enable the sulfur content to be reduced to be-
low 0.005 %. Consequently, and through the in-
fluence exerted on the nature of the precipitation,
the anisotropy of the steel’s properties is reduced
considerably, as may be seen from the percent-
age reductions of area at fracture of fine-grained
structural steels in the thickness direction of the
sheet (Fig. 8) [26]. Figure 9 [26] shows that the
fatigue resistance is also improved.
Where damage occurs, the leak-before-
failure behavior imparted by high toughness is
exceptionally favorable because the risk of sud-
den failure as a result of unstable crack propaga-
tion is practically eliminated. The high purity of Figure 9. Influence of the TN process on the dynamic
fine-grained steels, together with the fine disper- strength of steel StE 355 (stress ratio R = 0, thickness of plate:
sion of their nonmetallic inclusions, notably the 50 mm)
sulfides, is very favorable with regard to corro- A) Untreated; B) Calcium treated (TN process); a) Trans-
verse; b) Longitudinal; c) Normal
sion resistance. Coarse sulfides promote the for-
mation and growth of cracks both in hydrogen-
induced crack formation and in stress corrosion operating at up to ca 800 ◦ C [29]. These materi-
cracking [27]. Upon chemical exposure to aque- als are also very important in reactor technology.
ous solutions, the sulfides, especially under the According to their maximum service tempera-
influence of the hydrolytic acidification that oc- tures that can be maintained for long periods,
curs in cracks, may be converted to H2 S, which the following groups are distinguished:
is a vigorous promoter of hydrogen cracking.
It is now believed that crack growth in anodic 1) For temperatures up to ca. 400 ◦ C: un-
stress corrosion cracking is also promoted by hy- alloyed steels, in some cases melted as
drogen. That would explain why steel StE 355, fine-grained structural steels, whose main
in particular, behaves favorably towards such strength-related property is the high-tempe-
crack-initiating media as alkalis, nitrates, and rature yield strength. These steels are stan-
liquid ammonia. This steel is now a standard dardized in DIN 17 155 (boiler plate types),
material for these media. For greater safety, the DIN 17 175 (pipes) and DIN 17 102 (fine-
finished apparatus should be subjected to stress grained structural steels) and are suitable for
relief annealing. all fusion welding methods. Typical steels
Considerable progress has been made belonging to this group are the grades HI
through efforts to improve the economy of struc- (1.0345), St 35.8 (1.0305), and WStE 355
tural steels by raising their strength. Starting (1.0565).
from steel St 52-3, it has been possible to raise 2) For temperatures of 400 – 550 ◦ C: unalloyed
the yield strength from 355 to ca. 900 MPa. The and low-alloy steels having good long-term,
first step in this direction consisted in raising the high-temperature strength-related property
alloy contents of normalized structural steels. values. The main alloying elements are man-
But the scope for improvement in this way was ganese (up to 1.3 wt %), chromium (up to
limited by the fact that increasing the alloy con- 2.5 wt %), and molybdenum (up to 1.2 wt %),
tent impairs the cold cracking resistance in weld- vanadium also being used occasionally (up to
ing. Agreement has therefore been reached that 0.5 wt %). These materials are standardized
the yield strength of normalized steels should in DIN 17 155, DIN 17 175, DIN 17 240 (nuts
not exceed 500 MPa. and bolts), and DIN 17 245 (steel castings).
Considerably higher yield strengths, even at These steels are suitable for fusion welding,
low alloy contents, are obtainable by quenching though preheating and post-welding anneal-
and tempering. In the case of heat-resistant struc- ing may be necessary, details of which can
tural steels, air tempering is preferred. Water be found in the standards.
quenching followed by tempering, on the other 3) For temperatures of 550 – 600 ◦ C: marten-
hand, is more favorable for steel needing high sitic steels containing up to ca. 12 wt % chro-
toughness. By far the most important represen- mium and additions of molybdenum, vana-
tative of this group of steels in terms of quan- dium, nickel, and tungsten [30]. These are
tity is StE 690, whose minimum yield strength standardized in DIN 17 459 (sheet, pipes,
is 690 MPa (Euronorm 137). Steels with com- forgings) and in DIN 17 245 (steel castings).
parable yield strengths are also used on a large These steels are supplied in the quenched
scale for pressure vessels and other chemical ap- and tempered state; a typical representa-
paratus, such as the pressure-bearing parts of tive is X 20 CrMoV 12 1 (1.4922). Being air-
multistory vessels. StE 890 has been used to an hardenable, these steels must be kept at 250
increasing extent since the mid 1980s [28]. to 450 ◦ C during welding, after which they
must be cooled to ca. 120 ◦ C and then imme-
diately annealed.
5.1.2. Steels with High-Temperature 4) Temperatures of 600 – 800 ◦ C: austenitic
Strength steels containing 16 – 21 wt % chromi-
um, 11 – 32 wt % nickel, and additions
High-temperature structural steels are used of molybdenum, tungsten, niobium, tanta-
in the chemical industry mainly for heavily lum, aluminum, and other elements, e.g.,
stressed parts of steam boilers (e.g., collectors, X 8 CrNiNb 16 13 (material no. 1.4961),
drums, piping) and for pressure vessels and tubes X 8 CrNiMoNb 16 16 (material no. 1.4981),
Table 2. Approximate temperature limits for the use of steels in a weakly oxidizing flue-gas atmosphere
Steel Material number Standard Approximate temperature, ◦ C
St 35.8 1.0305 DIN 17 175 500

St 45.8 1.0405 DIN 17 175 500
15 Mo 3 1.5415 DIN 17 155 530
13 CrMo 44 1.7335 DIN 17 155 560
10 CrMo 9 10 1.7380 DIN 17 175 590
X 20 CrMoV 12 1 1.4922 DIN 17 175 600
X 8 CrNiNb 16 13 1.4961 DIN 17 459 750
X 8 CrNiMoNb 16 16 1.4981 DIN 17 459 750
and X 8 NiCrAlTi 32 21 (material no. Resistance to scaling is obtained mainly

1.4959), which are standardized in DIN by alloying with chromium, but further im-
17 459. provements are possible if silicon and alu-
minum are added. The most commonly
These steels are welded with filler metals of used heat-resistant steels are standardized in
the same composition, and at the lowest possi- Stahl-Eisen-Werkstoffblatt 470-76. Distinc-
ble heat input to avoid hot cracking of the weld tions are made between the ferritic steels,
metal. such as X 10 CrAl 7 (1.4713), X 10 CrAl 13
As austenitic steels are very expensive, they (1.4724) and X 10 CrAl 24 (1.4762); the ferritic-
are used only in the zones which reach the austenitic steel X 20 CrNiSi25 4 (1.4828); and
highest temperatures, outside of which low- austenitic steels such as X 15 CrNiSi 20 12
alloy steels are used. Special techniques have (1.4828), X 15 CrNiSi 25 20 (1.4841) and
to be used to form welds between ferritic and X 10 CrNiAlTi 32 20 (1.4876).
austenitic steels because of the diffusion pro- The above-mentioned publication also gives
cesses that occur in welding and because of the long-term heat resistance values for periods of
differences in thermal expansion [31]. up to 105 h. The highest service temperatures
For temperatures above 800 ◦ C only iron – listed, which extend to 1200 ◦ C, apply to air.
chromium – nickel alloys and nonferrous alloys They may be reduced greatly by admixtures to
based on cobalt or nickel are suitable [32], [33]; the air, e.g., of water vapor or sulfur-containing
see also Section 5.3. or carburizing matter, because the reaction prod-
Table 2 gives approximate figures for the ucts do not form sufficiently thick surface layers.
highest temperatures at which a number of steels Within certain temperature ranges, heatresis-
with high strength at elevated temperature can be tant steels tend to become brittle. Ferritic steels
used in a weakly oxidizing flue-gas atmosphere. with ≥ 12 wt % chromium do so between 400
Long-term heat stability values are compiled in and 530 ◦ C. This so-called 475 ◦ C embrittle-
[34]; the importance of these values in calculat- ment can be eliminated by annealing briefly
ing the useful lives of components subjected to above 600 ◦ C. In the case of ferritic steels with
this exposure is discussed in [35]. ≥ 17 wt % chromium and austenitic steels, an
intermetallic iron – chromium σ-phase, which
causes severe embrittlement, is formed between
5.1.3. Heat-Resistant Steels 600 and 900 ◦ C. It endangers particularly the
weld interfaces.
Heat-resistant steels are those that have good
Within the same temperature range,
strength-related property data and are distin-
austenitic steels precipitate chromium carbides,
guished by exceptional resistance to exposure
which further reduce the toughness. The steel
for short or long periods to hot gases or combus-
most severely affected is X 15 CrNiSi 25 20
tion products at temperatures exceeding 550 ◦ C,
(1.4841), which should be used only above
and which are thus resistant to scaling [36]. Ro-
900 ◦ C. The σ-phase and the carbides can be
tary furnaces, cracking units, and muffle fur-
redissolved by annealing above 1000 ◦ C, fol-
naces are examples of chemical plant in which
lowed by quenching.
these conditions arise.
The heat-resistant steels can be welded by and DIN 17 102 for group 2, and Stahl-Eisen-
the usual methods, provided the guidelines for Werkstoffblatt 685 – 82 for cast steel with good
alloyed steels are followed. Suitable filler met- low-temperature toughness.
als are listed in Stahl-Eisen-Werkstoffblatt 470- In the welding of steels for low temperatures
76. It should be noted that in ferritic steels with it is necessary to use filler materials that give
≥ 12 wt % chromium, coarse grains, which can a weld metal whose strength and toughness are
no longer be removed by heat treatment, are equal to those of the base material [37–39].
formed at temperatures above 900 ◦ C.
Heat-resistant cast steel, as used in the
manufacture of pipes by centrifugal casting, 5.1.5. Steels Resistant to Pressurized
for example, is standardized in Stahl-Eisen- Hydrogen [40], [41]
Werkstoffblatt 471-76.
Steels for high-pressure plant in the chemical
industry can divided into the following two
5.1.4. Steels for Low Temperatures groups:
Refrigeration is very important in the chem- 1) Steels for components subjected to purely
ical industry, e.g., in the fractional distilla- mechanical loads or to pressurized hydrogen,
tion of hydrocarbons or storage and trans- in both cases at temperatures of ≤ 200 ◦ C,
portation of liquid gases. Steels for the pres- 2) Steels for components exposed to pressur-
sure vessels must still have sufficient tough- ized hydrogen at temperatures > 200 ◦ C,
ness at the lowest operating temperature. The
degree of low-temperature toughness depends For the conditions of group 1, as present
particularly on the steel’s composition and heat in the production of low-density polyeth-
treatment. Notched-bar impact energies, mea- ylene (pressures of up to about 400 MPa),
sured on DVM (Deutscher Verband für Material- mainly unalloyed and low-alloy heat-treatable
forschung und -prüfung e. V., Berlin) longitudi- steels are used; these are standardized in DIN
nal specimens, of ≥ 40 and ≥ 60 J/cm2 , for cast 17 200 and in the case of large forgings, in
steel and other steels, respectively, are regarded Stahl-Eisen-Werkstoffblatt 550-76. If relatively
as evidence of sufficient low-temperature tough- good corrosion resistance is required, stainless
ness. Hence the lowest service temperature of a heat-treatable chromium and chromium – nickel
steel with good low-temperature tenacity is that steels according to DIN 17 440, and occasion-
at which the notch impact energy is still above ally hardenable stainless steels, are used instead
this limit. Steels for low temperatures can be di- [42]. The periodic alternation of the pressure
vided into four groups: subjects the components to a severe fatigue-
1) Unalloyed aluminum-killed steels for service inducing stress. Their shape stability therefore
temperatures down to − 50 ◦ C in the nor- depends decisively not just on the choice of ma-
malized state and − 80 ◦ C in the heat-treated terials, but also on their being designed to suit the
state; e.g., TTSt 35 (1.1101). conditions of exposure as well as on satisfactory
2) Unalloyed and low-alloy weldable fine- fabrication and installation [43].
grained structural steels in the normal- Hot pressurized hydrogen, which is needed
ized state for service temperatures down to in many high-pressure syntheses (e.g., ammo-
− 60 ◦ C, e.g., TStE 380 (1.8910). nia synthesis and pressure hydrogenation) dis-
3) Nickel-alloyed heat-treatable steels with sociates on the surface of many steels, diffuses
1.5 – 9 wt % Ni for service temperatures of into the metal, and reacts with carbon to form
− 100 to − 190 ◦ C, e.g., 12 Ni 19 (1.5680). methane, thus causing decarburization, embrit-
4) Austenitic chromium – nickel steels for ser- tlement, and cracking:
vice temperatures extending close to absolute
zero; e.g., the steels specified in DIN 17 440 Fe3 C + 2 H2 → 3 Fe + CH4
and DIN 17 441.
This reaction between hydrogen and cemen-
The relevant quality standards are DIN tite occurs mainly at the grain boundaries, the
17 173 and DIN 17 174 for groups 1 and 3
Table 3. Composition of pressurized-hydrogen-resistant steels
Steel type Material number Composition, wt %
C Cr Mo V Others
25 CrMo 4 1.7218 0.22/0.29 0.90/1.20 0.15/0.25

16 CrMo 9 3 1.7281 0.12/0.20 2.0/2.5 0.30/0.40
26 CrMo 7 1.7259 0.22/0.30 1.5/1.8 0.20/0.25
24 CrMo 10 1.7273 0.20/0.28 2.3/2.6 0.20/0.30
10 CrMo 11 1.7276 0.08/0.12 2.7/3.0 0.20/0.30
10 CrMoV 10 1.7766 0.15/0.20 2.7/3.0 0.20/0.30 0.10/0.20
20 CrMoV 13 5 1.7779 0.17/0.23 3.0/3.3 0.50/0.60 0.45/0.55
X 20 CrMoV 12 1 1.4922 0.17/0.23 11.0/12.5 0.80/1.20 0.25/0.35
X 8 CrNiMoVNb 16 13 1.4988 0.04/0.10 15.5/17.5 1.10/1.50 0.60/0.85 Ni: 12.5/14.5
N: 0.07/0.13
grains thus losing their cohesion. Hydrogen and hydrogen throughout the range of temperatures
methane accumulate, giving rise to high pressure used in normal high-pressure processes.
whose cleaving action leads to internal microc-
racks. Together with the stresses exerted on the
component and the loss of mechanical strength,
this results finally in pronounced brittle fracture.
The resistance of carbon steels to attack by
pressurized hydrogen depends partly on the am-
bient conditions, but also on the microstruc-
ture, cold working, effects of welding, impu-
rities, and heat treatment. Elements that form
stable carbides, such as chromium, molybde-
num, tungsten, vanadium, titanium, and nio-
Figure 10. Resistance diagram for the attack of pressurized
bium, can be added to the steel to prevent the hydrogen on steels (Nelson diagram)
reaction between hydrogen and cementite. The a) 1.25 Cr 0.5 Mo steel; b) 5.0 Cr 0.5 Mo steel; c) 8.0 Cr
pressurized-hydrogen-resistant steels now in use 0.5 Mo steel; d) 2.25 Cr 1.0 Mo steel; e) 2.0 Cr 0.5 Mo steel;
contain up to 16 wt % Cr, and also in many f ) 1.25 Cr 0.5 Mo steel; g) 1.0 Cr 0.5 Mo steel; h) 0.5 Mo
steel; i) Mild steel
cases 0.2 – 1.5 wt % Mo. Some types are addi-
tionally alloyed with up to 0.85 wt % V (Table 3).
The low-alloy ferritic steels are suitable for fu-
sion welding, provided that they are preheated. 5.1.6. Stainless Steels [45]
The chromium steels have to be kept at 250 –
450 ◦ C throughout welding, and partially an- Among the highly alloyed steels, the most im-
nealed immediately afterwards. The austenitic portant group comprises those that are chem-
steel (1.4988) tends to suffer hot cracking on ically resistant. They have chromium contents
welding. Short-term tests give very little indica- ≥ 14 wt %. As the steels of this group re-
tion of the limits to the use of steels of this kind, sist heat as well as chemicals, this group also
because the time factor is much too important includes a considerable number of the heat-
and the attack of pressurized hydrogen on steels resistant steels discussed in Section 5.1.3. Of-
has a significant incubation period. As an illus- ten they contain nickel in addition to chromi-
tration, Figure 10 gives stability limits for vari- um. The more highly alloyed corrosion-resistant
ous steels, as compiled by Nelson [44]. It can (acid-resistant) steels must additionally with-
be seen that even at low hydrogen partial pres- stand general corrosion and localized corrosion
sures (e.g., 2 MPa) an unalloyed steel should be in relatively aggressive corrodents (salt solu-
used only below 300 ◦ C. Austenitic steels with tions; acids, even at fairly high concentrations).
18 % Cr and ca. 9 % Ni have good resistance Characteristic alloying components, apart from
to pressurized hydrogen; they can be exposed to chromium and nickel, are molybdenum, copper,
and in some cases silicon.
There are many kinds of steels and alloys, sistance to stress corrosion cracking. They
each being represented by a material number are therefore used mainly under conditions
(DIN 17 007) or by chemical composition (DIN which may cause fatigue corrosion and stress
17 006). corrosion cracking in austenitic steels.
The mechanical properties of steels are deter-
mined by the microstructure, which depends on Pure iron has a ferritic structure. The alloy-
composition and heat treatment. Stainless steels ing elements that may be added to iron are ei-
are divided according to microstructure into four ther ferrite-forming (chromium, molybdenum,
groups: silicon, titanium) or austenite-forming (carbon,
nitrogen, nickel, manganese).
1) Martensitic (hardenable) steels with The austenitic chromium – nickel steels, with
> 0.12 wt % C and ≤ 15wt % Cr. They are or without molybdenum, are used in the
hardened at temperatures > 1000 ◦ C (e.g. solution-heat-treated state (solution heat treat-
cutting steels). After being hardened they ment temperature 1000 – 1100 ◦ C). At solu-
can be improved by tempering at 500 to tion heat treatment temperatures these steels
600 ◦ C – their strength thus being reduced to are close to the boundary of the α + γ field
a desired lower level – and henceforth com- in the iron – chromium – nickel phase diagram
bine high strength with good ductility. (Fig. 11). As the content of chromium increases,
In the heat treatment, a ferritic structure, with more nickel or nitrogen must be added to main-
precipitated carbides of high chromium contain the austenitic structure. If the content of mo-
tent of type M23 C6 or M7 C3 , is formed. Fix- lybdenum is raised, then it is also necessary to
ation of chromium and the formation of chro- increase the content of austenitizers and/or to
mium-depleted zones reduces the resistance reduce the chromium content.
to corrosion. To equalize the chromium con-
tent of the ferritic matrix again it is necessary
to anneal the steel for a fairly long time at
elevated temperature. Although this restores
the corrosion resistance to some extent, it im-
pairs the strength. As some of the chromium
is still bound as carbide, the corrosion resis-
tance after annealling procedure is still con-
siderably poorer than that of the martensite.
2) Ferritic steels with body-centered cubic lat-
tice (α-phase). Those of greatest importance
are the ferritic chromium steels with ca.
17 wt % chromium. Their mechanical and
technical properties, however, are unsatis-
factory; when welded, they tend to become
coarse-grained and brittle. Nevertheless they
have the advantage of resisting stress corro-
sion cracking in chloride-containing media.
3) Austenitic steels with face-centered cubic
lattice (γ-phase). Particularly important are Figure 11. Ternary phase diagram of Fe – Cr – Ni (section
the austenitic chromium – nickel steels with at 1100 ◦ C)
ca. 18 wt % Cr and 10 wt % Ni, but without
addition of molybdenum. Their strength is With increasing chromium content, and es-
relatively low and their ductility very good. pecially increasing molybdenum content, the
In chloride-containing corrodents, however, tendency to segregate intermetallic compounds
they undergo transgranular stress corrosion (σ-phase, χ-phase, Laves phase, Fe2 Mo), in-
cracking. creases greatly (see Fig. 12). If the precipitation
4) Ferritic – austenitic steels combine good tendency is strong enough, intermetallic com-
mechanical properties with improved re- pounds may already be precipitated during the
relatively short-lived heat exposure of welding. The matrix therefore loses its resistance to cor-
Hence the addition of molybdenum, which is de- rosion.
sirable for reasons of corrosion chemistry, has an In ferritic chromium steels and austenitic
upper limit. In the case of austenitic chromium – chromium – nickel steels, the chromium-rich σ-
nickel steels it is about 6 wt % Mo. phase may precipitate on annealing at 600 –
900 ◦ C. For ferritic chromium steels with up
to ca. 18 wt % chromium this precipitation has
no importance, while in the case of molybde-
num-free austenitic chromium – nickel steels it
is, at the most, important only in connection
with the welded material. For reasons of weld-
ing technique (prevention of hot cracking) the
welded material of normal austenitic steels al-
most always contains some δ-ferrite, which de-
composes when the steel is annealed. In a corro-
sion exposure this decomposed δ-ferrite may be
selectively dissolved. Damage must be expected
Figure 12. Precipitation fields of chromium-rich carbides where a coherent δ-ferrite network is present
M23 C6 , σ- and χ-phase, molybdenum-rich Laves phase
(Fe2 Mo), and of a complex nitride (Z-phase) for the steel
(proportion of δ-ferrite in the structure > 10 %).
X 2 CrNiMo 18 14 3 The designations of the most important stain-
less steels for chemical plant are compiled in
Addition of nitrogen retards the precipita- DIN 17 440 (Table 4, see next page).
tion of the intermetallic phases and compounds Chemical engineering also uses a number of
considerably, as well as improving the mechan- other special materials notable for their high re-
ical properties by introducing nitrogen atoms sistance to pitting corrosion and stress corrosion
into interstices in the metal lattice. Nitrogen- cracking, as well as to mineral acids (Table 5,
alloyed austenitic and ferritic – austenitic steels see next page).
are therefore of industrial importance. Particularly high molybdenum contents are
In ferritic – austenitic steels, the ferritizers present in the steels listed in Table 6 (see next
chromium and molybdenum are enriched in the page). The stability of the austenite is due to
ferrite phase, whose nickel content is corre- nickel and nitrogen.
spondingly depleted. The austenitic phase con- Unlike ferritic and austenitic steels, fer-
tains, conversely, more nickel and less chromi- ritic – austenitic steels have a two-phase struc-
um and molybdenum. These differences of con- ture, which, in contrast to the composition
centration are relatively slight, however, and are of austenitic steels, is obtained by raising the
only important for the use of ferritic – austenitic contents of ferrite-stabilizing elements, such
steels in borderline cases. The alloy composition as chromium and silicon, and reducing the
of these steels is also chosen such that the ferritic austenite-stabilizing nickel content (Table 7, see
and austenitic phases are present in the structure page after next). By virtue of their high yield
in approximately equal proportions and the chro- strength of at least 450 MPa, steels of this kind
mium content of the austenite is not less than are used for components which, while exposed
17 wt %. to corrosive media, are additionally subjected to
Annealing within certain temperature ranges wear (cavitation, erosion) and vibration. Being
may cause carbides, nitrides, and intermetallic more resistant than commercial austenitic steels
compounds to be precipitated in the microstruc- to stress corrosion cracking in neutral chloride
ture of stainless steels. Owing to the special im- solutions, they are also being used increasingly
portance of chromium and molybdenum in im- to handle aggressive cooling water. A commonly
parting corrosion resistance to stainless steels, used material of this group is X 2 CrNiMoN 22 5
the precipitation of phases and compounds that (1.4462), which, in addition to about 22 wt %
contain these elements exert strong effects. The Cr, has a nickel content of about 5.5 wt %, an
segregation of chromium- and molybdenum- Mo content of about 3 wt %, and an austenitic
rich phases depletes the matrix in these elements. structure proportion of about 60 % [46], [47].
Table 4. Composition of stainless steels
Short name (DIN) US Material Composition, wt %

Standard number
(AISI)
C Cr Mo Ni Others
Ferritic and martensitic steels

X 7 Cr 13 403 1.4000 <0.08 12.0 – 14.0
X 7 CrAl 13 405 1.4002 <0.08 12.0 – 14.0 Al 0.10 – 0.30
X 10 Cr 13 410 1.4006 0.08 – 0.12 12.0 – 14.0
X 15 Cr 13 1.4024 0.12 – 0.17 12.0 – 14.0
X 20 Cr 13 420 1.4021 0.17 – 0.22 12.0 – 14.0
X 40 Cr 13 1.4034 0.40 – 0.50 12.0 – 14.0
X 45 CrMoV 15 1.4116 0.42 – 0.48 13.8 – 15.0 0.45 – 0.60 V 0.10 – 0.15
X 8 Cr 17 430 1.4016 <0.10 15.5 – 17.5
X 8 CrTi 17 439 1.4510 <0.10 16.0 – 18.0 Ti ≥ 7× % C
X 8 CrNb 17 1.4511 <0.10 16.0 – 18.0 Nb ≥ 12× % C
X 6 CrMo 17 434 1.4113 <0.07 16.0 – 18.0 0.90 – 1.20
X 12 CrMoS 17 430 F 1.4104 0.10 – 0.17 15.5 – 17.5 0.20 – 0.30 S 0.15 – 0.35
X 22 CrNi 17 431 1.4057 0.15 – 0.23 16.0 – 18.0 1.5 – 2.5
Austenitic steels
X 12 CrNiS 18 8 303 1.4305 <0.15 17.0 – 19.0 8.0 – 10.0 S 0.15 – 0.35
X 5 CrNi 18 9 304 1.4301 <0.07 17.0 – 20.0 8.5 – 10.0
X 5 CrNi 19 11 305/308 1.4303 <0.07 17.0 – 20.0 10.5 – 12.0
X 2 CrNi 18 9 304 L 1.4306 <0.03 17.0 – 20.0 10.0 – 12.5
X 10 CrNiTi 18 9 321 1.4541 <0.10 17.0 – 19.0 9.0 – 11.5 Ti > 5× % C
X 10 CrNiNb 18 9 347 1.4550 <0.10 17.0 – 19.0 9.0 – 11.5 Nb > 8× % C
X 5 CrNiMo 18 10 316 1.4401 <0.07 16.5 – 18.5 2.0 – 2.5 10.5 – 13.5
X 2 CrNiMo 18 10 316 L 1.4404 <0.03 16.5 – 18.5 2.0 – 2.5 11.0 – 14.0
X 10 CrNiMoTi 18 10 316 Ti 1.4571 <0.10 16.5 – 18.5 2.0 – 2.5 10.5 – 13.5 Ti > 5× % C
X 10 CrNiMoNb 18 10 316 Cb 1.4580 <0.10 16.5 – 18.5 2.0 – 2.5 10.5 – 13.5 Nb > 8× % C
X 5 CrNiMo 18 12 316 1.4436 <0.07 16.5 – 18.5 2.5 – 3.0 11.5 – 14.0
X 2 CrNiMo 18 12 316 L 1.4435 <0.03 16.5 – 18.5 2.5 – 3.0 12.5 – 15.0
X 2 CrNiMo 18 16 317 L 1.4438 <0.03 17.0 – 19.0 3.0 – 4.0 15.0 – 17.0
X 2 CrNiN 18 10 304 LN 1.4311 <0.03 17.0 – 19.0 9.0 – 11.5 N 0.12 – 0.20
X 2 CrNiMoN 18 12 316 LN 1.4406 <0.03 16.5 – 18.5 2.0 – 2.5 10.5 – 13.5 N 0.12 – 0.20
X 2 CrNiMoN 18 13 316 LN 1.4429 <0.03 16.5 – 18.5 2.5 – 3.0 12.0 – 14.5 N 0.14 – 0.22
Table 5. Composition of special alloyed stainless steels
Steel type, Material Composition, wt %
short name (DIN) number C Si Mn Cr Ni Mo Other
X 3 CrNiMoN 17 13 5 1.4439 ≤0.04 ≤1 ≤2 17.5 13.5 4.5 N

X 2 NiCrAlTi 32 20 1.4558 ≤0.04 ≤0.7 ≤1 21.5 33.5 Ti, Al
X 1 NiCrMoCu 25 20 1.4539 ≤0.02 ≤1 ≤2 20 25 4.5 Cu
X 1 CrNiMoN 25 25 2 1.4465 ≤0.02 ≤0.7 ≤2 25 23.5 2.3 Al, Cu
X 1 NiCrMoCuN 31 27 1.4563 ≤0.02 ≤0.7 ≤2 27 31 3.5 Cu
NiCr21Mo 2.4858 ≤0.03 ≤0.5 ≤1 21.5 42 3 Ti, Al
Table 6. High-alloy stainless steels containing ≥ 6 wt % molybdenum
DIN designation ASTM designation Composition, wt % Trade mark
C Cr Ni Mo Cu N
S 31254 0.02 20 18 6.1 0.7 0.2 Awesta

254 SMO
1.4529 0.02 20 25 6.5 1 0.15 Nirosta
4529
0.02 17 16 6.3 1.6 0.16 VEW
A 963
0.03 20 24 6.0 AC 6 X
Table 7. Composition of ferritic – austenitic (duplex) steels
Name/material number Short designation (DIN) Typical composition, wt %
C Si Mn Cr Mo Ni N
1.4462 X 2 CrNiMoN 22 5 3 0.012 0.34 0.65 22.1 3.0 5.7 0.14

Ferralium 255 X 2 CrNiMoCu 25 5 0.019 1.4 1.4 26 3.3 5.5 0.2
Noridur 9.4460 G–X 3 CrNiMoCuN 24 6 0.03 1.5 1.5 25 3.1 6 +
A 905 X 3 CrMnNiMoN 25 4 4 0.034 5.8 26 2.3 3.7 0.36
A specially developed austenitic steel that ferritic steels has been marked by the use of
contains about 4 wt % Si (X 2 CrNiSi 18 15, special methods for obtaining low C + N con-
1.4361) and has already undergone trials un- tents in their manufacture (ELI = extra low in-
der practical conditions has remarkably good re- terstitial steels) [50]. Three groups can now be
sistance to highly concentrated nitric acid and distinguished: 1) steels with 25 – 28 wt % Cr,
chromic acid. As Figure 13 shows, its advan- without nickel, in some cases with an addi-
tages are particularly pronounced at HNO3 con- tion of Mo, and in all cases with a C + N con-
centrations above 75 %, where it is superior to tent limited to 0.015 wt % (superferrites); 2) mo-
stainless steels of all other types [48]. In the lybdenum-containing steels with 18 wt % Cr,
meantime a variant has been developed for ex- which, although the proportions of the afore-
tremely severe HNO3 exposure (5.3 wt % Si, mentioned interstitial elements have been low-
17.5 wt % Ni, 0.015 wt % C) [49]. ered, are additionally stabilized with titanium
or niobium; and 3) stabilized molybdenum-
LIVE GRAPH and nickel-containing ferritic steels with high
Click here to view Cr contents, such as X 1 CrNiMoNb 28 4 2 (Re-
manit 4575) and X 2 CrNiMoTi 25 4 4 (Monit).
The superior toughness of the last-mentioned
steel types, as compared with that of a conven-
tional Cr steel, is illustrated by the transition
temperature of the notch impact strength.
Stabilized ferritic steels should be of partic-
ular interest in connection with the handling of
corrosive media, especially chloride-containing
cooling waters (e.g., river water), owing to their
good corrosion properties, suitability for weld-
ing, and availability as semifinished products, as
well as for economic reasons [51].
Figure 13. Area-related mass loss rate of stainless steels in For reasons of cost, and because of certain
boiling nitric acid (exposure time: 50 – 90 d) design problems, stainless cast steel is often pre-
a) X 2 CrNiSi 18 15; b) X 2 CrNi 18 9; c) X 1 CrMo 26 1; ferred to stainless rolled and wrought steels as a
d) X 1 CrNi 25 21 material for chemical plant. The chemical com-
position and mechanical properties of stainless
Ferritic steels have also undergone special de- cast steels are fairly similar to those of the rolled
velopment. Because the mechanical properties and wrought steels. Table 8 lists several impor-
of the welded joints were unsatisfactory, the tant types, especially those used for chemical
commercial types used until now were rarely pumps.
chosen for chemical plant. A substantial im-
provement may be expected from the titanium-
stabilized chromium and chromium – molybde- 5.1.6.1. Technical Properties
num steels of low carbon and nitrogen con-
tent and from the nickel-alloyed chromium – The mechanical properties of the four groups of
molybdenum steels. Progress in the field of stainless steels are shown in Table 9.
Table 8. Cast stainless and special steels
Steel type Designation Material Composition, wt %

number
C Si Mn Cr Ni Mo Cu Others
Cast ferritic stainless G-X 8 CrNi 13 1.4008 ≤0.09 ≤1.0 ≤1.0 13.0 1.5 ≤0.5
steel
Cast martensitic G-X 5 CrNi 13 4 1.4313 ≤0.07 ≤1.0 ≤1.5 13.0 4.0 ≤0.7
stainless steel
Cast austenitic G-X 6 CrNi 18 9 1.4308 ≤0.07 ≤2.0 ≤1.5 19.0 10.0
stainless steel
G-X 6 CrNiMo 18 10 1.4408 ≤0.07 ≤1.5 ≤1.5 19.0 11.0 2.5
G-X 6 CrNiMo 1713 1.4448 ≤0.07 ≤1.0 ≤2.0 17.0 13.5 4.5
G-X 5 CrNiNb 18 9 1.4552 ≤0.06 ≤1.5 ≤1.5 19.0 10.0 Nb ≥ 8× %
C
G-X 5 CrNiMoNb 18 10 1.4581 ≤0.06 ≤1.5 ≤1.5 19.0 11.5 2.3 Nb ≥ 8× %
C
G-X 7 CrNiMoCuNb 18 18 1.4585 ≤0.08 ≤1.5 ≤2.0 17.5 20.0 2.3 2.1 Nb ≥ 8× %
C
Cast special austenitic G-X 7 NiCrMoCuNb 25 20 1.4500 ≤0.08 ≤1.5 ≤2.0 20.0 25.0 3.0 2.0 Nb ≥ 8× %
steel C
G-X 3 CrNiSiN 2013 9.4306 ≤0.04 4.5 4.5 20.0 13.0 ≤0.05 N
Cast G-X 3 CrNiMoCu 24 6 9.4460 ≤0.04 ≤1.5 ≤1.5 25.0 6.0 2.4 3.1 N
ferritic – austenitic
stainless steel
Table 9. Mechanical properties of the four main steel types
Steel type Ferritic a Martensitic b Austenitic c Austenitic – ferritic d
Yield strength, MPa ca. 300 450 – 600 ca. 230 e ca. 500 f
Tensile strength, MPa 450 – 650 600 – 950 ca. 600 ca. 750
Fracture strain, % ca. 25 14 – 18 45 ca. 30
Notch impact energy, J g 30 – 55 ca. 150
a
Normal steels with 16 – 18 wt % Cr, annealed.
b
Quenched and annealed.
c
Solution annealed.
d
Annealed at 1100 ◦ C and quenched.
e
0.2 % yield strength.
f
1 % yield strength;
g
DVM specimen, longitudinal.
Between their melting points and room tem- in the pearlitic and martensitic forms, without
perature, ferritic steels are pure or mainly fer- intermediate stages. They are hardened by heat-
ritic. The production of a fine-grained structure ing to 980 – 1100 ◦ C, depending on carbon con-
requires forming at temperatures below 800 ◦ C, tent, cooling in oil or air, and tempering at a
heating beyond 800 ◦ C, and cooling. Heating temperature above 600 ◦ C. The steels contain-
above 1000 ◦ C (welding) enlarges the grain, thus ing less than 0.4 wt % carbon serve as heat-
embrittling the steel and causing precipitation treatable materials with good mechanical prop-
of carbides. Temperatures above 1100 ◦ C affect erties, while those with higher carbon contents
the structure to such an extent that the steel are used as hardened steels. Certain types are
breaks when subsequently loaded. These steels resistant to very high temperatures and to pres-
cannot be hardened by heat treatment. Being surized water. Having good resistance to erosion
less expensive than austenitic steels, and more and cavitation as well as high fatigue strength,
resistant to chloride-containing solutions, they they are used also for propellers and impellers.
are used for pipelines intended for chloride- Austenitic steels with low chromium and nickel
containing waters, as well as for heat exchang- contents are so unstable that martensite may
ers and condensers. Martensitic steels exist only be formed at low temperatures or through cold
forming. High chromium contents favor the for- mands are particularly severe, as in the case of
mation of ferritic structures. Fine granulation re- components subjected to vibration, the surface
sults from recrystallization during hot forming. quality can be improved by subsequent grinding.
The grain-growth rate is much lower than that of Unstabilized 17 wt % chromium steels that
ferritic steel. The final heat treatment consists of have been welded must always be annealed since
heating to 1000 – 1100 ◦ C and quenching in wa- they are otherwise sensitive to intergranular cor-
ter or air. Hardening by heat treatment is not pos- rosion, even in mild corrodents. Where this treat-
sible; the strength is improved by cold or hot – ment is impracticable, stabilized grades should
cold forming. The most conspicuous properties be used. Although the latter benefit from heat
of these steels are a low yield strength, high resis- treatment, it is not absolutely necessary. Stabi-
tance to fracture, high strength at elevated tem- lized steels and molybdenum-containing steels
peratures, resistance to pressurized water, heat also exhibit lower growth tendency. Apart from
resistance, permanent strain at low loads, and a imparting resistance to intergranular corrosion,
tendency to creep. An important application is additions of stabilizing elements also improve
the fabrication of pressure vessels. the resistance to pitting corrosion.
In austenitic – ferritic steels the ratio of fer- The principal welding methods for austenitic
rite to austenite is determined by the compo- steels are TIG, MIG, and submerged-arc weld-
sition and heat treatment. It increases with the ing. Apart from using steels that have no inter-
annealing temperature and rate of cooling. At- granular susceptibility after welding (stabilized
tention is drawn to the risk of 475 ◦ C embrit- steels and ELC types) it is particularly impor-
tlement (hardness increase, loss of toughness, tant to avoid hot cracking and loss of corrosion
and loss of chemical resistance through sepa- resistance through precipitation of intermetal-
ration into phases of high iron and chromium lic phases. Appropriate recommendations can be
content [52] and σ-phase formation), as well found in the processing guidelines.
as to the fact that, in comparison with purely
austenitic steels, these steels are less sensitive
to stress corrosion cracking. Their applications 5.1.6.2. Chemical Properties
include pump manufacture. Special grades with
high wear resistance are used for bushings. The resistance of stainless steels to corrosive
Ferritic, austenitic, and ferritic – austenitic media is determined by their passive behavior,
stainless steels can be welded by practically all which depends in turn on the alloying elements
the well-known methods. The argon arc (TIG, and their concentrations.
MIG) process, resistance welding (spot or seam In this connection, chromium is particularly
welding), and the plasma arc welding and elec- important, but the effects of nickel, molybde-
tron beam welding are particularly suitable for num, and copper are also significant. In partic-
ferritic chromium steels. Austenitic chromium – ular, chromium reduces the passivation current
nickel steel is recommended as the electrode ma- density and the residual current density of the
terial in addition to material of the same com- steel in the passive state. The main effect of
position as the base. If, for reasons of corrosion molybdenum is a reduction of the passivation
(particularly the risk of stress corrosion crack- current density and facilitation of repassivation,
ing), either of these materials cannot be used, which promotes the transition from the active to
an austenitic filler can serve for the lower layers the passive state.
and a ferritic filler for the cover pass. In view of In general it is considered that a corrosion
the marked grain growth tendency, as little heat rate of 0.1 mm/a (0.1 g m−2 h−1 ) represents the
as possible should be introduced. It is therefore highest degree of corrosion resistance attainable
advisable to use thin electrodes and low currents. under practical conditions. Corresponding data
As scale formation may be accompanied can be found in stability tables and diagrams and
by the formation of chromium-depleted surface in manufacturers’ literature. Often, however, sta-
zones, protective gas should be used to pre- bility diagrams, of which Figure 14 is an exam-
vent scale formation on welding. Cleanliness of ple, apply only to chemically pure corrodents. In
the seam, which must be without splashes and the case of sulfuric acid, for example, even rel-
undercutting, is also important. Where the de- atively small amounts of oxidizing agents(NO− 2,
LIVE GRAPH Fe3+ ) permit the use of stainless steels in sulfuric
Click here to view
acid at concentrations up to ca. 50 % and tem-
peratures considerably higher than those shown
in Figure 14. Thus figures for resistance to pure
corrodents should in many cases be regarded as
initial approximations. The influences of venti-
lation, i.e., the corrodent’s oxygen content, and
of the state of motion (e.g., laminar or turbulent
flow) must be taken into account also.
Uniform surface corrosion is of relatively mi-
nor importance for stainless steels. Localized
corrosion, however, may lead quickly to com-
ponent failure even where the corrosion rate is
low, and must therefore be avoided as far as pos-
sible. Normally, the susceptibility of metallic
materials to localized corrosion increases with
the resistance to general corrosion. In localized
corrosion of stainless steels, the locally active
areas are very small compared to the area of
the passive surface. Therefore, the local anodic
dissolution current density is very high. Dam-
age caused to passive materials by stress corro-
sion cracking and fatigue corrosion, which oc-
cur with virtually no loss of mass, is particu-
LIVE GRAPH
larly hazardous. The corrosion may penetrate
Click here to view even relatively thick components within a short
time. The types of localized corrosion that are
most important in stainless steels are intergran-
ular corrosion (grain-boundary attack), pitting
corrosion (pit formation), stress corrosion (cor-
rosion cracking), and fatigue corrosion (corro-
sion fatigue cracking).
Intergranular corrosion is a selective process
in which the areas close to the grain boundaries
are corroded. In all cases it has one of the fol-
lowing causes:
1) Depletion of alloying elements important to
chemical resistance in areas close to grain
boundaries, caused by formation of precipi-
tates, in which these elements have accumu-
lated, at the grain boundaries. In joint weld-
ing, these precipitates may be formed in the
heat-affected zones bordering on the weld
seams.
2) Chemical attack on precipitates at the grain
boundaries, e.g., by concentrated nitric acid
on precipitates of titanium carbonitrides in
titanium-stabilized steels.
Figure 14. Isocorrosion curves of chromium – nickel – mo-
lybdenum stainless steels in sulfuric acid
3) Preferential attack by accumulations of ac-
A) 0.05 % C, 17 % Cr, 13 % Ni, 5 % Mo; B) 0.05 % C, 20 % companying and trace elements in the steel,
Cr, 25 % Ni, 3 % Mo, 2 % Cu e.g., phosphorus, silicon, and boron (which
stimulate the anodic metal dissolution at the highest temperature that still causes susceptibil-
grain boundaries). ity to intergranular corrosion and by the shortest
4) Cell formation between the matrix and pre- annealing time leading to sensitization of grain
cipitates at the grain boundaries. boundaries. This shortest annealing time (repre-
sented by the “nose” of the grain-boundary cor-
In stainless steels, the depletion of the al- rosion field) is situated in the temperature range
loying elements chromium and molybdenum re- around 650 ◦ C for molybdenum-free austenitic
sulting from precipitation of carbides with high steels and in the range around 750 ◦ C for mo-
chromium and molybdenum contents is the most lybdenum-containing steels.
important cause of intergranular corrosion in in- When the temperature falls after welding, it
dustry. passes through the range in which austenitic
At low temperatures the solubility of car- chromium – nickel steels become susceptible to
bon in austenitic chromium – nickel steels and intergranular corrosion. The following steps are
nickel – chromium alloys is very low, but it in- taken to make the steel resistant to intergranular
creases markedly as the temperatures rises. The corrosion after welding:
carbon dissolved in the austenitic solid solution
at high annealing temperatures may precipitate 1) The carbon content is reduced to levels at
at the grain boundaries at lower annealing tem- which neither temperature nor the exposure
peratures as a carbide of type M23 C6 with high time causes sensitization (ELC steels).
chromium and molybdenum content. In this way 2) Stabilization with additions of the
zones of depleted chromium and molybdenum carbide-forming element titanium or nio-
content, which grow together to form coherent bium/tantalum. The affinity of these alloying
chromium-depleted areas as the carbide precip- elements for carbon is greater than that of
itation progresses, are formed round the pre- chromium. They form special carbides or
cipitated carbides. Through the precipitation of carbonitrides of the type M (C, N). Due to
chromium-rich carbides (75 – 90 wt % Cr) the the affinity of both elements for nitrogen,
chromium content in the vicinity of the grain the steel’s nitrogen content, as well as its
boundaries falls below the so-called resistance carbon content, must be taken into account
limit of ca. 12 wt % chromium. in calculating the stabilization ratio.
In ferritic chromium steels, the rate at which
chromium-rich carbides are precipitated is very
high. After annealing at temperatures above
850 ◦ C, even very rapid cooling cannot pre-
vent their precipitation, and the formation of
a structure susceptible to intergranular corro-
sion. In the temperature range around 800 ◦ C,
however, the very high diffusion rates permit-
ted by the body-centered cubic lattice of the
α mixed crystal causes rapid replenishment of
chromium by diffusion from the chromium-
rich matrix into the chromium-depleted grain
boundary areas. As a reduction of the car-
bon content would not eliminate intergranu-
lar susceptibility until an extremely low level
Figure 15. Diagram of grain-boundary disintegration
a) Solubility limit for carbon; b) Precipitation of chromium- had been reached (< 0.005 wt %), stabilization,
rich carbides; c) Intergranular corrosion even of ferritic chromium steels, by addition of
niobium/tantalum, and especially titanium, has
The susceptibility to intergranular corrosion great industrial importance. Pitting corrosion of
is indicated by the grain-boundary corrosion stainless steels occurs only when they are in the
fields in the plot of annealing time versus anneal- passive state, and is then caused almost exclu-
ing temperature (Fig. 15, see above). The shape sively by chloride ions in aqueous solution. It
and sizes of these fields are best described by the is therefore also known as chloride corrosion.
In the initiating step of pitting corrosion chlo- Stress corrosion cracking of stainless steels
ride ions are adsorbed locally by the passive with mainly transgranular progression of the
layer, whereupon the passivity breaks down. The corrosion cracks may occur in the following cor-
mechanism of this corrosion has not yet been rodents:
fully explained. 1) Chloride solutions (threshold temperature
In the pitting corrosion of stainless steels, the 50 ◦ C);
influence of potential is important. Pitting cor- 2) Alkaline solutions (threshold temperature at
rosion only occurs when the potential exceeds 40 – 50 wt % NaOH, 100 ◦ C). In addition, in-
the pitting potential. In the presence of a corro- tergranular cracking occurs at high tempera-
sive medium, pitting corrosion therefore occurs tures in dilute alkaline solutions.
only if the corrosion potential of the steel is more
positive than the pitting potential. If the steel is in the sensitized state in which
With regard to the attacking medium, the it is susceptible to intergranular cracking, and
main factors by which the pitting potential is the tensile stress and potential exceed critical
lowered (and therefore the risk of pitting corro- values, intergranular stress corrosion cracking
sion heightened) are increase of chloride con- occurs also in, e.g., water at high temperatures
centration and temperature, and reduction of pH (Fig. 16) [55].
[53].
With regard to the material, the pitting poten-
tial can be shifted towards more positive poten-
tials by raising the chromium content and espe-
cially the molybdenum content; the alloying ele-
ments nickel and manganese, on the other hand,
have practically no influence.
The effects of chromium and molybdenum
are described, and the resistances of the various
alloys estimated, with the help of the pitting re-
sistance equivalent PRE [54]:
PRE = wt %Cr + 3.3 × wt %Mo
Over a wide range of percentages of these

elements, the pitting potential depends linearly
on the pitting resistance equivalent, in as far as Figure 16. Concentration ranges of dissolved oxygen and
the structure is that given by solution annealing. chloride that may lead to stress corrosion cracking (SSC) of
Deviations are attributable to homogenization type 304 stainless steels in water at temperatures in the range
260 – 300 ◦ C. Applied stresses in excess of yield strength
of the structure by relatively high nitrogen con- and test times in excess of 1000 h, or strain rates greater
tents. Stress corrosion cracking, which is like- than 10−5 s−1
wise initiated mainly by chlorides, accounts for • = Sensitized, SCC; ◦ = Sensitized, no SCC; = Annealed,
most of the damage suffered by stainless steels. SCC; = Annealed, no SCC
The basic prerequisites of stress corrosion crack-
Under conditions that cause stress corrosion
ing are as follows:
cracking the following materials can be used in-
1) The action of a specific corrodent on a ma- stead of normal stainless austenitic 18 Cr 10 Ni
terial susceptible to stress corrosion crack- steels: stainless ferritic chromium steels with
ing, i.e., the presence of a critical mate- 17 – 28 wt % chromium, with or without mo-
rial/corrodent system. lybdenum; austenitic – ferritic steels (duplex
2) Static tensile stresses, possibly superim- steels), whose use is restricted in some cases
posed by infrequent dynamic loads. Only to temperatures below 300 ◦ C; austenitic steels
tensile loads are effective. Pressure does not with increased nickel and/or molybdenum con-
cause stress corrosion cracking; in fact, in tent; and nickel-based alloys. Apart from molyb-
many cases it is an effective means of pre- denum, an alloying element that decisively im-
venting corrosion of this type. proves the stress corrosion cracking resistance
of stainless austenitic steels is nickel (at nickel with the highest N content is the one most resis-
contents exceeding about 40 wt %, stress corro- tant to boiling 35 % MgCl2 solution. In boiling
sion cracking no longer occurs). Corrosion fa- seawater all the steels achieved times to failure
tigue is the term used for crack damage which of more than 1000 h at loads above the 0.2 %
occurs in a component exposed simultaneously yield strength [60].
to alternating mechanical stress and a corrodent.
It may be caused in all metallic materials by un-
specific corrodents, differing in this respect very
much from stress corrosion cracking, for whose
occurrence specific corrodents are responsible.
The main symptom of corrosion fatigue is the
loss of endurance strength.
Fatigue cracking of stainless steels differs ac-
cording to whether they are in the active or pas-
sive states. In the active state numerous cracks
are formed, whereas in the passive state few
cracks, or perhaps just a single precrack, are
formed. Damage to stainless steel plant through
fatigue cracking is, however, relatively rare [56].
Figure 17. Stress corrosion behavior of nitrogen-containing
stainless steels in boiling MgCl2 solution (35 wt %, 123 ◦ C)
5.1.6.3. Development State of Stainless
Cr – Ni Steels
The steel X 3 CrNiMnMoNbN 23 17 5 3
The corrosion resistance of stainless steels is (1.4565) is commercially available. With a
benefitting from the attainment of particularly pitting resistance equivalent of about 48 (in
high degrees of purity, as given by electroslag which the high nitrogen content is taken into
remelting, for example. At the same time the account) it is more resistant to pitting corrosion
strength-related properties are being improved than any other stainless steel (cf. Fig. 18). Only
without loss of ductility. NiCr 22 Mo 9 Nb, better known as Incoloy 625,
To make possible the increases in Cr and Mo performs comparably well.
content on which these improvements depend
it is necessary to increase the nitrogen content.
This is achieved by renitrogenizing the steel un-
der pressure and simultaneously adding alloying
elements that increase the nitrogen’s solubility
[57], [58], e.g., manganese.
Of two steels now undergoing tri-
als, namely X 3 CrNiMoNoN 23 27 6 4 and
X 3 CrNiMnMoNbN 23 17 8 4, the latter is su-
perior in respect of strength-related properties
in consequence of precipitation hardening by
a finely dispersed intermetallic Z-phase (0.2 %
yield strength at room temperature ca. 500 MPa;
at 500 ◦ C, > 300 MPa). This steel, which is with-
out Nb and therefore free from precipitation, is
superior in ductility (notch impact energy at
Figure 18. Pitting resistance equivalent (PRE) and critical
room temperature > 300 J), though at 500 ◦ C it pitting corrosion temperature for various steels and Incoloy
still has a 0.2 % yield strength of ca. 250 MPa 625 in a 10 wt % solution of FeCl3 · 6 H2 O
[59]. Some mechanical properties of alloy 1.4565
The stress corrosion cracking behavior of are as follows:
steels of this type is shown in Figure 17. The steel
Next Page
0.2 % Yield strength ≥ 500 N/mm2

furic acid and pure phosphoric acid. Their re-
0.2 % Yield strength sistance to soil corrosion and seawater attack
at 300 ◦ C ≥ 300 N/mm2 is also good. Depending on their composition
Notch impact energy
at − 269 ◦ C ≥200 J
and the form of the graphite, austenitic cast ma-
Elongation > 50 % at room temperature terials [62], [63] withstand corrosion by alka-
Reduction of area > 70 % at room temperature lis and sulfuric acid. The austenitic grades that
withstand moderately high and high tempera-
As the nitrogen contents of the aforemen-
tures are used for pumps, valves, cylinder lin-
tioned steels in the molten state are below the
ings, waste-gas pipes, and furnace parts, for ex-
solubility limit, these materials have good weld-
ample. The corrosion-resistant grades are used
ing behavior. The filler metals used for them
in the food, artificial silk, and plastics indus-
at present are relatively highly alloyed nickel-
tries as well as for pipes and vessels. Men-
based materials of the Ni – Mo – Cr type.
tion should also be made of the thermal shock
stability of GGL(laminar)NiCr 30 3 (material
no. 0.6676) and the low-temperature ductility of
5.2. Cast Iron [60], [61] GGG(nodular)NiMn 23 4 (material no. 0.7673).
The term cast iron is used for unalloyed, low-
alloy, and highly alloyed iron – carbon cast ma- LIVE GRAPH
Click here to view
terials containing ca. 2 – 5 wt % carbon and
0.8 – 3 wt % silicon, the carbon being mainly
in the form of graphite. The fundamental struc-
ture of unalloyed and low-alloy cast iron is
ferritic, ferritic – pearlitic, or pearlitic; that of
highly-alloyed cast iron may be any of these, but
also austenitic. The main alloying elements are
nickel, chromium, and copper. The main quality
standards are DIN 1691, for unalloyed and low-
alloy lamellar graphite cast iron; DIN 1693, for
unalloyed and low-alloy spheroidal graphite cast
iron; and DIN 1694, for austenitic cast iron.
Mechanical properties of the various types of
cast iron are listed in Table 10. The strength of
gray cast iron depends on the thickness of the Figure 19. Mean tensile strength of gray cast iron versus
the section thickness of the casting (according to DIN 1691)
casting’s cross section (wall thickness). Empir-
ical values for the strength of castings are given
in Figure 19. A special grade that withstands hot nitric acid
The exceptionally low plastic deformability and hot sulfuric acid is the iron – silicon mate-
and impact strength of lamellar graphite cast iron rial containing 14 – 18 wt % silicon. Its hardness
in comparison with nodular graphite cast iron and brittleness constitute a great disadvantage
are explained by the graphite lamellae, which because they restrict the choice of shaping tech-
act as internal notches. Unalloyed and low-alloy niques to casting and grinding.
lamellar graphite cast iron and nodular graphite Lamellar and nodular graphite cast iron can
cast iron are attacked only slightly by pure sul- be welded hot with filler materials of the same
Table 10. Mechanical properties of the various types of cast iron
Cast iron type Tensile strength σ u , MPa Fracture strain, % Notch impact energy, J
Unalloyed and low-alloyed laminar 100 – 450 <1

Unalloyed and low-alloyed nodular 400 – 800 2 – 22 9 – 14 (−20 ◦ C)
Austenitic laminar 140 – 280 1–3
Austenitic nodular 390 – 500 1 – 40 7 – 34
Previous Page
composition, and cold with filler materials of must be used in hot and cold forming. The fur-
different composition [64], [65]. nace atmosphere for heat treatment should be
sulfur-free and reducing or neutral; if freedom
from sulfur cannot be ensured, the furnace at-
mosphere should be slightly oxidizing.
5.3. Nickel and Nickel Alloys [66–68]
Owing to their excellent corrosion resistance to LIVE GRAPH

Click here to view
various aggressive media, nickel and its alloys
are of growing importance in chemical engi-
neering. Furthermore, Ni – Cr alloys, especially
those with additions of silicon and aluminum,
have good high-temperature strength by virtue
of their high creep strengths, and good heat-re-
sistance to hot gases and combustion products.
The most important unalloyed nickel
grades are Ni 99.6 (2.4060), nickel content
≥ 99.6 wt %; LC-Ni 99.6 (2.4061), nickel con-
tent ≥ 99.6 wt %; Ni 99.2 (2.4066), nickel con-
tent ≥ 99.2 wt %; LC-Ni 99 (2.4060), nickel
content ≥ 99.0 wt %.
The nickel content (according to DIN 17 740)
may include up to 1 wt % cobalt. Ni 99.6 may
contain up to 0.08 wt % carbon, and Ni 99.2
up to 0.1 wt % carbon; after prolonged expo-
Figure 20. Corrosion resistance of pure nickel in sodium
sure to temperatures above about 300 ◦ C, the hydroxide, related to concentration and temperature [72]
carbon may be precipitated as grain boundary
graphite, thus making the material brittle [69].
All the welding methods normally used for
Frequent use is therefore made of LC (low-
steel, except submerged-arc welding [74], are
carbon) Ni, which has a maximum carbon con-
suitable for nickel. Suitable weld filler mate-
tent of 0.02 wt % [70], [71].
rials are available for combinations with un-
Plant consisting of nickel or nickel-plated
alloyed or low-alloy steels, austenitic stainless
steels is used mainly to produce and process
steels, and nickel – copper, copper – nickel, and
alkalis [71], [72]. The good resistance of pure
nickel – molybdenum alloys. Nickel parts can
nickel to sodium hydroxide solution can be seen
also be joined by brazing and soldering.
in Figure 20. Nickel is also used to handle acid
Cast nickel [70] has the characteristic prop-
halides [73], seawater, brackish water, dilute air-
erties of forged nickel, but is always slightly al-
free and nonoxidizing mineral acids and salt so-
loyed with carbon, silicon, and manganese to
lutions, and fatty acids. It can also be exposed
improve the flow of the molten metal and den-
to dry chlorine or hydrogen chloride at temper-
sity of the castings.
atures up to 535 ◦ C.
Nickel has good high-temperature strength.
Up to about 300 ◦ C its yield strength and ten- 5.3.1. Nickel – Copper Alloys
sile strength undergo practically no change [69].
Nickel is very sensitive to sulfur and sulfur com- In chemical engineering only two alloys with
pounds [69], [70], [74]. Above 400 ◦ C sulfur more than 50 wt % nickel have gained impor-
penetrates nickel along the grain boundaries and tance, namely NiCu30Fe (2.4360, Inconel alloy
forms a eutectic mixture of nickel and nickel 400) and NiCu30Al (2.4375), which are stan-
sulfide, embrittling the material. This process is dardized in DIN 17 743. Both are sold as sheets,
rapid at 550 – 650 ◦ C. The surface must there- strip, pipe, rods, wires, and forgings.
fore be cleaned thoroughly before welding and The alloy NiCu30Fe can be exposed to sea-
each annealing treatment. Sulfur-free lubricants water and brackish water, solutions of nonoxi-
dizing salts, alkalis [75], cold or warm nonox- The molybdenum-free alloy NiCr15Fe, like
idizing acids [73], and dry bromine. It is also nickel, has good resistance to caustic alkalis,
resistant to hydrofluoric acid [76], though stress even surpassing it in this respect under oxidizing
corrosion cracking may occur in hydrofluoric conditions in consequence of its high chromium
acid vapors containing air, as well as to a lesser content [77].
extent in the liquid phase. Stress corrosion crack- NiCr15Fe, NiCr23Fe and NiCr29Fe have
ing has been caused in these alloys by corrosive greater high-temperature strength than nickel
media containing mercury or its compounds. and can be exposed to oxidizing sulfur-free at-
Where there is a risk of stress corrosion cracking, mospheres at temperatures up to 1100 ◦ C, and
stress relief annealing should be carried out at to reducing sulfur-free atmospheres at up to
550 ◦ C, and in exceptional cases at up to 650 ◦ C, 1150 ◦ C. These alloys are also used in nitrid-
and followed by slow cooling in the furnace. As ing gases (480 – 600 ◦ C) and under carburizing
NiCu30Fe is expensive, solid sheet is often re- conditions (800 – 950 ◦ C). Like pure nickel and
placed in the manufacture of process plant by the other nickel alloys, they are sensitive to sul-
steel sheet plated with this alloy. fur and its compounds at temperatures above
NiCu30Al is an age-hardenable alloy with ca. 400 ◦ C; this must be taken into account
similar corrosion behavior to NiCu30Fe. Be- where processing, e.g., by welding, is envisaged.
cause of the risk of stress corrosion cracking it Nickel – chromium – iron – molybdenum alloys
should be used in the age-hardened state; it can- combine the good resistance of nickel – molyb-
not be exposed to hydrofluoric acid, however. denum alloys under reducing conditions with
Both materials are weldable by the usual the good resistance of nickel – chromium alloys
methods; they can also be brazed. Soft soldering under oxidizing conditions. This explains their
is less frequently used. Like pure nickel, both al- good resistance to acids and salt solutions. With
loys are sensitive to sulfur and sulfur compounds the low-carbon grades and those stabilized with
above ca. 400 ◦ C. titanium or niobium there is virtually no risk of
intergranular corrosion.
Chromium – nickel casting alloys (60/40,
5.3.2. Nickel – Chromium Alloys [68] 50/50 and 35/65) are used in chemical engineer-
ing and have good resistance to corrosion by fuel
Nickel – chromium alloys, with various iron ash [78].
contents and up to ca. 9 wt % molybdenum and
2 wt % copper, are normally used where the
corrosion resistance of highly alloyed stainless 5.3.3. Nickel – Molybdenum and
steels is inadequate. They exhibit good resis- Nickel – Molybdenum – Chromium Alloys
tance to acids and to pitting corrosion, crevice
corrosion, and stress corrosion cracking. The Nickel – molybdenum and nickel – molybde-
types most important in chemical engineering, num – chromium alloys are among the chemi-
together with their main applications, are listed cally most resistant metallic materials. The main
in Table 11.
Table 11. Nickel – chromium alloys
DIN designation Material no. U.S. trade name Exposure tolerated
NiCr15Fe 2.4816 Inconel alloy 600 seawater, cooling water, alkalis, hot gases, combustion products
NiCr23Fe 2.5851 Inconel alloy 601 as 2.4816
NiCr29Fe 2.4642 Inconel alloy 690 alkalis
LC-NiCr15Fe 2.4817
NiCr20CuMo 2.4660 Carpenter 20 Cb-3 sulfuric acid, phosphoric acid
NiCr21Mo 2.4858 Inconel alloy 825 seawater, cooling water, alkalis
NiCr21Mo6Cu 2.4641 sulfuric acid, phosphoric acid, seawater, cooling water
NiCr22Mo6Cu 2.4618 as 2.4641
NiCr22Mo7Cu 2.4619 Hastelloy alloy G-3 acids, mixed acids
NiCr22Mo9Nb 2.4856 Inconel alloy 625 acids, seawater, cooling water
NiCr21Fe18Mo 2.4603 Hastelloy alloy G-30 acids, HNO3 – HF pickling acid
representatives of this group are listed in Ta- strated by the time – temperature precipitation
ble 12. diagram of Hastelloy alloy C-4 (Fig. 21).
LIVE GRAPH
Click here to view
Table 12. Nickel – molybdenum and
nickel – molybdenum – chromium alloys
Material no. Designation US trade name
2.4617 NiMo28 Hastelloy alloy B-2

2.4610 NiMo16Cr16Ti Hastelloy alloy C-4
2.4819 NiMo16Cr15W Hastelloy alloy C-276
2.4608 NiCr21Mo14W Hastelloy alloy C-22
Nickel – molybdenum alloys are not passi-

fiable, since they contain no chromium. Their
good resistance to reducing acids is explained
by the low rate of corrosion in the active state,
for which molybdenum is responsible.
The alloy NiMo30 (2.4810), consisting of Figure 21. Time – temperature sensitization diagrams for
nickel, 26 – 30 wt % molybdenum and 5 – 7 wt % Hastelloy alloy C-276 (a) and Hastelloy alloy C- 4 (b); test
iron withstands hydrochloric acid at all confor intercrystalline corrosion in accordance with ASTM G-
28
centrations. Nickel – molybdenum alloys of this
kind cannot be used under oxidizing conditions,
Hot and cold forming of these high-nickel
however, because even atmospheric oxygen in-
materials is difficult owing to their high water
creases the rate of corrosion considerably. Al-
resistance and work-hardening tendency. They
loying with chromium makes them passive in
are weldable by all the commonly used methods.
oxidizing corrodents, and therefore resistant to
In the production of weld joints it is advisable,
corrosion under these conditions also. In addi-
tion they retain their low rates of corrosion in in the interest of good corrosion resistance, to
start by making a thin root pass and then to weld
the active state; therefore, like NiMo16Cr16Ti
the filler and cover passes while cooling the root
(2.4610) and NiCr21Mo14W (2.4608), for ex-
side of the weld. If the design and size of a com-
ample, they can be used under reducing and ox-
ponent permit heat treatment, solution annealing
idizing conditions. NiCr21Mo14W has proved
at 1150 ◦ C, followed by water quenching, is rec-
itself under severely oxidizing conditions.
Since the corrosion resistance of nickel – ommended [79]. Steel can be explosion-cladded
molybdenum and nickel – molybdenum – chro- with any of these alloys, and they are often used
mium alloys depends on molybdenum and/or for this purpose. Above 400 ◦ C they are sensitive
chromium, precipitation of intermetallic com- to sulfur and sulfur compounds, like all materi-
pounds containing these elements may make the als with high nickel contents; this must be taken
materials susceptible to intergranular corrosion. into account in connection with annealing and
Precipitation of molybdenum-rich compounds welding.
leads to intergranular susceptibility in the active
state (in hydrochloric acid, for example), while 5.4. Aluminum and Aluminum Alloys
precipitation of compounds rich in chromium
causes susceptibility to intergranular corrosion The high strength and low density of aluminum
and intergranular crack formation in the passive make it highly suitable for lightweight struc-
state [79]. tures. Its economic value in the chemical in-
Exact proportioning of the alloying elements, dustry, however, depends more on its corrosion
but, above all, minimization of the silicon and behavior [82], [83]. Pure and very pure alu-
carbon contents (< 0.03 wt %) and additional minum according to DIN 1712 comprise the
stabilization [80], [81], give alloys that tolerate grades Al 99, Al 99.5, Al 99.8, and Al 99.99.
hot forming, annealing, and welding without ac- The good corrosion resistance of aluminum,
quiring intergranular sensitivity; this is demon- in spite of its very negative standard electrode
potential of − 1.66 V, is due to the formation a fine-pored top layer (Fig. 23), which can be
of nonconducting Al2 O3 passive films. The cor- dyed and compacted [84]. Hard anodizing is an
rosion resistance depends on the purity of the anodic oxidation process that gives particularly
material, which for chemical plant should not hard and wear-resistant oxide films for techni-
be below 99.5 wt % Al. As the protective Al2 O3 cal purposes [85]. Apart from aluminum itself,
surface layer is largely insoluble in the pH range numerous wrought and cast alloys based on Al –
of 4.5 – 8.8 (Fig. 22), aluminum materials have Mg, Al – Mn, Al – Mg – Si, and Al – Zn – Mg are
very good resistance to corrosion in approxi- suitable for hard anodizing.
mately neutral aqueous media. The corrosion
behavior and the main applications are listed in
Table 13 [82].
LIVE GRAPH
Click here to view
Figure 22. Influence of pH on the solubility of the Al2 O3

film on aluminum
Because the Al2 O3 passive film is non- Figure 23. Structure of an oxide film on aluminum, pro-
conducting, relatively thick corrosion-inhibiting duced by anodizing
Al2 O3 layers can be produced by anodic oxida-
tion. They consist of a very thin and almost non- High-purity aluminum is used in chemi-
porous dielectric underlayer (barrier film) and cal engineering mainly as a cladding material.
Table 13. Examples for the corrosion behavior of aluminum alloys in various media
Corrosive environment Corrosion resistance∗ Application
Al 99.5 AlMg AlCuMg
Ethanol
water-containing 1–2
dry 5
Acetylene, dry 1 2–3 Pressure bottles
Liquid ammonia, dry 1–2 1–2 Cooling elements
Ethane 1 1 Pressure bottles
Atmosphere
industrial 2–3 3–2 3 Construction, cars
marine 1–2 1 3–5 Shipbuilding
Benzene 1 1 1 Tanks, apparatus
Gasoline 1 1 1–3
leaded, wet 3–6
Distilled water 1–2 1–2
Freon 1 1 Cooling machines
Ice 1 1 2 Cooling plant
Seawater 2–3 1–2 3–5
∗
1 = good resistance; 2 = resistant; 3 = low resistance; 4 = still usable; 5 = barely resistant; 6 = not resistant
Super-pure aluminum and AlSi 12 are outstand- typical representative of the materials obtained
ingly resistant to highly concentrated nitric acid in this way is AlMg4.5Mn, which has good
(Fig. 24), even at high temperatures. They also strength-related properties and corrosion resis-
withstand concentrated acetic acid well [86]. tance and is used both for purposes involving
seawater contact and in chemical engineering.
LIVE GRAPH Additions of Mn and Cr improve the resistance
Click here to view
to chloride-induced pitting corrosion [88].
LIVE GRAPH
Click here to view
Figure 24. Corrosion behavior of Al 99.5 in nitric acid
The main alloying elements that are used to

increase the strength of aluminum are Mg, Si,
Zn, Cu, and Mn. Wrought alloys are standard-
ized in DIN 1725, Part 1, and cast alloys in DIN Figure 25. Breakthrough potentials for intergranular
1725, Part 2. Both groups include self-hardening corrosion
(alloy hardening) and hardenable (precipitation a) Al8 Mg5 ; b) AlMg7 phase with grain boundary precipi-
hardening) materials. tates; c) AlMg7 phase, homogenized
Aluminum – manganese alloys are of the self-
hardening type. Alloys containing 0.8 – 1.5 wt % Age-hardenable Al – Cu – Mg alloys (2.8 –
Mn are easy to process and exhibit corrosion re- 4.8 wt % Cu, 0.4 – 1.8 wt % Mg) have high
sistance similar to that of pure aluminum. strength (e.g., AlCu4Mg2: σ u = 440 MPa) but
The main representatives of the self- low corrosion resistance. Apart from having
hardening materials are Al – Mg alloys, whose little resistance to atmospheric corrosion, they
strength is further improved by cold form- are particularly susceptible to stress corrosion
ing. Their corrosion resistance is approximately cracking [89].
equal to that of pure aluminum (Al99.5), which Age-hardenable Al – Mg – Si alloys with
they even surpass where seawater is concerned good heat forming behavior (0.4 – 3.5 wt % Mg,
(cf. Table 13). AlMg3, AlMg5, AlMg2Mn0.8, 0.3 – 1.5 wt % Si) are more resistant to corro-
and AlMg4.5Mn therefore belong to the group sion than Al – Cu – Mg alloys. Although rela-
of aluminum materials known as seawater resis- tively high silicon contents raise the strength,
tant. they reduce the resistance to intergranular cor-
However, with increasing magnesium con- rosion by causing the formation of heteroge-
tent (especially for Mg >5 wt %), the suscep- neous grain boundary precipitates. Therefore,
tibility of Al – Mg alloys to intergranular corro- where corrosion is expected, it is preferable to
sion increases through the formation of Al8 Mg5 choose materials with low silicon contents (e.g.,
grain-boundary precipitates (Fig. 25). There is AlMgSi0.5). These materials, however, are not
also a risk of susceptibility to stress corrosion fully resistant to pitting and intergranular corro-
cracking [87]. sion in media with high chloride contents.
The stability can be raised by reducing the After artificial ageing, the alloys based on
magnesium content and adding manganese. A Al – Zn – Mg, and especially Al – Zn – Mg – Cu,
have higher strength (up to 530 MPa) than all containing NH3 ) results from the formation of
other aluminum materials, but they are suscep- oxide films which consist of Cu2 O or CuO (de-
tible to pitting and intergranular corrosion in pending on the nature of the medium and the
chloride-containing media. corrosion potential) and which afford good pro-
Important cast aluminum alloys for mechani- tection. In outdoor applications, including those
cal and chemical plant are those based on Al – Si in marine climates, copper is substantially re-
(5 to 20 % Si), Al – Mg (3 to 10 % Mg), or Al – sistant; this explains its use in the construction
Mg – Si or Al – Si – Mg; apart from having high industry. Its main field of application, however,
strength and adequate ductility, they are distin- is plant for drinking, cooling, and industrial wa-
guished by good corrosion resistance, including ter [82]. Here, too, it has good resistance, though
resistance to seawater. under unfavorable conditions (as when deposits
Various treatments and methods are used to are formed or the nature of the water is unsuit-
protect aluminum from corrosion. High-strength able) pitting corrosion cannot be entirely ruled
aluminum alloys, for example, are frequently out [92].
plated with pure aluminum (Al99.5). Nonmetal- In inorganic and organic acids the corrosion
lic inorganic coatings such as chromate and rate depends largely on the presence of oxidiz-
phosphate increase the corrosion resistance and ing agents. In nonoxidizing acids in the absence
also serve as primers for paints [83]. of oxygen and at room temperature this rate re-
The thickness of the natural oxide film on alu- mains low; in oxidizing acids such as sulfuric
minum can be increased by boiling the metal in acid, it increases with the oxygen content.
deionized water or by steaming it, as a result of In aqueous ammonia solutions under condi-
which an AlOOH (boehmite) layer with a thick- tions in which surface films are not formed (high
ness of 1 – 2 µm is formed above the Al2 O3 bar- alkalinity), copper is attacked severely. In ap-
rier layer [84]. Another possibility is the use of proximately neutral solutions capable of form-
impressed current or sacrificial anodes (zinc) to ing surface films, especially aqueous media con-
reduce the potential below the values at which taining NO− 2 , some susceptibility to stress cor-
the risk of pitting or intergranular corrosion is rosion cracking, even on the part of pure copper,
critical [84]. cannot be entirely excluded [93].
Alloying, particularly with Zn, Al, Ni, or
Sn, raises the strength of copper. In the case
of Cu – Zn alloys (DIN 17 660) single phase
5.5. Copper and Copper Alloys [90], [91]
α-phase alloys (Zn ≤ 37 wt %) and (α + β)-
alloys (37 – 46 wt % Zn) are distinguished, the
The good corrosion behavior of copper and former being more resistant to corrosion. The
copper-based alloys has led to their extensive (α + β)-alloys tend to suffer preferential attack
use under moist atmospheric conditions and in on the β-phase, which has the higher Zn con-
the handling of drinking water, industrial wa- tent. The alloys of both types, but above all the
ter, and water at high temperatures. Their many (α + β)-alloys, suffer dezincification corrosion
outdoor applications as fresh water pipes, fit- in chloride-containing waters (Fig. 26, see next
tings, condensers, heat exchangers in seawa- page). Dezincification of the α-phase alloys is
ter desalination plants, in chemical apparatus, counteracted by adding As, Sn, Sb, and P as addi-
and for many other purposes are explained not tional alloying elements [94]. Among the ternary
only by good resistance to corrosion but also by alloys, CuZn28Sn and CuZn20Al (2 wt % Al)
their good workability, strength-related proper- have been used successfully for many years as
ties, and high thermal and electrical conductiv- materials for cooler, condenser, and heat ex-
ity. changer tubes in cooling waters with relatively
In accordance with its position in the low contamination levels. CuZn20Al is remark-
electrochemical series (standard potential able also for its good resistance to seawater and
Cu/Cu+ = 0.34 V) copper (DIN 1787) has good also to erosion – corrosion.
resistance to corrosion, as do high-copper alloys. In cooling water containing NH3 or H2 S there
The good resistance to approximately neutral to is a risk of stress corrosion cracking. The criti-
alkaline aqueous media (not including water cal stress for ammonia-inducedstress corrosion
and CuAl8. In their resistance to seawater they

even surpass pure copper [82]. In addition to the
increased Al content, their improved resistance
results from the formation of adherent, highly
protective oxide films that contain Cu2 O and
Al2 O3 [96].
The two-phase (α + β)-alloys (Al >7.8 wt %)
are less resistant. The heterogeneous multiphase
alloys (Al >10 wt %), which, apart from the α-
phase, also contain the γ2 -phase and (depending
on the heat treatment) martensitic phases, suffer
not only corrosion at relatively high rates, but
Figure 26. Dezincification of α-brass in tap water also preferential dealuminization. Additions of
Ni, Fe, and Mn improve the corrosion behav-
ior of the heterogeneous alloys (e.g., CuAl11Ni,
LIVE GRAPH
Click here to view CuAl10Fe, CuAl9Mn). Aluminum bronzes are
used in process plant manufacture, where their
applications include pump parts (gears) and fit-
tings, including those of seawater pumps, and
condenser tubing.
Although the homogeneous α-alloys are
those most resistant to uniform corrosion and
dealuminization, they show heightened suscep-
tibility to ammonia-induced stress corrosion
cracking; this applies particularly to Cu – Al ma-
terials with about 4 wt % Al (Fig. 27). The het-
erogeneous materials with Al >8 wt %, on the
other hand, have good resistance to stress corro-
sion cracking, but are sensitive to selective cor-
rosion [95].
Technically interesting Cu – Sn materials (tin
bronzes) standardized in DIN 17 662 contain
up to 9 wt % and up to 14 wt % Sn, respec-
tively, depending on whether they are wrought
Figure 27. Influence of the content of alloying elements on alloys or cast alloys [82]. Their strength depends
ammonia-induced SCC of copper alloys on the tin content and degree of cold forming.
a) CuAl; b) CuNi; c) CuZn With favorable working properties and resis-
Upper curves: tensile strength; Lower curves: SCC treshold
stress tance to alternating stresses, together with re-
sistance to corrosion in neutral salt solutions
cracking in Cu – Zn materials decreases with in- and alkaline solutions (except those containing
creasing Zn content, and is only about 10 MPa NH3 ), they are used for screws, springs (CuSn2),
for Cu70Zn30 (Fig. 27) [95]. Residual stresses pipes (CuSn6) and chemical plant components
in components that have not been sufficiently (CuSn4, CuSn6).
annealed may therefore suffice to initiate crack Cast materials consisting of binary Cu – Sn
formation. To prevent stress corrosion cracking, bronzes and multicomponent alloys with addi-
stress relief annealing, followed by testing for tions of Pb (Sn – Pb bronzes) or Zn (gun metal)
residual stresses according to DIN 50 916, is have proved themselves in marine technology,
necessary. machinery, and process plant. Owing to their lu-
Of the Cu – Al alloys standardized in brication properties, which are outstanding in
DIN 17 665, the homogeneous α-alloys some cases, they are used for bearings, screws,
(Al ≤ 7.8 wt %) are among those that withstand worm gears, toothed wheels, pumps, and turbine
corrosion, examples being CuAl5, CuAl5As blades, etc.
LIVE GRAPH
Copper – nickel alloys (DIN 17 664 and DIN Click here to view
17 658) form a continous mixed-crystal series,

which improves their corrosion behavior. The
Cu – Ni materials of technical interest (CuNi10,
CuNi20, CuNi30), which generally contain iron
and manganese additions, are among the copper-
based materials most resistant to corrosion. At
levels of up to about 1.5 wt %, iron further im-
proves the corrosion behavior. The good corro-
sion resistance of the frequently used materi-
als CuNi10Fe and CuNi30Fe results from the
formation of oxidic surface films consisting of Figure 28. Mean crack velocity v of CuNi10Fe1.5 in 1 M
Cu2 O on the metal side and complex corrosion [(NH4 )2 SO4 + NH3 ] (pH 9, 50 ◦ C) as a function of the elec-
products with high percentages of Fe and Ni on trode potential
a) Homogenized; b) Aged (50 h, 500 ◦ C)
the solution side [97].
The high corrosion resistance of Cu – Ni – the material must be exactly suited to the condi-
Fe materials, especially in seawater, but also tions of use.
in ammonia-containing media (brackish water),
explains their growing importance in marine
technology (seawater desalination plants) and 5.6. Lead and Lead Alloys [82], [99]
as tube materials for condensers, coolers, and
heat exchangers [82]. These alloys also with- Lead owes its good corrosion resistance to its
stand erosion – corrosion and cavitation well. ability to form dense, firmly adherent surface
Chloride-induced pitting corrosion occurs occa- films consisting of lead sulfates, carbonates,
sionally under unfavorable conditions. In com- or oxides, depending on the corrosive medium
parison with other copper-based materials, Cu – [99].
Ni – Fe alloys with Ni contents of ≥ 10 % ex- In outdoor applications and approximately
hibit substantially better resistance to ammonia- neutral waters the protection from corrosion
induced intergranular stress corrosion cracking arises from the formation of basic lead carbon-
(Fig. 27). They are immune to stress corrosion ates of low solubility (Pb(OH) 2 · 2 PbCO3 ),
cracking in chloride-containing media [97]. which may also contain lead sulfates. In acids
As the Cu – Ni – Fe alloys of technical in- and alkalis, lead normally suffers severe surface
terest tend to form Fe – Ni-rich grain bound- corrosion (Fig. 29). However, it is distinguished
ary precipitates at 350 – 650 ◦ C [98], it is as- by outstanding resistance to sulfuric acid and
sumed that the homogenized, precipitation-free good resistance to phosphoric acid and chromic
materials are those most resistant to intergran- acid; this results from the low solubility of the
ular stress corrosion cracking. Hence the ho- sulfate, phosphate, or chromate surface films
mogenized state has always been preferred for [99]. Lead is therefore a useful material for fit-
component fabrication. Investigations into the tings, pipes, pump parts, and other mechanical
influence of the state of precipitation on the components and also for leadings (reaction ves-
stress corrosion cracking behavior of the alloy sels, electrolysis tanks) [82], [100].
CuNi10Fe1.5 in ammonia-containing solutions For greater strength and finer grain, lead
have shown, however, that specific heat treat- is alloyed with antimony (0.5 – 13 wt % Sb).
ments are capable of producing material states Lead – antimony alloys can be age hardened
considerably superior to the homogeneous states (precipitation hardening), which gives them fur-
[97] (Fig. 28). It has also been demonstrated that ther strength (hard lead). These alloys are used
the stress corrosion cracking behavior is deter- particularly where mechanical stresses must be
mined exclusively by the hardness of the mate- withstood in addition to corrosion, as in the case
rial [97]. of accumulator plates, pumps, valves, and im-
The variety of copper-based materials is such pellers [82]. The corrosion resistance can be fur-
that reliable usedepends on very careful choice: ther improved by small additions of As and Se.
LIVE GRAPH capable of reducing the hydrogen overvoltage

Click here to view and accelerating oxygen reduction, thus shifting
the potential of the metal into the passive range
and consequently improving its corrosion resis-
tance (Fig. 30) [101].
LIVE GRAPH
Click here to view
Figure 30. Potential – time curves of lead alloys in boiling

70 % H2 SO4
a) Pb Cu Sn Pd (0.05 0.12 0.1); b) Pb 99.9 Cu – 0.1 Pd; c) Pb
99.985 – 0.1 Pd; d) Pb Cu Sn Au (0.04 0.05 0.1); e) Pb Cu
Sn (0.12 0.12); f) Pb 99.985 – 0.1 Au; g) Pb 99.9 Cu; h) Pb
99.985
Figure 29. Dependence of the corrosion behavior of lead in
aqueous solutions on pH Accordingly, alloys consisting of highpurity
a) HNO3 ; b) Acetic acid; c) Ba(OH)2 ; d) NaOH
lead and copper, or where particularly good cor-
Compared to pure lead, alloys based on Pb – rosion resistance is needed, of lead and pal-
Cu or Pb – Cu – Sn, and also alloys of the Pb – ladium, are used for chemical apparatus. The
Cu – Sn – Pd type with extremely low contents Pb – Cu – Sn – Pd alloys also have relatively high
of Cu (0.01 – 0.1 wt %), Sn (0.05 – 1.12 wt %), creep strength [101].
and Pd (0.10 wt %), have improved resistance to
corrosion by hot and boiling sulfuric acid [101];
see Table 14. 5.7. Zinc and Zinc Alloys
Table 14. Linear corrosion rate of multicomponent lead alloys in
boiling sulfuric acid In DIN 1706 a distinction is made between high-
purity zinc (Zn 99.995, Zn 99.99, Zn 99.95) and
Alloy Corrosion rate, mm/a
technical zinc (Zn 99.5, Zn 98.5 and Zn 97.5).
50 % 70 % 80 % Through outdoor exposure and even mild
H2 SO4 H2 SO4 H2 SO4
chemical exposure (contact with drinking wa-
Pb 99.9 Cu 0.48 8.23 a ter, for example) zinc forms protective surface
Pb Cu Pd (0.06, 0.1) 0.12 0.21 0.22 films that consist mainly of basic zinc carbon-
Pb Cu Au (0.06, 0.1) 1.86 0.10 0.30
Pb Sb Pd (1.1, 0.1) 0.17 0.19 a ates and which adhere to the metallic zinc fairly
Pb Cu Sn Pd (0.05, 0.12, 0.10) 0.01 0.10 0.26 firmly. Zinc is severely attacked by hot water and
Pb Cu Sn Pd (0.10, 0.13, 0.2) 0.01 0.05 0.19
Pb Cu Sn Au (0.04, 0.05, 0.10) 0.15 0.23 1.95
steam. A fairly high corrosion rate can also be
Pb Ni Sn Pd (0.10, 0.10, 0.10) 0.09 0.28 2.80 expected in industrial air containing SO2 [82].
Pb Te Sn Pd (0.10, 0.10, 0.10) 0.09 0.29 3.50 Zinc is not resistant to acids and strong alkalis.
a
Dissolves. The main use of zinc is the protection of steel
from corrosion, where it is used mainly in the
As the solubilities of Cu and Pd in lead are ex- form of metallic coatings, but also as sacrificial
tremely low, these alloying elements are present anodes.
in the precipitated state, and fine dispersion of The most important zinc alloys are the die
the particles is beneficial. The precipitates are casting alloys GD-ZnAl 4 and GD-ZnAl 4Cu 1;
in plant manufacture they are of only minor im- 5.9. Titanium, Zirconium, Niobium, and
portance. Tantalum [102], [103]
The refractory metals of groups 4 and 5 of the

5.8. Tin and Tin Alloys periodic table have now gained considerable im-
portance in the fabrication of chemical plant.
The purity requirements for tin as specified in Having excellent passivity, which results from
DIN 1704 range from 98 to 99.90 wt % Sn. the formation of oxidic surface films, such ma-
Due to the formation of oxidic surface films terials as titanium, tantalum, niobium, and zirco-
of low solubility, tin has good corrosion behav- nium are outstandingly resistant to many media.
ior in outdoor applications and in water [82].Tin In VdTÜV-Werkstoffblatt 230/1 unalloyed ti-
is attacked severely by halogens, halogen com- tanium is allocated to four groups having differ-
pounds, and alkalis. It is substantially resistant ent degrees of purity and strength (Table 15). As
to numerous foods and drinks. It also has good the forming behavior of types belonging to group
resistance to corrosion by organic acids (acetic, IV is limited, only those belonging to groups I
citric, maleic, tartaric, and lactic acid), espe- to III are normally used in chemical engineer-
cially in the absence of oxygen. Tin is used ing. The corrosion resistance of these types can
mainly in the food industry as a protective metal- be improved by alloying with 0.15 – 0.25 wt %
lic coating on appliances and containers. palladium [104].
Tin – lead alloys with 30 – 60 wt % Sn (e.g., In the United States, unalloyed titanium (C.P.
SnPb40, PbSn50, PbSn40), possibly with ad- Ti = commercially pure titanium) is classified in
ditions of Sb and Cu, are used as soft sol- four groups (grades 1 to 4; see Table 16) but the
ders (DIN 1707). Tin alloys with Sn contents percentages of permissible additives are greater
of 80 – 91 wt % are important bearing materials than those laid down in VdTÜV-Werkstoffblatt
(sliding bearings); examples are Sn80Sb12 (5 – 230/1. Two palladium-alloyed titanium types are
7 wt % Cu, 11 – 13 wt % Sb, 1 – 3 wt % Pb) and termed grade 7 and grade 11.
Sn80Sb18 (16 – 20 wt % Sb, 1 – 3 wt % Pb). The high price of Pd explains the introduc-
tion of the molybdenum- and nickel-containing
Table 15. Grades of unalloyed titanium
Material Material number Max. impurity content, wt % Yield strength
Fe O N C H (1 %), MPa
Ti I 3.7025 0.15 0.12 0.05 0.06 0.013 200

Ti II 3.7035 0.20 0.18 0.05 0.06 0.013 270
Ti III 3.7055 0.25 0.25 0.05 0.06 0.013 350
Ti IV 3.7065 0.30 0.35 0.05 0.06 0.013 410
Table 16. U.S. Classification of titanium
Type ASTM B-265-79 Composition, wt % (max.)
grade Fe O N C H Pd Others
C.P. 1 0.20 0.18 0.03 0.10 0.015

C.P. 2 0.30 0.25 0.03 0.10 0.015
C.P. 3 0.30 0.35 0.05 0.10 0.015
C.P. 4 0.50 0.40 0.05 0.10 0.015
C.P.-Pd 7 0.30 0.25 0.03 0.10 0.015 0.12 – 0.25
C.P.-Pd 11 0.20 0.18 0.03 0.10 0.015 0.12 – 0.25
C.P.-Mo + Ni 12 0.30 0.25 0.03 0.08 0.015 0.2 – 0.4 Mo
0.6 – 0.9 Ni
∗
Ticorex-A 0.03 0.05 0.008 0.004 0.0015 0.05 Ru
0.5 Ni
∗
Nippon Mining Co.
alloy grade 12, which, like the ruthenium- and brackish water, nitric acid, acetic acid, chromic
nickel-containing alloy Ticorex A, is superior acid, moist chlorine, chlorine dioxide, bleaching
to unalloyed titanium in crevice corrosion resis- solutions, sodium chlorate, and sodium chlorite.
tance. The use of palladium as an alloying element
Finally, mention should be made of a titanium extends the range of applications of titanium in
alloy containing 5 % tantalum which has been acids with reducing effects, such as sulfuric acid
developed to the production stage in Japan. It and hydrochloric acid, and improves the resis-
has improved resistance to nitric acid. tance to crevice corrosion [104].
A Werkstoffblatt for the alloy tantalum – 2.5 Corrosion resistance data for titanium, zir-
tungsten, in which growing interest is being conium, and tantalum are compiled in Table 19
shown on account of its strength, is in prepa- (see next page). A common feature of the special
ration. metals is a pronounced sensitivity to hydroflu-
The mechanical properties of titanium, zirco- oric acid and fluorides, with a risk of hydrogen
nium and tantalum, and also a selection of their embrittlement in the case of extreme exposures.
physical data, are compiled in Tables 17 and 18. Titanium cannot be used in hydrochloric acid
The fundamental corrosion-chemical proper- or sulfuric acid. However, its resistance to these
ties of these materials for chemical plant are media can be improved considerably by adding
oxidizing agents. Titanium and zirconium can-
1) The stability of titanium under oxidizing con- not be used in fuming nitric acid, because of
ditions the possibility of pyrophoric reactions and stress
2) The stability of zirconium under reducing corrosion cracking.
and alkaline conditions Of the refractory metals, tantalum has by far
3) The stability of tantalum under oxidizing and the best corrosion behavior in hot, concentrated
reducing conditions. mineral acids, apart from hydrofluoric acid. In
In the case of titanium, which is the most fa- hot, concentrated sulfuric acid its corrosion re-
vorable material in this group with respect to sistance is comparable with that of glass or cast
density, particular attention must be drawn to ferrosilicon and is surpassed only by that of no-
its resistance to chlorides and oxidizing agents. ble metals such as gold and platinum. It is also
For example, titanium has been used success- highly resistant to hydrochloric acid and phos-
fully for heat exchangers exposed to seawater, phoric acid and has no pyrophoric tendency in
Table 17. Mechanical properties of titanium, zirconium, and tantalum
Property Titanium Zirconium Tantalum
3.7035 3.7055 grade 702

group II group III
Tensile strength, MPa 400 – 550 470 – 600 295 – 442 274
0.1 % Yield strength, MPa 280 360 197 – 295 196
Creep strength
150 ◦ C (105 h), MPa 150 170 176 255
250 ◦ C (105 h), MPa 110 130 117 225
Elongation, % 22 18 25 – 35 15
Hardness HB 30, MPa 1400 1600
Hardness HV 30, MPa 1180 – 1570 825 – 1470
Table 18. Some physical properties of tianium, zirconium, and tantalum
Property Titanium Zirconium Tantalum

3.7025 (Ta-ES)
Density, g/cm3 4.5 6.53 16.6

mp, K 1 975 2 125 3 271
Thermal conductivity, J m−1 s−1 K−1 17 21 55.25
Modulus of elasticity (300 K), GPa 108 94.176 172.5
Table 19. Corrosion resistance of titanium, zirconium, and tantalum
Medium Concentration, wt % T , ◦C Corrosion rate, mm/a
Titanium Zirconium Tantalum
Hydrochloric 5 20 <0.05 <0.05 <0.001

acid 15 35 2.4 <0.08 <0.001
(aerated) 37 35 15.0 <0.08 <0.001
Sulfuric acid 10 35 1.2 <0.05 <0.001
(aerated) 40 35 8.5 <0.05 <0.001
Nitric acid (fuming) inflamm. in air inflamm. in air resistant
0.001 all not resistant not resistant not resistant
Sodium 10 100 <0.05 <0.05 1.0
hydroxide 40 80 <0.1 <0.05 not resistant
fuming nitric acid. Tantalum is, however, at- LIVE GRAPH

Click here to view
tacked by oleum, even at room temperature, and
also by hot alkaline solutions. Although it has
high ductility, its strength can be increased con-
siderably by alloying with 2 – 10 wt % W, with
little effect on the corrosion resistance. Tanta-
lum – tungsten alloys exhibit good resistance to
sulfuric acid, which may be seen in Figure 31
[105]. The alloy most favorable in this respect is
Ta2.5W.
LIVE GRAPH
Click here to view
Figure 32. Comparison of the corrosion resistance of tan-

talum and Hastelloy alloy B in hydrochloric acid
Alloying tantalum with niobium gives favor-

ably priced materials with similar resistance to
corrosion that have a good chance of becoming
established in the chemical industry and of play-
ing a part similar in importance to that of tanta-
lum itself. This applies particularly to use in ni-
tric acid. Figure 33 shows the corrosion rates of
tantalum – niobium alloys in sulfuric acid (70 %)
at 165 ◦ C. As, however, the rate of corrosion in-
Figure 31. Corrosion rates of tantalum – tungsten alloys in creases with the niobium content, only alloys
sulfuric acid (96 %) containing up to 40 wt % Nb are of technical
At normal pressure tantalum and its alloy interest. The mechanical properties of tantalum,
with 2.5 wt % tungsten are completely resistant tantalum alloys, and niobium are shown in Ta-
to hydrochloric acid at all concentrations and ble 20.
temperatures [106]. If, however, hydrochloric
acid is handled under pressure in tantalum appa- Table 20. Mechanical properties of tantalum, tantalum alloys, and
niobium
ratus, damage through hydrogen absorption, and
finally through hydrogen embrittlement, is pos- Property Ta Ta 2.5 W TaNb Nb type 2
60/40
sible. An autoclave insert failed in consequence
of hydrogen embrittlement after being in use for Tensile strength, MPa 225 290 276 170
0.2 % Yield strength, MPa 140 205 193 105
only 8 h. The range of conditions under which Elongation, % 15 25 25 25
tantalum is at risk through hydrogen embrittle-
ment is shown in Figure 32.
LIVE GRAPH Construction Materials in Chemical Industry 641
Click here to view
LIVE GRAPH
Click here to view
Figure 33. Corrosion rates of tantalum – niobium in boiling Figure 34. Corrosion of zirconium in hydrochloric acid
70 vol% sulfuric acid at 165 ◦ C a) 5 mm/a; b) 0.5 mm/a; c) 0.13 mm/a
a) Ta–75 Nb; b) Ta–60 Nb; c) Ta–50 Nb; d) Ta–40 Nb; e) Ta–
25 Nb; f) Ta
The components may consist entirely of the
Under oxidizing conditions zirconium is of- special metal or of suitable composites. In many
ten less resistant than titanium. Its resistance cases nonadherent lining or sheathing of the sub-
to nonoxidizing media nevertheless greatly ex- strate material is sufficient; cladding is appro-
ceeds that of titanium. Zirconium is thus practi- priate where heavy loads are exerted, good heat
cally passive in hot, fluoride-free sulfuric acid. transmission is needed, or negative pressure ex-
Zirconium, like titanium, is resistant to many or- ists. As the special metals tend to form inter-
ganic acids, but is severely attacked by hydroflu- metallic phases with steel at high temperatures
oric acid. Unlike the other refractory metals, zir- (1000 ◦ C), they are normally applied by explo-
conium is resistant to hot alkaline solutions and sion cladding, possibly with intermediate layers
is therefore the most suitable material for these (e.g., copper) [110], [111].
media in many cases. Although special metals have good weld-
Zirconium also has good resistance to cor- ing behavior, their reactions with atmospheric
rosion by hydrochloric acid (Fig. 34), though it gases must be taken into account. Hence weld-
is vital to ensure that oxidizing agents, such as ing is only possible under an inert gas or in high
Fe(III) or Cu(II) compounds, are not present. At vacuum. It is essential to avoid alloying with
30 ◦ C and an acid concentration of 32 %, as lit- iron-based materials in welding. Since the melt-
tle as 5 ppm of such a compound increases the ing point of tantalum, for example, is roughly
corrosion rate ten-fold (from 7.6×10−4 mm/a to twice as high as that of steel, specially designed
7.6×10−3 mm/a) [107], [108]. For critical cor- butt-welds are necessary in the processing of
rosion conditions, heat treatment for 3 h at 750 – explosion-cladded metal sheet (cf. Fig. 35, next
790 ◦ C, especially after welding, is advisable in page) [112].
order to maximize the resistance [109].
Refractory metals have a wide range of appli-
5.10. Organic Materials [113–115]
cations in the chemical industry. They are used
for reactors, columns, agitators, pipelines, fit- To an increasing extent the growing require-
tings, bellows, and pumps, for example. Sensing ments on the availability and reliability of chem-
heads, such as thermo-feelers, magnetic floats ically exposed plant components are necessitat-
and membranes, that must also function reli- ing the use of particularly corrosion-resistant
ably under adverse conditions are protected by materials. In this respect the chemical nature
cladding with special metals. Heat exchangers of organic materials gives them certain advan-
made from special metals and consisting of coils, tages over metallic and inorganic nonmetallic
rods, candle-shaped elements, or tube bundles materials, provided the operating temperatures
are used to cool or heat corrosive media. do not reach critical levels. In many cases they
are well suited for plant that handles the media 5.10.1. Selection Criteria
most commonly encountered at chemical works,
namely hydrochloric acid, caustic soda solu- The stability required of plastics varies accord-
tion, hypochlorite solution, sulfuric acid, wa- ing to whether a plastic component must sim-
ters, and salt solutions of all kinds. The main ply withstand corrosion, or fulfil structural func-
types of organic materials are thermoplastics, tions also. In general no risk arises if the phys-
thermosetting plastics, elastomers, glass-fiber- ical properties of a coating or facing consisting
reinforced plastics, and foamed plastics. Com- of a synthetic material are impaired through the
posite and surface coating materials are being action of a medium; but the same process in a
used increasingly too (see → Corrosion). statically or dynamically stressed part may lead
to its premature failure. Similarly, swelling and
stress corrosion cracking may be nonhazardous,
and the quality of joints relatively unimportant,
in nonstructural plastics, but hazardous, or crit-
ical, in those with structural functions. The per-
meability of polymers is less serious in compo-
nents than in coatings, especially those on metal-
lic substrates. Thus the envisaged conditions of
use must be carefully considered before mate-
rials are chosen. As important parameters, the
solutions to which the components will be ex-
posed, including all their consituents (such as
solvents, amines, phenols, compounds with high
vapor pressures, oxidizing agents), the maxi-
mum and long-term service temperatures, the
pressures and vacuum conditions, and the static
and dynamic loads, must receive special atten-
tion. Only when the various factors have been
established can a list of foreseeably suitable ma-
terials be drawn up for more detailed consider-
ation.
5.10.2. Properties and Application Criteria
Figure 35. Design of a butt-weld for explosion-cladded Unlike the surface removal corrosion of metallic
sheet (mild steel/tantalum with copper intermediate layer) materials, the action of liquid media on organic
– · – Hardness curve in tantalum cover strip; —- Hardness materials leads mainly to swelling, caused by
curve in tantalum cladding; – – – Hardness curve in copper absorption of the medium. In many cases the
intermediate layer
degree of swelling of an organic material in in-
dividual media and the dependence of swelling
One of the most important processing meth- on time and temperature as well as its possible
ods for plastics is welding. A survey of the weld- reversibility constitute adequate criteria for the
ing methods is given in [116]. A comprehen- determination of suitability. The stability data
sive account of the design of plastic components, published in manufacturers’ and other literature
with detailed consideration of strength calcula- are usually based on swelling tests. These data
tions and dimensioning, is contained in VDI- are adequate where coatings or linings, e.g., of
Taschenbuch T 21 [117]. rubber or plastics, are concerned, and in a num-
ber of other cases.
Where static or dynamically loaded parts are
concerned, swelling tests alone must be consid-
ered tentative, enabling one merely to draw up
a shortlist of materials for further consideration. Original shaping (e.g., by injection molding,
Here it is far more important to ascertain how the extrusion, or welding) requires higher temper-
strength of materials is affected by prolonged ex- atures, however (170 – 200 ◦ C). The upper ser-
posure to chemicals, the degree to which creep vice temperature limit is 60 ◦ C, or possibly a
occurs, and whether or not the conditions are lower temperature, depending on the chemical
favorable to stress corrosion cracking. Losses exposure.
of long period creep resistance caused by liquid
media are preferably expressed as resistance fac- Polyethylene is a partly crystalline mate-
tors. A resistance factor is the ratio of the time to rial with high impact strength at temperatures
failure in the test medium to the time to failure in down to ca. − 100 ◦ C. High-density polyethyl-
water [118]. In some media this ratio depends on ene is preferred for chemical plant because it
the mechanical stresses exerted on the sample; in has greater strength and stiffness than the low-
other cases it is largely independent of them. Re- density types. It can be shaped thermoplasti-
sistance factors for glass-reinforced plastics can cally at temperatures above 130 ◦ C and welded
be derived from the differences in creep behavior at ca. 200 ◦ C. The upper service temperature
in tensile tests under various ambient conditions limit is 60 ◦ C, or 80 ◦ C if glass fibers are in-
(as ratios between creep moduli, for example) corporated. The resistance to nonoxidizing me-
[119]. dia is excellent. The swelling caused by hydro-
The stress corrosion cracking of organic poly- carbons leads to losses of strength that can be
mers is generally an entirely physical process, taken into account with the aid of resistance fac-
with diffusion and swelling processes and in- tors. The susceptibility to stress corrosion crack-
ternal and/or external stresses playing a major ing increases with the degree of crystallization,
part [120]. The term is used only where crack- but falls with increasing molecular mass. High
ing caused by exposure to chemicals, like that molecular mass material is less easily processed,
of metals, occurs exclusively in the presence of however, and its properties may suffer if it is ex-
tensile stresses. Tests are performed in various posed to elevated processing temperatures for
media and at various temperatures on panels or long periods.
pipes subjected to constant deformation or con-
stant stress in the long period tensile creep test
[118]. Susceptibility to stress corrosion crack- Polypropylene (PP) has properties similar
ing is increased by exposure to wetting agents, to those of polyethylene, but greater impact,
organic acids, solvents, and oxidizing media, by notched impact, and shock resistance, especially
shaping and jointing operations, by internal and at temperatures below 0 ◦ C. The upper service
external stresses, by prolonged exposure to high temperature limit is 80 ◦ C, or 100 ◦ C if glass
temperatures in processing, by temperature al- fibers are present. Polypropylene is almost as
teration, and by notching. In many cases the sen- resistant to chemicals as hard polyethylene, but
sitivity of finished parts to stress corrosion crack- more sensitive to oxidizing media and more
ing can be reduced by thermal after-treatment. strongly swelling in organic solvents. In com-
The thermoplastics most widely used in mon with hard polyethylene it has a certain per-
chemical engineering are PVC [poly(vinyl chlo- meability to organic media.
ride)], PE (polyethylene), PP (polypropylene) The applications of polypropylene include
and PB (polybutene). exhaust ducts, internal chimney tubing, sepa-
rators, rotary filters, filter fabrics and pressure
Poly(vinyl chloride) has been used for plates, hydrocyclones, and gas scrubbers.
decades due to its outstanding resistance to
chemicals. It is harder and tougher than other Polybutene (PB) is one of the more recent
thermoplastics, but at temperatures below 20 ◦ C polymeric materials that have gained acceptance
it has less impact strength than polyethylene in chemical engineering. Its strength properties
(PE) and polybutene (PB). Above its soften- lie between those of soft polyethylene (LD-PE)
ing temperature of 80 ◦ C, poly(vinyl chloride) and polypropylene. Its long period creep resis-
can be shaped by plastic deformation. The most tance exceeds even that of polypropylene. Al-
favorable deformation range is 110 – 130 ◦ C. though polybutene is soluble in several organic
solvents at elevated temperatures, its suscepti- used directly for mechanically stressed parts un-
bility to stress corrosion cracking is low. The less reinforcing materials and fillers have been
upper service temperature limit is 90 ◦ C. The incorporated. Having high cross-link density,
main applications of polybutene are high-tempe- thermosetting plastics are insoluble and can-
rature pressure pipes, filter pressure plates, strip- not be melted, and their strength and long pe-
wound vessels, and pumps. riod creep resistance are without the marked de-
pendence on temperature exhibited by thermo-
Polytetrafluorethylene (PTFE) is the ther- plastics and elastomers. Individual parts can be
mally and chemically most resistant plastic used joined to one another with catalytically harden-
in chemical engineering. Its service tempera- ing cements.
ture range extends from − 200 to 250 ◦ C. It is Solid parts made from glass-reinforced reac-
chemically resistant to virtuallly all media ex- tion resins are distinguished not only by chem-
cept molten alkalis and elemental fluorine. How- ical stability but also by relatively low weight,
ever, fillers added to the plastic to improve its together with high strength, and by good emer-
extrudability or mechanical strength may reduce gency running behavior. They are being used in-
its resistance to chemicals. The outstanding abh- creasingly for composite structures exploiting
esive behavior and exceptionally favorable slid- the high stability and heat resistance of glass-
ing properties deserve special mention. Applica- fiber-reinforced reactive resins with the supe-
tions include pipe linings, bellows, hoses, pump rior chemical resistance of thermoplastic coat-
parts, tube bundle heat exchangers, steam re- ings and linings.
lease nozzles, conveyor belts, seals, stuffing box For exposure to aggressive media, parts con-
packings, and filter fabrics. sisting entirely of glass-reinforced plastics usu-
ally receive an at least 2.5 mm thick coating con-
Poly(vinylidene fluoride) (PVDF) is a part- sisting mainly of resin. This protective coating,
ly crystalline plastic of high thermal stability. It in which the proportion of glass is low, acts
can be used at temperatures up to 100 ◦ C, or, as a barrier to corrosion and protects the load-
if glass-filled, up to about 120 ◦ C. PVDF is re- bearing, glass-reinforced structure from the ac-
sistant to most organic and inorganic acids. In tion of destructive media. The resins used are
alkalis, especially caustic soda solution, it tends unsaturated polyester, vinyl ester, epoxy, or fu-
to suffer stress corrosion cracking. Its main ap- rane resins.
plication is in pipelines used to convey acids. Table 21 gives a general idea of the cor-
rosion resistance of reaction resins used in
Elastomers and ebonite based on natural or the fabrication of apparatus and pipes. Glass-
synthetic rubber [121], [82] are used mainly fiber-reinforced resins are used for corrosion-
for surface protection (see → Corrosion). Elas- resistant articles of all kinds, especially pipes
tomers also have many applications in chemi- for waste water and waste air disposal, stacks,
cal engineering as seals, membranes, bellows, siphons, vats, transportation and storage con-
vibration dampers, hoses, and Moineau pump tainers, down-pipes, filter pressure plates, and
stators, as well as being used for space-saving frames. The upper service temperature limits ex-
folding containers for the transportation of cor- tend to about 120 ◦ C, depending on the resin in
rosive materials by land and sea. question.
Table 21. Chemical resistance of reaction resins ∗
5.10.3. Thermosetting Plastics Resistance towards
Type of resin Acids Alkalis Solvents Oxidizing

The main materials in this group are phe- agents
nolic, furane, epoxy, vinyl ester, and unsatu- Polyester +/0 +/− 0/− +
rated polyester (UP) resins. They are filled with Vinyl ester +/0 + 0/− +
glass fibers, graphite, or quartz and processed to Epoxy 0/− + +/0 +/−
Furane + + + 0/−
tamping compositions, hot molding compounds,
∗
sheet, and putties. Being brittle, they are rarely + = resistant; 0 = conditionally resistant; − = not resistant
More frequently, however, parts consisting are described in [123]. The use of organic mate-
of glass-reinforced plastics are provided with rials in the form of corrosion-resistant coatings
linings. The lining materials most widely used and linings represents an important application
at present are the thermoplastics polypropylene in chemical engineering (see → Corrosion).
(PP), unplasticized polyvinyl chloride (PVC-U)
and polyvinylidene fluoride (PVDF).
In the fabrication of composite structures,
thermoplastic liners are normally produced as a
first step and than reinforced with a glass-filled
reaction resin. Thermoplastic linings consisting
of sheet material are placed end to end and joined
by welding. The normal welding techniques are
hot gas, heated tool, and hot gas extrusion weld-
ing.
Figure 37. UP-GF tanks and pipes with PVC liners, con-
taining HCl and NaOCl solutions
5.11. Inorganic Nonmetallic Materials

5.11.1. Glass [124], [125]
Pipelines, apparatus, and even entire plants are
now being produced increasingly from borosili-
cate glass in order to solve exceptionally critical
corrosion problems. A complete range of glass
parts for assembly by the user, ranging from sim-
ple pipe sections and moldings to fittings, vessels
and column components, and even to complex
heat exchangers and their accessories, is now
commercially available.
Borosilicate glass has a very wide range of
uses and can be exposed permanently to temper-
atures up to 200 ◦ C. It is permanently stable to
virtually all media except hydrofluoric acid and
strong alkalis. Above 200 ◦ C it is attacked fairly
severely by all acids, especially phosphoric acid
[126]. Other advantages include the smoothness
Figure 36. PVC-lined UP-GF apparatus of its surfaces, catalytic inertness, and nontoxi-
city.
Figure 36 depicts a PVC-lined UP-GF ap- Glass can be combined with other materials –
paratus, seen here as a demonstration exhibit plastics and metals, for example – thus open-
with parts removed to show structural details. ing up a wide range of technical possibilities.
Another application is shown in Figure 37. This Glass apparatuses for heating purposes can be
is a storage facility for solutions containing HCl provided with elements consisting of stainless
and NaOCl, consisting of UP-GF tanks and pipes steel, highly corrosion-resistant nickel alloys, ti-
with PVC liners. The design of parts consist- tanium, or tantalum. Pumps and valves of all
ing of glass-reinforced plastics is described in kinds can be sealed with polytetrafluoroethyl-
[122]. Properties, processing, and applications ene components. PTFE is also used in the form
of bellows to compensate for thermal expansion chemical engineering. It is highly resistant to

and to damp vibration. Important applications of corrosion by organic and inorganic acids, alka-
borosilicate glass include distillation and rectifi- lis, alcohols and many solvents, and other or-
cation units, absorbers and gas scrubbers, nitric ganic compounds. It is easily worked, has high
acid concentrators, acid recovery plant, cleaning thermal conductivity, and withstands even se-
units, and piping. vere temperature shocks. As graphite is a brittle
Although quartz glass is very resistant to ther- material with practically no plastic deformation,
mal shock due to its extremely low coefficient the parts must be so designed that tensile and
of thermal expansion, its high cost limits techni- shear stresses are avoided as far as possible.
cal use to special articles (e.g., observation win- The main applications of graphite are heat ex-
dows). changers of all kinds, columns, sprinkling cool-
The use of enamel coatings, made from vit- ers, centrifugal pumps, valves, pipelines, and
reous enamels and partly crystalline enamels, small parts of many kinds. The use of graphite
to protect tanks, apparatus, columns, pipelines, in plant for production of dry hydrogen chloride
pumps and other items from corrosion is de- and in the treatment of waste water and waste
scribed in → Corrosion). air deserves special mention.
5.11.2. Graphite [82], [127], [128] 5.11.3. Refractory and Acid-Resistant

Bricks [129–132]
Graphite has been used as a special material in
chemical engineering since the mid-1930s. Heat This term covers ceramic materials that are still
exchangers, simply cemented together from free from deformation at temperatures exceed-
panels and strip, were the first application. Now, ing 1600 ◦ C and still do not soften at those ex-
all structural elements, such as pipes, solid and ceeding 1800 ◦ C. Bricks are normally shaped
hollow cylinders, slabs, panels, and profiles, can and fired, but are sometimes used in the form of
be produced from impregnated graphite (hard- castings. Apart from refractoriness, such prop-
fired carbon or electrographite). erties as softening under pressure, thermal con-
As the various graphite production meth- ductivity, chemical resistance, resistance to tem-
ods give porous materials, impregnation with perature alternation, abrasion resistance, shape
phenol – formaldehyde or furane condensation stability, and slagging tendency are of great im-
resins by the vacuum-pressure process is nec- portance.
essary if impermeability to gases and liquids Refractory bricks serve to enclose spaces in
is required, the effect of this treatment being which reactions take place and must last as long
that all the pores are closed. The quality of as possible under the given conditions. In view of
the finished material depends on the proper- the variety of these conditions they must be cho-
ties of the chosen resin. This applies particu- sen for then intended application in accordance
larly to the permeability, corrosion resistance, with their chemical and technological proper-
and upper service temperature limits (which are ties. The following classification of refractory
in the region of 165 ◦ C). For greater stability materials is based on their main consituents:
and higher service temperature limits, alterna- products of high silica content, alumina-based
tive impregnating agents, such as polytetrafluor- materials, basic refractory bricks, neutral refrac-
ethylene, are used. Carbon filling of the pores in tory products, carbon bricks, and silicon carbide
graphite can be carried out by impregnating with bricks.
cokable materials, which are then decomposed For corrosion protection in difficult cases,
thermally, this treatment being repeated several chemical apparatus can be lined with corrosion-
times. The resulting material has good corrosion resistant bricks, tiles, or moldings. These are at-
resistance and a high service temperature limit, tached to the wall or to one another with mortar
but is less strong and more brittle than the resin- or putty. Sealing and insulating layers may be
impregnated grades. used additionally between the wall of the appa-
Resin-impregnated electrographite is the ratus and the lining.
synthetic carbon material most widely used in
5.11.4. Engineering Ceramics [133], [134] and under vacuum at working temperatures of
up to 1950 ◦ C.
Oxide Ceramics. The most important oxide
ceramic material is aluminum oxide, Al2 O3 . Silicon Carbide. Silicon carbide has not
Beryllium oxide has applications as a moderator only high strength (bending strength up to
in nuclear reactors, and zirconium dioxide as a 650 MPa), but also a low coefficient of thermal
rocket material. In Table 22 the main mechan- expansion of only 4.8×10−6 K−1 and a high
ical and thermal properties of aluminum oxide thermal conductivity of 42 W K−1 m−1 . These
are compared with those of hard metal. A con- properties explain the very good resistance of
spicuous property of Al2 O3 is its great hardness. silicon carbide products to changes of tempera-
The strength values are practically constant over ture. Since silicon carbide also has excellent re-
a wide temperature range. This is because the in- sistance to corrosion, it is used as a structural ma-
crease in plasticity (and hence in the ability to terial for components subjected to severe ther-
dissipate local peak stresses) which occurs as mal and chemical loads.
the temperature rises compensates for the ther- Silicon carbide is used mainly as a grinding
mally induced loss of strength. On the other hand agent, e.g., for grey cast iron, nonferrous met-
the impact strength (unnotched) of 0.2 J/cm2 at als, glass, and ceramics. With great resistance to
20 ◦ C, is low compared to the notched impact temperature alternation and corrosion, SiC ther-
strength of 100 J/cm2 for structural steel. Thus mocouple protection tubes are used in contact
Al2 O3 is a brittle material. with liquid aluminum in aluminum holding fur-
Table 22. Properties of Al2 O3 ceramic and a hard metal
naces. Silicon carbide products are used for the
muffles of indirectly heated smelting furnaces
Property Al2 O3 WC Hard metal for zinc, aluminum, copper and their alloys, and
ceramic with 6 % Co
for tank linings. With good electrical conduc-
Density, g/cm3 3.9 14.9 tivity at high temperatures, coupled with resis-
Bending strength, MPa 300 1900 tance to oxidation, SiC heating elements are used
Compression strength, MPa 2500 5000
Breaking elongation in <0.1 ca. 0.5 in oxidizing atmospheres at temperatures up to
compression test, % 1500 ◦ C.
Modulus of elasticity, GPa 390 620
Vickers hardness 1750 1600
Thermal conductivity, 30 80 Silicon Nitride. The most remarkable prop-
W m−1 K−1 erties of silicon nitride include good resistance to
Coefficient of thermal expansion, 8 5
10−6 /K chemical attack by acids and molten nonferrous
metals, resistance to temperature fluctuation (co-
efficient of thermal expansion 3×10−6 K−1 ),
Alumina has very good corrosion resis- and heat resistance. The bending strength of
tance, withstanding acids, molten metals, many hot-pressed silicon nitride is about 700 MPa at
glasses, and slag. It has advantages over 20 ◦ C and still as high as 290 MPa at 1400 ◦ C.
metals particularly where corrosive and ther- At 1000 ◦ C dense silicon nitride still has a 100-
mal stresses are superimposed on mechanical h long-term creep resistance of 200 MPa. In the
stresses. case of the aluminum industry, materials are
One of the commonest applications of alu- needed that are not wetted by the molten metal,
mina ceramics is therefore the sealing of pas- have good resistance to temperature fluctua-
sages leading into vessels and spaces in which tion, and high strength at temperatures up to ca.
corrosive media are present. In the form of slide 800 ◦ C. As silicon nitride meets these require-
rings and mechanical seals alumina is superior to ments, it is used for, among other things, ther-
all other materials in resistance to corrosion and mocouple protection tubes and ascending pipes
wear. Its use is therefore leading to the replace- in low-pressure casting. The hardness of silicon
ment of conventional stuffing boxes on rotat- nitride gives it high wear resistance, which, to-
ing shafts by mechanical seals, especially where gether with the low friction coefficient (µ = 0.1 –
high rotation speeds occur. Aluminum oxide can 0.2), favors its use as a material for bearings and
be used in oxidizing and reducing atmospheres sliding contacts. Slide rings, roller bearings, and
tube drawing plugs are typical applications. Sil- 12. Merkblätter der Arbeitsgemeinschaft für
icon nitride is also used as a cutting material. Druckbehälter.
Ceramic materials are often used in the chem- 13. M. Litzkendorf: Über den Zusammenhang
ical industry in the form of thermally sprayed zwischen Korrosion und Festigkeitsverhalten
coatings that afford protection against wear and hochlegierter Chrom- und
corrosion. This field of application is described Chrom-Nickel-Stähle, Dissertation, TH
in → Corrosion). Darmstadt 1974.
14. K. Wellinger, H. Uetz: “Gleitverschleiß,
Spülverschleiß, Strahlverschleiß unter der
Mitwirkung von körnigen Stoffen,” VDI
6. References Forschungsh. 449 (1955) .
15. T. Günther Chem. Ing. Tech. 42 (1970)
1. E. Gaube et al.: “Werkstoffe für den 774 – 780.
Apparatebau in der chemischen Technik,” in: 16. DECHEMA: DECHEMA-Werkstoff-Tabelle,
Winnacker-Küchler, 4th ed., vol. 1, Frankfurt, published since 1953. D. Behrens
pp. 452 – 503 (ed.): DECHEMA Corrosion Handbook, VCH
2. H. Titze: Elemente des Apparatebaues, 2nd Verlagsgesellschaft, Weinheim , vol. 1 (1981)
ed., Springer Verlag, Berlin – Heidelberg – – vol. 6 (1990), to be continued.
New York 1967. 17. F. Ritter: Korrosionstabellen metallischer
3. K. Wellinger, F. Eichhorn, P. Gimmel: Werkstoffe, 4th ed., Springer Verlag, Wien
Schweißen, Kröner, Stuttgart 1964. 1958.
4. O. Becken: “Grundlagen und Anwendung,” in: 18. H. Gräfen, K. Steiger: “Zerstörungsfreie
Handbuch des Schutzgasschweißens, part I, Prüfungen bei Betrieb und Instandhaltung von
Deutscher Verlag für Schweißtechnik, Krefeld Chemieanlagen,” DECHEMA Monogr. 99
1969. (1985) 137 – 157.
5. J. Ruge: “Werkstoffe,” in: 2nd ed., vol. 1, 19. H. Adrian, F. Brühl: “Die Entwicklung der
Springer Verlag, Berlin – Heidelberg – New hochfesten schweißbaren Stähle für den
York 1980. Stahlbau und ihre Anwendung und
6. W. Schönherr: “Über die Eignung der Verarbeitung,” Stahl Eisen 86 (1966)
Werkstoffe zum Schweissen und thermischen 645 – 662, 670 – 672.
Trennen,” Schweissen Schneiden 23 (1971) 20. K. Schaar: “Hochfeste Stähle im
441 – 442. Druckbehälterbau,” Tech. Überwach. (Essen)
7. G. Habenicht: Kleben, Grundlagen, 7 (1966) 145 – 150.
Technologie, Anwendung, 2nd ed., Springer 21. K. H. Piehl: “Herstellung, Eigenschaften,
Verlag, Berlin – Heidelberg – New York – Verarbeitung und Anwendung von hochfesten
London – Paris – Tokyo – Hongkong – Feinkornbaustählen,” Rheinstahl-Tech. 7
Barcelona 1990. (1969) 71 – 83.
8. R. J. Schliekelmann, F. Mittrop: Metallkleben 22. F. Heisterkamp, L. Meyer: “Mechanische
– Konstruktion und Fertigung in der Praxis, Eigenschaften perlitarmer Baustähle,”
Deutscher Verlag für Schweißtechnik, Krefeld Thyssenforschung 3 (1971) 44 – 65.
1971. 23. F. Heisterkamp, D. Lauterborn, H. Hübner:
9. M. Pfender: “Über das Festigkeitsverhalten “Technologische Eigenschaften,
metallischer Werkstoffe und Verarbeitbarkeit und
Konstruktionsteile,” in: Das Gesicht des Anwendungsmöglichkeiten perlitarmer
Bruches metallischer Werkstoffe, vols. 1 and 2, Baustähle,” Thyssenforschung 3 (1971)
Allianz-Versicherungs-AG, München 1956. 66 – 76.
10. K. Wellinger, H. Dietmann: 24. E. Weber, W. Rudat: “Herstellung der
Festigkeitsberechnung, Kröner, Stuttgart 1969. Stahlrohre,” in: Rohrleitungen, Theorie und
11. D. Broek: Elementary Engineering Fracture Praxis, Springer Verlag, Berlin – Heidelberg –
Mechanics, Noordhoff International Publ., New York 1967.
Leyden 1974. H. Blumenauer, G. Pusch: 25. W. Dahl, H. Hengstenberg, H. Behrens:
Technische Bruchmechanik, VEB Deutscher “Sprödbruchverhalten unlegierter und
Verlag für Grundstoffindustrie, Leipzig 1982 niedriglegierter Baustähle im
(distributed by Springer, Vienna – New York). Kerbschlagbiege- und Zugversuch in
Abhängigkeit von Korngrößen, Temperatur,
Vorverfestigung und Alterung,” Stahl Eisen 40. H. Spähn: “Druckwasserstoffangriff auf

88 (1968) 578. unlegierter und niedriglegierter Stähle im
26. C. Straßburger: “Stahl – auch weiterhin ein Temperaturbereich oberhalb 200 ◦ C,” in D.
moderner Werkstoff,” Thyssen Tech. Ber. 13 Kuron (ed.): Wasserstoff und Korrosion,
(1987) no. 1, 89 – 102. Bonner Studien-Reihe, Verlag Irene Kuron,
27. E. Lenz, N. Wieling: “Einflußgrößen auf die Bonn 1986, pp. 155 – 201.
Riß-initiierung und auf das Rißwachstum in 41. H. H. Buchter: Apparate und Armaturen der
niedriglegierten Feinkornbaustählen in Chemischen Hochdrucktechnik, Springer
Hochtemperaturwasser,” Vorträge der Verlag, Berlin – Heidelberg – New York 1967.
20. Sitzung des Arbeitskreises Bruchvorgänge, 42. W. Wessling, F. Schmöning, H. E. Bock:
Frankfurt 1988, Deutscher Verband für “Aushärtbare nichtrostende Stähle,” Sie und
Materialforschung und -prüfung, Berlin 1988, wir, Company brochure, Stahlwerke
pp. 127 – 167. Südwestfalen, 1970, no. 6, pp. 41 – 59.
28. D. Uwer, H. Dißelmeyer: “Erfahrungen mit 43. H. Sigwart: “Werkstofftechnische Grundlagen
der Herstellung, Verarbeitung und Anwendung der Konstruktion,” in Dubbel: Taschenbuch für
des hochfesten wasservergüteten Baustahles den Maschinenbau, 13th ed., vol. 1, Springer,
XAB090,” Schweissen Schneiden 38 (1986) Berlin – Heidelberg – New York 1970.
no. 9, 430 – 436. 44. American Petroleum Institute, Refining
29. C. Florin et al.: “Über die Grundlagen der Department: Steels for Hydrogen Service at
Warmfestigkeit, dargestellt an legierten Elevated Temperatures and Pressures in
Stählen,” Arch. Eisenhüttenwes. 41 (1970) Petroleum Refineries and Petrochemical
777 – 787. Plants, API-Publication 941, 3rd ed., May
30. H. Wisniowski: “Hochwarmfeste 1983.
12 %-Chromstähle,” DEW Tech. Ber. 9 (1969) 45. Nichtrostende Stähle, 2nd ed., Verlag
117 – 134. Stahleisen, Düsseldorf 1989.
31. H. Wirtz: “Anwendung,” in: Verhalten der 46. H. Wehner, H. Speckhardt: “Zum
Stähle beim Schweißen, 2nd ed., vol. 2: Ausscheidungs- und Korrosionsverhalten eines
Deutscher Verlag für Schweißtechnik GmbH, ferritisch-austenitischen
Düsseldorf 1977. Chrom-Nickel-Molybdän-Stahles nach
32. K. Bungart: “Hochtemperaturwerkstoffe auf kurzzeitiger Glühbehandlung unter besonderer
Nickel- und Kobaltbasis,” DEW Tech. Ber. 9 Berücksichtigung des Schweißens,” Z.
(1969) 146 – 162. Werkstofftech. 10 (1979) 317 – 332.
33. H. Kiessler: “Normung hochwarmfester Stähle 47. W. Wessling, H. E. Bock, W. Fuchs: “Neuere
und Legierungen,” DEW Tech. Ber. 9 (1969) Entwicklungen von korrosionsbeständigen
110 – 117. Sonderstählen für das Chemiewesen,” Z.
34. Ergebnisse deutscher Zeitstandversuche, Werkstofftech. 4 (1973) 186 – 195.
Verlag Stahleisen mbH, Düsseldorf 1969. 48. E.-M. Horn, A. Kügler: “Entwicklung,
35. W. Ruttmann, H. Kaes: “Bedeutung der Eigenschaften, Verarbeitung und Einsatz des
Änderung der Langzeitwerte,” Mitt. Ver. hochsiliciumhaltigen Stahls X2CrNiSi1815,”
Großkesselbetr. 48 (1968) 1 – 9. Z. Werkstofftech. 8 (1977) 362 – 370.
36. K. Bungardt, H. Krainer, H. Schrader: 49. G. Hochörtler, E.-M. Horn: “Austenitic
“Nichtrostende, hitzebeständige sowie Stainless Steel With Approximately 5.3 %
hochwarmfeste Stähle und Legierungen,” Silicon,” Met. Corros. Proc. Int. Congr. Met.
Stahl Eisen 84 (1964) 1796 – 1811. Corros. 8th 2 (1981) 1471.
37. D. Schneider: “Schweißverbindungen an 50. R. Oppenheim, H. Kiesheyer, Thyssen
kaltzähen Stählen im Druckbehälterbau,” Tech. Edelstahl Tech. Ber. 8 (1982) 97 – 100,
Überwach. (Essen) 7 (1966) 317 – 321. 111 – 114.
38. K.-A. Ebert: “Betrachtungen zum 51. K. Fäßler, H. Spähn: “Werkstoffauswahl bei
Lichtbogenhandschweißen der kaltzähen wasserseitiger Beanspruchung,” in:
Stähle,” Schweissen Schneiden 18 (1966) “Wärmeaustauscher,” DECHEMA Monogr. 87
125 – 137. (1980) 51 – 72.
39. H. Jesper, K. Achtelik: Kaltzähe Stähle, 52. E.-M. Horn, D. Kuron, H. Gräfen:
publication no. 33, Nickel-Informationsbüros “Lochkorrosion an passiven
GmbH, Düsseldorf 1964. Legierungssystemen der Elemente Eisen,
Chrom und Nickel,” Z. Werkstofftech. 8 68. U. Heubner et al.: Nickel Alloys and
(1977) no. 2, 37 – 68. High-Alloy Special Stainless Steels, VDM,
53. E.-M. Horn, VDI Ber. 235 (1975) 39 – 45. Expert Verlag, Sindelfingen 1987.
54. K. Lorenz, G. Medawar, Thyssenforschung 1 69. G. R. Pease: Metallkundliche Vorgänge beim
(1969) no. 3, 97 – 108. Schwei-ßen von Nickel und Nickellegierungen,
55. R. W. Staehle, M. O. Speidel (eds.): Handbook publication no. 6, International Nickel
on Stress Corrosion Cracking and Corrosion Deutschland GmbH, Düsseldorf 1957.
Fatigue, ARPA (Advanced Research Projects 70. Nickel-Eigenschaften, Verarbeitung und
Agency), Washington 1978. Verwendung, publication no. 32, 1st ed.,
56. H. Spähn, Z. Phys. Chem. (Leipzig) 234 International Nickel Deutschland GmbH,
(1967) 1. Düsseldorf 1964.
57. M. A. Harzenmoser, P. J. Uggowitzer: “Neue 71. Beständigkeit von Nickel und
aufgestickte austenitisch-rostfreie Stähle und Nickellegierungen gegenüber Ätzalkalien,
Duplexstähle,” in: Moderne Stähle, vol. 1, publication no. 8, 3rd ed., International Nickel
Verlag der Schweizerischen Akademie der Deutschland GmbH, Düsseldorf 1963.
Werkstoffwissenschaften, Zürich 1987, 72. W. Z. Friend: Corrosion of Nickel and
pp. 205 – 218. Nickel-Base Alloys, J. Wiley and Sons, New
58. F. P. Pickering: “Physical Metallurgical York – Chichester – Brisbane – Toronto 1980.
Developments of Stainless Steels,” in: 73. Wiggin, Huntington: Korrosionsbeständige
Stainless Steels 84, The Institute of Metals, Legierungen, publication no. 3385, Nickel
London 1985. Alloys International S.A., Brüssel 1969.
59. G. Gümpel, T. Ladwein, E. Michel, F. H. 74. Schweißen von Nickel und seinen Legierungen,
Strom: “Entwicklungen bei austenitischen publication no. 9, 1st ed., International Nickel
Stählen mit erhöhten Festigkeitseigenschaften Deutschland GmbH, Düsseldorf 1967.
für den Einsatz im chemischen Apparatebau,” 75. Nickel-Kupfer-Legierungen, publication
Thyssen Edelstahl Tech. Ber. 14 (1988) no. 1, no. 20, 2nd ed., International Nickel
12 – 25. Deutschland GmbH, Düsseldorf 1966.
60. Gußeisen Handbuch, Gießerei-Verlag GmbH, 76. Korrosionsbeständigkeit nickelhaltiger
Düsseldorf 1963. Werkstoffe gegenüber Fluor, Fluorwasserstoff,
61. K. Röhrig, D. Wolters: “Gußeisen mit Flußsäure und anderen Fluorverbindungen,
Lamellengraphit und karbidischen Gußeisen,” publication no. 59, 1st ed. , International
in: Legiertes Gußeisen, vol. 1, Gießerei-Verlag Nickel Deutschland GmbH, Düsseldorf 1970.
GmbH, Düsseldorf 1970. 77. A. J. Sedricks: Corrosion of Stainless Steels,
62. Die Ni-Resist-Gußeisenwerkstoffe, publication J. Wiley and Sons, New York – Chichester –
no.16, 3rd ed., International Nickel Brisbane – Toronto 1979.
Deutschland GmbH, Düsseldorf 1968. 78. Chrom-Nickel-Legierungen gegen
63. O. Nickel: “Eigenschaften und Anwendungen
Brennstoffaschen-Korrosion, publication
austenitischer Gußeisenwerkstoffe in
no. 2942 D , International Nickel Deutschland
Erdölraffinerien und petrochemischen
GmbH, Düsseldorf 1965.
Werken,” Erdöl Kohle Erdgas Petrochem. 18
79. H. Gräfen, G. Böhm: “Die interkristalline
(1965) 121 – 127, 197 – 205.
Korrosion von Ni-Mo- und
64. H. Grundmann: Schweißen von
Ni-Mo-Cr-Legierungen,” Z. Metallkd. 51
Gußeisenwerkstoffen und Stahlguß, Deutscher
(1960) 245 – 252; Nickel-Ber. 19 (1961) 3 – 9.
Verlag für Schweißtechnik GmbH, Düsseldorf
80. H. Gräfen: “Eigenschaften von
1971.
Ni – Cr – Mo-Legierungen und ihre
65. U. Draugelates: “Konstruktionsschweißen von
Verbesserungsmöglichkeiten,” Chem. Ing.
Eisengußwerkstoffen mit Kugelgraphit,
Tech. 35 (1963) 229 – 235.
Leistungsstand und Verbindungsgüte,” VDI
81. R. Köcher: “Neue Werkstoffe für den
Ber. 469 (1982) 95 – 103.
Chemie-Apparatebau und ihre
66. K. E. Volk (ed.): Nickel und
schweißtechnische Verarbeitung,” VDI Z. 112
Nickellegierungen, Springer Verlag, Berlin –
(1970) 749 – 808.
Heidelberg – New York 1970.
67. W. Betteridge: Nickel and Its Alloys, 82. W. Schatt (ed.): Werkstoffe des Maschinen-,
MacDonald and Evans Ltd., Estover – Anlagen- und Apparatebaues, VEB-Verlag,
Plymouth 1977. Leipzig 1983.
83. Aluminium-Zentrale (ed.): 103. K. Rüdinger: “Moderne Werkstoffe, Auswahl

Aluminium-Taschenbuch, Aluminium-Verlag, – Prüfung – Anwendung, Übersichten über
Düsseldorf 1984. Sondergebiete der Werkstofftechnik für
84. W. Huppatz, in: H. Gräfen et al. (eds.): Die Studium und Praxis,” Z. Werkstofftech. 9
Praxis des Korrosionsschutzes, Expert Verlag, (1978) 181 – 188.
Grafenau 1981, pp. 64 – 81. 104. K. Rüdinger: “Technologische Eigenschaften
85. A. Oechslin: “Hartanodisieren von und Korrosionsverhalten einer Titanlegierung
Aluminiumlegierungen,” Schweiz. Alum. mit 0,2 % Palladium,” Werkst., Korros. 16
Rundsch. 19 (1969) 8. (1965) 109 – 115.
86. F. F. Berg: Korrosionsschaubilder, 105. H. Schussler: Corrosion Data Survey on
VDI-Verlag, Düsseldorf 1965. Tantalum, Fansteel Inc., North Chicago, Ill.,
87. W. Hornig, Diplomarbeit, Universität 1972, p. 104.
Erlangen-Nürnberg 1977. 106. H. Dickmann, E.-M. Horn, U. Gramberg:
88. H. Holten, H. Sigurdsson, Werkst. Korros. 28 Erfahrungen mit hochschmelzenden Metallen
(1977) 475 – 477. in der Chemietechnik, VDI-W Meeting, Köln,
89. E. Wendler-Kalsch, VDI-Ber. 365 (1980)
Dec. 6 – 7, 1984, pp. 87 – 95.
17 – 35.
107. D. R. Knittel, R. T. Webster: “Corrosion
90. Kupfer – Eigenschaften, Verarbeitung,
Resistance of Zirconium and Zirconium
Verwendung, Deutsches Kupfer-Institut e.V.,
Alloys in Inorganc Acids and Alkalis,” in:
Berlin 1961.
91. Kupfer und Kupferlegierungen in Industrie und E. W. Kleefisch (ed.): “Industrial Applications
Handwerk, Deutsches Kupfer-Institut, e.V., of Titanium and Zirconium,” ASTM Spec.
Berlin 1952. Tech. Publ. 728 (1981) 191 – 203.
92. O. v. Franqué, Sanit., Heiz., Klimatech. 1984, 108. R. D. Knittel: “Zirconium,” in: P. A.
nos. 1 + 2, 34 – 40, 94 – 97. Schweitzer (ed.): Corrosion and Corrosion
93. E. Wendler-Kalsch in: Korrosion in Kalt- und Protection Handbook, Marcel Dekker, New
Warmwassersystemen der Hausinstallation, York – Basel 1983, pp. 209 – 210.
DGM, Oberursel 1984, pp. 51 – 70. 109. T. Günther: “Zusammenhang zwischen Gefüge
94. E. E. Langenegger, F. P. A. Robinson: “The und Korrosionsverhalten bei Zirconium,”
Role of Arsenic in Preventing the Werkst. Korros. 30 (1979) publication no. 5,
Dezincification of α-Brass,” Corrosion 308 – 321.
(Houston) 25 (1969) 137 – 143. 110. R. Köcher: “Nichteisenmetalle im Apparate-
95. D. H. Thompson, A. W. Tracy, Metals Trans. und Anlagenbau,” Chem. Ing. Tech. 55 (1983)
1949, 100. A. W. Blackwood, N. S. Stoloff, no. 10, 752 – 762.
ASM Trans. Q. 62 (1969) 677. 111. U. Gramberg, E.-M. Horn, K.-O. Cavalar:
96. E. Wendler-Kalsch, Z. Werkstofftech. 13 “Explosionsplattierte Bleche in Anlagen,
(1982) 129 –137. Erfahrungen aus der Chemietechnik,” VDI-W
97. H. Vogel, Dissertation, Universität Meeting: Explosionsplattieren – ein modernes
Erlangen-Nürnberg 1985. Verfahren zur Herstellung von
98. H. Vogel, E. Wendler-Kalsch, Z. Metallkd., 75 Hochleistungsverbundsystemen, Düsseldorf,
(1984) 217 – 221. Dec. 1, 1983, pp. 29 – 35.
99. W. Hofmann: Lead and Lead Alloys, Springer 112. R. Köcher, Werkst. Korros. 28 (1977)
Verlag, Berlin – Heidelberg – New York 1970. 166 – 173.
100. W. W. Krysko: “Homogen verbleiter Stahl als 113. Kunststoff-Handbuch (12 vols.), Hanser,
Konstruktionswerkstoff,” Werkst., Korros. 15 München 1963 – 1975.
(1964) 631 – 633, 726 – 728, 991 – 995; 17 114. H. Domininghaus: Die Kunststoffe und ihre
(1966) 235 – 238. Eigenschaften, 3rd ed., VDI-Verlag,
101. H. Gräfen, D. Kuron: “Neuentwicklung von
Düsseldorf 1988.
Bleilegierungen aufgrund elektrochemischer
115. W. Nestler: “Kunststoffe im Apparatebau,”
Untersuchungen über das Korrosionsverhalten
Kunststoffe 60 (1970) 719 – 732.
in Schwefelsäure,” Werkst., Korros. 21 (1970)
116. Th. Hadick: “Die schweißtechnische Praxis,”
3 – 16.
in: Schweißen von Kunststoffen für Praktiker
102. M. Hörmann, D. Lupton, H. Heintze, E.-M.
und Konstrukteur, vol. 6, Deutscher Verlag für
Horn: “Sondermetalle und ihre Anwendung im
Schweiß-technik GmbH, Düsseldorf 1970.
Chemieapparatebau,” Z. Werkstofftech. 18
(1987) 139 – 147, 186 – 194.
117. R. Taprogge: Konstruieren mit Kunststoffen, 126. A. Peters: “Chemisches Verhalten und
VDI-Taschenbuch 21. VDI-Verlag, Düsseldorf physikalische Daten von Borosilikatglas,”
1971. Haus Tech. Vortragsveröff. 211 (1969) 6 – 10.
118. G. Ehrbar: “Kunststoffe im chemischen 127. F. Brandmair: “Zweckmäßige
Apparatebau,” Kunststoffe 53 (1963) Apparatekonstruktionen aus Kunstkohle und
845 – 854. Elektrographit und deren Einsatzgebiete,”
119. E. Dolfen: Bemessungsgrundlagen für Werkst. Korros. 17 (1966) 10 – 17.
tragende Bauelemente aus glasfaserverstärkten 128. H. Wurmseher: “Graphit im chemischen
Kunststoffen, insbesondere aus durch Apparatebau,” Tech. Mitt. 62 (1969)
Glasseidenmatten bewährten Polyesterharzen, 226 – 230.
Dissertation, TH Aachen, 1968. 129. F. Harders, S. Kienow: Feuerfestkunde,
120. F. Fischer: “Spannungsrißbildung und Springer Verlag, Berlin – Göttingen –
Spannungsrißkorrosion bei Kunststoffen,” Z. Heidelberg 1960.
Werkstofftech. 1 (1970) no. 2, 74 – 83. 130. K. Konopicky: Feuerfeste Baustoffe, Verlag
121. S. Boström: Kautschukhandbuch, vol. 5, Stahleisen, Düsseldorf 1957.
Verlag Berliner Union, Stuttgart 1962, 131. J. Agst: Die feuerfesten Baustoffe, 6th ed.,
pp. 340 – 369. Scimarowsky and Agst, Kapellen/Moers 1971.
122. R. Grünewald: “Konstruieren mit
132. F. K. Falcke: Kleines Handbuch des
glasfaserverstärkten Kunststoffen,”
Säureschutzbaues, Verlag Chemie, Weinheim
Kunststoffberat. Rundsch. Tech. 5 (1967)
1966.
356 – 361.
133. H. Lahnang, H. Scholze: “Keramische
123. H. Haferkamp: Glasfaserverstärkte
Werkstoffe,” in: Keramik, part 2: 6th ed.,
Kunststoffe, VDI-Taschenbuch 17.
Springer Verlag, Berlin – Heidelberg – New
VDI-Verlag, Düsseldorf 1970.
124. S. Lohmeyer et al.: “Kontakt und Studium,” in: York – Tokyo 1983.
Werkstoff Glas, vol. 22, Lexika-Verlag, 134. H.-J. Bargel et al. in H.-J. Bargel, G. Schulze
Grafenau/Württemberg 1979. (eds.): Werkstoffkunde, 5th ed., VDI-Verlag,
125. H. Scholze: Glas, 2nd ed., Springer Verlag, Düsseldorf 1988.
Berlin – Heidelberg – New York 1977.
Corrosion 653
Corrosion
Hubert Gräfen, Bayer AG, Leverkusen, Federal Republic of Germany
Elmar-Manfred Horn, Bayer AG, Leverkusen, Federal Republic of Germany
Hartmut Schlecker, Bayer AG, Leverkusen, Federal Republic of Germany
Helmut Schindler, Bayer AG, Leverkusen, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . 654 4. High-Temperature Corrosion . . . 695

2. Basic Electrochemistry . . . . . . . 654 4.1. Principles of High-Temperature
2.1. Electrochemical Equilibrium . . . 654 Corrosion . . . . . . . . . . . . . . . . 695
2.2. Electrochemical Kinetics . . . . . . 656 4.1.1. Thermodynamic Principles . . . . . 695
2.2.1. Corrosion Elements . . . . . . . . . . 657 4.1.2. Kinetics of Scaling . . . . . . . . . . 696
2.2.2. Mixed Electrode and Mixed Poten- 4.2. Oxidation of Alloys . . . . . . . . . 698
tial . . . . . . . . . . . . . . . . . . . . . 658 4.3. Sulfurization of Metals and Alloys 698
2.2.3. Overpotential and Polarization . . . 658 4.4. Corrosion by Combustion Gases . 699
2.3. Current Density – Potential 4.5. Effect of Ash, Deposits, and Salts 700
Curves . . . . . . . . . . . . . . . . . . 659
4.6. Corrosion by Synthesis Gases . . 701
2.4. Hydrogen Overpotential and Acid
4.7. Oxidation Behavior of Technical
Corrosion . . . . . . . . . . . . . . . . 662
Alloys . . . . . . . . . . . . . . . . . . 702
2.5. Oxygen Overpotential and Oxy-
gen Corrosion . . . . . . . . . . . . . 663 4.7.1. Steels . . . . . . . . . . . . . . . . . . . 702
2.6. Protective Film Formation and 4.7.2. Nickel Alloys . . . . . . . . . . . . . . 705
Passivity . . . . . . . . . . . . . . . . . 665 4.7.3. Cobalt Alloys . . . . . . . . . . . . . . 705
3. Types of Electrolytic Corrosion . 667 5. General Corrosion Protection
3.1. Uniform and Nonuniform Surface Procedures . . . . . . . . . . . . . . . 706
Corrosion . . . . . . . . . . . . . . . . 667 5.1. Corrosion Protection by Coating 706
3.2. Forms of Localized Corrosion 5.1.1. Metal Coatings . . . . . . . . . . . . . 706
without Applied Mechanical 5.1.2. Inorganic Nonmetallic Protective
Stress . . . . . . . . . . . . . . . . . . . 668 Coatings . . . . . . . . . . . . . . . . . 710
3.2.1. Pitting Corrosion . . . . . . . . . . . . 668 5.1.2.1. Enamel . . . . . . . . . . . . . . . . . . 711
3.2.2. Crevice Corrosion . . . . . . . . . . . 672 5.1.2.2. Brick Lining . . . . . . . . . . . . . . 713
3.2.3. Selective Corrosion . . . . . . . . . . 673 5.1.2.3. Thermally Sprayed Coatings . . . . 713
3.2.3.1. Intergranular Corrosion . . . . . . . . 674 5.1.3. Organic Lining and Coating Materi-
3.2.3.2. Spongiosis . . . . . . . . . . . . . . . . 677 als . . . . . . . . . . . . . . . . . . . . . 714
3.2.3.3. Dezincification . . . . . . . . . . . . . 678 5.1.3.1. Rubber Linings . . . . . . . . . . . . . 715
3.2.3.4. Line- and Layer-Type Corrosion . . 679 5.1.3.2. Rubber – Plastic Composite Linings 716
3.3. Forms of Local Corrosion under 5.1.3.3. Linings Consisting of Thermally
Mechanical Stress . . . . . . . . . . 681 Crosslinkable Thermosetting Plas-
3.3.1. Stress Corrosion Cracking . . . . . . 681 tics . . . . . . . . . . . . . . . . . . . . 717
3.3.1.1. Unalloyed and Low-Alloy Steels . . 682 5.1.3.4. Reinforced Reaction Resin Coat-
3.3.1.2. Stainless Steels . . . . . . . . . . . . . 684 ings, Crosslinkable with Catalysts . 717
3.3.1.3. Nonferrous Metals . . . . . . . . . . . 686
5.1.3.5. Thermoplastic Linings . . . . . . . . 718
3.3.1.4. Special Types of Stress Corrosion
5.1.3.6. Paints and Powder Coatings . . . . . 719
Cracking . . . . . . . . . . . . . . . . . 686
5.2. Inhibitors . . . . . . . . . . . . . . . . 720
3.3.1.5. Hydrogen-Induced Cracking at Low
Temperatures . . . . . . . . . . . . . . 688 6. Electrochemical Corrosion
3.3.1.6. Hydrogen Corrosion at Elevated Protection . . . . . . . . . . . . . . . . 721
Temperatures . . . . . . . . . . . . . . 690 7. Corrosion Testing . . . . . . . . . . 722
3.3.2. Corrosion Fatigue . . . . . . . . . . . 692 7.1. Introduction . . . . . . . . . . . . . . 722
3.3.3. Differentiation Between Types of 7.2. Test Methods . . . . . . . . . . . . . 724
Corrosion Cracking . . . . . . . . . . 694 8. References . . . . . . . . . . . . . . . 726
654 Corrosion
1. Introduction
When in use, all materials are exposed to envi-
ronmental effects that can impair or even destroy
their usefulness or that of components made out
of them. Most of the damage in the case of met-
als is caused by corrosion – reactions with the
environment which can lead to a measurable
change in the material (cf. DIN 50 900, Part
1 [2]). The reactions are mainly electrochemi-
cal, although they can also involve chemical or
metallo-physical processes.
Material changes due exclusively to mechan-
ical effects are attributable to wear rather than
to corrosion. However, a corrosive reaction with
Figure 1. Corrosion as a phase interface reaction
the environment can be brought about by erosion a) Metal; b) Solid, liquid, or gaseous medium; c) Phase
of protective coatings (erosive corrosion). boundary
The tendency of metals to change with loss of
energy into the disordered, more stable thermo-
dynamic state represented by compounds is the
reason for corrosion. However, kinetic barriers, 2. Basic Electrochemistry
mainly provided by the formation of protective
layers, often make metals resistant to corrosion If the corrosive medium is an electrolyte solu-
and allow them to be used in technological ap- tion, the resulting corrosion reactions are elec-
plications. trochemical. This means that material transport
The types of material changes brought about in the form of metal ions and charge exchange
by corrosion are manifold. A distinction is made in the form of electrons take place at the metal –
between uniform and nonuniform surface corro- solution phase boundary because of the conduc-
sion, pitting, selective corrosion, and cracking. tivity caused in the liquid phase by mobile anions
Of these, the local corrosion processes are par- and cations and the electron conductivity of the
ticularly critical. metals.
Since corrosion reactions generally occur on Aqueous corrosive media are electrolyte so-
the metal surface, they are termed interfacial lutions, and hence by far the greatest proportion
processes and can be represented by a phase di- of damage arising through corrosion is due to
agram. A distinction is made between the metal electrochemical processes. Since in metals these
phase, the liquid, gaseous, or solid medium, and are largely identical with electrolysis processes,
the phase boundary (Fig. 1). The corrosion pro- metal corrosion in aqueous media is best de-
cess takes place at the metal – medium phase scribed as electrolytic corrosion. The most im-
boundary and is therefore a heterogeneous reac- portant definitions are set out in DIN 50 900, Part
tion in which the structure and condition of the 2 [3].
reaction surface play a significant role. Essential
points, for example, are whether the surface is
uncoated, whether it is covered with an adhesive, 2.1. Electrochemical Equilibrium
compact or loose, porous coating, or whether its
properties have been changed by machining and When a piece of metal is dipped into water a
processing. Furthermore, the corrosive medium number of processes take place. Metal atoms
must be transported to the surface, and the cor- leave the solid phase and enter the liquid as
rosion products removed. Hence, material trans- cations. This disturbs the equilibrium in the
port phenomena, including free convection and metal phase; the metal now contains a surplus
diffusion into surface layers, must be taken into of electrons, thus becoming electrically nega-
account. tive, while a positively charged ion cloud forms
Corrosion 655
in the liquid. This cloud is held close to the metal at the metal surface until an electrochemical
surface by the attractive force of the electrons, equilibrium is reached between the electrons in
resulting in an electrical double layer in which the metal and in the solution.
an electrical field, directed from the ion cloud Gas electrodes are a further important type
to the metal surface, exists. The dissolution of of electrode in corrosion. These involve the for-
the metal is self-inhibitory because all departing mation, on the metal surface, of gases from dis-
metal ions must overcome this field. With in- solved ions, or of ions from dissolved gases. In
creasing concentration of the ion cloud, the exit this instance the metal has the function of con-
energy released is less and less capable of sup- suming or providing electrons. In pure form such
plying the energy needed to overcome the elec- processes occur on metals (e.g., platinum) which
trical field, which results in a dynamic equilib- themselves exhibit no reaction with electrolyte
rium: the rate of metal dissolution equals the rate solutions. Of greatest importance in corrosion
of metal deposition, with the exchange current processes are hydrogen and oxygen electrodes.
density i0 . The double layer results in a potential The reduction of hydrogen ions in acid solu-
difference between metal and solution (Fig. 2A). tions (2 H+ + 2 e− → H2 ) and the reduction of
dissolved oxygen in approximately neutral solu-
tions (O2 + 4 e− + 2 H2 O → 4 OH− ) are the most
important cathodic reactions.
Standard Potentials and Electrochemical

Series. The potential of the electrodes (half
cells) described above is measured by connect-
ing them by means of a solution bridge to a
second electrode, whose potential is used as a
reference. The potential difference between the
two half cells, with zero current flow, is then
measured. An electrode potential U measured
Figure 2. Formation of a potential difference between elec- in this way differs from the absolute potential
trode and electrolyte ∆ ϕ by an unknown constant which is dependent
A) µM + (metal) > µM z+ (solution); on the reference electrode. The potential differ-
z
B) µM z+ (metal) < µM z+ (solution) ence arising at the point of contact of the elec-
µ = Chemical potential trolyte solutions (diffusion potential) can largely
be eliminated by interposing concentrated salt
If ions of the metal are already present in the solutions with ions of identical mobility. The ad-
liquid when the metal electrode is immersed, far ditional potential changes caused by the instru-
fewer metal ions will go into solution. If the con- ment leads between electrode and instrument in
centration is higher than that of the equilibrium each of the two cells can be disregarded since
double layer, metal ions will deposit on the metal they are in opposing directions.
surface and return to the solid state, and the di- The hydrogen electrode in a given concentra-
rection of the potential difference at the phase tion (platinized platinum electrode immersed in
boundary is reversed (Fig. 2B). a solution with a H+ activity of 1 and purged with
A potential difference also forms with an H2 at 100 kPa) is generally used as the standard
electrode that is not attacked by the electrolyte electrode; its potential is arbitrarily set at zero.
solution (e.g., platinum): through electron loss The potentials of electrodes measured against
or gain, the dissolved substances are changed the standard hydrogen electrode are designated
into an oxidized or reduced form (redox couple). by the symbol U H . Figure 3 (see next page)
An example is the following redox system: shows the determination of the electrode poten-
tial of silver. The potentials of other metal elec-
Fe3+ + e− → Fe2+
trodes, relative to the standard hydrogen elec-
The immersed inert electrode acts as an electrode, in a solution of their own salts with metal-
tron donor or acceptor. Electrons are exchanged ion activity 1 are called standard potentials.
656 Corrosion
The change in equilibrium potential U 0H in

this instance depends on the activity quotient of
the oxidized and reduced species in solution. The
equation for a gas electrode, e.g., the hydrogen
electrode, is as follows:
0 RT RT
UH =UH + lnaH+ − lnpH2 (3)
zF zF
The deviations from U 0H are due to the activ-
ity of the hydrogen ions and the hydrogen partial
pressure. If both are unity, then U 0H = U H and the
conditions of the standard hydrogen electrode
prevail.
Figure 3. Determination of the electrode potential of silver 2.2. Electrochemical Kinetics

a) High-impedance voltmeter; b) Solution bridge
If two half cells with differing electrode poten-
The electrochemical series of metals is a list- tials are joined together, an electrochemical ele-
ing of the standard potentials U 0H of metals de- ment (voltaic cell) arises with a current flow from
termined at 25 ◦ C. Some of the most important the more negative to the more positive electrode,
standard potentials are listed in Table 1. caused by the potential difference between the
two electrodes (Fig. 4). Since the electrons re-
Table 1. Some important standard potentials
leased at the anode through metal dissolution
Electrode U 0H , V migrate to the cathode and are consumed there
(in this instance by metal deposition) the flow of
Mg/Mg2+ − 2.350
Al/Al3+ − 1.660
current continues as long as the reaction partners
Zn/Zn2+ − 0.762 remain available. The constant electrical field
Fe/Fe2+ − 0.440 arising at one electrode at equilibrium, described
Ni/Ni2+ − 0.236 in Section 2.1 (double layer), is not evident in
Sn/Sn2+ − 0.141
Pb/Pb2+ − 0.126 this case and, therefore, cannot slow down the
H2 /H+ 0.000 process. Accordingly, an electrochemical reac-
Cu/Cu2+ + 0.345 tion can only take place when the electrode po-
O2 /OH− + 0.402
Ag/Ag+ + 0.800
tential deviates from the equilibrium potential,
Hg/Hg2+ + 0.861 whereby the rate of dissolution of the metal or
Cl2 /Cl− + 1.359 reaction of the electrons is described by a current
Au/Au3+ + 1.500 intensity I, which is equivalent to the respective
mass conversion in accordance with Faraday’s
Equilibrium electrode potentials at other con- Law. For the dissolved metal mass ∆M and the
centrations are calculated from the Nernst equa- transported electric charge Q in A · s the follow-
tion: ing equation applies:
0 RT −∆M =Ar Q/z F (4)

UH =UH + ·lnaMz+ (1)
zF
where Ar is the relative atomic mass of the metal,
where R is the gas constant, z is the valency z is the ion valency, and F is the Faraday con-
of the metal ions, F is the Faraday constant, stant (96 520 A · s or 26.8 A · h). This constant
and aM z+ is the activity of potential-determining gives the amount of charge required for the dis-
metal ions in the solution. For a redox electrode solution of 1 mol of a metal. For example, 1 A · h
the equation is dissolves 1.04 g of pure iron. As a rule of thumb,
RT aox
the following applies for unalloyed steels:
0
UH =UH + ·ln (2)
zF ared 0.1mAcm−2 1gm−2 h−1
Corrosion 657
few lattice constants to macroscopic areas. Fig-

ure 5 shows a comparison between a galvanic
and a corrosion cell. The corrosion cell, like the
galvanic cell, can arise only when at least two
electrode processes take place, one providing the
electrons and the other consuming them. This
corresponds to the composition of a galvanic cell
consisting of at least two half cells.
Figure 4. Electrode cells

A) Daniell cell; B) Concentration cell
a) External resistance; b) Diaphragms; c) ZnSO4 solution;
d) CuSO4 solution; e) Dilute CuSO4 solution; f) Concen-
trated CuSO4 solution
In contrast to electrolysis with current supply, Figure 5. Comparison of a galvanic cell and a corrosion cell
in spontaneous corrosion with current yield, the A) Galvanic cell; B) Corrosion cell
dissolving electrode is known as the anode and a) Anode; b) Cathode
its counterpart, at which, for example, cations Anode process: M → M2+ + 2 e− (dissolution of metal)
are deposited, as the cathode. That is, the elec- Cathode process: 2 H+ +2 e− → H2 (evolution of hydro-
gen)
trode at which negative charges enter the elec-
trolyte solution is the cathode. Metal destruction (dissolution) takes place in
Voltaic cells can also be formed by combin- the material area with the more electronegative
ing metal – salt electrodes with metal – gas elec- potential (anode) since this is where the metal
trodes or metal – redox electrodes. The metal ions from the surface enter the solution. The
dissolution that occurs at the anode corresponds electrons released in the process migrate to the
to the partial process that leads to material electropositive cathode and are consumed there
destruction in electrochemical corrosion. This at the phase boundary by reducible substances
also occurs when the electrolytic solution ini- present in the solution (e.g., cations, dissolved
tially contains no metal ions, which is usually oxygen).
the case in corrosion processes, because only The anodic process (anode reaction) thus
one element is needed, which is formed by the consists of metal dissolution (oxidation)
coupling of an electron-delivering (anode) and
an electron-consuming (cathode) electrode. For M −→ M2+ + 2 e−
this to occur, the cathode potential must be the while the cathodic process (cathode reaction)
higher of the equilibrium potentials of the in- is a reduction:
dividual electrode reactions. Therefore, noble
metals such as gold do not corrode in aqueous a) 2 H+ + 2 e− −→ H2 hydrogen ion reduction
solutions because, with their high anodic po- b) O2 + 2 H2 O + 4 e− −→ 4 OH− oxygen reduction
tentials, more positive cathode reactions are no c) Cu2+ + 2 e− −→ Cu metal reduction
longer available.
d) Fe3+ + e− −→ Fe2+
In practice, the cathode reactions (a) and (b)

2.2.1. Corrosion Elements are particularly important because of their fre-
quency. In the corrosion of metals in acid solu-
A corroding metal – solution system forms an- tions, the reduction of hydrogen ions is the main
ode and cathode areas, whose sizes range from a reaction, whereas oxygen reduction is the main
658 Corrosion
reaction in the corrosion of metals in neutral, electrode process takes place is termed a work-
aerated electrolyte solutions (e.g., salt solutions, ing electrode and the resultant potential a work-
seawater, atmosphere). ing potential, then the difference between work-
ing potential and the Nernst equilibrium poten-
tial is called overpotential; it is caused by re-
2.2.2. Mixed Electrode and Mixed Potential action restraints. In general, polarization is de-
fined as the shift in potential of working elec-
A corroding metal surface represents a collec- trodes within a corrosion element. In such an
tion of corrosion elements, with the constancy, element, at least two electrode reactions occur,
the spread, and the attendant macroscopic in- whose overpotentials are superimposed, result-
terface of the anode and cathode surfaces de- ing in the polarization effect.
pending on the system. The distribution of local Transfer overpotential is the inhibition of
anodic and cathodic current densities ia and ic transfer of charge carriers (ions and electrons)
at the surface of an electrode can differ appre- as a result of the electrical field on the metal sur-
ciably. Possibilities are ia = ic , ia − ic =+ iE and face. The potential barrier between metal and
ia − ic =− iE . The current iE per unit area of the solution can only be overcome by ions of suf-
corrosion element can thus be zero, positive, or ficiently high energy, which requires a corre-
negative. Only in certain borderline cases are the sponding deviation from the equilibrium poten-
anode and cathode surfaces physically separated tial of the electrode reaction. In reversible elec-
from one another (local elements). The principle trochemical reactions, anodic current dominates
of additivity (a superimposition of all electrode for ∆U > 0, and cathodic current for ∆U < 0.
reactions taking place on a metal surface, see Near the equilibrium potential, the external cur-
Section 2.3), first formulated by Wagner and rent is the difference of the two partial current
Traud [4], makes these statements comprehen- densities:
sible. A multiple or mixed electrode of this kind
is homogeneous when iE is zero, and is heteroge- ∆U ·z F α+ ∆U ·z F α−
i=i0 exp −exp (5)
neous when, as a result of locally differing cur- RT RT
rent densities, it is nonzero. The mixed potential where i0 is the exchange current density at the
of a homogeneous mixed electrode is identical equilibrium potential of the reaction, and α is the
over the entire surface, whereas a heterogeneous charge transfer factor. For high overpotentials
mixed electrode exhibits different mixed poten- the second exponential expression is negligible
tials. and the equation simplifies to
Considering the corrosion system as a whole,
the sum of the cathode currents must equal the ∆U ·z F α
i=i0 exp ± (6)
sum of the anode currents for reasons of elec- RT
troneutrality. Thus the cathode and anode re- Taking logarithms and transforming gives the
actions affect one another reciprocally, and the Tafel equation,
slowest (most inhibited) determines the over-
∆U ·z F α 1
all reaction rate. In many cases the cathode re- logi=logi0 ± · (7)
RT 2.3
action is the slowest (cathode-controlled corro-
RT RT
sion). Lack of external current can only arise at ∆U = ± 2.3 logi0 ±2.3 logi (8)
zF α zF α
a given mixed potential, the free corrosion po-
tential. which in simplified form is written:
∆U =a+blogi (9)
2.2.3. Overpotential and Polarization For the anodic dissolution of metals the follow-
ing applies:
The corrosion behavior of metals cannot be pre-
dicted from the position of their standard poten- RT RT
a=−2.3 logi0 and b= 2.3
tials in the electrochemical series because the αz F αz F
potential of an electrode changes with the cur- Since a and b are constants, plotting the an-
rent density. If an electrode in which only one ode and cathode overpotential curves of a simple
Corrosion 659
electrode reaction in semi-logarithmic represen- the number of electrons n involved (change of

tation results in straight lines (Tafel lines) when valency). The concentration overpotential plays
the overpotential ∆U is plotted on the linear an important role where a reaction partner (e.g.,
and the current density i on the logarithmic axis oxygen) is consumed by corrosion. In this case
(Fig. 6). Individually, however, they cannot be the corrosion rate is determined by the rate of
directly measured; their superimposition gives transport (by convection and diffusion) of the
a sum curve, the actual overpotential curve, as oxygen required for the cathodic reaction. Since
shown by the dashed line in Figure 6. for each electrode reaction the supply of species
to, and removal from, the interface is essential,
any barrier to such diffusion processes leads to
a diffusion overpotential.
When one of the reaction steps at the metal
surface is a purely chemical reaction, any inhi-
bition of that reaction leads to a reaction overpo-
tential. It is conceivable, for example, that an ox-
idizing agent needed to sustain the cathodic re-
action is formed by a chemical reaction. If this is
the slowest individual process the reaction over-
potential will be determined by this reaction and
the transport of material to the electrode.
A further barrier to corrosion reactions is
Figure 6. Overpotential curve for a simple electrode reac- provided by electrical resistance. When the an-
tion odic and cathodic reactions at the metal surface
a) Overpotential curve for the anode reaction; b) Overpoten-
tial curve for the cathode reaction take place with locally different current densi-
U 0H = Equilibrium potential; i0 = Exchange current density ties (heterogeneous mixed electrode), resistance
in the current circuits can cause a measurable
The value of α generally lies between 0.45 drop in potential (resistance polarization). This
and 0.55; as an approximation a value of 0.5 can resistance polarization is a linear function of
be used. The constant b indicates the gradient of the current. Resistance polarization frequently
the straight lines. For z = 2, b is almost always arises through the formation of passive films.
0.05 – 0.06 V (for z = 1, b is 0.1 – 0.12 V). Since The resulting relationship between the change
in a number of electrode reactions the situation in potential and the current usually no longer
is complicated by the occurrence of multistep follows Ohm’s law, but instead is subject to a
reactions, the Tafel equation has only limited logarithmic relationship.
applicability.
In the dissolution and deposition of most met-
als, the activation energy is small and hence the 2.3. Current Density – Potential Curves
transfer overpotential is low. In transition metals
Theoretical predictions of the overpotential
such as iron and nickel it is much higher. Con-
( polarization) at a given current density are gen-
spicuously high overpotentials indicate elec-
erally not possible, and it is impossible to deter-
trode processes in which hydrogen and oxygen
mine the current densities to be expected during
are involved.
corrosion (a measure of the corrosion rate) from
The effect of concentration c, resulting from
the equilibrium potentials. The relationship bet-
the concentration changes at the electrode, leads
ween potential and current density can normally
to a concentration overpotential:
only be determined experimentally.
RT The results of such measurements are known
∆U =2.3 log c (10)
nF as current density – potential curves. They repre-
◦
At 18 C, 2.3 R T/F = 0.058 V. Consequently, sent cumulative curves given by the superimpo-
a concentration shift (more precisely a change sition of the current density – potential curves of
in activity) by a factor of 10 results in a po- the individual reactions. For simple electrodes
tential shift of 58, 29, or 19 mV, depending on with defined electrode processes, these are the
660 Corrosion
overpotential curves (see Fig. 6). For metals ex- Since only the cathode branch (hydrogen re-
posed to electrolytic attack, superimposition of duction) is of interest on the overpotential curve
several overpotential curves gives the actual cur- of the hydrogen electrode (right) and only the an-
rent density – potential curves that are of signif- ode branch (metal dissolution) on the iron elec-
icance in corrosion testing and research. Fig- trode (left), the curve can be simplified, as shown
ure 7 illustrates how two overpotential curves su- in Figure 8. Electrical resistance in the circuit of
perimpose to form a current density – potential a dissolving metal electrode always leads to re-
curve when both reactions take place at a metal duced metal dissolution.
surface. The potential is plotted on the abscissa
and the current density on the ordinate. This pre-
sentation corresponds to the normal practice of
measuring current density at a given potential.
Figure 7 shows the superposition of the overpo-
tential curves of a hydrogen and an iron elec-
trode. The metal surface on which the two reac-
tions occur appears to be without external cur-
rent, although current flows on the metal surface.
However, these are internal processes that have
no outward effect since the anodic current must
be the same as the cathodic current. In the ex-
ample given this means that the extent of metal
dissolution must be equal to the extent of hydro-
gen evolution. When there is no resistance in the Figure 8. Superposition of the anodic and cathodic partial
circuit, which can be assumed for electrolytes reactions to form a current density – potential curve (simpli-
with good conductivity, this condition is met fied version compared to Fig. 7)
– – – – = Partial current curves; —— = Cumulative current
at the common free corrosion potential (mixed curve; U corr = Corrosion potential
potential) U corr . The U corr is the intersection
of the measured cumulative current – potential Even though normal corrosion without exter-
curve with the abscissa and is also called the nal current is only shown by the point of in-
rest potential when the electrode reactions are tersection of the cumulative current density –
homogeneous. potential curve and the abscissa (U corr ), the an-
ode and cathode branches, i.e., the full course of
the curve measurable with external current sup-
ply, are still of interest since they reflect all the
peculiarities of the polarization curves involved.
From such diagrams, therefore, conclusions can
often be drawn as to the corrosion performance
of metals under given environmental conditions.
The procedure for determining a current den-
sity – potential curve is to immerse the metal
electrode in the corrosive medium. After an in-
cubation period, the mixed potential correspond-
ing to the outwardly currentless state becomes
established on the metal. If a circuit is now
placed on the electrode and external current is
applied, the result is a shift in potential (polar-
Figure 7. Superposition of two overpotential curves to form ization). Current density – potential curves are
a current density – potential curve
U a = Equilibrium potential of the overpotential curve for the
therefore also known as polarization curves. De-
anode reaction; U c = Equilibrium potential of the overpoten- pending on the direction of the external current
tial curve for the cathode reaction; U corr = Corrosion poten- imposed, this is termed anodic or cathodic po-
tial (rest potential) larization (anodic: potential becomes positive;
cathodic: potential becomes negative).
Corrosion 661
Determination of Corrosion Current Den- where icorr = corrosion current density in

sity. Simple, purely transfer-related electrode A/cm2 ; ba , bc = constants (gradients of the Tafel
reactions give cumulative current density – lines); and (di/dU)i=0 = gradient of the current
potential curves of the type shown by the un- density – potential curve at the rest potential in
broken line in Figure 9. At the points p1 and A cm−2 V−1 .
p2 it swings into the overpotential curves of the This procedure is useful when quantitative
respective part reactions, because beyond these determination based on Tafel lines is no longer
points, only the anodic or the cathodic reaction possible; for example, when the corrosion prod-
exists. At these points the equilibrium potentials ucts form deposits. The polarization resistance
of the reverse reaction are exceeded and super- is measured at the rest potential (free corrosion
imposition no longer occurs. These pure overpo- potential) within a range of ≤ 20 mV. The con-
tential curves thus form linear Tafel lines, which, stant B is often ca. 20 mV and can be determined
after reflection of the cathode curve in the x-axis, for exact measurements.
can be made to intersect by extrapolation in the An example of determining the corrosion rate
direction of the abscissa. The ordinate section at by this method is shown in Figure 10 [6]. How-
the point of intersection is then log icorr , i.e., the ever, for very small corrosion currents that are
log of the corrosion current density at the free independent of potential in some ranges (e.g., in
corrosion potential (rest potential), from which passive metals), this method cannot be used to
the corrosion rate can be calculated by Faraday’s determine the corrosion rate. Nor is the method
law (see Section 2.2). applicable when non-transfer-related part reac-
tions occur, e.g., when the corrosion current is
dependent on diffusion processes at the speci-
men surface. Also, the constant B can be time-
dependent when dense protective films form,
which further restricts the applicability of the
method [7].
Figure 9. Determination of the corrosion current density

icorr
a) Overpotential curve for the cathode reaction; b) Overpo-
tential curve for the anode reaction; c) Reflection of curve
a Figure 10. Determination of the corrosion rate icorr from
polarization resistances
The simple correlation between polarization ∆i[A/cm2 ]
icorr = 0.02V· ∆U [V]
resistance and corrosion rate at the free corro-
a) t = 80 ◦ C, icorr = 0.48 mA/cm2 ; b) t = 60 ◦ C,
sion potential developed by Wagner and Traud icorr = 0.09 mA/cm2 ; c) t = 40 ◦ C, icorr = 0.023 mA/cm2
[4], was later extended by Stern and Geary
for practical application [5]. By this method the For local corrosion phenomena, determina-
corrosion rate is estimated from the gradient of tion of the corrosion rate is of secondary im-
the current density – potential curve (polariza- portance. In fact, in processes limited to specific
tion resistance): potential ranges, the threshold potential (i.e., the
potential above which local corrosion begins),
1 di di which depends on both the corrosive medium
icorr = =B (11)
2.3 1
+ b1 dU i=0 dU i=0 and the alloy composition, is more important.
ba c
662 Corrosion
2.4. Hydrogen Overpotential and Acid or an electrochemical reaction takes place

Corrosion between an adsorbed hydrogen atom, a hydro-
nium ion, and an electron (Heyrovský reaction):
The cathodic reduction of hydrogen ions −
Had + (H+
aq )metalsurface + e −→ (H2 )ad
2 H+ + 2 e− H2 Thus there are two possibilities for the for-

takes place in a number of complex steps. Un- mation of adsorbed molecular hydrogen: two
der certain conditions, acid corrosion can induce Volmer reactions and one Tafel reaction, or one
hydrogen embrittlement when special effects Volmer reaction and one Heyrovský reaction
influence the kinetics of hydrogen reduction, (Fig. 11).
which takes place up to the stage of molecular
hydrogen formation (recombination). In many
metals, considerable overpotential is needed to
initiate hydrogen evolution. Furthermore, the ac-
tivity of metal surfaces can be impaired by con-
tamination with impurities. This principle is ap-
plied in deliberate inhibition (e.g., use of pick-
ling inhibitors, see Section 5.2). A slower re-
combination rate generally leads to a higher con-
centration of adsorbed hydrogen at the surface,
which in turn can result in increased diffusion of
atomic hydrogen into the metal. This may even-
tually lead to embrittlement in various metals
and alloys.
In aqueous solution, the hydrogen ion from
the dissociation of water (H2 O H+ + OH− ) or
acids (e.g., HCl H+ + Cl− ) is hydrated, form-
ing a hydronium ion:
H+ + H2 O −→ H3 O+
The hydronium ion (H+ aq ) must first diffuse

through the liquid to the metal surface
H+ +
aq −→ (Haq )metalsurface
Figure 11. Reaction schematic of cathodic hydrogen forma-
For discharge of the hydronium ion to oc- tion
A) By the Volmer – Tafel mechanism; B) By the Volmer –
cur, an electron must pass through the metal – Heyrovský mechanism (after Kaesche, see general refer-
electrolyte phase boundary; the discharge reac- ences)
tion (Volmer reaction) is therefore known as a Hatched area = Metal; shaded area = Boundary layer solu-
transfer reaction: tion
(H+ +
aq )MS = Hydronium ion H3 O on metal surface
(H+ −
aq )metalsurface + e −→ Had The formation of adsorbed molecular hydro-
Initially, the hydrogen remains adsorbed in gen is followed by the transition of H2 molecules
atomic form on the metal surface. For the forma- into the gaseous phase:
tion of molecular hydrogen, there are two pos- (H2 )ad −→ H2
sibilities: either two adsorbed hydrogen atoms
combine chemically to form an adsorbed hydro- This reaction sometimes consists of several
gen molecule (Tafel reaction): distinguishable individual steps. It is occasion-
ally observed with metals which dissolve in acid,
Had + Had = (H2 )ad for example, that the hydrogen bubbles always
Corrosion 663
occur at a few spots where bubble formation is Interpretation of the equation for pO2 = 100 kPa
presumably energetically favorable. In this case, is shown in Figure 12, in which, for compar-
the reaction consists of diffusion to those spots ison, the equilibrium potential of the hydro-
with subsequent desorption. For very slow hy- gen electrode for pH2 = 100 kPa is also given.
drogen evolution, bubble formation is unneces- It can be seen that the potential lines run par-
sary because the hydrogen molecules can dis- allel, and that at all pH values the equilibrium
solve rapidly enough in the aqueous phase, dif- potential of the oxygen electrode is more than
fuse through it to the liquid surface, and be des- 1.2 V higher than that of the hydrogen electrode.
orbed into the ambient gaseous phase. The tran- This explains why the presence of oxygen of-
sition of atomic hydrogen into the metallic phase ten promotes electrochemical corrosion. Quite
is discussed in Section 3.3.1.5. apart from the fact that a higher cathode poten-
The considerable overpotential for hydrogen tial normally increases the potential difference
evolution observed in many metals (in Hg and and hence the current density in local elements,
Pb, > 0.5 V) is due to inhibition in one of the anodic destruction processes are now possible
part reactions. The slowest partial process deter- at potentials that are above that of the hydrogen
mines the rate of the overall reaction. There is cathode and which cannot occur in the absence
practically no inhibition in platinum, which pos- of oxygen. An example is the behavior of copper,
sesses the lowest hydrogen overpotential. Other which is only attacked by electrolytes when oxy-
“active” metals are palladium, strontium, and gen is present. On a bare copper surface, the loss
rhodium. of metal is directly proportional to the quantity
of cathode-converted oxygen. In practice, how-
ever, there is usually fairly rapid formation of
2.5. Oxygen Overpotential and Oxygen oxidic protective films (consisting at room tem-
Corrosion perature mostly of Cu2 O and at higher temper-
atures mainly of CuO), which restrict corrosion
Acid corrosion arises only rarely in pure form to a harmless extent. Only when the formation
because it requires the corrosive solution to be of these films is inhibited can the oxygen corro-
completely free of air. However, this is not usu- sion of copper progress linearly as a function of
ally the case, and in acid solutions an additional time.
electrode process often occurs: LIVE GRAPH
Click here to view
O2 + 4 e− + 2 H2 O 4 OH−
An important feature of a corrosion process

is the reduction of the dissolved oxygen by for-
mation of hydroxyl ions (OH− ). Since the equi-
librium potential is linked through the concen-
tration of the OH− ions with the concentration
of the hydrogen ions (or H3 O+ ions) by the ionic
product of water
(aH+ ) · (aOH− ) =Kw = 10−14 (at25◦ C) ,
the equilibrium potential is pH dependent. The

standard potential is ca. 0.4 V at 25 ◦ C, a par-
tial pressure of 100 kPa, and an OH− ion activ-
ity of 1 ( pH 14). Equilibrium potentials under
other conditions can be calculated by the Nernst Figure 12. Equilibrium potentials for the oxygen and hydro-
equation: gen electrodes
RT RT The working potential of the oxygen elec-

0
UH =UH − lnaOH− + lnpO2 (12) trode generally differs greatly from its equilib-
F 4F
rium potential. This leads to a considerable over-
664 Corrosion
potential, which in most cases is a concentration in this instance does not have the importance
tion overpotential. Oxygen is consumed at the often attached to it in practice.
cathode, leading to depletion of oxygen in the
cathode boundary layer. If the cathodic process
is to continue, additional oxygen must be sup-
plied from the electrolyte. The amount of oxy-
gen converted electrochemically – and, there-
fore, the corrosion rate – depends on the rate of
subsequent oxygen supply, which is diffusion
controlled and is determined by:
1) The diffusion coefficient, which increases
with increasing temperature:
2) The difference between the oxygen concen-
Figure 13. Current – potential curve for oxygen corrosion
tration at the metal surface and in the corro- —— Partial current curve; – – – Current – potential curve at
sive medium, which increases with increas- oxygen concentration 2; ––– Oxygen concentration 1; –
ing oxygen content of the solution: ×–×– Oxygen concentration 2
3) The thickness of the boundary layer, which a) 2 H+ + 2 e− → H2 ;
b) O2 + 2 H2 O + 4 e− → 4 OH− ;
depends on whether the flow is laminar or c) M → M2+ + 2 e−
turbulent, with smaller thicknesses being as-
sociated with higher flow rates.
The following equation shows that areas in
The quantity of oxygen diffusing to the cath- which a mainly cathodic electrode process pre-
ode per unit time and area is directly propor- vails tend to alkalize through the accumulation
tional to the diffusion coefficient and the dif- of hydroxyl ions:
ference in oxygen concentration, and inversely
proportional to the thickness of the boundary O2 + 4 e− + 2 H2 O −→ 4 OH−
layer. Therefore, an increase in temperature and
a higher concentration of oxygen in the elec- If phenolphthalein is used as an indicator
trolyte increase the corrosion current density, for hydroxyl ions and potassium hexacyanofer-
whereas an increase in the boundary layer thick- rate(III) as an indicator for iron(II) ions, the an-
ness reduces the current density. ode and cathode areas can be made visible in the
The occurrence of a concentration overpoten- case of corroding iron. If, for example, an iron
tial in oxygen corrosion is clearly shown by the nail is placed in a gelatine solution mixed with
cathodic overpotential curve. As demonstrated these two indicators, after a while the head and
in Figure 13, a diffusion-limited current density point of the nail start to turn blue because of the
appears on the curve, which is indicated by the formation of Prussian blue, whereas the middle
parallelism of the cathodic current curve and the of the nail turns red. This experiment shows that
potential axis (diffusion current density). In this it is mainly the anodic process that takes place
region the current density can only be further in- at the mechanically worked points, whereas the
creased if the concentration of available oxygen cathodic process with the formation of hydroxyl
is increased. The figure also shows the behavior ions occurs in the middle of the nail.
of copper towards corrosive solutions containing This separation of the two distinct processes
oxygen. in oxygen corrosion can also be observed when
If the corrosion potentials in metals (mixed a ring of rust forms under a saltwater droplet
potentials) are within the range of the diffusion- on an iron surface some distance from the outer
limited current, the corrosion current density is edge of the droplet and not at the point of min-
independent of the potential. This leads to the imum oxygen supply. The dissolved iron ions
conclusion that normally the rate of oxygen cor- then combine as they diffuse with hydroxyl ions
rosion is determined solely by oxygen diffusion to form sparingly soluble iron hydroxide, which
to the cathode and that other factors are only of turns to rust on absorption of oxygen, and de-
minor influence. In particular, the pH of the solu- posits (Fig. 14).
Corrosion 665
proven since element formation does not occur

in sufficiently buffered solutions.
2.6. Protective Film Formation and

Passivity
The corrosion reactions described above require

an active, i.e., mainly bare, metal surface. In
Figure 14. Mechanism of corrosion under a saltwater droplet practice, however, many metals tend to form pro-
a) Air; b) Drop of salt solution; c) Rust ring; d) Iron; e) Ca- tective films which can have a major influence
thodic oxygen reduction 1/2 O2 + H2 O + 2 e− → 2 OH− ; on the electrolytic process. Dense films provide
f) Anodic metal dissolution Fe → Fe2+ + 2 e−
protection and are thus referred to as protective
The process can be written as follows: coatings or films. A protective iron oxide film is
known to form, for example, in boiler pipes. In
Fe → Fe2+ + 2 e− contrast, porous rust layers provide no protec-
2 Fe2+ + O −→ 2 Fe3+ + O2− tion. The good resistance of aluminum, which is
O + 2 e− −→ O2−
the result of an Al2 O3 film forming in air, can
also be produced artificially by anodic oxidation.
O2− + H2 O −→ 2 OH−
In addition to these marcroscopic protective
Fe2+ + 2 OH− −→ Fe(OH)2 films, a number of metals possess optically in-
2 Fe(OH)2 + O + H2 O −→ 2 Fe(OH)3 visible, pore-free oxide films with particularly
Fe(OH)3 −→ FeO(OH) + H2 O good protective action; this gives rise to the pas-
sivity of metals. The occurrence of passivity can
Using a simple test arrangement, Evans best be observed electrochemically. Figure 16
showed that different metal surface aeration in (see next page) shows an anodic metal dissolu-
oxygen corrosion results in the formation of lo- tion curve with the typical drop in current at the
cal elements (aeration elements) [8]. An im- onset of passivity. The metal initially dissolves
proved model experiment is illustrated in Fig- actively in the solution. With increasing poten-
ure 15. tial the dissolution current rises until a potential
(passivation potential, often called Flade poten-
tial U Fl ) is reached at which there is a sudden
sharp drop in metal dissolution. The very low
metal dissolution remains practically constant
over a relatively large potential range, the pas-
sive range, before rising again at the beginning
of the so-called transpassive range. To achieve
the passive state, the redox system (as Fig. 16
shows) must provide a cathodic current that is
Figure 15. Basic circuit diagram of an aeration cell at least as large as the anodic current needed to
a) Millivoltmeter; b) Input with inner conductor and screen; form the passive film at the passivation potential.
c) Short circuit resistance
A pore-free oxide film of ca. 10 nm thickness
Although the nitrogen-purged iron electrode then forms at the electrode surface, suppressing
(anode) is corroded, no corrosion is found on the previous intense metal dissolution.
the oxygen-purged iron electrode (cathode). The The minimal residual anodic current at the
actual effect consists of inhibition of the anodic electrode in the passive range is caused by the
process through the formation of OH− ions at slow dissolution and constant reformation of the
the O2 electrode. Consequently, the term aera- passive film. The passivation potential and the
tion element is somewhat misleading, in that the dissolution in the passive range differ for each
element formation in this corrosion process is metal or alloy. Of economic significance are
the result of a change in pH. This can be readily metals with a moderate passivation potential and
666 Corrosion
LIVE GRAPH
Click here to view
minimum dissolution in the passive state. Fig-
ure 17 shows current – potential curves of iron
and chromium in sulfuric acid. The passivation
of chromium begins more than 500 mV before
that of iron and requires a considerably lower
current density. The good passivation capability
of chromium can be imparted to iron by alloy-
ing with > 12 wt % chromium. This forms the
basis for the development of all stainless and
acid-resistant steels. Further improvements can
be obtained by adding nickel, molybdenum, and
copper to these alloys. Figure 17. Passive behavior of chromium and iron in sulfuric
acid
because the passive film exhibits local defects

as a result of external influences (special corro-
sive media) or structure-related effects (deposits,
grain boundary disturbances, segregation, etc.).
This leads to localized corrosion processes, in-
cluding selective corrosion, intergranular corro-
sion, and pitting corrosion. Under the influence
of static mechanical tensile stress, various types
of stress corrosion cracking can arise, while al-
ternating mechanical stress leads to corrosion
fatigue, which occurs in both fully active and
Figure 16. Current – potential curve for metal dissolution
with drop in current due to passivation
passive alloy systems.
a) Redox system 1: conservation of passivity; b) Redox sys- Figure 18 shows schematically the different
tem 2: generation of passivity types of corrosion together with the possible
U p = Rest potential in the passive state; U Fl = Flade poten- combinations which can arise in practice. Cor-
tial
rosion fatigue is not considered here because
Under certain circumstances the passiva- mechanistically it is not confined to passive
tion capacity of various alloys results in spe- alloys. It is therefore treated separately (Sec-
cial corrosion phenomena. These arise mainly tion 3.3.2).
Figure 18. Types of corrosion

Corrosion 667
3. Types of Electrolytic Corrosion mass loss over the entire surface (homoge-
neous mixed electrode), and nonuniform corro-
The surface of a material or component is sub- sion (shallow pit formation) as corrosion with lo-
ject to various environmental influences when cally different mass losses. The cause of nonuni-
in use. The mechanical, thermal, and chemical form corrosion is the presence of corrosion ele-
(corrosive) parameters may act individually, or ments (heterogeneous mixed electrode) [3]. The
two or even three factors can combine, the sig- common feature of both types of corrosion is
nificance of each differing according to the type the geometry of the damaged area. The surface
of stress. The corrosive factor, as shown in Fig- spread of these areas is generally greater than
ure 19, can be divided into chemical and elec- the depth. Accordingly, compared with localized
trochemical components. Electrochemical cor- types of corrosion such as pitting, these types of
rosion can take place with or without mechan- corrosion are limited in extent.
ical stress. The types of electrochemical corro- Uniform corrosion is without doubt the eas-
sion that occur are also shown in Figure 19 and iest form of corrosion to recognize and to con-
are discussed in more detail in the following sec- trol. In the ideal case, material loss runs parallel
tions. to the surface of the corroded component, the
reduction in wall thickness being given by:
3.1. Uniform and Nonuniform Surface ∆Mtot /·A

Corrosion where ∆M tot = total mass of the dissolved
metal, A = area of corroded surface, and
DIN 50 900, Part 1 [2] defines uniform surface = density of the metal. In terms of the corro-
corrosion as corrosion with practically equal sion current densities, this implies the equality
Figure 19. Overview of damage to metallic materials under operating conditions

668 Corrosion
of the real local corrosion current density I R and testing or by suspending a specimen of the ma-
the mean corrosion current density iR , (I R = iR ), terial in the corrosive agent and monitoring the
where the following relationship exists [9]: corrosion [11]. Suitable measures to combat uni-
form corrosion include greater wall thicknesses,
1
iR = IR ·dA a more resistant material, and cladding or pro-
A
tective coatings.
A practical example of almost uniform sur- In the case of nonuniform corrosion (shallow
face corrosion is as follows [10]: a pipe made of pit formation), the real corrosion current density
unalloyed steel St 35 (material no. 1.0308) used I R and mean corrosion current density iR are
at ca. 90 ◦ C for the transport of service water not equal. Accordingly, nonuniform corrosion
showed material erosion of the inner surface af- is characterized by a locally differing corrosion
ter three years in operation; a layer of corrosion rate. The conditions for this may occur, for ex-
product (mainly iron oxide) had formed on the ample, during the course of corrosion through a
inside with a practically constant thickness over nonhomogeneous covering of the reaction prod-
the entire area. Given the operating conditions, uct on the material.
the material corrosion had to be due to oxygen
corrosion.
A further example is illustrated in Figure 20. 3.2. Forms of Localized Corrosion
A thermometer protection tube made of the without Applied Mechanical Stress
highly corrosion resistant nickel alloy NiMo 30
(material no. 2.4810) was immersed at ca. 20 ◦ C This general term covers pitting corrosion,
in an aqueous, acidic chloride solution to which crevice corrosion, and selective corrosion, in-
sodium nitrite was added, releasing nitrogen ox- cluding the subgroups of intergranular corro-
ides. The protection tube, consisting of a larger- sion, spongiosis, dezincification, and line- and
diameter tube and a smaller-diameter tube exten- layer-type corrosion.
sion welded together, suffered severe corrosion
with the exception of the weld joint. A chro-
mium-containing filler metal of the type nickel 3.2.1. Pitting Corrosion
alloy NiMo 16 Cr (material no. 2.4812) had been In DIN 50 900, Part 1 [2], pitting in the broad-
used. The uniform surface corrosion of the chro- est sense is defined as the form of corrosion
mium-free alloy without passivation capability in which craterlike, surface-hollowing, or pin-
NiMo 30 is due to the presence of oxidants. Un- pricklike cavities occur (see Fig. 21). Outside the
der these conditions, the weld containing chro- pitted areas practically no surface corrosion is
mium is considerably more resistant. observed. The depth of the pitted area is gener-
ally equal to or greater than its diameter. Pitting
always arises when the material surface is co-
vered with a corrosion-resistant coating that has
pores or defects, the latter being there initially
or arising through a local reaction with the cor-
rosive medium. The following are regarded as
being protective layers:
1) A natural oxide scale or rolling scale in un-
alloyed or low-alloy steels;
2) Protective films (e.g., paint, bitumen coat-
Figure 20. Uniform corrosion of a thermometer protection ings, or oil films);
tube made of NiMo 30 (material no. 2.4810)
Welding filler: NiMo 16 Cr (material no. 2.4812)
3) Metallic coatings (e.g., zinc);
4) Salt layers formed under operating condi-
In practice, uniform surface corrosion is easy tions, such as the lead sulfate layers that form
to control in the majority of cases, especially on lead in sulfuric acid, or the copper(I) ox-
because the reduction in wall thickness during ide or malachite layer formed on copper in
operation can be monitored by nondestructive drinking water;
Corrosion 669
5) A film produced by the adsorption of in- solution containing oxygen, an electric current
hibitors (e.g., chromates); flows between the oxide film (the cathode) and
6) The passive film, usually consisting of only the bare metal (the anode). At the anode, iron
few molecular layers, such as found in iron, dissolves as iron(II) ions, whereas at the cath-
nickel, chromium, and iron- and nickel-based ode oxygen is reduced:
alloys with passivation capacity.
1/2 O2 + H2 O + 2 e− −→ 2 OH−
This oxygen reduction, which determines the

flow of current and hence the corrosion of the
iron at the uncoated spot, continues as long as
oxygen can diffuse unhindered to the cathode
(see Section 2.5). This local dissolution process
can even perforate sheet and piping. This kind
of corrosion can be avoided by completely re-
Figure 21. Shapes of pits in pitting corrosion moving the rolling scale.
Similarly, corrosion processes take place at
For pitting to occur in metals coated with pro- pores and defects in electrically conducting coat-
tective layers as in (1) to (3), there must be de- ings that are more noble than the base material.
fects in the protective coating and an electrolyte In paints, the propagation rate of cavities de-
solution acting as a corrosive medium. The re- pends on the possibility of substance transport
sulting corrosion element consists of the cath- through the coating.
ode (intact coating) and the anode (pores in the
coating). The attack on the base material in the Pitting Corrosion in Stainless Steels. The
region of the pores acts downwards. Depth pro- conditions that lead to chloride-induced pitting
gression depends on the size and activity of the corrosion in stainless steels in chemical plants
cathode surface. Pitting in cases (4) and (5) in are well-known and have been extensively ex-
corrosive media is due to an incomplete protec- amined for this group of materials [12].
tive layer on the material surface. The intensity Corrosion Parameters. Figure 22 (see next
of corrosion depends on the area ratio between page) shows the current density – potential curve
anode (uncoated surface) and cathode (coated of a material with passivation capacity in an ini-
surface). tially chloride-free corrosive medium. Starting
Pitting on materials with a passive coating, from the free corrosion potential U corr , the steel
such as unalloyed or low-alloy steels, stainless passes, with increasing anode polarization after
and acid-resistant ferritic chromium steels, and exceeding the passivation potential, through the
stainless and acid-resistant austenitic chromi- passive range and reaches the breakthrough po-
um – nickel steels, is caused by electrolytes that tential at U b . While in the active range, the alloy-
contain chloride, bromide, and, in some cases, ing elements go into solution in their lowest va-
iodide ions. Since chloride ions in particular are lencies, during corrosion above U b , iron(III) and
responsible for this kind of corrosion, it is of- chromium(VI) compounds are formed. If chlo-
ten called chloride corrosion. Halide ions (ex- rides are now added to the corrosive medium,
cluding fluoride, which does not cause pitting) an increase in current is observed at U p , this be-
are adsorbed at discrete locations of the passive ing due to pitting corrosion. Chlorides (and also
coating (formation of cavity nuclei). After an in- bromides and iodides) thus decrease the passive
duction period the passive coating is penetrated range of the material.
and pitting corrosion initiated. The pitting potential shifts to more negative
An example of localized corrosion in the form values with increasing chloride ion concentra-
of pits in natural protective coatings is the corro- tion, rising temperature, and decreasing pH; i.e.,
sion that arises through cracks in the rolling scale susceptibility to pitting increases. On the other
of unalloyed or low-alloy steels. If, for example, hand, the susceptibility to pitting in a given cor-
the rolling scale of a steel plate has spalled at rosive medium can be decreased by higher flow
a tiny point, and the sheet is immersed in a salt rates of the medium.
670 Corrosion LIVE GRAPH
Click here to view
Figure 22. Current density – potential curve of a passifiable

alloy, with and without pitting corrosion
U corr = Corrosion potential; U pas = Passivation poten-
tial; U p = Pitting potential; U b = breakthrough potential; Figure 23. Pitting potential of diffusion-annealed
ip = Passivation current density; ip = Passive current density X 3 CrNiMoN 17 13 5 (material no. 1.4439) in NaCl
solution as a function of chloride ion activity and
temperature
The dependence of the pitting potential U p LIVE GRAPH
on various factors has been explained for a Click here to view
number of austenitic chromium – nickel – (mo-

lybdenum) steels by using diffusion-annealed
specimens [13]. It was demonstrated, for ex-
ample, that the pitting potential U p is di-
rectly proportional to the logarithm of chlo-
ride ion activity. This is shown in Figure 23
for a nitrogen-alloyed steel with high molyb-
denum content (X 3 CrNiMoN 17 13 5, material
no. 1.4439). Note that pitting occurs, albeit at
high potentials, even at chloride ion concentra-
tions of 2 ppm. A temperature change results in
a parallel shift of the characteristic curve. The
temperature dependence of the pitting potential
is shown in Figure 24, in which U p is plotted
against the reciprocal of absolute temperature. Figure 24. Pitting potentials U p of diffusion-annealed
Figure 25 shows that an increase in the pH of X 3 CrNiMoN 17 13 5 (material no. 1.4439) in NaCl solu-
tions as a function of temperature
the corrosive medium shifts the pitting poten- a) 0.001 N NaCl solution; b) 0.01 N; c) 0.1 N; d) 1 N
tial U p to more positive values, to the extent of
55 – 60 mV per decade of the hydrogen ion con- LIVE GRAPH
Click here to view
centration. This value corresponds to the factor
2.3 RT/nF for n = 1 at 20 ◦ C in Equation (10),
which describes the dependence of the over-
potential on the concentration of the potential-
determining ion. A change in hydrogen ion ac-
tivity by a factor of 10 makes ∆U = 58 mV (see
Section 2.2.3):
∆U = (2.3RT /nF ) loga
Pitting in austenitic chromium – nickel steels Figure 25. Pitting potentials U p of diffusion-annealed
can be avoided in many cases by lowering the X 3 CrNiMoN 17 13 5 (material no. 1.4439) in NaCl solu-
chloride ion concentration, reducing the tem- tions as a function of temperature
a) 1 N, t = 40 ◦ C; b) 0.1 N, t = 80 ◦ C; c) 1 N, t = 80 ◦ C
perature, and raising the pH of the corrosive
medium as high as possible. If these measures
cannot be taken, or cannot be taken to an ade- Material Parameters. For a given steel, the
quate degree, other materials must be chosen. susceptibility to pitting decreases with increas-
ing surface finishing. A ground surface is more
Corrosion 671
susceptible to pitting than a pickled one, which factor of ca. 13 for nitrogen [16]; other authors
in turn is more susceptible than a polished sur- give values of 20 or even 30 [17]. However, the
face. A further decisive point is structural uni- effectiveness of nitrogen is clearly linked to spe-
formity. Rolled surfaces (i.e., surfaces parallel cific Cr and Mo percentages. To what extent ni-
to the rolling direction) are less prone to pit- trogen exercises its own pitting-inhibiting effect
ting than short-transverse-cut sections exhibit- or whether its structure-stabilizing influence is
ing open microsegregations. Oxide and sulfide the cause has yet to be clarified.
inclusions, carbide precipitates, and intermetal- The high-alloy, austenitic stainless steels
lic phases also increase susceptibility to pitting. X 2 CrNiMoN 17 13 5 (material no. 1.4439)
Cold forming can also cause a marked increase [18], X 1 CrNiMoN 25 25 2 (material no.
in the incidence of pitting, although the influ- 1.4465) [19], [20] and X 1 CrNiMoN 25 22 2
ence of cold forming has not yet been finally (material no. 1.4466) [21], which have PREs of
established and contrary results have also been ca. 31, are widely used in chemical engineering
found. [22–26]. Even higher PREs are exhibited by
Effect of Alloying Elements. For a standard the materials X 1 NiCrMoCu 25 20 5 (material
chromium – nickel steel (e.g., X 6 CrNiTi 18 10, no. 1.4539) [20], [27], X 1 NiCrMoCu 31 27 4
material no. 1.4541) with 17.0 – 19.0 wt % chro- (material no. 1.4563) [20], X 2 CrNiMoCuN
mium and 9.0 – 11.5 wt % nickel, the resistance 20 18 6 [20], [28], and X 1 NiCrMoCuN 25 20 6
to pitting can be improved by increasing the (material no. 1.4529) [20], [29]. These high-
contents of chromium and molybdenum, but is alloy materials have also proved successful in a
not affected by higher nickel concentrations. In wide variety of applications, such as chemical
stainless steels, 3 % chromium is equivalent to apparatus, flue gas desulfurization, and marine
ca. 1 % molybdenum. This finding led to the technology [25], [30–35].
formulation of a pitting resistance equivalent Factors affecting pitting corrosion in
(PRE), which is defined as [14]: austenitic chromium – nickel – (molybdenum)
steels are listed in Table 2. An example of pit-
PRE = wt%chromium + 3 × wt%molybdenum ting corrosion is given in Figure 27, which
shows a section of a forged T-piece made of
Some investigations have suggested a factor of X 5 CrNiMoTi 25 25 (material no. 1.4577) into
3.3 for molybdenum [15]. Figure 26 shows that which a thermocouple protection tube was in-
U p is directly proportional to the PRE. There- serted. In the gap between the steel wall and
fore, austenitic steels with the highest possible the protection tube, a sublimable, chloride-
chromium and molybdenum contents exhibit ex- containing salt accumulated causing consider-
tremely high pitting resistance. able pitting corrosion. The problem was solved
LIVE GRAPH by using the same material under changed plant
Click here to view
conditions.
Table 2. Parameters affecting the pitting corrosion of austenitic

chromium – nickel steels
Favoring pitting Hindering pitting
Material parameters
Rough surface polished surface
Inhomogeneous structure homogeneous structure
Cold forming
Figure 26. Pitting potential U p of austenitic chromium – Corrodent parameters

High chloride ion low chloride ion
nickel – molybdenum steels in a NaCl solution as a function
concentration concentration
of the pitting resistance equivalent (PRE) High temperature low temperature
Low pH value higher pH value
The positive effect of nitrogen on the resis- Stationary attacking agent higher flow rate
tance to pitting corrosion of stainless austenitic Alloying parameters
steels has recently been studied in greater detail. Low chromium contents high chromium contents
Low molybdenum contents high molybdenum contents
Examinations of austenitic materials with dif-
ferent Cr, Mo, and N contents indicated a PRE
Next Page
672 Corrosion
can also occur as pitting corrosion. It can be re-

garded as a variation of pitting corrosion.
Although the mechanism of crevice corrosion
has not yet been fully explained, the electrolyte
in the crevice contains less oxygen than the elec-
trolyte outside the crevice because diffusion is
impeded. The vast majority of crevice corrosion
phenomena can thus be explained by the for-
mation of an aeration element (see Section 2.5).
Through the lack of oxygen in the crevice, an-
odic regions form in which metal ions go into so-
lution. As a result, the conditions in the crevice
Figure 27. Pitting corrosion on a high-pressure T-piece of electrolyte usually change, this being towards
material no. 1.4577 at 180 ◦ C and 13 MPa as the result of ac- greater corrosiveness (e.g., lower pH through
cumulation of chloride in the gap between the pipe (a) and hydrolysis). The time dependence of oxygen de-
the thermometer protection tube (b)
pletion as a function of the crack width and depth
is shown in Figure 28 [40].
Pitting corrosion is not restricted to stainless LIVE GRAPH LIVE GRAPH
steels; other passive metals tend to undergo pit- Click here to view Click here to view
ting in solutions containing halides. These in-

clude, for example, aluminum and aluminum
alloys, nickel alloys with passivation capacity
such as NiMo16Cr16Ti, and titanium. Nickel-
based alloys are far less prone to corrosion at-
tack by chlorides than corrosion-resistant Cr –
Ni austenitic steels and are thus seldom at risk.
Aluminum alloys show some susceptibility and
have pitting potentials that are determined by
the chloride ion activity and temperature but not
by the pH. Because of the low electron conduc- LIVE GRAPH LIVE GRAPH
tivity of the oxide scale of aluminum, however,
the corrosion rate remains low if it is not en-
hanced by contact corrosion with metals such
as copper, iron, nickel, and their alloys, or with
electrically conducting deposits with rest poten-
tials more positive than the pitting potential of
aluminum (intensification of the cathode part re-
Figure 28. Dependence of oxygen depletion in crevice cor-
action) [36]. Under extreme conditions (e.g., in rosion on crack width and depth
a solution with 65 % ZnCl2 , 5 % HCl, and 1 % Crack width: A) 1.65 mm; B) 0.74 mm; C) 0.40 mm; D)
FeCl3 at 100 ◦ C) [37], titanium is prone to pitting 0.15 mm
corrosion. So far pitting has not been reported for Time: a) 6 min; b) 15 min; c) 30 min; d) 1 h; e) 1.5 h; f ) 2 h
tantalum and niobium.
Whether or not crevice corrosion occurs
largely depends on the crevice geometry.
3.2.2. Crevice Corrosion Crevice widths are particularly critical when the
distance between the crevice-forming surfaces is
Crevice corrosion is also a form of localized cor- less than 1 mm. Since the reactions taking place
rosion. It amounts to locally intensified corro- in the crevice cannot be influenced from the out-
sion in crevices and thus results exclusively from side, damage due to crevice corrosion can only
the design of a specific component [38], [39]. In be avoided through the prevention of crevices.
unalloyed steels it usually occurs as nonuniform In ferritic and austenitic stainless steels,
or uniform corrosion, and in stainless steels it crevice corrosion is almost always initiated by
Previous Page
Corrosion 673
local activation. This can be induced in a crevice

by oxidant depletion, if necessary supplemented
by halides. The passivity then breaks down. The
access of oxidants to the material surface, and
hence the passivity, may also be hindered by lo-
cal deposits.
Numerous incidences of damage in crevices
in components are due to crevice corrosion;
for example, in the critical areas between the
tubes and tube sheets in heat exchangers. Other
commonly found defects are crevices caused by
incomplete welding, especially of root passes,
which can lead to crevice corrosion under criti-
cal corrosion conditions (Fig. 29). Typical dam-
age due to crevice corrosion on a plate heat Figure 30. Crevice corrosion of a plate heat exchanger (ma-
terial no. 1.4449)
exchanger made of X 5 CrNiMo 17 13 (mate-
rial no. 1.4449) is illustrated in Figure 30. The The conditions for crevice corrosion are not
medium was an almost saturated sodium chlo- only present when the crevice is formed by
ride solution containing small amounts of free metallic materials, but also when the surface of
chlorine. The product temperature was 50 – a passive material is coated with nonconductors
70 ◦ C. The first plates were already porous after such as seals, packings, and product deposits,
five weeks at the points where the grooves touch under which the material can then be prone to
those of the neighboring sheet. The damage is pitting corrosion. Corrosive media containing
due to heavy local corrosion in the region of the chloride, which can neutralize passivity, are par-
points of contact (crevices). Remarkably, pipes ticularly dangerous in this respect.
operating with the same product and made of An example is a horizontal copper pipe for
the same material, but which do not present the drinking water, in which typical pitting corro-
conditions for crevice corrosion, have been in sion damage has formed under deposits. The first
use for more than ten years with negligible cor- perforations appeared after eight-months’ use.
rosion. The deposits consisted primarily of residual sol-
der paste and iron oxides and were found solely
in the bottom half of the pipe. After remov-
ing the deposited layers by pickling, numerous
pitted spots could be seen, mainly under pim-
ples in the protective coating. Since the cause of
damage can only be improper handling of sol-
der paste during soldering, this kind of damage,
which was frequently found some years ago in
the Federal Republic of Germany, ceased to exist
after the changeover to brazing. The corrosion-
inducing effect of iron oxides is obviously due
to their impairing the formation of a dense cop-
per(I) oxide layer. Iron oxides do not cause cor-
rosion damage when they come into contact with
previously formed, dense protective layers.
3.2.3. Selective Corrosion

Figure 29. Crevice corrosion of a pipe (material no. 1.4571)
(radiograph) Selective corrosion is defined as corrosion in
which specific microstructural constituents, re-
674 Corrosion
gions close to grain boundaries, or alloying com- alloy in question. For the austenitic chromium –
ponents are preferentially attacked [2]. nickel – (molybdenum) steels used for the fabri-
Intergranular corrosion, spongiosis, dezinci- cation of chemical plant equipment, the critical
fication, and line- and layer-type corrosion are temperature range is 400 – 800 ◦ C. Chromium
classified in this subgroup. Of particular impor- depletion through formation of chromium-rich
tance is intergranular corrosion. carbides, mostly of the type M23 C6 , is the main
cause of intergranular corrosion in these steels.
The precipitation of chromium nitrides – of im-
3.2.3.1. Intergranular Corrosion portance is only the chromium-rich nitride Cr2 N
[44] – can initiate intergranular corrosion, espe-
Intergranular corrosion in electrolyte solutions cially in ferritic steels. Since the intermetallic
arises when the resistance of zones close to phases in stainless steels contain appreciably
the grain boundary, compared with the resis- less chromium than carbides and nitrides and
tance of areas further from the grain boundary, their deposition is far slower, the chromium de-
is reduced due to microstructural changes in the pletion related to these phases is minimal.
grain boundary regions. This type of corrosion is Molybdenum depletion at grain boundaries
particularly characteristic of passive materials, through carbides rich in molybdenum and
in which large differences between the corrosion through intermetallic phases can also lead to
rates of the matrix and the grain boundary areas intergranular corrosion. For standard molybde-
are possible if the chemical composition of the num steels, molybdenum depletion is always
grain boundary zones is changed by discontinu- linked to a far greater chromium depletion and
ous precipitation processes in the supersaturated therefore plays only a minor role. In special
solid solution. Intergranular corrosion is charac- high-alloy molybdenum-containing steels, and
terized by the fact that grain boundary zones are especially in nickel-based alloys with very high
corroded preferentially in a groovelike manner molybdenum contents, molybdenum depletion
until individual grains are loosened and fall out is a major cause of susceptibility to intergran-
of the microstructure. Given heavy intergranu- ular corrosion. This is particularly significant
lar corrosion, the entire structure can collapse in the chromium-free alloy NiMo 30 (material
[41–43]. no. 2.4810).
The reduced resistance of the grain boundary In NiMo 30, molybdenum-rich carbides and
regions is due to the following: intermetallic phases of the type Ni4 Mo and
Ni3 Mo precipitate readily [45]. Figure 31 shows
1) Depletion of alloying elements that are im- intergranular corrosion in a welded pipe. In
portant for the maintenance of the corro- the meantime, NiMo 30 has been superseded
sion resistance in the grain boundary regions
through precipitation of phases containing
these elements along the grain boundaries;
2) Formation of microstructural components at
the grain boundaries that are preferentially
attacked in a corrosive medium;
3) Accumulation at the grain boundaries of im-
purities which stimulate anodic dissolution.
Of these causes, depletion of alloying ele-
ments has the greatest practical significance.
This occurs when grain boundary precipitates
are formed that contain one or more alloying el-
ements in a markedly higher concentration than
the matrix.
Precipitation processes of this kind are al-
ways caused by heat treatments, such as sen- Figure 31. Intergranular corrosion in the weld heat-affected
sitizing annealing, that are inappropriate for the zone of a pipe (made of NiMo 30) caused by hydrochloric
acid
Corrosion 675
by NiMo 28 (material no. 2.4617), which resists The effect of the solution annealing tempera-
the formation of grain boundary precipitates in ture is especially pronounced in stabilized steels
the weld heat-affected zone. (i.e., those that contain titanium and niobium for
In the high-silicon austenitic chromium – bonding of the carbon). With increasing solu-
nickel special steel X 1 CrNiSi 18 15 4, which tion annealing temperature, the curves encom-
has high resistance to concentrated nitric acid passing the area of susceptibility shift to lower
[46–48], susceptibility to intergranular corro- sensitizing temperatures and longer annealing
sion depends on the separation of a carbide times, as shown in Figure 33 [51]. The reason for
M23 C6 and on a π-phase of type M11 (C, N)2 , this shift is that with increasing solution anneal-
containing chromium, nickel, silicon, carbon, ing temperature, the amount of carbon which
and nitrogen [49]. is in solution and, therefore, available for pre-
The susceptibility to intergranular corrosion cipitation in the critical temperature range, also
of a chemically resistant steel depends on the increases. At the same time, grain coarsening
carbon content, the duration of sensitizing, the occurs, reducing the grain boundary surfaces
sensitizing temperature, and the temperature of available as precipitation sites. This also leads
prior solution annealing; it is represented in a to greater chromium depletion because the in-
time – temperature diagram. Curves of this type creased amount of available carbon on the grain
are shown in Figure 32 for an austenitic steel surfaces can then bind more chromium. How-
with ca. 18 % chromium, 8 % nickel, and vari- ever, the considerably lower susceptibility of sta-
ous carbon contents [50]. The curves encompass bilized steels to grain disintegration, compared
the respective area of susceptibility. with unstabilized steels, is due to the formation
of carbides, which leads to a lower concentra-
LIVE GRAPH tion of dissolved carbon. Since the solubility of
Click here to view
the carbides (TiC and NbC) decreases with de-
creasing temperature, proneness to intergranular
corrosion may be eliminated by annealing (sta-
bilization) these steels at a lower temperature
(900 – 950 ◦ C) to remove dissolved carbon by
precipitation of the carbides. Another possibil-
ity of lowering the susceptibility to grain disinte-
gration is to reduce the carbon content to below
0.03 % (ELC grades).
The carbon solubility is further reduced by
a higher nickel content, thus increasing the ten-
dency to precipitate. This shifts the grain disin-
Figure 32. Time – temperature sensitization curves of an un- tegration areas to shorter tempering times and
stabilized austentic steel (18 % Cr, 8 % Ni) as a function of higher temperatures, as demonstrated in Fig-
carbon content
Figure 33. Time – temperature sensitization curves of stabilized steels as a function of solution annealing and sensitizing
temperatures (test criterion: Strauss test)
A) Material no. 1.4541; B) Material no. 1.4550
676 Corrosion
ure 34, which compares the grain disintegration partially, and reprecipitate on cooling as M23 C6
curves of X 2 CrNi 19 11 (material no. 1.4306, at the grain boundaries, giving rise to chromi-
11 % Ni), the titanium-stabilized grade X 10 um-depleted grain boundary zones if the cooling
NiCrAlTi 32 20 (material no. 1.4876, 32 % Ni), rate is sufficiently high. In contrast to austenitic
and the alloy NiCr 15 Fe (> 72 % Ni). The car- steels, rapid cooling from a high temperature
bon content of the materials is ca. 0.02 % in is critical for ferritic steels; the higher mobil-
each case. Higher nitrogen contents also shift ity of the atoms in the body-centered cubic lat-
the beginning of precipitation to shorter times tice causes a high precipitation rate of the car-
(Fig. 35). In practice, however, grain disintegra- bides, and rapid post-diffusion of chromium into
tion is only expected above ca. 0.2 % N [44]. the depleted zones occurs. Ferritic steels with
17 % Cr can therefore suffer intergranular cor-
rosion in the high-temperature zone immedi-
ately adjacent to the weld if this is cooled so
rapidly after welding that chromium depletion
is not eliminated; an example is shown in Fig-
ure 36. Ferritic chromium steels can be stabi-
lized by addition of titanium or niobium, but
compared with the austenitic standard steels, a
comparatively higher concentration of these ele-
ments is necessary [52]. So-called superferrites
also exist, such as X 1 CrNiMoNb 28 4 2 (mate-
rial no. 1.4575), characterized by C + N contents
≤ 0.040 %, which greatly improves the weld-
ability of these materials.
Figure 34. Time – temperature sensitization curves of aus-
tentic steels
a) NiCr 15 Fe, 0.017 % C; b) X 10 NiCrAlTi 32 20, 0.021 %
C, 0.35 % Ti; c) X 2 CrNi 19 11, 0.020 % C
Figure 36. Intergranular corrosion in the weld heat-affected

zone of a 17 % Cr steel
A special form of intergranular corrosion is

Figure 35. Time – temperature sensitization curves of unsta-
bilized, nitrogen-containing, austenitic steels with ca. 18 % observed in titanium-stabilized stainless steels
Cr, 10 % Ni, and 0.01 % C containing ca. 17 wt % chromium: it is caused
by precipitation of titanium carbonitrides at the
Of the ferritic steels, those containing ca. grain boundaries. The carbonitrides are dis-
17 wt % chromium are of industrial signifi- solved by strongly oxidizing solutions such as
cance. Final heat treatment is performed at 750 – nitric acid, leaving grooves (Fig. 37). In such
850 ◦ C with subsequent air or water cooling. cases preference should be given to the niobium-
In unstabilized grades the carbon is practically stabilized grade since NbC is hardly attacked by
all precipitated as M23 C6 , without the forma- oxidizing acids [53].
tion of chromium-depleted zones. As the an- Marked susceptibility to grain disintegra-
nealing temperature rises, the carbon solubility tion can also be observed in the highly cor-
increases, the carbides dissolve completely or rosionresistant nickel-based alloys, such as
Corrosion 677
Figure 37. Intergranular corrosion of a Ti-stabilized 17 % Cr steel (X 7 CrTi 17) in boiling sulfuric acid
A) Mode of attack; heat treatment 30 min, 1300 ◦ C, water quenched; test time 24 h; U H = 650 mV
B) Depth of attack as a function of electrode potential; heat treatment: a) 30 min, 850 ◦ C, water quenched; b) As a) + 30 min,
1300 ◦ C, water quenched
the chromium- and molybdenum-containing

type NiMo 16 Cr (material no. 2.4812) (Fig. 38),
which is, however, no longer in use. In addition
to carbides, grain boundary precipitates in this
material also consist of an intermetallic chromi-
um- and molybdenum-rich intermetallic phase,
which leads to depletion of chromium and mo-
lybdenum in the grain boundary zones. The crit-
ical temperature range for precipitation is very
wide (500 – 1150 ◦ C) [45]. More recent types of
this family of alloys, such as NiMo16Cr16Ti
(material no. 2.4610) and NiCr21Mo14W (ma-
terial no. 2.4602), exhibit a considerably re-
duced susceptibility due to their lower carbon
and silicon contents (both < 0.1 %); thus, there Figure 38. Intergranular corrosion of NiMo 16 Cr as a result
is no further risk of intergranular corrosion in of improper heat treatment
practical applications [54–58].
Intergranular corrosion can also occur in
other metals and alloys in connection with grain 3.2.3.2. Spongiosis
boundary precipitation, for example, in AlMg5
alloy, NiCr30Fe, or titanium (in methanol with Spongiosis, also known as graphitization, is a
traces of water and HCl). Solution-annealed form of corrosion found only in gray cast iron.
austenitic chromium – nickel steels can suffer Because of inadequate formation of a protective
intergranular corrosion in strong oxidants such layer, ferrite and pearlite are converted primarily
as chromium-containing, azeotropic, or super- to iron(II) oxide hydrate, whereas the graphite
azeotropic nitric acid, even though no precipita- structure and the distribution and percentage of
tion can be detected. It is assumed that phos- the phosphide eutectic remain unchanged [2],
phorus contents above 0.01 wt % and silicon [59]. In this instance the metallic bond is lost,
contents above 0.1 wt % are responsible for this leading to complete loss of strength in the dam-
form of corrosion [41]. aged areas of the component (Fig. 39). The re-
678 Corrosion
markable feature of this process is that the outer per – aluminum (aluminum stripping), copper –
form of the component is so well maintained that tin (detinning), and copper – nickel (nickel strip-
tool marks can often be seen. ping) [62–65].
Dezincification can occur, for example, in tap
water, river water, seawater, and liquids contain-
ing chloride. The rate of this corrosion process is
increased by plastic deformation of the material
[66]. Dezincification can occur by two mecha-
nisms:
1) going into solution of both alloy constituents
(copper and zinc) through dissolution of the
solid solution and cementation of the more
noble component (copper);
2) selective dissolution of the less noble con-
stituent from the solid solution and accumu-
lation of the exposed atoms through surface
Figure 39. Spongiosis of a cast iron pump used for well wa- diffusion.
ter
The light areas in the picture are ferrite, the dark areas are It is assumed that the two mechanisms work
graphite. either simultaneously or one after the other [67],
[68].
Spongiosis occurs primarily in cast iron pipes
laid in acid earth or in calcareous loamy soil. It
can be avoided by applying adhesive, crack-free
protective coatings, such as those based on tar.
Damage caused by spongiosis is also observed
in cast-iron feed-water preheaters and pumps for
drinking water and seawater [59].
When ferritic or pearlitic cast iron comes into
contact with pure water or aqueous salt solu-
tions, spongiosis occurs. It begins without ex-
ception in the immediate vicinity of the graphite,
giving rise to a porous coating consisting of
graphite, carbides, sulfides, phosphides, and ni-
trides. A sufficiently high oxygen content in the
corrosive medium then leads to a greater de-
position of corrosion products on this primary
coating, which thereby becomes sealed, finally
forming a protective coating [60]. The advance
of spongiosis is therefore to be expected when
the corrosive medium has a low oxygen concen-
tration.
3.2.3.3. Dezincification
Dezincification is the selective corrosion of cop-

per – zinc alloys (brass) with more than 15 %
zinc, in which porous copper deposits form Figure 40. Types of dezincification
on the corroded parts [2], [61]. Although less A) Layer dezincification of a brass water faucet (GK-CuZn
common, similar phenomena have also been 37Pb); B) Plug-type dezincification in a brass pipe (CuZn
observed in other copper alloys such as cop- 28 Sn 1)
Corrosion 679
According to their appearance, a distinction rolled products. The cause of line-type corro-
is made between layer dezincification and plug- sion may be due to both the banded structure of
type dezincification (Fig. 40, see previous page). precipitations and microsegregation, i.e., insuf-
In layer dezincification the entire surface is cor- ficient concentration compensation.
roded practically uniformly. This form of cor- Because of the high degree of deformation,
rosion is observed when a component made of sheet products exhibit a particularly marked
a copper – zinc alloy comes into contact with sandwich structure with regard to the concen-
nobler metals in an electrolyte (e.g., seawater). tration distribution of the alloying elements. If
Crevices and cracks such as threads and surface the corrosion resistance of a material depends
damage promote corrosion [61]. on the concentration of the segregating alloying
Far more critical is plug-type dezincification, element, local differences in corrosion depth can
which mainly arises in heat exchanger tubes occur if fabricated parts are subjected to stress
upon deposition of sand grains, oil residues, rust, in the fiber direction. In practice this is the case
mussels, and algae with formation of aeration at the face of rolled-in tubes of heat exchangers,
elements. Even thick tubes can be perforated in the cutting edges of sieve trays, or valves and
this way [61], [69]. Dezincification can be im- valve seats in forged armatures [43], [72–76].
peded by adding small amounts of arsenic or A good example is provided by support rigs
phosphorus. of tube bundles made of material no. 1.4571,
which after several months’ exposure in a hot,
3.2.3.4. Line- and Layer-Type Corrosion
In these forms of selective corrosion the attack
occurs practically parallel to the rolling direc-
tion. Layer corrosion is observed in the alu-
minum alloys AlMg, AlZnMg, AlCuMg, and
AlZnMgCu. The material undergoes corrosion
in chloride-containing media by exfoliation par-
allel to the surface. This occurs if a rolling pro-
cess gives rise to a laminar structure of inter-
metallic compounds or when lamellar zones of
differing concentration were already present in
the ingot [70], [71]. Figure 41 shows layer cor-
rosion in an aluminum alloy [71].
Figure 41. Layer corrosion of an Al – Zn – Mg alloy

Figure 42. Transgranular stress corrosion cracking of a
In contrast to layer corrosion in aluminum al- steam coil support
loys, line-type corrosion can occur in many ma- A) Macroscopic view; B) Microsection showing selective
terials, although it is also linked to forged and corrosion along the ferrite lines (→)
680 Corrosion
weakly acidic, chloride-containing suspension bar. After 200 h in operation, signs of corrosion
had fractured because of transgranular stress that look like pitting appear. Figure 43B shows
corrosion cracking (see Section 3.3.1.2). One line- or band-like precipitation in the fiber di-
detail of the fractured fixtures, with many rection which is responsible for the pitting-like
cracks, on which clear signs of pitting cor- attack.
rosion can be seen, is shown in Figure 42 Figure 44 shows selective corrosion caused
(see previous page). Metallographic examina- by segregation. The SEM photographs of the
tion (see Fig. 42B) showed that the transgranu-
lar cracks produced selective corrosion, which
spread along the ferrite lines. At the point
marked by an arrow in Figure 42B it can be seen
that the extended ferrite islands were not dis-
solved; instead, the corrosion spread along the
segregated austenite rims [43].
Figure 43 shows a nozzle head made of
NiMo 30 (material no. 2.4810), which was
manufactured from a nonuniformly annealed
Figure 44. Selective corrosion caused by segregation on the

Figure 43. Selective corrosion of a NiMo30 (material face of a heat exchanger tube in boiling, highly concentrated
no. 2.4810) nozzle head in a region exhibiting lines of pre- HNO3 . Material: X 1 CrNiSi 18 15 4
cipitates A) Longitudinal section; B) and C) Scanning electron mi-
A) Nozzle head; B) Microstructure of nozzle head crographs of the attacked face
Corrosion 681
face of a heat exchanger tube made of X 1 Cr- rosive medium can cause local perforation of
NiSi 18 15 4 which was subjected to boiling, the layer (e.g., media containing chlorides with
highly concentrated nitric acid for 60 d showed passive, stainless austenitic CrNi steels), or its
evidence of line-type corrosion. The sides of the passivity can be impaired by the influence of the
corrosion crevices are coated with several layers prevailing tensile stress to the extent that only
of the corrosion product SiO2 [10], [49]. a locally incomplete protective layer is formed
Selective corrosion caused by differences in (e.g., solutions of alkali hydroxides or nitrates
concentration can be reduced by homogenizing with unalloyed steels). However, this simplified
heat treatment or by laying one weld pass over view of the formation of local anodes in stress
the edges of sheets and tubes. corrosion cracking merely explains the initial
stage during the induction period; it sheds no
light on the actual cracking period, for which
3.3. Forms of Local Corrosion under there are now several interpretations.
Mechanical Stress The most common interpretation of the
mechanism of cracking is based on a “pe-
3.3.1. Stress Corrosion Cracking riodic electrochemical – mechanical process”.
This suggests that cracking is an alternating se-
Stress corrosion cracking is one of the most un- quence of relatively slow anodic dissolution in
pleasant forms of corrosion because it usually the crack base and sudden mechanical crack
occurs unexpectedly and can very quickly lead to propagation. In some alloys intermittent crack-
cracking in equipment such as reactors, vessels, ing has actually been found, but in many other
and piping, and to fractures in components of all cases no evidence of stepwise cracking has been
kinds. Depending on the alloy system and cor- produced.
rosive medium, the characteristics are inter- or A further theory on the cracking mechanism
transgranular brittle cracking, branching out to is that it is a purely electrochemical process in
varying degrees into the material and eventually the base of the crack (active path corrosion), the
causing fracture of the remaining cross section. rapid crack propagation rate observed in most
General surface corrosion arising in this way is cases being due to greatly increased dissolution
either nonexistent or immeasurably small. De- of the material as a result of plastic deformation
posited corrosion products are seldom found. at the crack tip with simultaneous passivation
Normal anodic stress corrosion cracking is of the crack walls. Greatly increased dissolution
caused by a combination of mechanical ten- during the plastic deformation of a metal has
sile stress and local electrolyte dissolution pro- been demonstrated [78].
cesses when certain conditions are met. Firstly, A distinction is made between anodic and
the corrosive medium must have a specific ef- hydrogen-induced cathodic stress corrosion
fect on the respective alloy, and in addition the cracking, in which atomic hydrogen generated
alloy in contact with the electrolyte in this ma- from a cathodic process in a corrosion reaction
terial /corrosive medium system must be prone penetrates the metal lattice and, in combination
to stress corrosion cracking. The tensile stress with internal and external stresses, causes trans-
must also be sufficiently high. Susceptible sys- granular cracking and in heat-treated steels pref-
tems, for example, are stainless austenitic steels erentially intergranular cracking. This kind of
in chloride- containing solutions or unalloyed stress corrosion cracking thus belongs to the cat-
and low-alloy steels in nitrate solutions. In con- egory of hydrogen damage or embrittlement (see
trast, unalloyed and low-alloy steels are not sus- Section 3.3.1.5).
ceptible to stress corrosion cracking in chloride A more recent theory on the mechanism of
solutions. anodic stress corrosion cracking, based partly
Protective layers are a prerequisite for stress on tests on steels, combines the electrochemi-
corrosion cracking to occur on the surface of a cal process of local metal dissolution with hy-
component under the influence of an electrolyte. drogen embrittlement at the base of the crack
Local crack-inducing corrosion processes are caused by the atomic hydrogen forming during
caused by selective degradation of these protec- corrosion, which may be of major significance
tive or passive layers. In this instance, the cor- to crack propagation.
682 Corrosion
In addition to classic stress corrosion crack-

ing, systems are known in which the static ten-
sile stress is not sufficient to create cracking
(e.g., carbonate – bicarbonate solutions). In such
cases, critical slow strain rates are necessary to
initiate stress corrosion cracking. This type of
corrosion is called strain-induced or nonclassi-
cal stress corrosion [79–82].
3.3.1.1. Unalloyed and Low-Alloy Steels
In unalloyed and low-alloy steels, the corrosive

media (alkali, nitrates) produce passive protec-
tive layers which have a certain instability at
high-angle grain boundaries and are thus decom-
posed under sufficient stress, initiating local cor-
rosion. The resulting stress corrosion cracking is
therefore an intergranular process in these steels
(Fig. 45). It is assumed that the special activity of
the grain boundaries is determined by accumu-
lation of alloy phases. This theory is supported
by a number of test results. It has been found, for
example, that cementite and nitrides or carboni-
trides at the grain boundaries in unalloyed steels
Figure 45. Intergranular stress corrosion cracking of
produce a high susceptibility to stress corrosion Thomas steel (normalized) in a nitrogen-purged 20 wt %
cracking [83]. NaOH solution at 110 ◦ C
The susceptibility to stress corrosion crack-
On the basis of these observations the induc-
ing of a steel with 0.011 wt % carbon subject to
tion phase in intergranular cracking can be in-
different annealing conditions, measured under
terpreted as the preferential dissolution of inho-
constant tensile stress in boiling Ca(NO3 )2 so-
mogeneous grain boundaries with formation of
lution, is shown in Table 3 [83]. The marked im-
deep cavities with corresponding stress peaks,
provement when the carbon is kept in solution
which initiate the actual cracking. Basically, a
is clearly evident. Elements promoting passiv-
lower stress limit for the induction of intergran-
ity such as chromium and molybdenum clearly
ular stress corrosion cracking in a given corro-
reduce the tendency to cracking, although in al-
sive medium exists for each steel and for each
loyed steels of this kind, the type of heat treat-
structural state resulting from annealing, below
ment also plays a major role [84].
which stress corrosion cracking cannot be initi-
ated.
Table 3. Influence of grain interface cementite on the stress corrosion behavior of a mild, unalloyed steel a
Heat treatment Time to fracture in minutes at a tensile stress of
0.3 · σ u b 0.4 · σ u 0.5 · σ u 0.6 · σ u
Normalized (920 ◦ C, 20 min, air) 288 30 104 48

Normalized + 720 ◦ C, 24 h, liq. N2 > 15 000 > 15 000 132 54
(carbon held in solution)
Normalized + 730 ◦ C, 2 h, water + 500 ◦ C, 96 66 18 12
4 h, water (tertiary cementite precipitation)
a
Analysis of the steel: C 0.011 %, Si 0.02 %, Mn < 0.005 %, P 0.007 %, Si < 0.005 %, Ni 0.02 %; N, Al, Cr, and Mo lie beneath the
detection limit.
b
Ultimate tensile strength σ u (normalized) = 213 MPa.
Corrosion 683
Current density – potential curves for is no limit potential for cracking at the anodic
stressed and unstressed tensile test specimens in side), in alkali there is both a cathodic and an
crack-inducing media show that the unstressed anodic limit potential, as shown in Figure 48
specimen exhibits no rise in current until ca. [87]. In this instance, stress corrosion cracking,
900 mV U H , which indicates the start of grain as illustrated by the current density – potential
boundary corrosion (Fig. 46) [85]. At 20 % of the curve, is restricted to the potential range corre-
tensile strength σ u , corrosion begins at 400 mV, sponding to formation of a passive layer that is
i.e., a shift of 500 mV in the direction of the ac- initially disturbed at the grain boundaries. Sus-
tual corrosion potential in the steel. At a stress ceptibility disappears once complete passivation
of 0.4 σ u the grain boundary breakthrough po- has been attained. In alkali, initiation of crack-
tential reaches the corrosion potential, and the
steel can now rupture without external polar-
ization through stress corrosion cracking. As it
does, the critical tensile stress for dissolution is
reached.
LIVE GRAPH
Click here to view
Figure 46. The influence of load on the grain boundary

breakthrough potential U b Figure 47. Threshold tensile stresses for stress corrosion
Load: – – – unloaded; - - - - - 0.2 · σ u ; —— 0.4 · σ u cracking of the fine-grained structural steel StE 355 as a
(σ u = 438 MPa) function of the annealing temperature as determined with
unwelded and welded samples
In practice, the considerable influence of the Plain area = Tensile strength; – – Yield strength; xx
stress level can also be seen by the fact that weld Threshold stress for stress corrosion cracking; Hatched
area = Range of stress corrosion cracking
seams are preferentially attacked by stress cor-
rosion cracking on account of shrinkage stresses
and the stresses caused by structural changes due LIVE GRAPH
Click here to view
to the effect of heat input during welding.
The susceptibility to stress corrosion crack-
ing of unalloyed and low-alloy steels is thus in-
dicated by the extent to which the grain bound-
ary breakthrough potential shifts under tensile
stress. If, for a low tendency to shift, the stress
limit needed to induce cracking is greater than
the yield strength, industrial application of a
steel of this kind is possible given careful moni-
toring of the nominal stress. The structural com-
position formed through annealing is also of im-
portance, as is shown in Figure 47 for the fine- Figure 48. Current density – voltage curves of unalloyed
grained structural steel StE 355 [86]. steels in alkaline solution and position of stress corrosion
Stress corrosion cracking in alkali-metal hy- cracking
droxide solutions shows a number of variations. a) 33 % NaOH, boiling, holding time 60 s per measuring
point [88]; b) 35 % NaOH, boiling, holding time 30 s per
Whereas in nitrate solutions the grain boundary measuring point [214]; c) 35 % KOH, 80 ◦ C, holding time
breakthrough potential only means a restric- 5 h per measuring point [87]; d) Anodic partial current –
tion of the potential range of stress corrosion voltage curve for dissolution of iron in 4 N KOH (ca. 20 %),
cracking towards the cathodic direction (there 90 ◦ C [77]
684 Corrosion
ing requires tensile stresses comparable to the the vapor phase had condensed, and in low-
yield strength. In contrast to nitrate solutions, temperature storage (− 33 ◦ C) [97].
therefore, the limit stress to initiate stress corro- Transgranular stress corrosion cracking also
sion cracking in alkali is characterized in most occurs in solutions of CO – CO2 – H2 O contain-
cases by the requirement for small amounts of ing oxygen [98], [99]. Unalloyed and low-alloy
permanent elongation [88]. steels may also be sensitive to anodic stress
In alloyed air-hardened steels (e.g., 13 CrMo corrosion cracking in aqueous CO2 solutions.
4 4), thorough tempering at 750 ◦ C is needed af- Note, however, that considerable hydrogen per-
ter welding to eliminate the hardness structure. meation has been observed under critical condi-
Only when the hardness is below 220 HV are tions (t > 40 ◦ C, pCO2 > 1 MPa, σ > 0.5 · σ ys ); a
these steels resistant to stress corrosion crack- certain amount of hydrogen-induced stress cor-
ing. rosion cracking in the overall cracking activity
In addition to the known corrosive effects must therefore be assumed [100, 101].
of alkali-metal hydroxide and nitrate solutions,
intergranular stress corrosion cracking in unal-
loyed and low-alloy steels in contact with ammo- 3.3.1.2. Stainless Steels
nium carbonate [82], [89], [90] and crude meth-
anol (methanol with a low concentration of im- Chloride-containing corrosive media can give
purities) has now also been observed [91], [92]. rise to transgranular stress corrosion cracking in
When this group of materials comes into contact austenitic stainless steels (e.g., steels of compo-
with various other aggressive substances, stress sition 18 % Cr, 10 % Ni, or 18 % Cr, 12 % Ni, and
corrosion cracking occurs, primarily with trans- 2 % Mo). It occurs particularly often through the
granular characteristics. high chloride content of cooling water (usually
river water) in heat exchanger tubes: in many
cases in the region of salt deposits that arise
through local evaporation with insufficient wa-
ter throughput or incomplete filling of the tube
[102].
Alkali-metal hydroxide solutions can also
cause stress corrosion cracking in austenitic
stainless steels (Fig. 50; see next page), albeit
only at elevated temperature, often above the
boiling point of the corrosive medium (Fig. 51;
see next page). Therefore, damage occurs only
occasionally and primarily in pressure vessels.
However, in Figure 52 (see next page) lower tem-
perature limits are given [103].
It must be assumed in transgranular stress
corrosion cracking that local accumulations of
foreign atoms in areas with lattice defects out-
side the grain boundaries, i.e., dislocations and
slip lines, are responsible for local activation,
Figure 49. Stress corrosion cracking in an unalloyed steel which can often be recognized by the formation
storage tank for liquid ammonia of etch pits in the presence of corrosive media
In the past, cases of this sort of crack dam- or through a particular proneness to pitting.
age in storage tanks and transportation contain- Less prone to stress corrosion cracking are
ers for liquid ammonia (both at room tempera- high-alloy austenitic steels that contain more
ture and at 0 ◦ C) were found in increasing num- chromium and nickel or have additional copper
bers (Fig. 49) and simulated in laboratory ex- and molybdenum contents. Particularly resistant
periments [93–96]. In a few cases the forma- are nickel-based alloys with chromium and/or
tion of cracks was even observed in areas where molybdenum, in which stress corrosion cracking
Corrosion 685
LIVE GRAPH
Click here to view
Figure 52. Stress corrosion cracking (SCC) of austenitic

stainless steels in sodium hydroxide solution: temperature
and concentration limits [103]
a) Rapid stress corrosion failure (one day), unsensitized;
b) Delayed SCC failure, unsensitized type 304; c) Delayed
SCC failure, sensitized type 304; d) Delayed SCC failure
Figure 50. Stress corrosion cracking of a loop sample of type 304, both sensitized and unsensitized (100 – 300 d);
X 10 CrNiMoNb 18 10 (material no. 1.4580) caused by an e) Tentative safe SCC limit
alkaline solution at 280 – 300 ◦ C and 3 MPa
occurs only under extreme stress. Commercial
ferritic stainless chromium steels also show very
LIVE GRAPH high resistance, but for other reasons (e.g., weld-
Click here to view ing sensitivity) are seldom used in equipment
fabrication. Ferritic – austenitic steels are read-
ily applicable in approximately neutral halide
solutions. Apart from chlorides, which are re-
sponsible for most of the damage, bromides and
iodides can also cause stress corrosion cracking,
although such cases are rare.
A tensile stress limit must also be exceeded
for transgranular stress corrosion cracking to
occur in stainless steels. The limit stresses are
shown in Table 4 for three standard steels in boil-
ing 42 % MgCl2 solution – the standard labora-
tory solution for investigating stress corrosion
cracking [104]. The limit stresses are always
lower than the yield stress, as the comparison
with the 0.2 % yield strength shows. Compo-
nents are usually designed with a 150 % safety
margin based on the yield strength. The nominal
Figure 51. Stress corrosion cracking regions of various stresses calculated for the individual steels are
metallic materials in sodium hydroxide also listed in Table 4. The limit stress is higher
a) 18/8 CrNi; b) 18/8/2 CrNiMo; c) Monel; d) Nickel; e) In- than the nominal stress only for the steel with
conel the material no. 1.4550. This does not, however,
—— Boiling curve at 100 kPa
ensure safety against stress corrosion cracking,
686 Corrosion
Table 4. Comparison of the yield strength and the nominal stress σ N present with normal laying out with the limit stress necessary to initiate
stress corrosion cracking for three austenitic steels
σ0.2
Steel 0.2 % yield strength, MPa Limit stress, MPa σN = 1.5 , MPa
Mat. no. Designation (DIN 17 006)
1.4550 X 6 CrNiNb 18 10 180 160 120

1.4435 X 2 CrNiMo 18 14 3 200 130 132
1.4429 X 2 CrNiMoN 18 133 280 100 155
since stress peaks and local yield processes can- activity of the grain boundaries, as shown in Fig-
not be avoided in these highly ductile steels, ure 53 for alloy AlMg 9 as a function of heat
which, for example, are not usually heat-treated treatment [106].
after welding. It must also be expected that, as LIVE GRAPH
Click here to view
pitting begins, the required degree of stress is
reached because of the excess stress at the edges
of the pits. Transgranular stress corrosion crack-
ing can occur in the presence of halides under
two conditions:
1) Below the limit stress through shifting of the
corrosion potential towards the pitting poten-
tial by oxidants, whereby, depending on the
corrosive medium, the increase in potential
need sometimes only be small, and subse-
quent exceeding of the limit stress through
excess stress at the location of pitting;
2) Above the limit stress through the occurrence
of local yield processes with the formation of
local corroded spots on the steel surface with
high current density and due to perforation Figure 53. Stress corrosion cracking behavior (a – c) of loop
of the surface layer by slip lines as the start samples in 3 % NaCl solution (lifetime in alternate immer-
of cracking. sion test) and chemical activity (hydrogen evolution) (d)
of the grain boundaries in hydrochloric acid for 1 mm alu-
If stress-relief annealing is to be carried out minum alloy sheet with 9.1 % Mg
on stainless austenitic steels to avoid stress cor-
rosion cracking, temperatures above 900 ◦ C are At a tempering temperature of 180 ◦ C, the
required because of the high strength at elevated activity of the grain boundaries is particularly
temperatures. The use of more resistant materi- high, and the life of loop-shaped specimens in
als can therefore be regarded as a more suitable the alternating immersion test in sodium chlo-
alternative. ride solution is particularly short. In Cu – Zn al-
loys, cracking unter stress corrosion cracking
conditions depends on the structure, intergran-
3.3.1.3. Nonferrous Metals ular cracking being prevalent in α alloys and
transgranular in β alloys.
In the presence of specific corrosive media, non-
ferrous alloys are also prone to stress corrosion
cracking. Some aluminum alloys that contain 3.3.1.4. Special Types of Stress Corrosion
Zn and Mg, for example, are sensitive to chlo- Cracking
ride solutions and seawater, and copper alloys,
especially brass, are attacked by moist ammo- An uncommon type of stress corrosion, which is
nia, causing cracking [105]. In aluminum alloys of importance in practice, is transgranular crack-
cracking is intergranular, and the formation of ing of copper-containing stainless austenitic Cr –
the cracks is related to the degree of chemical Ni – Mo steels in sulfuric acid. Cracking de-
Corrosion 687
pends on the concentration and temperature of to aerated sulfuric acid as the corrosive medium.
the acid and the level of mechanical stress [107]. A notable feature is that cracking does not oc-
In boiling sulfuric acid, the critical concentration cur at all temperatures and concentrations, but
range in which the transgranular stress corrosion only above a given corrosion rate, which under
cracking, depicted in Figure 54, occurs is 20 – the conditions in this case is around 0.2 mm/a.
60 %. In many cases copper deposits on the steel,
which is due to the prior corrosion of the copper-
containing solid solution.
The formation of copper-containing protec-
tive layers, which apparently exhibit local de-
fects under the influence of tensile stress, is a pre-
requisite for this type of corrosion. There must
therefore first be a minimum corrosion rate, as
otherwise the required concentration in the so-
lution for copper deposition cannot arise. How-
ever, if the corrosion rate is too high, a copper
layer will not form to a sufficient extent and no
cracking occurs. In this case, too, the suscepti-
bility of copper-containing, austenitic stainless
steels to stress corrosion cracking can be elim-
Figure 54. Transgranular stress corrosion cracking of stain-
less steel X 5 CrNiMoCuNb 18 18 in sulfuric acid inated by increasing the nickel content to over
A) Tensile specimen, stress 0.3 · σ ys , 50 % H2 SO4 , boiling; 32 %.
B) Bent-beam specimen, 30 % H2 SO4 , boiling
LIVE GRAPH
Click here to view
Figure 55. Iso-corrosion curves of X 5 CrNiMoNuNb 18 18

and field of SCC
Hatched area = Stress corrosion cracking region; ◦ = Sample Figure 56. Intergranular stress corosion cracking of a
without stress corrosion cracking; × = Sample with stress loop sample of X 3 CrNiMoN 17 13 5 (material no. 1.4439)
corrosion cracking; —— = Boiling curve caused by saturated ammonium nitrate solution at 180 ◦ C
In addition to the isocorrosion curves of the Transgranular stress corrosion cracking is in-
steel X 5 CrNiMoCuNb 18 18, Figure 55 shows duced not only in austenitic stainless steels but
the stress corrosion cracking zone. The data refer also in nickel alloys by aqueous alkaline solu-
688 Corrosion
tions. Since the initiation temperature for crack- In mild steels, blisters, cracks, and terraced
ing is high, often exceeding the boiling point of fractures (caused by slag and sulfide lines) can
the alkaline solution, it occurs primarily in pres- occur under sufficiently high hydrogen uptake
sure vessels. The precise conditions are set out in and static tensile stress below the yield point at
Figure 51 [108]. In ammonium nitrate solutions low temperature (e.g., room temperature): this
a type of intergranular stress corrosion crack- results from the formation of high pressure hy-
ing (see Fig. 56, see previous page) of high-alloy drogen in structural defects as shown in Fig-
austenitic stainless steels is observed at temper- ure 57 [110]. Residual stress is often sufficient
atures close to the decomposition point of am- to generate local plastic deformation and initiate
monium nitrate [109]. cracking.
3.3.1.5. Hydrogen-Induced Cracking at Low

Temperatures
The absorption of atomic hydrogen at tempera-

tures below 100 ◦ C changes the toughness and
ductility of steel; the effect increases with in-
creasing steel strength. This can be recognized
by the disappearance of the distinctive yield
point and the loss of reduction of area and elon-
gation in tensile testing.
The quantity of hydrogen Hab being absorbed
by the metallic phase from an electrolyte solu-
tion in which hydrogen ions are discharged, cor-
responds only to the hydrogen gas pressure in the
solution (generally 100 kPa, given undisturbed
equilibrium between Had and H2 gas):
Only when the steps involving recombination of

atomic hydrogen are inhibited can an increased Figure 57. Terrace-shaped fractures in a natural gas pipeline
Had concentration and hence a higher value for of unalloyed steel (X 42 API Std 5 LX) caused by condensate
containing H2 S
Hab occur. Some substances result in a partic-
ularly high retention of atomic hydrogen on a
steel surface in corrosion reactions by inhibiting Cracking occurs far more readily and rapidly
recombination. They are known as promoters or in intermediate-strength steels. In cold parts of
poisons, and include compounds of S, P, As, Se, high-pressure petrochemical plants, cracks are
Te, and Sb (e.g., thiocyanates and thiosulfates) often found in shaped components made of heat-
as well as CO and cyanides. They cause a con- treatable steel through the attack of condensates
siderable increase in the concentration of hydro- containing H2 S. The same applies to equipment
gen absorbed in the metal, which formally corre- for drilling and extracting natural gas [111].
sponds to an increased hydrogen pressure in the Hydrogen-induced embrittlement in high-
gas phase. This can give rise to considerable em- strength steels is less dependent on the occur-
brittlement of steel even under normal pressure. rence of local internal hydrogen pressure zones,
Apart from AsH3 , COS, HCN, and CO, above because they cannot induce local plastic defor-
all H2 S is responsible for many cases of damage, mation in such steels. It depends on the inter-
in particular in the chemical, petroleum, petro- action between dissolved and mobile hydrogen
chemical, and electroplating industries. and stress fields, precipitation regions, and crack
Corrosion 689
tips during a local plastic deformation process. cess (see Fig. 59A). They arise when the yield
The proneness to embrittlement by plastic de- limits are exceeded at the edges of hydrogen-
formation under the influence of low-pressure filled cavities through diffusion of atomic hy-
molecular hydrogen was reported by Hofmann drogen into the surrounding area, leaving a con-
et al. [112]. fined, speck-shaped brittle fracture with a bright
With pure molecular hydrogen, atomic hy- fracture surface. In this process the hydrogen
drogen can originate on places of plastic defor- dissociates at the plastically deforming cavity
mation (notches, scratches) by interaction bet- wall.
ween molecules and the resulting active surface
of steels. The absorbed hydrogen causes crack
initiation and propagation. This occurs particu-
larly under low-cycle fatigue conditions. Dam-
age occurs, e.g., at inner die marks in high-pres-
sure gas cylinders for hydrogen transport that are
often filled and emptied [113], [114].
A purely optical differentiation between
hydrogen-induced cracks and cracks produced
by anodic stress corrosion cracking is often ex-
tremely difficult. Figure 58 shows a case that
occurred in a spiral-welded natural gas pipeline
made of St 52.3 as a result of condensate contain-
ing H2 S and CO2 in the region of the weld and in
a neighboring stress zone. The observation that
weld seam areas and cold-formed zones are par-
ticularly prone to cracking is a general one. The
proneness to cracking of welded equipment in
the presence of nascent hydrogen can usually be
eliminated by stress-relieving annealing.
Figure 59. An exploded carbon monoxide lightweight

steel bottle made of a heat-treatable manganese steel
(σ ys = 840 MPa)
A) General view and fracture surface; B) Fragment showing
course of crack: a) Micrograph
Figure 58. Hydrogen-induced crack formation in a spiral-
welded natural gas pipeline (made of St 52.3) caused by
condensate containing H2 S and CO2 An example of the tremendous effect
hydrogen-induced cracking can have on high-
A striking feature is provided by the “fish strength steel is the explosion of a light steel bot-
eyes” sometimes seen in fractures, indicating tle (40 L volume) upon filling (Fig. 59). It was
that hydrogen was involved in the bursting pro- made of a low-alloy heat-treatable manganese
690 Corrosion
steel with a yield strength of 840 MPa and a ten-

sile strength of 950 MPa. The bottle had been in
use for 2 1/2 years, filled with technically pure
CO up to 20 MPa [108], [115]. In addition to the
presence of CO as promoter, a major part in this
damage was played by the existence of a corro-
sive water sump in the bottle since the reaction
leading to the formation of atomic hydrogen is
electrolytic. Numerous cracks were found in the
area covered with water.
Just how important the absolute absence of
moisture films is, especially in bottles made
of high-strength steel, is shown by the damage
in the form of hydrogen-induced stress corro-
sion cracking caused after several years of being
filled with pure CO2 (8 – 10 MPa) to a number of Figure 60. Corrosion of a weld of a titanium pipe
fire extinguisher bottles, which burst. The initia- A) General view; B) and C) Embrittlement as the result of
tor and source of hydrogen was the weakly acidic hydrogen absorption (structure exhibiting hydride needles);
carbonic acid formed through the presence of bending angle up to fracture 12◦ (A) and 4◦ (B)
water, which acted on the mostly horizontally-
positioned bottles along the inner surface of the
cylinder and caused cracking [115]. Ultrahigh-
strength steels are so prone to hydrogen-induced 3.3.1.6. Hydrogen Corrosion at Elevated
stress corrosion cracking that they can suffer Temperatures
brittle fracture under the effect of atmospheric
humidity. The effect of pressurized molecular hydrogen
If there is a danger of electrolyte-induced on steel must be borne in mind in a number of
atomic hydrogen formation and it is not possi- high-pressure syntheses, e.g., in high-pressure
ble to eliminate the electrolyte (e.g., by drying), hydrogenation and ammonia production. At suf-
the use of steels as soft as possible and care- ficiently elevated temperatures (> 230 ◦ C) pres-
ful stress-relieving annealing of the components surized hydrogen decarburizes carbon steels.
should be considered. Since austenitic Cr – Ni The results of this process are embrittlement,
steels in standard supply form and after normal poorer mechanical properties, grain-boundary
processing are practically unaffected by hydro- loosening and a splitting effect at defect sites
gen they can be used in difficult cases. caused by reaction products. As a consequence,
Because of their tendency to hydride forma- brittle fractures occur (Fig. 61).
tion, the embrittlement of titanium, zirconium,
and tantalum by hydrogen is particularly pro-
nounced. The proneness to gas absorption re-
stricts the use of these metals. They are not only
attacked by nascent hydrogen, they also become
brittle at elevated temperatures in gases contain-
ing nitrogen and oxygen. In addition to uniform
corrosion, these metals also show hydrogen em-
brittlement in corrosion reactions in acidic so-
lutions (Fig. 60). In the case of tantalum, hydro-
gen embrittlement can occur after long periods
in use, even when the corrosion rate is practi-
cally negligible (e.g., several thousandths of a
millimeter per year) [116].
Figure 61. Brittle fracture of a fitting (T-piece) as a result of
pressurized hydrogen attack
Corrosion 691
Figure 62. Damage to a St 35.8 pipe (NH3 plant) by pressurized hydrogen
Figure 62 shows decarburization and grain The reaction generally occurs in areas ad-
loosening in the microstructure of an unalloyed jacent to the grain boundaries, with the grains
steel as a result of pressurized hydrogen at- losing their cohesion. In addition to methane,
tack. The visible changes within the corroded recombined hydrogen molecules accumulate at
areas cause significant changes in mechanical the loosened points producing a high pressure,
properties. In the decarburized zone, the tensile which leads initially to internal microcracking.
strength, elongation, reduction in area, and hard- Component stress and lowered mechanical prop-
ness drop to very low levels as the carbon content erties finally combine to produce marked brittle
decreases. fracture.
Even the first observations of damage of this Apart from the ambient conditions, the re-
kind in the development of ammonia synthesis sistance of carbon steels to pressurized hydro-
showed that the effect of pressurized hydrogen gen attack depends on the grain size, cold form-
on steel is both chemical and physical [117]. The ing, welding effects, impurities, and heat treat-
physical effect presumably takes place in differ- ment. To prevent the reaction of hydrogen with
ent stages. Since molecular hydrogen does not pearlite, carbon-bonding elements such as chro-
diffuse in the steel, the first step must be surface mium, molybdenum, tungsten, vanadium, tita-
adsorption with dissociation at elevated temper- nium, and niobium, whose carbides are consid-
ature. In this process the metallic wall acts as a erably more stable than cementite, can be added
catalyst. With pure, dry pressurized hydrogen, to the steel. These alloying elements consider-
for example, dissociation produced by yielding ably increase the resistance of steels to hydrogen
phenomena on the steel surface can supply crit- attack [118].
ical quantities of diffusible hydrogen even at Steels resistant to pressurized hydrogen that
room temperature. are now in use contain 2 – 6 % chromium and
The next step after formation of adsorbed hy- often a further 0.2 – 0.6 % molybdenum. Some
drogen is absorption of the hydrogen. The en- types are additionally alloyed with vanadium up
suing chemical effect of hydrogen on steel is to 0.85 % and tungsten up to 0.45 %. Short-
marked by decarburization of pearlite and for- term testing gives little information on where
mation of hydrocarbons, usually methane: the limits of application of such steels lie, espe-
cially since corrosion by pressurized hydrogen
Fe3 C + 2 H2 −→ 3 Fe + CH4
692 Corrosion
normally starts after a considerable incubation sively at the crack beginning, the area of slower
period. However, experience gained with a wide crack propagation, but are not much in evidence
variety of installations does provide reliable in- at the crack tip, the area of mostly rapid prop-
dicators. Figure 63, for example, shows the re- agation. Extensively corroded cracks indicate a
sistance limits for various steels [119]. Even at high number of cycles to failure, low load am-
low hydrogen partial pressures (e.g., 2 MPa) a plitude, and severe corrosion. The component
carbon steel should not be used above a temper- finally breaks when the remaining cross section
ature of 300 ◦ C; small amounts of molybdenum is stressed to such an extent by the continuing
are sufficient to increase resistance appreciably. corrosion fatigue that it cracks through sponta-
Austenitic steels with 18 % chromium and ca. neous rupture. As an example Figure 65 shows
10 % nickel possess good resistance to pressur- damage to a pipe elbow made of 13 CrMo 4 4
ized hydrogen attack and can be used with hy- steel caused by alternating thermal stress with
drogen over the the entire temperature range of simultaneous exposure to steam (low frequency,
common high-pressure processes. long service period, marked corrosion).
Figure 63. Resistance diagram for the attack of pressurized

hydrogen on steels (Nelson diagram) [119]
a) 1.25 Cr 0.5 Mo steel; b) 5.0 Cr 0.5 Mo steel; c) 8.0 Cr
0.5 Mo steel; d) 2.25 Cr 1.0 Mo steel; e) 2.0 Cr 0.5 Mo steel;
f ) 1.25 Cr 0.5 Mo steel; g) 1.0 Cr 0.5 Mo steel; h) 0.5 Mo Figure 64. Wöhler curves, in air, after precorrosion, and un-
steel; i) Mild steel der corrosion fatigue conditions
a) Fatigue strength in air; b) Fatigue strength after precorro-
sion; c) Corrosion fatigue
3.3.2. Corrosion Fatigue
If in addition to alternating mechanical stresses

a component is exposed to a constant corrosive
effect through the environment, the resulting
damage is called corrosion fatigue. The Wöhler
curve describes the fatigue behavior of a metallic
material without corrosion. The corrosive influ-
ence shifts the area of fatigue strength for finite
life (< 107 load cycles) to lower numbers of cy-
cles and shows in addition, as depicted in Fig-
ure 64, no further fatigue strength [120]. Accord-
ingly, only a fatigue strength for finite life de-
pending on different parameters can be achieved Figure 65. Cracks in a pipe elbow made of 13 CrMo 4 4
caused by alternating thermal stress and by corrosion
under a load combination of this kind. Conditions: 340 ◦ C, steam, 105 h (11.4 a)
The corrosion process itself is localized by
slip processes at the surface generated by the In addition to the metallographic examina-
mechanical stress. The corrosive effect can also tion, microfractography can also be used to iden-
be recognized from the corrosion products that tify the cause of damage since in areas where
often deposit in cracks. These are found exten- corrosion of the rupture surface and deposition
Next Page
Corrosion 693
are not too extensive, striations are often found In passive steels the current rises only after lo-
in corrosion fatigue (Fig. 66), indicating the ac- cal activation, at which point the cracking stage
tion of alternating stress [121]. The decision as to begins immediately. This is because only one
whether pure fatigue failure or corrosion fatigue crack forms in the otherwise passive surface,
is involved can be facilitated by the appearance causing extreme localization of the corrosion
of corrosion phenomena or products on the rup- process and hence a correspondingly high cur-
ture surface. rent density at the crack base, which explains the
extraordinarily rapid crack propagation. Stain-
less steels can of course become fully active
in appropriate corrosive media, whereupon their
corrosion fatigue behavior is similar to that of ac-
tive steels. Whereas a single smooth break gen-
erally occurs in the passive state, without any
further signs of corrosion attack [124], the in-
dicators in corrosion fatigue in the active state
are numerous cracks, a fissured break due to the
converging of various crack levels, and general
corrosion attack. A comparison of active and
passive corrosion fatigue is shown in Figure 67
[125].
Figure 66. Fatigue striations on the fracture surface of an oil
cooler pipe made of brass SoMs 76, cracked by corrosion fa-
tigue due to river water
Electromechanical methods have also been

employed to study the mechanism of corrosion
fatigue [122]. If the potential changes occurring
at the surface of the specimen during corrosion
fatigue are recorded, three stages of corrosion
are found for steels with an active surface.
In the preliminary stage, potential drops in
the negative direction are observed, the cause of Figure 67. Active and passive corrosion fatigue
which can be seen as the appearance of slip lines A) Active state: severe corrosive attack, fissuring of the frac-
on the specimen surface with increased activ- ture surface, several cracks; B) Passive state: no evidence
ity, i.e., increased rate of reaction with the elec- of corrosive attack, smooth fracture surface, no secondary
cracks
trolyte.
In the second stage, these local anodes in- Since a frequently repeated minimum stress
crease in number and area, forming notches with amplitude is needed to initiate corrosion fatigue
high mechanical stress and hence high dissolu- in stainless steels in passivating solutions, it must
tion, which is marked by a further denobling of be assumed that this load limit is connected with
the potential. the mechanical stress capacity of passive layers.
In the final stage, interaction of localized cor- Only when particularly marked slip starts at one
rosion and increased notching finally leads to point on the surface will the layer be cracked.
cracking and thus to the spontaneous rupture of At that point a constantly repetitive process be-
the remaining cross section. gins, in which a new activation process at the
If corrosion fatigue of unalloyed and low- same spot always follows repassivation. Each
alloy steels is allowed to occur potentiostatically new passivation process consumes metal, deep-
and the changes in current are measured as cor- ens the corrosion, and increases the stress peak
rosion progresses, it is seen that marked current until, because of the constantly rising stress,
peaks only occur at the stage of rapid crack prop- repassivation is no longer possible. The resis-
agation [123]. tance of passive metallic materials under fatigue
Previous Page
694 Corrosion
conditions in electrolytes is therefore largely de- to these are added the increased corrosion resis-
pendent on three factors: tance of the materials used, since greater chem-
1) the extent of the load amplitude in relation to ical resistance plays a decisive role in achieving
the mechanical strength of the material and longer life.
the passive layer; An especially noteworthy feature is a process
2) the passivation properties of the electrolyte; known as low-cycle corrosion fatigue, in which
3) the passivation tendency of the material, as a stress producing constantly repetitive defor-
determined by its alloying elements. mation amplitudes and corrosion cause damage
after only a low alternating load cycle. The in-
The mechanical properties of the alloy de- teraction of plastic alternating strain and a cor-
termine the occurrence of slip. The higher the rosive electrolyte solution leads to rupture, es-
fatigue strength in air the greater the stress am- pecially in components with notches or fissures,
plitude needed to initiate sufficiently extensive after only a small number of load cycles if the
slip, i.e., the higher the resistance to corrosion corrosion is long-acting due to the low cycle
fatigue in the passive state. frequency, especially in the tensile phase (slow
In the case of “protective layers” the mechan- change in load). Embrittlement and crack prop-
ical strength and the adhesion of these layers agation also be caused under these conditions
and their healing capacity in corrosive media are by gases (e.g., H2 ) and media that show hardly
of special significance in corrosion fatigue. For any corrosive effect under static load (see Sec-
thicker layers, which themselves are subject to tion 3.3.1.5).
fatigue, a special Wöhler curve applies, whose
path is determined by the fatigue strength of the
layer if it is lower than that of the base mate- 3.3.3. Differentiation Between Types of
rial (Fig. 68). If the operating stress is below Corrosion Cracking
the fatigue strength of the material but above
that of the protective layer, the layer cracks at The term stress corrosion cracking often refers to
the points of highest stress, and local corrosion very different types of cracking under corrosive
begins. The corrosion that forms provides the attack. A clear distinction must be made between
starting point for subsequent cracks. Corrosion their corrosion mechanisms. The different types
fatigue of metallic materials with protective lay- of corrosion cracking are set out in Table 5 (see
ers is therefore preceded by a period of strain- next page). The distinction between the types of
induced corrosion, formerly known as stress- corrosion cracking is made difficult by overlap-
induced corrosion [126]. ping. This overlapping is found in particular bet-
ween nonclassical stress corrosion cracking and
corrosion fatigue and between corrosion fatigue
in the passive state and strain-induced corrosion
cracking.
In the more recent literature the term strain-
induced corrosion is commonly found, which is
a generic term for nonclassical stress corrosion
cracking, corrosion fatigue with low cycle fre-
quency, and strain-induced corrosion cracking.
For the purposes of a clear distinction between
Figure 68. Cracking of a protective layer as a precondition the different types of cracking this term should
for corrosion fatigue (strain-induced corrosion)
a) Corrosion fatigue; b) Fatigue strength in air; c) Fatigue
be replaced by the following:
strength determined by the protective layer
1) strain-induced stress corrosion cracking for
To increase the resistance to corrosion fa- nonclassical stress corrosion;
tigue, the same steps can be taken that give high 2) low cycle corrosion fatigue for strain-
structural strength (good surface, no notches or induced fatigue corrosion with low-
grooves, avoidance of stress peaks through good frequency load cycles on materials and pro-
geometrical design and processing). However, tective layers;
Corrosion 695
Table 5. Types of corrosion cracking [127]
Type of cracking Stress corrosion cracking Corrosion fatigue Strain-induced

corrosion cracking a
Classical Nonclassical Active Passive

(stress-induced) (strain-induced) state state
Type of stress constant elongation continuous strain (ε̇ > 0) pulsating strain alternating elongation
(strain rate ε̇ = 0) (with nonstatic load)
Specimen and test smooth clamped notched tensile test smooth tensile specimen, pulsating any form of specimen,
method specimen (constant specimen (constant load) or oscillating test alternating load
elongation) (mechanical and
chemical)
smooth tensile test
specimen (slow strain rate)
Corrosion system critical system no critical system parameter values
parameter values
only in systems with
film formation
Characteristics of inter- or transgranular mostly transgranular transgranular
cracking
Number of cracks often many cracks many cracks few single few cracks
cracks
a
Formerly known as stress-induced corrosion
3) strain-induced corrosion cracking for corro- pressure of the metal oxide is equal to the oxy-
sion with cracking of materials with protec- gen pressure of the surrounding atmosphere. At
tive layers as a result of layer damage on lower oxygen pressures the compound decom-
elongation change and corrosion during shut- poses into its elements.
down periods (non-stationary operation). At room temperature, therefore, practically
all metals and metal alloys – with the exception
of gold, whose oxide decomposition pressure is
greater than the oxygen partial pressure of air –
4. High-Temperature Corrosion are unstable in air and form surface oxide films.
At higher temperatures, all metal compounds de-
4.1. Principles of High-Temperature compose in principle. This is also the case at
Corrosion moderate temperatures for the oxides of silver,
mercury, platinum, and palladium, whose oxy-
4.1.1. Thermodynamic Principles gen partial pressures (decomposition pressures)
between 140 ◦ C and ca. 800 ◦ C exceed the oxy-
The reaction of a metal M in normal state gen pressure of air. At elevated temperatures,
(100 kPa) with an oxidizing gas X2 produces a however, this also applies to the oxides of cop-
solid reaction product MX, which usually forms per, iron, and other less noble metals. For most
a layer on the surface (M/MX/X2 ). The free en- oxides, however, the oxygen partial pressures re-
thalpy of such a reaction is negative for practi- quired for dissociation are too low to be achieved
cally all metal oxides, i.e., oxides are stable in experimentally, or else the decomposition tem-
atmospheres containing oxygen. Metals there- peratures are above the boiling points of the met-
fore are not stable, and oxidation or corrosion als or metal compounds.
occurs always, although it is not visible in many The decomposition pressure of a metal oxide
cases because of the low reaction rate. pO2 , i.e., the oxygen partial pressure of the sur-
With rising temperature the free enthalpy rounding atmosphere at which the oxide is just
approaches zero. This means that at a given stable at a given temperature, can be calculated
temperature, equilibrium exists between metal, from Equation (13):
metal oxide, and oxygen (100 kPa pressure). All
phases are stable next to one another, i.e., un-
G0 =RT ln 1/pO2 = 4.574T logpO2 (13)
der the prevailing conditions the decomposition
696 Corrosion
Equilibrium values (e.g., decomposition pres- pounds with anion and cation vacancies both can
sures) therefore determine the existence of com- migrate, as they can when an equal number of
pounds in metal oxidation, but the rate at which cations and anions are present at interstitial lat-
they form is a kinetic problem. Because of the tice sites.
formation of layers of low porosity that separate Nonstoichiometric compounds show elec-
metal and gaseous phase, the reaction rates of tron defects in addition to ion defects because
metals vary appreciably. Corrosion resistance in of electroneutrality. In chemical terms this can
metals therefore means that the oxidation rates be equated to the occurrence of ions of dif-
under the conditions in which they are used in ferent valency (e.g., Fe3+ in FeO). Since the
practice are low. electrons are more mobile than ions by a fac-
tor of 103 – 106 , these compounds are prac-
tically pure electron conductors (semiconduc-
4.1.2. Kinetics of Scaling tors). They can be divided into electron-surplus
conductors, and electron-deficient conductors,
When a clean metal surface is subjected to at- according to whether the electric current is trans-
tack from an oxidizing gas X2 , e.g., oxygen, ni- ported by free electrons or by defect electrons.
trogen, or chlorine, an oxidized film forms bet- The mechanism of metal oxidation can be
ween gas and metal, provided that the reaction divided into an initial phase and a phase of
product is not fragile or volatile and the oxy- diffusion-controlled scaling. During the initial
gen is not completely soluble in the structure. phase, reaction steps occur that are largely con-
This film is usually pore-free and gas-tight, and trolled by processes taking place at the phase
separates the reaction partners M and X2 . How- interfaces, such as:
ever, the reaction does not come to a standstill
at elevated temperatures. Thus, at least one of 1) cleavage of the molecules of the oxidizing
the reaction partners must diffuse through the medium into atoms and chemisorption;
MX film. The mechanism and the rate of diffu- 2) formation of a nonepitactic, polycrystalline,
sion of the reaction partners through the reaction primary oxide film;
products are decisive factors in the reaction of 3) occurrence of monocrystalline, epitactic nu-
metals with gases. They are closely linked with clei on the metal surface and the spread of
imperfections in the MX layer. these nuclei through lateral propagation.
All crystalline solids exhibit defects in and
departure from the ideal lattice structure, par- These steps of the first reaction phase take
ticularly at elevated temperature. Either lattice place rapidly at elevated temperatures and high
points remain unoccupied (vacancies) or lat- partial pressures of the oxidizing medium with
tice elements deposit between the regular lattice formation of protective films. After the forma-
points (interstitial lattice points). These point de- tion of thin layers, a protective film propagates,
fects determine material transport in a solid. In as is observed in the scaling of Fe, Ni, and Co at
addition, there are a number of linear and face moderate and elevated temperatures, in the form
defects (dislocations, grain boundaries, etc.), of a dense layer. The reaction can only then con-
which although of importance to the mechan- tinue if at least one of the reactants can diffuse
ical properties of a solid are less significant for through the scale. At elevated temperatures, pos-
material transport. itive partial pressures of the scaling atmosphere,
When metals react with gases, the main cor- and a certain layer thickness, the phase boundary
rosion products are ionic compounds which can reactions are generally rapid. Therefore, trans-
be stoichiometric or nonstoichiometric. Gener- port processes such as the diffusion of oxygen
ally, only defect ions (ion conductors) arise in to the metal or the transport of metal through
stoichiometric compounds (e.g., AgCl, NaCl). the initial layer or scale, become the slowest and
Four border cases of imperfections are possible: hence the rate determining process (Fig. 69). Af-
When cation vacancies in the lattice and cations ter layer formation the oxidation reaction thus
at interstitial lattice sites are found in an undis- continues by way of diffusion of the metal or
turbed anion lattice, the cations are mobile. In nonmetal in the form of ions, electrons, or de-
the opposite case the anions are mobile. In com- fect electrons through the film.
Corrosion 697
where k is a constant. Knowledge of the rate-

determining step is needed if the oxidation rate
is to be influenced. This can be determined from
detailed kinetic measurements. As the scale
increases in thickness, however, diffusion in
the scale will at some point become the rate-
determing partial step. The mechanism of scale
formation also determines whether a crack in the
film surface layer can mend or not. If metal ions
and electrons migrate outwards, the oxide film
propagates at the oxide – atmosphere interface
and the crack quickly closes. But when oxygen
ions migrate inwards the oxide film propagates
at the metal – oxide interface and the crack can-
not close.
The mechanical properties of the oxide film,
in particular the formability and state of stress,
determine the occurrence of cracks. If the forma-
bility of the film is poor the contact between
metal and oxide is lost as long as ion migration of
the metal is from the inside to the outside. Oxy-
gen migration from the outside to the metal –
oxide interface leads to formation of a new oxide
scale, which propagates into the metal.
Wagner’s Theory of Metal Oxidation.

Figure 69. Transport processes and layer growth Assuming that only ions and electrons migrate
A) Layer growth with preferential oxygen diffusion; B) in the scale and not neutral atoms, Carl Wag-
Layer growth with preferential metal diffusion; C) Diffusion ner established a formula in the 1930s whereby
processes and phase interface reactions for the oxidation of
iron at > 570 ◦ C the parabolic scale constant of a pure metal can
be calculated from the free formation enthalpy
of the corrosion product, the electrical conduc-
tivity of the protective layer, and the transport
Time Laws. For the formation of very thin numbers of cations, anions, and electrons in the
films (about 10 nm) at low temperature, log- film [128]:
arithmic, reciprocal-logarithmic, or cubic time
laws can be deduced. If diffusion determines the (a)
px2
rate of formation of thick and compact scale, a
300 1
parabolic time law applies k= (U1 +U2 ) U3 xdlnpx2 (17)
96500N ·ε Z2
(i)
dx k px2
= (14)
dt x
where:
which in integrated form reads:
k = rational scale constant in mol cm−1 s−1
N = Loschmidt’s number
x2 = 2k t (15)
ε = elementary charge
where x is the thickness of the scale, t is the re- Z2 = charge of the nonmetal in the protective
action time, and k is the scale constant. If the film
rate is determined by phase boundary reactions U = transport number with index 1 for
a linear law applies cation, 2 for anion and 3 for electron
(U 1 + U 2 + U 3 = 1)
dx/dt=k or x=kt (16) x = electrical conductivity in Ω−1 · cm−1
698 Corrosion
p = partial pressure of the nonmetal X2 with by adding less noble metals. In this case the ox-
index i at the interface M/MX and index ide of the alloying element is more stable than
a at the interface MX/X2 . that of the base metal. The oxidation rate will be
The rate of oxidation with rate-determining lower if the concentration is high enough for the
diffusion in the scale is calculated from this formation of a sealed oxide film, and the diffu-
equation. This is the maximum oxidation rate sion rate of the ions and electrons in this oxide is
for a gas-tight protective layer. The equation ap- lower than in the oxide of the base metal. Exam-
plies for the oxidation, sulfurization, nitriding, ples of such oxides are Cr2 O3 , Al2 O3 , and SiO2 .
and halogenation of a metal (X2 = O2 , S2 , N2 , The metals of these oxides provide the scale re-
halogen). Two border cases can be differentiated sistance of heat-resistant alloys. The metals Ag,
with the equation. For (U 1 + U 2 ) 1 (ion con- Cu, Ni, and Fe can dissolve oxygen. If these met-
ductors), k is determined by the parameter U 3 , als contain small amounts of less noble metals
the electron transport number. For U 3 1 (elec- (Al, Cr, Si, Ti) these can be oxidized within the
tron conductors), k is determined by (U 1 + U 2 ). metal phase (internal oxidation). Internal oxida-
tion does not occur as long as the concentration
of the alloying elements is so high that a sealed
oxide film of the alloying element forms on the
4.2. Oxidation of Alloys surface.
Whereas the oxidation rate of pure metals for the

case of rate-determining diffusion of ions and 4.3. Sulfurization of Metals and Alloys
electrons in the protective film can be predicted,
this is not possible for the oxidation of alloys. The reaction of metals and alloys with sulfur
It will probably never be possible to predict the is basically identical to oxidation with oxygen.
oxidation rate of alloys because too many ef- Thus, Wagner’s formulae are also applicable
fects can overlap. The following effects must be here. However, the sulfurization rate of most
considered in the oxidation of alloys: metals is far higher than the oxidation rate in
1) the influence of the base metal, air or oxygen because of the following:
2) composition of the alloy, 1) Most sulfides show far greater disorder than
3) formation enthalpy of the oxides, sulfides, the corresponding oxides. Therefore, sub-
and halides in question, stance transport in them is greater.
4) effect of dissolved oxides of the alloy com- 2) Some sulfides form relatively low-melting
ponents on the disorder of protective oxide eutectics with metals. The protective effect
or sulfide films, of the film is thereby lost. Examples of this
5) formation of mixed oxides, are:
6) formation of ternary oxides or sulfides,
7) diffusion within the alloy, Fe – FeS mp 965 ◦ C
8) solubility and diffusion of oxygen in the FeO – FeS mp 940 ◦ C
metal phase (internal oxidation), Fe – FeO – FeS mp 925 ◦ C
Co – Co4 S3 mp 880 ◦ C
9) relationship between the formation rate of Ni – Ni2 S3 mp 645 ◦ C
different oxides.
Adding more noble metals has little influence
on the oxidation of the base metal. The more no- The low melting point of the Ni – Ni2 S3 eu-
ble metal will accumulate in metallic form, e.g., tectic is the reason for the high sensitivitiy of
Cu in steel (danger of red shortness), at the al- high-nickel materials to sulfur. The resistance to
loy – scale interface. Higher contents can lead to attack by sulfur can be improved by adding chro-
a marked retardation of oxidation because diffu- mium. However, the protective effect of chromi-
sion within the alloy could become the slowest um is not as high for attack by S2 as it is for at-
partial step. tack by O2 (see Figs. 70 and 71, next page) [129,
If the oxidation rate of a metal is to be 130].
changed appreciably this can only be achieved
Corrosion 699
LIVE GRAPH
Click here to view 1) the fuel has been burnt completely (air sur-
plus) or not (air deficiency),
2) the fuel contains sulfur,
3) the combustion gases contain ash or dust par-
ticles.
The effect on the scaling behavior of steel
of air surplus and deficiency from sulfur-
containing fuels and sulfur-free fuels is shown
schematically in Figure 72. In sulfur-free gases,
oxidation with surplus air is somewhat greater
than in incompletely burnt gases. In gases con-
taining sulfur the situation is reversed. In com-
bustion gases containing oxygen, the sulfur con-
tent of the gas has practically no influence,
whereas the scaling rate increases in incom-
pletely burnt gases [132]. The behavior depicted
in Figure 71 is observed in many cases. To under-
stand this behavior, thermodynamic and kinetic
Figure 70. Influence of the silicon and chromium contents considerations are necessary.
on the scaling resistance of steel during annealing in air for
120 h
—- 0.5 – 1.0 % Si; – – – 2.0 – 3.0 % Si
LIVE GRAPH
Click here to view
Figure 71. Dependence of the sulfurization constant k of Figure 72. Scaling of soft steel at 850 ◦ C in combustion
steels on the chromium content in the temperature range gases from sulfur-containing and sulfur-free fuel
– 1000◦ C
800 a) 0.15 % SO2 ; b) SO2 -free
2
k= ∆m A
· 1t
The isothermal section through the Fe – O – S
∆m = Mass increase, g; A = Surface area, m2 ; t = time, min
system (Fig. 73) shows how the stability of the
individual phases changes as a function of the
oxygen and sulfur pressure. For a given sulfur
content of a gas, the oxides are stable at high
4.4. Corrosion by Combustion Gases oxygen pressure; at low oxygen pressure, how-
[131] ever, the sulfides are stable. That is why ox-
ides are stable in fully burnt gases containing
The effect of combustion gases from fossil fuels sulfur, and sulfides are stable in incompletely
on metals depends on whether burnt gases because of their very low oxygen
700 Corrosion
pressure. These thermodynamic considerations fore be investigated with the same electrochem-
alone, however, are not sufficient to avoid sulfide ical methods as are employed to study corrosion
formation in gases containing sulfur and oxy- in aqueous media (Fig. 76) [135].
gen. Kinetic measurements show that where ox-
ides exist, both oxide and sulfide form simulta- LIVE GRAPH
Click here to view
neously if scaling does not follow a parabolic
time law, i.e., if the diffusion of ions and elec-
trons in the oxide film is not the slowest partial
step [131].
Figure 74. Dependence of the mass increase of steel

X 20 CrNiSi 25 4 (material no. 1.4821) after annealing for
6 h in V2 O5 - containing oil ashes on the oxygen content of
the gas
a) Synthetic oil ash (V2 O5 : Na2 O = 3), annealing tempera-
ture 800 ◦ C; b) Natural oil ash (V2 O5 : Na2 O = 1), annealing
temperature 700 ◦ C
Figure 73. Isothermal section through the Fe – O – S system

at 700 ◦ C
4.5. Effect of Ash, Deposits, and Salts

Many corrosion problems arise through deposi-
tion of ash and dust on the metal surface. These
deposits can react at elevated temperatures, even
in the solid state, with the protective films of
metals and alloys to form new compounds with
different transport properties. However, corro-
sion becomes particularly intense when fusible
phases form because either the deposits con-
tain components with relatively low melting
points, or low-melting eutectics arise between
the deposits and protective films. A well-known
phenomenon is oil ash containing vanadium
(Fig. 74) [133], which in the presence of surplus
oxygen creates a critical oxidation rate. Other
oxides such as PbO, MoO3 , and B2 O3 can also
form low-melting eutectics. Alkali-metal sul-
fates are also often responsible for increased
corrosion (Fig. 75) [134]. The reactions are ex-
tremely complex. Since most salts and oxides in
Figure 75. Corrosion rates of various high temperature and
molten state are dissociated into ions, electro- heat-resistant steels embedded in pure potassium sulfate af-
chemical processes, similar to those in aqueous ter annealing for 700 h at 650 ◦ C in an air – steam environ-
solutions, take place. These reactions can there- ment containing SO2 (dew point 165 ◦ C)
Corrosion 701
proven that this steel can be used for years in the

ammonia cycle-gas at 450 ◦ C. After ten years the
penetration depth of nitration is 1 mm at most.
LIVE GRAPH
Click here to view
Figure 76. High-temperature corrosion in salt melts Figure 77. The effect of a H2 – NH3 gas mixture on various
A) Schematic of corrosion; B) Dependence of the corrosion steels (t = 450 – 520 ◦ C; p = 32.5 – 90 MPa)
in salt melts on the potential (at 750 ◦ C for 23 h)
a) 10 CrMo 9 10; b) X 10 CrAl 18; c) X 10 CrAl 24
LIVE GRAPH
Click here to view
4.6. Corrosion by Synthesis Gases
In high-pressure synthesis the corrosive effect of

hydrogen is not the only problem: there is also
the problem of corrosive gas mixtures involved
in the reaction. Their reaction products must also
be taken into account. In ammonia synthesis, for
example, there is the additional aspect of the ni-
triding effect of ammonia, which results in the
formation of a nitride layer and embrittlement
of the material beneath this layer. The behavior
of various steels in an ammonia – hydrogen gas
mixture is shown in Figure 77 [136].
After Armco iron, austenitic steels are least
prone to corrosion. Ammonia has a nitriding
and embrittling effect on unalloyed and lowalloy
steels at 250 ◦ C, and in austenitic steels corro- Figure 78. Depth of nitriding of various steels following
sion begins at ca. 350 ◦ C (Fig. 78) [137]. How- nitridation in ammonia for an annealing time of 300 h
ever, a standard 18-8 CrNi steel shows only a a) 13 CrMo 4 4; b) 17 CrMoV 10; c) 10 CrMo 9 10;
very shallow nitriding depth, and experience has d) X 8 Cr 17; e) X 8 CrNiNb 16 13
702 Corrosion
Carbon monoxide is also important in that

2 CO −→ CO2 + C
it is frequently used as synthesis gas, e.g.,
in methanol synthesis. Under pressure, car- Since this reaction is highly exothermic, in-
bon monoxide attacks unalloyed and low-alloy dividual apparatus parts can overheat [139]. In
steels above 130 – 140 ◦ C, forming iron pen- this way expansion has occurred in high-pres-
tacarbonyl. Above 350 ◦ C, corrosion practically sure vessels; the carbonyl produced must there-
ceases again because the carbonyl becomes un- fore be removed.
stable. In high-alloy chromium and chromium –
nickel steels the damage is appreciably less.
Chromium steels with 30 % Cr and austenitic 4.7. Oxidation Behavior of Technical
steels with 25 % Cr and 20 % Ni are completely
stable. Figure 79 shows the corrosive effect of
Alloys
CO on various steels in a short-term test with
pure CO – H2 mixtures at two CO partial pres- 4.7.1. Steels
sures [138]. A striking feature is the shift in the
corrosion maximum of the 18-9 CrNi steel at the The scaling of steels in air has so far been inves-
higher CO partial pressure. This possibly corre- tigated more thoroughly than in other corrosive
sponds to the beginning of nickel carbonyl for- media. Behavior in air is often the basis for a
mation, which after a period of time leads to a comparison of steels with respect to their appli-
chromium-enriched and, therefore, more stable cability. However, since the corrosion conditions
surface layer. in technical gases can differ appreciably from
LIVE GRAPH
those in air, extrapolation of parameters deter-
Click here to view mined in air to the service behavior of steels is
only possible to a limited extent.
The time function of oxidation is described
by the equation:
∆mn =kt
where ∆m is the mass loss or increase, t the

time, k the scale constant, and n a dimensionless
exponent. The exponent n indicates the type of
rate-determining reaction step and gives infor-
mation on resistance. Values of n ≥ 2 generally
indicate resistance capacity, and values < 2 often
imply lack of resistance. If n and k are known,
metal losses can be calculated for any corrosion
time. However, n is frequently variable because
of transition from resistance to lack of resistance
(breakdown), e.g., through a change in the oxide
composition of alloy steels. Unalloyed steels can
be used in air up to 550 ◦ C and low-alloy steels
up to ca. 600 ◦ C. The applicability of high-alloy
Figure 79. Corrosion behavior of various steels in CO – H2 steels is determined by the alloy contents, with
gas mixtures at two CO partial pressures
a) Boiler plate; b) 3.3 Cr/0.3 Mo; c) 13.1 Cr/0.34 Mo; special importance attached to Cr, Si, and Al, as
d) 16.2 Cr; e) 18-9 CrNiCO partial pressure: · = 12.5 MPa; demonstrated in Figures 70, 80, and 81 [140].
∗ = 35 MPa Water vapor and carbon dioxide in air generally
If the iron carbonyl produced on CO attack is worsen the scaling behavior of steels. The resis-
carried into the synthesis cycle, carbonyl decom- tance of steels in water vapor is of particular im-
position can occur at elevated temperatures with portance in steam boilers and heat exchangers.
the formation of active, pyrophoric iron, which To date it has been investigated at temperatures
in turn catalyses thereaction up to 800 ◦ C.
Corrosion 703
LIVE GRAPH Resistance to carbon dioxide is required of

Click here to view
certain components in gas-cooled nuclear reac-
tors, e.g., in heat exchanger tubing and fuel ele-
ment cladding, where temperatures up to 800 ◦ C
exist. Data on high-temperature corrosion in
carbon dioxide provide further indication of the
performance of heat-resistant steels in exhaust
gases arising from combustion of pure gases, es-
pecially when corrosion tests are run in carbon
dioxide containing water vapor. Basically the
same time laws apply to scaling in carbon diox-
ide as to scaling in air, but with carbon dioxide,
graphite deposits in the scale can occur in un-
alloyed and low-alloy steels, and carburization
in austenitic steels. The penetration of carbon
Figure 80. Influence of the chromium content of steels con-

taining 0.15 % C and 0.7 – 0.9 % Si on the scaling resistance
in air
Annealing temperature, ◦ C: a) 800; b) 700; c) 600
LIVE GRAPH
Click here to view
LIVE GRAPH
Click here to view
Figure 81. Influence of the Al and Cr contents on the scaling

resistance of steel when annealed in air for 120 h
a) 6 % Cr; b) 2 % Cr; c) 0 % Cr
—— 600 ◦ C; – – – 700 ◦ C
Scaling in water vapor on low-alloy steels is

similar to that measured in air at a temperature
some 50 – 100 ◦ C higher. This applies to high-
alloy steels even at elevated temperatures. Of
significance here is the shift of breakdown to-
wards greater scaling: the breakdown in low-
alloy steels can be about 50 ◦ C lower and in
high-alloy steels up to 150 ◦ C lower. The im-
proved scaling behavior provided by Cr, Si, and
Al corresponds to that obtained in air. A posi-
tive effect has also been found for molybdenum. Figure 82. Scaling behavior of a steel similar to 13 CrMo 4 4
In steels with higher chromium content, nickel and dependence on the water content of carbon dioxide at
makes a pronounced improvement. 500 ◦ C
704 Corrosion

Figure 83. Dependence of the lifespan of Ni – Cr alloys on temperature in various gases

A) NiCr 80 20; B) NiCr 30 20 (Fe-containing)
Curve Gas composition, vol %
H2 CO CO2 CH4 N2 O2
a 40 20 40
b 20 13 7 2 58
c 25 7 4 3 59 2
d (air)
into an alloy can lead to the following processes, content, on the other hand, has a negative ef-
which alter properties and reduce scaling resis- fect. In addition to high carbon dioxide pres-
tance: sure, it is the cause of premature breakdown,
i.e., the formation of noncovering oxide films,
1) lower melting point (by ca. 350 ◦ C in Ni – Cr whereby in addition to the time of breakdown,
alloys); the scaling rate after breakdown is also influ-
2) carbide formation with chromium deple- enced. For dry gas (< 5 – 10 ppm H2 O) scal-
tion: cubic Cr23 C6 , triclinic Cr7 C3 , and or- ing follows a parabolic time law; higher wa-
thorhombic Cr3 C2 ; ter contents (see Fig. 82, previous page [141])
3) formation of a brittle, intermetallic σ-phase. give practically straight lines, with gradients that
Graphite contents in the scale lead to a loos- increase with increasing water content. Good-
ening of the oxide film and accelerate the oxida- ison et al. found in low-alloy steel at 420 ◦ C
tion rate. and 2.9 MPa gas pressure the following rela-
The addition of carbon monoxide to carbon tion between water content and scaling rate after
dioxide reduces the scaling rate. The effect is breakthrough [142]: mass increase in g/m2 after
particularly marked in the low-temperature re- 1000 h = 5× water content in ppm. In contrast,
gion in unalloyed and low-alloy steels. Water methane and hydrogen contents delay break-
Corrosion 705
through in unalloyed and low-alloy steels. Nio- strength of oxide films can also be greatly im-
bium and small amounts of rare earths (ca. 0.1 % proved by small additions of cerium, lanthanum,
cerium or yttrium) also have a positive effect on and calcium (ca. 0.1 %) (Ni – Cr heat conduct-
the scaling resistance of steels. ing alloys). The influence of temperature and
atmospheric composition on the performance
of Ni – Cr and Ni – Cr – Fe heat conducting al-
4.7.2. Nickel Alloys loys is shown in Figure 83 (see previous page)
[143]. The sharp drop in life span is caused by
Nickel alloys with more than 15 % Cr show good the formation of liquid carbide eutectics through
oxidation properties, which are due largely to the carbon absorption. Generally, higher application
presence of an outer Cr2 O3 layer. The adhesive temperatures than in air are possible, as is shown
by the curve drawn for performance in air.
Nickel has a high affinity for sulfur and com-
bines with it to form the eutectic Ni – Ni3 S2 ,
which melts at 645 ◦ C. However, even at ca.
100 ◦ C below this temperature, annealing in sul-
furous gases leads to penetration of sulfur into
the nickel, especially along the grain boundaries
(Fig. 84).
In reducing gases, intergranular damage due
to sulfur (H2 S) is more pronounced than in
oxidizing gases (SO2 ). Generally, the resis-
tance of nickel – chromium alloys to sulfur at-
tack increases with increasing chromium con-
tent. Suitably good values are achieved with al-
loys NiCr 50 50 and NiCr 60 40.
4.7.3. Cobalt Alloys
Oxidation of Co – Cr alloys is in many ways sim-

ilar to that of Ni – Cr alloys. The rate of cobalt
oxidation is faster than for nickel. Under equiv-
alent conditions CoO is even richer in cation va-
cancies than NiO.
Small Cr contents increase the rate of reac-
tion, but at 20 % Cr the reaction rate starts to
decrease and exhibits a minimum at 25 – 30 %
Cr (see Fig. 85). The minimum value depends
on the pressure. More chromium is needed to
stabilize a protective film since the diffusion co-
efficient of chromium in cobalt is lower than for
chromium in nickel. However, since the adhe-
sion strength of the film on Co – Cr alloys is
poorer than on Ni – Cr alloys – despite the identi-
cal oxidation rate of the Cr-containing Co alloys
with Cr2 O3 protective film – the practical oxida-
tion resistance is lower. Other alloying elements,
as Figure 85 shows, have little influence on scale
Figure 84. Cross section of a nickel sheet after annealing in
nitrogen containing 0.5 % sulfur dioxide resistance [144].
A) Annealing at 600 ◦ C; B) Annealing at 640 ◦ C
706 Corrosion
LIVE GRAPH Cladding: roll cladding, explosive cladding,

Click here to view weld overlay cladding;
Lining;
Coating: immersion, electrolytic metal deposi-
tion, diffusion deposition, hot dip metal coat-
ing, evaporation coating, and metal spray
coating.
Roll Cladding. Strip and sheet metal are

mainly produced by this method. Prerolled base
and coating materials with clean surfaces are
heated to the required temperature and rolled
in contact with one another. Strength-reducing
oxidation in the bonding zone can be avoided
either by rolling the base metal/cladding sand-
wich within a hermetically sealed envelope of
low-cost steel or by interleaving layers of nickel
Figure 85. Influence of alloying elements on cobalt oxida- or mild steel between the base and cladding.
tion at 1000 ◦ C Steel as a base metal can be clad with stain-
a) Al; b) Mo; c) W; d) Ni; e) Cr
less steels, silver, nickel, copper, aluminum, and
their alloys. Roll-clad semifinished products can
be further processed by well-established fabri-
5. General Corrosion Protection cation methods, although care must be taken in
Procedures hot forming and heat treatment.
The process for cladding tubes is carried out
in two stages: backward impact extrusion of a
5.1. Corrosion Protection by Coating
multilayer solid followed by forward extrusion
The best possible corrosion protection can be of the tube blank [145]. Forming with high-
achieved through the choice of suitable materi- pressure hammers facilitates the binding pro-
als (see → Construction Materials in Chemical cess [146]. For unalloyed steel as the base ma-
Industry). Given extensive corrosion attack, this terial, stainless steel and titanium have so far
can mean compulsory use of expensive mate- been examined as cladding materials; interleav-
rials that may not always prove satisfactory in ing sheaths such as Cu – Ni – Fe alloys are re-
mechanical terms. A way out of this dilemma is quired when cladding with titanium.
provided by a composite system: the underlying
function of such a system is provided by a cheap Explosive Cladding. By using high-energy
base material with good mechanical properties shock waves, composite systems can be pro-
while the corrosion resistance is imparted by a duced from materials which for metallurgical
coating material with relatively low thickness. or technological reasons can be neither roll-clad
nor weld overlay plated [147]. In this process,
the schematic for which is given in Figure 86,
5.1.1. Metal Coatings the cladding material impacts the substrate at
high speed. If the collision angle reaches a crit-
Of the various procedures for forming metal – ical value, a liquid metal jet, which is essential
metal composite systems, cladding is the most for a solid bond to form, is ejected from the con-
significant. Materials of greater thickness are tact region. Practically all metals can be com-
combined by various processes with the base bined with one another by explosive cladding.
material. Compared with cladding, lining or the Because of the small depth of the binding zone,
other coating methods are of minor importance. the mechanical properties are generally not im-
A distinction can be made between the follow- paired. While cladding of flat or tubular products
ing: is the state of the art, problems still arise when
Corrosion 707
using this method to produce other curved com- involved which cannot be combined thermally.
posite systems. Thus, in such cases design measures must be
taken to prevent the substrate and cladding ma-
terials from mixing [149].
Weld Overlay Cladding is primarily eco-

nomical for fairly thick plates and large forg-
ings. On account of their low cost and only slight
penetration, two processes are particularly sig-
nificant: submerged arc welding [150] with strip
electrodes and plasma hot-wire welding [151].
Figure 86. Schematic of explosive cladding In submerged arc welding the strip electrode
a) Expanding detonation products (swathes); b) Accelerated is fed from a coil into the flux bed and fused
coating sheet; c) Cladded coating sheet; d) Undulating bind- in the arc. The width of the weld deposit corre-
ing zone; e) Metal interface layers flowing in a laminar or sponds approximately to the width of the elec-
turbulent manner under high pressure; f) Collision point,
very high pressure (1000 – 10 000 MPa); g) Jet of material at trode, and mixing with the substrate depends on
high speed; h) Air in a collision state; i) Air at atmospheric the process parameters. The procedure is prefer-
pressure; j) Advancing collision front in the air; k) Deto- ably used to clad stainless steels. Because of burn
nation front in the explosive; l) Unused explosive; m) Base off and mixing, the electrode must be overal-
plate or substrate; n) Sheet to be clad
loyed to compensate for the loss of important
Like roll-clad products, explosively clad met- elements.
als can be further processed by all fabrication In plasma hot-wire deposition welding, an os-
procedures, although special welding conditions cillating plasma jet under inert gas melts the sur-
may be required. The problems of heat treating face of the base material. Wires of the cladding
systems of this kind are exemplified by the prop- material are fed into the molten layer, melt
erties listed in Table 6 for a combination of fine- through the passage of current, and form the
grained structural steel and titanium. cladding. The heat input in this process is small.
Consequently mixing is very limited, as are
Table 6. Heat treatment of fine-grained structural steel and titanium thermal influences on the base material. There
Treatment Temperature, ◦ C is practically no burn off, and the method is
far more widely applicable than submerged arc
WStE 460
Hot forming > 800
welding [152], [153].
Normalizing 900 – 940 There are two nonwelding methods in which
Recrystallization annealing > 600 the coating material is also in molten form. In
Stress-relieving annealing 530 – 580
Titanium homogeneous lead coating, lead is melted with
Carbon diffusion from steel into titanium > 550 burners and applied to the steel surface. Inter-
Iron diffusion from steel into titanium > 800
Hot forming > 650
mediate coatings, e.g., tin solder, are needed to
Recrystallization annealing > 500 improve adhesion.
Stress-relieving annealing 400 – 500 Centrifugally cast composite pipes are used
for special applications (e.g., cracking tubes in
the petrochemical industry) [154]. Initially the
Joining of semifinished clad products is an casting of the outer shell is produced in a rotat-
important step in the production of components ing cast-iron mold. After a suitable cooling pe-
and equipment. This presents no particular prob- riod, during which the inner surface of the cast-
lems in roll cladding because base material and ing must be protected against oxidation, the melt
coating can be welded seperately. However, to to form the inner shell of the composite pipe is
obtain the desired properties of the system the poured in. Practical experience has been gained
respective recommendations must be observed with a composite of unalloyed or low-alloy steels
[148]. with high-alloy, corrosion-resistant grades.
Joining explosive-clad semifinished prod-
ucts, on the other hand, presents a number of Lining. A further possibility of protecting
problems because metal combinations are often equipment and components against corrosion
708 Corrosion
consists of lining with corrosion-resistant ma- ple, is deposited on steels both directly and on
terials. This lining is generally attached to the an intermediate copper layer [161]. A chromium
base material (as long as a thick-walled self- coating on nickel or copper intermediate layers
supporting liner is not preferred) by local weld- also offers good application possibilities.
ing. In this case strips of the lining material are Coating with tantalum by molten salt elec-
welded to the base material and the edges of trolysis [162] has gained importance in chemical
the lining material welded to these strips. If the engineering. This process has proved successful
two materials cannot be welded to each other, a primarily for fairly small parts since it provides
form-fitting bond is used, whereby the lining ma- compact, nonporous coatings with good adhe-
terial is mechanically locked into conical slots sion and thicknesses above 200 µm. Base ma-
in the base material. This corrosion protection terials include steels, copper, nickel, and their
measure has declined: one reason is the design alloys [163], [164].
problems presented by a lining subjected to al- In the diffusion coating process the coating
ternating thermal stress. material is deposited at elevated temperature
A special lining method is the Resista from the pulverized or gaseous state. The metal
Clad process, which allows thin liners (0.15 – diffuses into the lattice of the base metal with
2.5 mm) to be applied during manufacture. The formation of a high-alloy surface zone. To pro-
base and lining materials (e.g., steel, nickel al- duce zinc or aluminum coatings (sherardizing
loys, titanium, tantalum) are attached to one an- and alitizing), the part to be coated is embedded
other by resistance welding with an intermedi- in powders of the corresponding metal chlorides.
ate layer. Depending on the service conditions, Chromium coatings are deposited by inchromiz-
the distance between the weld seams can vary ing from gaseous or molten chromium(II) chlo-
from 20 to 150 mm. Apparatus such as vessels, ride.
columns, and heat exchangers can be operated in
vacuum (seam distance ca. 20 mm). Depending Hot-Dip Metal Coating is being used in-
on the coating material, service temperatures of creasingly in automated, continuous plant, in
up to 350 ◦ C are possible [155–157]. Appara- particular for the production of semifinished
tus and equipment manufactured by the Resista products, but also for mass-produced parts. The
Clad method have also been successfully used part is immersed in a molten bath of a coating
in flue gas desulfurization [158]. metal with a comparatively low melting point.
This is a common method for coating with zinc,
Coating. With regard to the protection they tin, aluminum, and lead.
offer against corrosion, the methods listed above
for producing coatings [159] are generally only Evaporation Coating [165] involves the
of minor importance in chemical engineering production of very pure, nonporous surface
because they cannot guarantee adequate resis- coatings by condensation of vacuum-evaporated
tance under the extreme conditions encountered metallic materials (physical vapor deposition,
in some areas of the chemical industry. PVD). However, the extremely low coating
Through immersion, metals such as copper or thickness permits application of evaporation-
silver are deposited from an aqueous solution or coated parts in chemical engineering only in ex-
molten salt onto the material to be protected. The ceptional cases.
coating thickness is ca. 1 µm and the adhesion
strength is not always satisfactory. Metal Spray Coating involves wire melt
In electrolytic methods, deposition of metals spraying and powder spraying from gas, arc
is improved by using a constant or pulsating di- spraying, or plasma spraying torches. Powder
rect current along the principle of electrolysis spraying is important for metals (and several
[160]. Voltages of 1 – 10 V and current densi- nonmetals) that cannot be made into wires. Com-
ties of 5 – 100 mA/cm2 are used. Depending on mon to all these processes are the melting of the
the base metal, coating metals such as nickel, coating material in the heat source as it leaves
copper, zinc, tin, chromium, silver, and gold can the torch, the atomization of the coating mate-
be applied to the base material either directly rial, and the impinging and adhesion of the metal
or with intermediate layers. Nickel, for exam- droplets on the bare metal surface of the object
Corrosion 709
to be coated. As the adhesion of sprayed metal A prerequisite for good resistance to corro-
coats is entirely mechanical, the adherence de- sion is that the protective coating must be dense
pends very much on the physical nature of the and free from pores. Flame-sprayed coatings,
substrate. A roughened and clean (shot-blasted) with their low density and numerous oxide inclu-
surface is therefore a prerequisite for good ad- sions, are therefore unsuitable in many cases for
herence. exposure to aggressive media. Plasma-sprayed
The most important materials used for chemi- coatings are denser and more homogeneous.
cal plant include metals with high melting points Plotting current density against potential
and good resistance to corrosion, such as tan- curves is a quick way of investigating the elec-
talum and molybdenum, but also titanium and trochemical behavior of thermally sprayed coat-
nickel alloys, including hard metal alloys. ings and gaining an initial impression of their
Alloys based on Ni – Cr and Co – Cr, con- resistance to corrosion. Figure 88 shows current
taining borides, silicides, and carbides, and ap- density – potential curves for plasma-sprayed
plied by powder flame spraying, are used to pro- Ni – Ta – Cr – B alloys (containing τ -borides) in
tect components from corrosion and wear. The 0.1 N sulfuric acid. All three alloys show good
inherent pore volume of a coating can be re- resistance to corrosion by virtue of their chemi-
duced to about 1 % by a subsequent densify- cal composition and the fact that the coatings are
ing heat treatment [166]. Figure 87 shows the very dense. Figure 89 shows the microstructure
structure of a flame-sprayed and subsequently of a coating of this type on unalloyed steel. Al-
densified hard metal coating consisting of Ni – though alloys forming τ -borides are still under
Cr – Si – B. The Si and B form fluxes by alloying development, they will become increasingly im-
and lower the melting point. Exceptional hard- portant in the protection of chemical plant com-
ness (60 – 70 RC ) and good adherence can be ponents [167].
obtained when W2 C is introduced into the sur- LIVE GRAPH
face of the substrate. A conveyor screw made Click here to view
of mild steel (St 37) protected by Ni – Cr – Si –

B provides an example of the improvements in
durability achievable by these techniques. The
useful life in this instance was increased 12-fold.
The life of an iron sludge pump casing spray-
coated with a W2 C/Ni – Cr – Si – B alloy, which
was subsequently densified at 1050 ◦ C was ex-
tended 10 times. Note that subsequent thermal
densification may distort the component and al-
ter the structure of the material.
Figure 88. Current density – potential curves for various al-

loys containing τ -borides in 0.1 N H2 SO4
a) Ni25Ta8CrB; b) Ni20Cr3TaB; c) Ni38Ta7CrB
The high-velocity flame spraying (Jet-Kote)

process, which became commercially available
only a few years ago, is similar to powder flame
spraying, but differs in that the spray particles are
accelerated to high velocities in the gun, with the
result that the adherence and density of the coat-
ing are superior to those achieved by conven-
tional powder flame spraying. However, some
Figure 87. Microstructure perpendicular to the surface of kinds of spray powder cannot be applied by this
a flame-sprayed and densified coating of a Ni – Cr – Si – B technique. Figure 90 shows the good adherence
alloy and low porosity of a Hastelloy C-4 coating ap-
plied by the Jet-Kote process.
710 Corrosion
Spray coatings consisting of metals with high

melting points are applied mainly by plasma
spraying, as used particularly for oxide ceramic
coatings. Coat thicknesses of 0.1 to several mil-
limeters are feasible and good adherence is ob-
tained. The coating is relatively dense, but con-
tains individual closed pores. Vacuum or low-
pressure plasma spraying is a further devel-
opment of atmospheric plasma spraying. The
process is carried out in a pressure chamber
(Fig. 91), which is evacuated to 20 Pa. While
the spraying is in progress, argon is introduced
until the pressure reaches about 5 kPa. The re-
sulting inertization prevents the reactions bet-
ween molten particles and the surrounding atmo-
sphere that occur in atmospheric plasma spray-
ing [168]. This modification gives the process
substantial advantages over conventional plasma
spraying. In particular, the method enables reac-
tive metals such as Ti, Ta, and Nb to be applied
Figure 89. Microstructure perpendicular to the surface of a
as very dense, nonporous coatings. At present
plasma-sprayed Ni – Ta – Cr – B alloy containing τ -borides the process suffers from the limitations imposed
by the dimensions of the chamber and the high
cost (¤0.75 million).
Figure 91. Vacuum chamber for plasma spraying of Ti, Ta,

and Nb
5.1.2. Inorganic Nonmetallic Protective

Coatings
Important inorganic nonmetallic coatings used

Figure 90. Hastelloy C-4 coating applied by powder flame for the protection of chemical plant include,
spraying (Jet-Kote process) above all, enamels with high silicon dioxide
and low boric acid contents, brick linings based
on silicates and carbon, as well as thermally
Corrosion 711
sprayed coatings based on metal oxides and resins (see Table 8). In general it can be as-
metal carbides (see Table 7). Metal nitrides and sumed that the oxide and silicate coating and
metal borides are also used, but less often be- lining materials used for chemical plant are out-
cause chemically they are less resistant. Hav- standingly resistant to acids (except hydrofluo-
ing low thicknesses of ≤ 20 µm, coatings formed ric acid and phosphoric acid), salt solutions, and
on metal and plastic substrates by chemical and organic compounds of all kinds. As a rule they
physical deposition from the gas phase (CVD resist aqueous alkaline solutions up to 50 ◦ C.
and PVD) are of only minor importance in cor- Unimpregnated carbon materials withstand tem-
rosion protection. The same applies to protec- peratures up to 400 ◦ C, while those that are im-
tive coatings formed by reaction of the metal pregnated with synthetic resins are stable up to
surface with acidic phosphate, chromate, or ox- 180 ◦ C. With silicate materials the chemical at-
alate solutions; these are used particularly as tack, which occurs almost entirely on the sur-
passivating primers for paints. Lining with tubes face, depends greatly on the pH and water con-
and other shaped parts consisting of fusion-cast tent of the attacking medium. Water-free acids,
basalt [169] has gained some importance as a except phosphoric acid, do not attack silicate
means of protecting plant from corrosion and materials. The resistance of carbon materials de-
abrasion, and the same is true of the use of tung- pends on the resistance of the resin impregnating
sten carbide platelets for screw cladding [170]. agents and putty joints.
Table 7. Inorganic nonmetallic protective coatings used in Table 8. Main properties of the constituents of the enamel/mild
chemical engineering steel system
Material Applications a Property Enamel Boiler plate
Enameling (0.8 – 2.2 mm) Adhesive strength, steel/enamel, 100

Vitreous or partly crystalline Acidic and organic media up to MPa
Compressive strength, MPa 800 – 1000 2000 (60 %
230 ◦ C (340 ◦ C b )
compression)
(except HF and H3 PO4 )
Tensile strength, MPa 70 – 90 400
Alkaline media up to 60 ◦ C
Brick lining Coefficient of thermal expansion 80 – 135×10−7
Acid-resistant bricks Neutral, acidic, and organic media (20 – 400 ◦ C), K−1 95×10−7
up to 200 ◦ C Compressive prestress, MPa 130
Carbon bricks and Nonoxidizing acidic, alkaline, or Elastic modulus, GPa 70 210
electrographite, impregnated organic media up to 180 ◦ C Vickers hardness, MPa 6000 1100
Carbon bricks and Nonoxidizing media up to 400 ◦ C Fracture strain, % 0.15 – 0.3 25
electrographite, Yield strength, MPa 200
unimpregnated Impact force (DIN 51 155), N 40 – 80
Refractory bricks Lining of reaction zones in which Coefficient of thermal conductivity, 3.35 188
temperatures of up to ca. 1600 ◦ C kJ m−1 h−1 K−1
occur Specific heat (10 – 100 ◦ C), 0.84 0.46
Thermally sprayed coatings kJ m−1 h−1 K−1
Metal oxides Wear protection, neutral and acidic Specific resistivity, Ω · cm 12
10 – 10 14
0.002
media up to 100 ◦ C Dielectric strength (room 20 – 30
Metal carbides Wear protection, neutral and temperature), kV/mm
alkaline media up to 80 ◦ C Density, g/cm3 2.5 7.8
Ceramic – metal mixtures Special applications and Softening point, ◦ C 790
(cermets) intermediate coatings Melting point, ◦ C 960 1510
CVD and PVD coatings Corrosion-inhibiting wear Enamel thickness, mm 1–2
protection
a
The indicated temperature limits depend on the agressiveness
and concentration of the medium and may in certain cases be too
high. If no experience is available, it is advisable to carry out
corrosion tests. 5.1.2.1. Enamel
b
With increased compressive prestressing, which extends the
temperature range to 340 ◦ C and enhances the resistance to An enameling is a highly stable combination
thermal shock [175].
consisting of enamel (an inorganic oxide-based
glass flux) and a metallic substrate. Known in the
The resistance of protective materials de- process industries as chemical enamel, the com-
pends mainly on whether they are based on bination of enamel with steel has for decades
oxides or on silicates, consist of carbon, or been firmly established in chemical processing
have been sealed by impregnation with synthetic plants. Its stability is such that many chemical
712 Corrosion
processes are dependent on it, and many prod-

LIVE GRAPH
ucts can only be manufactured economically in Click here to view
enameled apparatus [171]. By virtue of their
structure [172] – highly stable silicate glass in
a firm bond, created by fusion, with supporting
steel – the traditional domain of enamel coatings
is processes that involve reactions with acids at
high temperatures. However, the development
of enamel formulations and enameling technol-
ogy have considerably extended this traditional
field of application: enamel is now being used
increasingly as an all-round material for expo-
sure to neutral and alkaline media as well [173].
This applies equally to vitreous enamels and to
the partly crystalline ceramic enamels. Table 8
lists the main properties of the partners in the
enamel/unalloyed steel system. The stability of
this system, represented as iso-corrosion curves
for a corrosion rate of 0.1 mm/a, is shown in
Figures 92 and 93 for characteristic acids and
alkali. Stability tests are performed at atmo- Figure 92. Iso-corrosion curves (0.1 mm/a) for chemical
spheric pressure according to DIN/ISO 2743, enamel in acids
2744, and 2745, and under pressure according
to DIN 51 174. The temperature dependence of
the corrosion rate obeys the Arrhenius equa- LIVE GRAPH
Click here to view
tion. A corrosion rate of 0.1 mm/a is normally
the highest at which enameled apparatus can
be used economically, and it should not be ex-
ceeded, especially in cases where intermediate
exposure to alkali is involved, e.g., in neutraliza-
tion reactions and cleaning processes. Vitreous
and ceramic enamels differ little in their resis-
tance. If a glassy cover coating is not present, the
chemical resistance of partly crystalline enam-
els is in some cases considerably lower than that
of glassy coatings of comparable composition.
Ceramic enamels are considerably superior to
vitreous enamels in mechanical behavior, es-
pecially impact resistance, and to some extent
also in resistance to abrasion. The acid resis-
tance of enamels can be improved considerably
by adding small amounts of SiO2 to the acid,
which has a marked inhibiting effect [174]. Figure 93. Iso-corrosion curves (0.1 mm/a) for chemical
Special enamels are now available which, enamel in alkali
for example, are 300 % more resistant to al-
kali (though less resistant to acids than normal 1200 ◦ C [175]. These high-temperature enam-
enamels), which show considerably less ten- els give additional protection from scale forma-
dency to attract deposits because they have sub- tion and corrosion to alloys and metals that are
stantially improved surface quality (owing to an intrinsically heat-resistant, thus simultaneously
increase in surface tension), or which, because prolonging the useful lifetime of the plant and
they contain refractory ingredients, can be fired enabling it to withstand high temperatures. A no-
on heat-resistant substrates at temperatures up to table improvement in the already high standard
Corrosion 713
of chemical enameling is expected to result from

the use of an enamel that combines the property
patterns of vitreous and ceramic enamels. This
product, introduced at Achema 1988 [176], has a
reinforcing mechanism which is independent of
the matrix material and absorbs the energy that
tends to cause fractures. This “in situ” micro-
reinforcement enables the mechanical stability
of chemical apparatus coated with this enamel
to surpass even that of plant coated with good
ceramic enamels, without concessions having to
be made in regard to chemical stability.
5.1.2.2. Brick Lining
Acid-resistant bricks, carbon bricks, and electro-

graphite afford additional protection to parts of
plants which, owing to the severity of the chem-
ical or thermal exposure, are not adequately pro-
tected by coatings and linings.
Refractory bricks and other materials are
used, both with and without a lining between the Figure 94. Schematic of a chemically resistant brick lining
steel and bricks, to enclose reaction chambers. a) Substrate (concrete or steel); b) Resistant sealing com-
Depending on the conditions to be withstood, pound; c) Bonding cement; d) Bricks or tiles; e) Pointing
cement
the products used include basic and neutral ma-
terials with high silicon dioxide contents, carbon
bricks, and silicon carbide bricks. The structure These can be applied reliably by flame spray-
of a chemically resistant brick lining is shown ing, detonation spraying, or plasma spraying.
schematically in Figure 94. Metal oxides, metal carbides, or their mixtures
are melted in a plasma flame at ca. 20 000 ◦ C
and sprayed onto the surfaces of the work-
5.1.2.3. Thermally Sprayed Coatings pieces; coatings with a thickness of 0.1 mm
to several millimeters can be produced in this
Improvements in sprayable materials and spray- way. Subsequent heat treatment of the coating
ing techniques have already resulted in the wide- can make it almost nonporous through the for-
spread use of thermally sprayed coatings con- mation of a glassy phase. Most of the pores,
sisting of inorganic nonmetallic materials [177]. which account for 1 – 20 % of the volume, are
Table 9. Classification of spraying methods
Method Energy source Operating Partial velocity, Spraying material Capacity, kg/h
temperature, K m/s
Product form Material
Flame spraying fuel gas, 3200 50 – 200 wire mostly metals 5 – 8 (metals)
acetylene – oxygen
powder all types 1 – 2 (ceramics)
Jet-Kote high-speed fuel gas, slow-burning 2900 350 – 600 powder metals and 2–6
flame spraying ceramics
Detonation spraying fuel gas 3500 650 powder all types 4–6
Plasma spraying electricity 3000 – 20 000 350 – 450 powder all types 4 – 8 (metals)
2 – 4 (ceramics)
Arc spraying electricity 4000 150 wire metals 15 – 20
Next Page
714 Corrosion
closed. Corrosion-resistant coatings can be built 5.1.3. Organic Lining and Coating Materials
up without difficulty by spraying several coats
on top of one another. In Table 9 the principle The range of high-molecular lining and coat-
spraying processes are classified according to ing materials has increased substantially, both
rate of application, supplementary spraying ma- with respect to types and grades of materials
terials, and source of energy. Figure 95 shows a and with respect to their properties and applica-
polished section through a wear-resistant coat- tions. In general it can be said that modification
ing on a channel entrance in a graphite exchanger of well-known and proven materials by copoly-
[178]. merization has improved important mechanical
properties of linings and coatings, such as their
impact resistance, while compounding with ran-
domly distributed conductive carbon has en-
hanced the electrical conductivity of plastics
so much – without appreciably impairing their
mechanical and chemical stability – that the lin-
ings or coatings can now even be exposed to
combustible liquids and vapors (Figs. 97, 98, 99)
[179].
Figure 97. Schematic of materials with covered particle

structure [180]. The diameter of the electrically conduct-
ing particles is considerably smaller than that of the plastic
Figure 95. Polished section through a plasma-sprayed coat-
particles
ing on a channel entrance in a graphite heat exchanger
A) Original structure; B) Deformed structure (e.g., after pro-
cessing)
Coatings of these types can be produced on
carbon steels and stainless steels. Another appli-
cation is shown in Figure 96. The fiber deflection
roll shown here, which is coated with Al2 O3 ,
lasts three times longer than an otherwise iden-
tical roll with hard chromium plating.
Figure 98. Section through an electrically conducting

pressed sheet, consisting of high-density polyethylene filled
with carbon black and having a covered particle structure
Figure 96. Fiber deflection roll, spray coated with Al2 O3
Previous Page
Corrosion 715
ence this process include temperature, tempera-

ture gradient, the vapor pressure of the medium,
the thickness of the lining, and the chemical
affinity of the lining material and of the medium
to which it is exposed.
Protective Coatings and Linings. Protec-

tive coatings or linings consisting of organic
materials are applied to metals, especially steel,
to glass-filled UP, VE, and EP resins, and to con-
crete and masonry. They protect the substrate
from chemical attack. Recommendations for the
design and production of the items to be pro-
tected can be found in VDI-Richtlinie 2532 for
metals and in VDI-Richtlinie 2533 for concrete
and masonry; recommendations on the choice
of coating materials and methods are given in
VDI-Richtlinie 2531.
Figure 99. Specific resistivity as a function of carbon black 5.1.3.1. Rubber Linings
content
a) Uniform carbon black distribution; b) Covered particle
structure
Rubber linings (see also VDI-Richtlinie 2537)
consist of ebonite or soft rubber based on natu-
ral or synthetic polymers. They account for the
Table 10 gives a general idea of the thermal largest group of materials used for surface pro-
stability of coatings as a function of chemical ex- tection in chemical plant. Synthetic elastomers
posure. Standards and guidelines concerning or- are becoming more and more important since
ganic lining and coating materials can be found they have greater chemical and mechanical sta-
in DIN 28 053, 55 929; VDI 2531 – 2539; TRbF bility than natural materials, and less suscepti-
401 – 403; and DVS 2202, 2301. bility to mechanical damage.
Halogen butyl and self-vulcanizing systems
Effects of Media. Polymers, unlike metals, based on the chloroprene rubber Baypren have
are subject to swelling rather than corrosion. become established and proved their worth, es-
Chloride-induced pitting corrosion, to which pecially where they have been used for in situ
austenitic Cr – Ni steels are particularly suscep- treatment of large items such as storage tanks,
tible, is unknown in polymeric materials. Stress waste water purification plant and flue gas desul-
corrosion cracking, however, is possible un- furization equipment [182]. The sulfochlori-
der conditions that cause the medium to attack nated polyethylene Hypalon has good resistance
the polymer chemically [181]. Stress corrosion to acidic and alkaline oxidizing agents and to
cracking can only occur, however, if, at the same chromic acid and chlorine bleaching solution.
time, stresses resulting from manufacture, coat- Being more highly cross-linked, ebonite lin-
ing or lining, or the conditions of use are present. ings are even more resistant to swelling and per-
Where polymeric materials are concerned, at- meation than soft rubber linings. As, however,
tention should be paid to diffusion and perme- they have to be vulcanized in workshop auto-
ation, irrespective of stability behavior. Even if claves, their use is generally restricted to rela-
the protective material is stable, gaseous or va- tively small items whose volume does not ex-
porous substances may penetrate organic coat- ceed about 100 m3 .
ings and linings and, if corrosive, attack the sub- Plant components of up to about 1000 m3 in
strate, thus resulting in loss of adhesion, blister volume can also be ebonite-lined on site if hot
formation, and failure of the coating or lining water or piped steam is available for vulcaniza-
to protect the substrate. The factors which influ- tion. For adequate cross-linking, the steel must
716 Corrosion
Table 10. Organic lining and coating materials used in chemical engineering
Material a Application b
Acids, salt Alkaline solutions Oxidizing agents Organic media

solutions
Thermoplastic linings (1 – 4 mm)

PVC with plasticizer 50 ◦ C 50 ◦ C 50 ◦ C
PVC without plasticizer 60 ◦ C 60 ◦ C 60 ◦ C
PE-HD 60 ◦ C 60 ◦ C 30 ◦ C
PP with contact adhesive 50 ◦ C 50 ◦ C 30 ◦ C
PP with fabric lamination 80 ◦ C 80 ◦ C 30 ◦ C
PVDF (partly fluorinated) 100 ◦ C 80 ◦ C 30 ◦ C
E/CTFE (partly fluorinated) 100 ◦ C 100 ◦ C 80 ◦ C 30 ◦ C
FEP, PFA (fully fluorinated) 120 ◦ C 120 ◦ C 120 ◦ C 120 ◦ C
PTFE (fully fluorinated) 200 ◦ C 200 ◦ C 200 ◦ C 200 ◦ C
Rubber linings (3 – 4 mm)
Soft rubber based on natural and synthetic rubbers Nonoxidizing acidic to alkaline media up to 90 ◦ C
(NR, CR, IIR, NBR, CSM, FPM)
Ebonite based on natural and synthetic rubbers Nonoxidizing acidic to alkaline media up to 110 ◦ C
(NR, NR/IR, SBR, NBR)
Graphite-filled thermosetting plastic linings (4 – 5 mm)
PF 120 ◦ C 120 ◦ C
FU 120 ◦ C 120 ◦ C 120 ◦ C
EP 100 ◦ C 120 ◦ C 80 ◦ C
Reinforced reaction resin coatings
Glass fiber laminate coatings (3 – 0.5 mm)
UP-GF and VE-GF 70 ◦ C 50 ◦ C 30 ◦ C 30 ◦ C
FU-GF 70 ◦ C 70 ◦ C 70 ◦ C
EP-GF 70 ◦ C 70 ◦ C 30 ◦ C 30 ◦ C
Grouts and sprayed coats, reinforced with
glass flakes (1 – 2 mm)
UP and VE, based on bisphenol A 100 ◦ C
VE, based on epoxy – novolak acrylate 150 ◦ C
Paint and powder coatings (0.2 – 2 mm)
Liquid coating materials
Catalyst-curing resins (PUR, EP, UP, VE) Nonoxidizing acidic to alkaline media up to 80 ◦ C
Thermosetting resins (PF, EP, PF/EP) Nonoxidizing acidic to alkaline or organic media up to 120 ◦ C
Thermoplastic powders
PE-HD Nonoxidizing acidic to alkaline media up to 50 ◦ C
E/VAL Nonoxidizing acidic to alkaline media up to 50 ◦ C
PA Nonoxidizing neutral and alkaline or organic media up to 60 ◦ C
PVDF (partly fluorinated) Acidic to neutral media up to 80 ◦ C
E/TFE, E/CTFE (partly fluorinated) Acidic to neutral media up to 80 ◦ C
PFA, FEP (fully fluorinated) Acidic to alkaline or organic media up to 150 ◦ C
a
E/TFE Ethylene/tetrafluoroethylene, E/CTFE Ethylene/chlorotrifluorethylene, EP Epoxide, E/VAL Ethylene/vinyl alcohol, FEP
Tetrafluorethylene/hexafluoropropylene, FU Furane, PA Polyamide, PCTFE Polychlorotrifluroethylene, PE-HD High density
polyethylene, PF Phenol formaldehyde, PFA Perfluoro-alkoxyalkane, PP Polypropylene, PTFE Polytetrafluoroethylene, PUR
Polyurethane, PVC Poly(vinyl chloride), PVDF Poly(vinylidene fluoride), UP Unsaturated polyester, VE Vinyl or phenacrylic ester,
UP-GF Fiberglass-reinforced unsaturated polyester, VE-GF Fiberglass-reinforced vinylester, FU-GF Fiberglass-reinforced furane, EP-GF
Fiberglass-reinforced epoxide, CR Chloroprene rubber, CSM Chlorosulfonyl polyethylene, FPM Vinylidene fluoride/hexafluoropropylene
copolymer, IIR Isobutane – isoprene rubber, NBR Nitrile – butadiene rubber, NR Natural rubber, SBR Styrene – butadiene rubber.
b
The indicated temperature limits depend on the aggressiveness, concentration, and penetration capability of the medium and may in
individual cases be too high. If no experience is available, corrosion tests are recommended.
be heated to 90 – 95 ◦ C, which is only possible hydrochloric acid containing chlorine and sol-
if effective exterior insulation is provided. The vents without suffering damage. It was installed
largest tank known to have been ebonite-lined on at the New Martinsville works of Mobay in the
site has a capacity of 8000 m3 . It has a triple-ply United States.
lining, which was applied as a 5-mm thick single
sheet and consists of a soft rubber adhesive layer,
a diffusion-proof ebonite layer, and a corrosion- 5.1.3.2. Rubber – Plastic Composite Linings
resistant soft rubber layer. Since 1982 this tank The stability of rubber linings, especially to or-
has been continuously exposed to concentrated ganic compounds that diffuse readily in rubber
Corrosion 717
and damage it severely, can be improved by the polyester, vinyl ester, epoxy, and furan resins,
simultaneous use of plastics. In such cases a sup- and, like those described in Section 5.1.3.3, they
plementary lining consisting of a thermoplas- are thermosetting. The structure of a laminate
tic chosen for its resistance to organic or oxi- coating is shown in Figure 100. Plant protected
dizing compounds is applied on top of a soft in this way generally consists of steel, but in
rubber or ebonite lining. Where the item to be some cases of concrete. Coatings highly resis-
protected will be exposed to temperatures of up tant to acids, alkali, or even solvents can be
to 50 ◦ C in practical use, the polypropylene or produced, depending on the type of resin cho-
polyvinylidene chloride sheets, which are the sen. Storage tanks for concentrated chlorine
preferred materials, can be bonded to the rubber bleaching solution have been protected suc-
reliably with an isocyanate cross-linking chloro- cessfully with fiberglass-reinforced unsaturated
prene rubber adhesive. For higher temperatures, polyester resins based on bisphenol A fumarates
as reached in reaction vessels, for example, a or vinylesters based on bisphenol A acrylates.
bond must be formed by vulcanizing the rubber For more than 10 years fiberglass-filled vinyl
in contact with the plastic [183] or by placing esters based on epoxy – novolak acrylates have
a fabric on the rubber, applying a heat-resistant been protecting tanks of up to 5000 m3 for the
epoxy resin to it, adding the thermoplastic sheet, treatment of acidic or alkaline wastewater con-
and applying pressure by means of a vacuum taining organic compounds. Fiberglass – furan
[184]. (FU) laminates withstand solvents best, even at
elevated temperatures. At the moment, however,
the lack of ductility exhibited by FU resins re-
5.1.3.3. Linings Consisting of Thermally stricts their application to containers of up to
Crosslinkable Thermosetting Plastics 100 m3 in volume. Because of the differences
between the expansion coefficients of the sub-
Phenol, furan, and epoxy resins are the main strate and coating, fiberglass laminates can only
representatives of this group. After addition of be exposed to temperatures of up to 70 ◦ C.
plasticizers, graphite, and fibers they are ap-
plied like rubber linings as 4 – 6 mm thick sheets
and cross-linked three-dimensionally in pres-
sure vessels. In common with rubber linings they
can also be applied to items made of steel or
fiberglass-filled plastics. The cross-link densi-
ties of the finished linings are so high that the
material is neither soluble nor capable of melt-
ing, and its strength and creep resistance are not
dependent on temperature to the same extent as
Figure 100. Structure of a laminate coating (schematic)
those of thermoplastics. Thermosetting plastics a) Substrate (steel or concrete); b) Primer (ca. 0.1 mm);
are used mainly to line columns, flues, and other c) Grout (1 mm); d) Glass mats (2 mm); e) Glass veil; f) Seal-
plant items that have to withstand severe expo- ing coat (0.2 mm)
sure to chemicals and heat.
Grouts and Spray Coats Reinforced
5.1.3.4. Reinforced Reaction Resin Coatings, with Glass Flakes. Thermosetting unsaturated
Crosslinkable with Catalysts polyester (PE) and vinyl ester (VE) resins re-
inforced by glass flakes, which have a thick-
Fiber-Reinforced Laminate Coatings. ness of only a few microns and lie parallel
Fiber-reinforced reaction resins (see also VDI- to the surface of the substrate, are applied as
Richtlinie 2536) are used mainly to coat large grouts and sprayed coats, especially to protect
storage tanks on site. Generally the coating is gas ducts in flue gas desulfurization units, even
a fiberglass-mat-reinforced laminate, but some- in cases where condensates form [185]. Other
times it is applied by the fiber spraying tech- applications of these easily applied coatings,
nique. The coatings are based on unsaturated which, when silanized flakes are used, are also
718 Corrosion
relatively diffusion-proof, include the covers

of large rubber-lined, brick-lined, or laminate-
coated tanks. Details of their structure are given
in Figure 101.
Figure 101. Structure of a grout coating reinforced with

glass flakes (schematic)
a) Steel; b) Primer (ca. 0.1 mm); c) Grout (ca. 0.9 mm, 3×2-
mm glass flakes); d) Grout (ca. 0.9 mm, 3×2-mm glass
flakes); e) Topcoat (ca. 0.1 mm) Figure 102. PTFE lining with welded-in sockets, before as-
sembly
LIVE GRAPH
Click here to view
5.1.3.5. Thermoplastic Linings
These are available as semi-finished goods in

the form of foils, sheets, panels, and tubes.
The preferred materials are poly(vinyl chloride)
with or without plasticizers (PVC-U, PVC-P),
high-density polyethylene (PE-HD), polypro-
pylene (PP), poly(vinylidene fluoride) (PVDF),
ethylene chlorotrifluoroethylene (E/CTFE),
tetrafluoroethylene/hexafluoropropylene (FEP),
and polytetrafluoroethylene (PTFE). They are Figure 103. Permeability of PTFE in water at 137.5 ◦ C and
0.34 MPa as a function of density
used to protect plant made of steel, concrete, a) Ram-extruded products; b) Paste-extruded products;
or fiberglass-reinforced unsaturated polyester, c) Peeled foil
vinyl ester or epoxy resins, and their application
in the manufacture of vessels and other plant is
increasing rapidly. Except for PTFE, which can Thermoplastic lining materials, with the ex-
be processed only by the sintering technique ception of PTFE, are attached to the substrate
and calls for special methods where forming with contact adhesives or with heat-resistant sys-
and welding are required, all of these thermo- tems based on unsaturated polyester (UP), vinyl
plastic lining materials can be formed, welded, or phenacrylic ester (VE), or epoxide (EP), the
and bonded without difficulty. Figure 102 shows adhesive or resin composition being applied to
a loose-insert lining of PTFE peeled foil with a glass or synthetic fiber fabric, the underside of
welded-in sockets which merely have to be at- which is fused into the pipe or panel. For ser-
tached to the flanges of the vessel and its sockets vice temperatures above 80 ◦ C it is particularly
after the insert has been introduced. If the lined desirable to use glass fabric because this im-
apparatus is to have a long useful life, especially proves resistance to hydrolysis. The use of knit-
at high service temperatures, the apparatus must ted glass fiber is always recommended if the lam-
be well insulated against loss of heat and should inated sheet is likely to be deformed consider-
have ventilation openings in the wall beneath the ably while being processed, as in the fabrication
lining. Figure 103 shows how the resistance of of round-bottomed vessels, columns, or large
such linings to permeation by gases and steam pipes. The structure of a thermoplastic/fiberglass
depends on the density of the PTFE and there- laminate is shown schematically in Figure 104.
fore on the production process [186]. The weld joint is additionally reinforced by a
Corrosion 719
fabric-reinforced cover tape. This reinforcement 5.1.3.6. Paints and Powder Coatings
is particularly necessary in the case of linings
that must be antistatic or electrically conductive, Liquid Coating Materials. Liquid coating
especially because these cannot be tested for materials are classified as physically dry-
pores and cracks with high-voltage instruments. ing (here the coating material gels after the
Liners of this kind having good ductility are now solvent or dispersing agent has evaporated),
available as copolymers with carbon contents of thermally cross-linking, or catalytically cross-
less than 5 wt %. They have superseded the brit- linking. Their applications depend on the poly-
tle homopolymers in which up to 25 % of carbon mer base, the thickness at which the coat can
had to be incorporated [188]. Figure 105 shows be applied, and–where heated plant items are
the structure of Bekaplast, a composite consist- concerned–on the magnitude and direction of
ing of a thermoplastic liner and concrete. the heat flow. In the chemical industry tube
bundle heat exchangers coated on the cooling
water side with stoving finishes are an impor-
tant application of liquid coating materials in
which they have shown that they are able to
withstand the respective operating conditions
continuously for up to ten years. Large storage
tanks are being coated increasingly with epoxy-
based high-solids formulations or with solvent-
free polyurethane (PU), EP, UP, or VE resins
Figure 104. Structure of a fiberglass/thermoplastic laminate by the low- or high-pressure process, and with
[187]
a) Thermoplastic; b) Thermoplastic patch strip; c) Weld;
or without heat, depending on the technical re-
d) Carbon-filled resin target; e) FRP; f) Fiberglass quirements of the system. The PU and EP resins
are also modified with mineral coaltar pitch, par-
ticularly to reduce their cost and improve their
stability to aqueous media [190].
Powder Coatings. Temperature sensitive

plant items can be coated reliably with thermo-
plastics or thermosetting plastics by the tech-
niques of fluidized-bed sintering, powder sin-
tering, flame spraying, and electrostatic powder
coating. The range of applications is similar to
that of catalytically and thermally cross-linking
resins. Details of surface protection by powder
plastics that are melted to form coatings can be
found in VDI-Richtlinie 2538.
In powder sintering, the powder is sprinkled,
tipped, or flung onto the metal parts after they
have been heated to 200 – 400 ◦ C. Excess pow-
der is removed and the plastic coat formed by
melting is reheated until it becomes a continu-
ous film.
In fluidized-bed sinter coating the heated sub-
strate is dipped into a fluidized bed of the plastic
powder. A 0.1 – 1.5 mm-thick film is formed, de-
pending on the heat content of the part.
In electrostatic powder spraying, the plas-
Figure 105. Structure of a Bekaplast lining [189] tic powder is sprayed by compressed air from
a) Casing; b) Bekaplast panel; c) Concrete; d) Reinforcement a spray nozzle to which a high DC voltage is
720 Corrosion
applied. The current gives the plastic particles The following compounds are used as in-
an electric charge which causes most of them hibitors in acid solutions: amines, amino-
to land on the earthed substrate as soon as this imidazolines, amino- and nitrophenols, ami-
enters the vicinity of the polymer dust cloud. notriazole, aldehydes, benzothiazol, dibenzyl
The difference in polarity between the substrate sulfoxide, dithiophosphonic acids, guanidine
and the particles and the throwing power ensures derivatives, ureas, phosphonium salts, sulfo-
that the metal object is uniformly coated, even nium salts, sulfonic acids, thioethers, thioureas,
on surfaces that do not face the cloud. The resid- and thiocarbanoyl disulfides. Amino alco-
ual powder is separated in a cyclone and reused. hols, aminobenzimidazole, benzoates, quinoline
Films with a thickness of 50 – 1000 µm can be derivatives, cinnamates, fatty amines, polyether
obtained, depending on the coating equipment amines, silicates, and triazoles are used as in-
and properties of the powder. The powder, which hibitors in neutral or weakly alkaline solutions,
adheres to the metal through Coulomb forces, while for strongly alkaline solutions, aldehydes
is melted in a stove to form a continuous film. and fatty amines are used.
Not only components, but also complete appa- Inhibitors exist for the protection of metals
ratuses, are treated in this way. and their alloys [196–200] and for the most var-
ied of uses, including pickling acids, service wa-
ter, brine, coolants, oils, heat-transfer agents,
5.2. Inhibitors [191], [192] and electroplating baths [201–203]. Often, us-
ing a combination of several inhibitors gives a
Inhibitors are substances that reduce or elimi- synergistic effect, whereby the protective action
nate the aggressiveness of a corrosive medium achieved generally far exceeds the sum of the
and are either already contained in the corrosive effectivenesses of the individual components.
medium or are specifically added to it. A distinc- For the chemical industry inhibitors in open
tion is made between electrochemical, chemical, and closed water circulation systems and in oil
and physical inhibitors [193]. refining are highly significant [203]. In oil re-
Electrochemical inhibitors retard or prevent fineries, for example, the cracking that may oc-
the anodic and/or cathodic partial reactions, i.e., cur in heat-treatable steels through the action
they influence the reaction at the metal/corrosive of weakly acidic solutions containing H2 S and
medium interface. Chemical inhibitors can re- H2 O can be eliminated by the addition of ammo-
act both with the material and form protective nia saturated with oxygen. The H2 S is oxidized
coatings and with the medium itself or its con- to polysulfide, which forms a good protective
stituents and thus diminish its aggressiveness. coating on the steel [111].
Physical inhibitors form adsorption layers on the Corrosion inhibitors for mineral oils include
metal surface, which block the corrosion reac- alkyl imidazoles, amines, aminopyridines, qua-
tion. Inhibitors that influence the electrochemi- ternary ammonium salts, alkyl sulfonates, borate
cal electrode reactions are subdivided according esters, hydroxy amines, naphthenic acids, phos-
to their mode of action and site of action in the phate esters, and stearates.
area of the metal/medium phase boundary, the Oxygen and carbon dioxide corrosion can
subdivision being between interface inhibitors, cause serious economic loss in water circulation
electrolyte film inhibitors, membrane inhibitors, systems in which water is heated, evaporated,
and passivators. and condensed. Oxygen-binding additives of-
Industrial application of inhibitors involves fer good protection (hydrazine, Levoxin, sodium
acidic, neutral, and alkaline solutions as well as sulfite) and are used extensively in boiler feed
the gas phase [194]. Physical and electrochem- water preparation. Carbon dioxide corrosion can
ical inhibitors can be used for acids, whereas be controlled by neutralizing and film-forming
all three types are employed in neutral and al- amines and by vapor phase inhibitors. In prac-
kaline solutions. Gas and vapor phase inhibitors tice derivatives of phosphoric acid, organophos-
(i.e., substances with high vapor pressure) have phates, and chelates have proved successful as
gained importance, especially in atmospheric inhibitors in open cooling circulation systems.
corrosion protection in storage and transporta- Note, however, that there are conditions un-
tion [195]. der which inhibitors can give rise to detrimental
Corrosion 721
local corrosion (pitting corrosion). This is the (e.g., paint). This kind of protective coating is
case when the amount of inhibitor is insuffi- often combined with cathodic protection in or-
cient. Under these conditions only part of the der to keep the current demand low. The attack
surface can be covered, thus giving rise to a local of acidic solutions on equipment parts cannot
element. Corrosive attack is particularly exten- therefore be prevented in general by a cathodic
sive at the uncovered anode areas because of in- protection system. Cathodic polarization with-
creased corrosion current density, and deep cav- out evolution of large amounts of hydrogen is
ities penetrate into the material. Similarly, if the at best a possibility with copper alloys in acidic
inhibitor is too readily reduced at the cathodic solutions [205].
areas of the metal surface, increased corrosion For these reasons the cathodic corrosion pro-
can result because compact protective films are tection of chemical plant parts is restricted to
not formed. Since there are no universally appli- neutral solutions, service water, and alkali. Var-
cable inhibitors they must be carefully selected ious types of anode are available for the protec-
and examined for each specific case. In doing so, tion of container interiors. Platinized disk elec-
inhibition of metal dissolution is not the only trodes, bar anodes, and titanium basket anodes
point to be considered; there is also hydrogen are used [206], [207]. They are now supplied
absorption [203]. ready for installation and are designed in such a
In many cases corrosimeters are successfully way that in continuous operation they can emit
used to monitor inhibition. 8 – 10 A at a current density of 6 – 8 A/dm2 .
Aluminum and ferrosilicon anodes are suit-
able for the protection of hot-water tanks [208].
6. Electrochemical Corrosion The use of aluminum anodes in a hot-water appa-
Protection ratus by the Guldager electrolysis method [209]
has additional effects: an indirect protective ac-
Potential plays an essential role in corrosion pro- tion on subsequent piping, since a protective film
cesses. Not only the corrosion rate but also the (1 – 1.5 mm thick) is built up by anode-formed
occurrence of local corrosion phenomena, such aluminum oxide hydrates. In addition to alka-
as pitting and stress corrosion cracking, depend lization at the cathode, a shift in the CaCO3 –
on the potential. If the critical potential range for CO2 equilibrium leads to partial softening of
corrosion is known, a condition can be estab- water, CaCO3 being deposited at the cathode.
lished through polarization in which no corro- Corrosion protection through imposition of
sion occurs or it is negligible. Depending on the a passive state in metallic materials by anodic
direction of the polarization this electrochemical polarization has found some applications in the
corrosion protection is anodic or cathodic [204]. chemical industry.
In addition to the well-known application of The practical design of equipment for anodic
cathodic corrosion protection to underground protection requires intensive laboratory studies
pipelines, there has been an increased use for to determine the passivation current densities
the internal protection of containers and pipes. and the potential range of passivity as a func-
Initially, galvanic anodes were used to this ef- tion of various parameters such as temperature,
fect, like the ones now used, for example, to pro- concentration, and rate of flow for the respec-
tect the interiors of tankers and boilers. However, tive application. The properties of the cathode
since these anodes are often subject to heavy in- material must also be studied.
herent corrosion, especially with the highly ag- The protective current must be potentiostat-
gressive media often found in the chemical in- ically controlled if the material to be protected
dustry, external current systems with insoluble shows rapid activation on disconnection. Inter-
anode material have now largely replaced these. mittent operation may also be chosen, whereby
The possibilities of cathodic protection are the protection current connects or disconnects
limited in two respects. The cathodic polariza- on dropping below or rising above a limit poten-
tion required for protection can lead to cathode tial.
corrosion in some systems. Hydrogen evolution All common systems can be used as refer-
can also cause damage such as embrittlement of ence electrodes, e.g., calomel, Ag/AgCl, and
the steel and debonding of a protective coating Mg/MgO electrodes, which help to monitor the
722 Corrosion
apparatus and control the on-off processes. Plat- stalled initial electrical direct current output of
inum, platinized materials, tantalum, and lead the potentiostats is > 25 kW, corresponding to
are used as cathode materials in acidic solutions. an energy requirement of 2.5 W/m2 for the sur-
Nickel is suitable in alkaline solutions. face needing protection [213].
Anodic protection against acidic solutions Owing to the narrowness of the potential
has been used in a number of chemical processes range within which stress corrosion cracking oc-
and in the transportation and storage of liquids. curs in unalloyed and low-alloy steels in alkali,
Unalloyed steels can be protected in this way anodic protection against this particular kind of
in salt solutions with nitrates and sulfates and corrosion can be provided by impressed current.
in nitric and sulfuric acid [210], although there As the current densities needed to maintain pas-
are limits imposed in sulfuric acid by tempera- sivity are quite low, this form of protection is also
ture and concentration [211]. Stainless chromi- economically favorable, particularly for large
um and chromium – nickel steels are particularly plant equipment that cannot be annealed. Ca-
suited to anodic protection. It has so far been thodic protection, though theoretically possible,
practiced with H2 SO4 , oleum, and H3 PO4 . cannot be recommended, since excessive surface
In the production of sulfuric acid, including corrosion caused by removal of top layers from
heat recovery and the reconditioning and recy- the steel surface would have to be tolerated as
cling of spent acids, it is necessary to handle the alternative to stress corrosion cracking. Fur-
acids at elevated temperatures and various con- ther reasons are that higher current densities are
centrations. Corrosion damage that considerably needed and that a power failure would immedi-
impairs the availability of plant has occurred in ately end the protection. A passivated surface,
sulfuric acid coolers, for example. Damage of on the other hand, does not become active im-
this kind can be prevented by anodic protection. mediately, so that anodic protection can also be
The commonly used austenitic stainless operated intermittently.
steels exhibit satisfactory resistance to corrosion Anodic inhibition of stress corrosion crack-
by sulfuric acid at low concentrations (< 20 %), ing was first provided on an industrial scale in
and high concentrations (> 70 %) below a criti- a large plant for the production of hydrogen
cal temperature. If at high sulfuric acid concen- by electrolysis of potassium hydroxide solution
trations (> 90 %) the temperature exceeds ca. [87]. In November 1968, after preliminary tri-
70 ◦ C, corrosion, differing in severity accord- als on a laboratory scale, the chemical indus-
ing to the composition of the steel concerned, try’s first anodically protected large-scale plant,
occurs, and the steel may alternate between the a sodium hydroxide solution evaporator with
active and passive states [212]. a capacity of 142 t, was put into operation. In
Anodic protection enables materials to be the meantime further plants have been equipped
used under unfavorable conditions, provided in the same way [215]. The structure of the
they are passifiable in sulfuric acid. In the han- evaporator and the arrangement of the counter
dling of sulfuric acid at concentrations of 93 – electrodes and reference electrodes are shown
99 %, Cr – Ni steels (material nos. 1.4541 and schematically in Figure 106.
1.4571) can be used economically at tempera- Because of its good passivity, titanium is also
tures up to 160 ◦ C. This allows operation within suited for anodic protection, e.g., in mineral and
a range of temperatures (120 – 160 ◦ C) suitable organic acids; tantalum cathodes are generally
for heat recovery. used [216].
The anodic protection technique now enables
air coolers and tube bundles in sulfuric acid
plants to be protected from corrosion reliably 7. Corrosion Testing [217–219]
and economically. In 1966 anodic protection was
provided in the Federal Republic of Germany 7.1. Introduction
for the air coolers of a sulfuric acid production
plant for the first time. Since then, a combined In the design of chemical apparatus, apart from
cooler surface area exceeding 10 000 m2 in air- process technology, material selection is espe-
cooled and water-cooled sulfuric acid plants has cially important. With careful attention paid to
been protected in this way worldwide. The in- economy, material selection must take account
Corrosion 723
temperature, dissolved gases, impurities, solids,

and the flow rate must be carefully considered.
Because of the many parameters involved, when
material specimens are incorporated in a test or
production plant, efforts should always be made
to ensure that the specimens are subjected as
close as possible to operating stress. The mate-
rial specimen is geared to the types of corrosion
expected.
Material specimens are mostly attached to in-
ternals, e.g., to an agitator or a thermometer pro-
tection tube. To avoid unwanted polarization of
the specimens through contact with plant com-
ponents and a subsequent incorrect measure-
ment, the specimens are bolted with insulating
sleeves. In many cases it is sufficient to wrap the
bolts with PTFE tape. At low flow rates and low
temperatures the specimens can be incorporated
with the help of plastic binding or tape.
If corrosion tests in pilot plants are not pos-
sible, laboratory tests sufficiently close to prac-
tice should be carried out. These should also be
carried out when operating tests do not clearly
indicate the time function of corrosion processes
and thus more intense corrosion conditions can
complete the picture.
Three groups of variables determine the cor-
rosion of metallic materials [220]:
1) material variables (chemical composition,
Figure 106. Anodic protection of a caustic vaporizer (con-
tent 115 m3 , surface area 2400 m2 ) against stress corrosion
heat treatment, and surface condition);
cracking 2) corrosive medium variables (pH, tempera-
a) PTFE; b) Cathode; c) Anode; d) Central tube e) Liquor ture, flow rate);
entry; f ) Ring electrode; g) Insulation; h) Stirrer; i) Poten- 3) potential.
tiostat; j) Electrode E2 ; k) Vaporizing tubes; l) Electrode E1 ;
m) Filling level In a laboratory test used as the basis for mate-
rial selection the biggest problem is the correct
of all the requirements arising out of the operat- choice of these variables, which is the determin-
ing function of the chemical apparatus and the ing factor for simulating operating conditions.
manufacturing process of the product. It is often Chemical corrosion tests focus primarily on
difficult to comprehend and take account of the resistance to surface and selective corrosion.
interaction of mechanical and chemicocorrosion In general the effect of material and corrosive
stresses, which are often compounded by wear. medium variables can be understood with these
The resistance parameters needed to select a methods. The variable potential, on the other
material can be obtained in two ways: hand, is more or less undefined and can expe-
1) by incorporating suitable test specimens in rience time changes depending on the proper-
test plants or in existing, not yet optimally ties of the various partial reactions involved in
designed production plants; corrosion. The fluctuation range of the poten-
2) by corrosion testing in the laboratory. tials found in practice cannot be taken into ac-
Both methods of corrosion testing are similiar count in the immersion test. Often, therefore,
in that on the corrosive medium side a number the results obtained in chemical corrosion test-
of important parameters such as concentration, ing using electrochemical methods must be fur-
724 Corrosion
ther differentiated to take account of the vari- specimens under temperature-controlled condi-
able potential. If the corrosion rate determined tions [222].
in chemical corrosion testing depends heavily on Sensitivity to stress corrosion cracking can
the potential, chemical testing has little to offer, be determined with elastically or plastically pre-
but if there is only little potential dependence it stressed specimens, such as those of the Jones,
is more reliable. U-bent, and C-ring types (Fig. 107, see next
By means of electrochemical corrosion tests, page) [225–227]. Specimens sensitive to stress
the dependence of corrosion on the potential can corrosion cracking can also be produced by in-
be investigated and indicators obtained as to the troducing heavy tensile stresses into the surface
parameters which influence the potential. There by means of stress-inducing grinding [228].
can be fundamental differences between the re- Laboratory corrosion tests are discussed in
sults of chemical and electrochemical corrosion [221], [223]. To adjust the parameters of tem-
tests. This is due to the fact that in chemical perature and/or pressure it may be necessary to
tests the potential can change with time. This perform corrosion tests in an autoclave.
is deliberately avoided in electrochemical tests, In pilot and production plants, the flow con-
with partly increased predictability and partial ditions are determined by the nature of the ap-
restriction of the potential practical uses, e.g., paratus and process, but in laboratory tests they
in the event of strong time dependence. Depen- have to be individually chosen. To determine the
dence on the following variables is a major con- effects of static or very gently moving media it
sideration in electrochemical corrosion tests: pois sufficient to stir the medium with an agitator.
tential U H (in relation to the standard hydrogen If, however, exposure of the material to flowing
electrode), current density i (in relation to the media is expected, special corrosion tests are es-
geometric surface of the specimen), and time t. sential for simulation: for example, circulation
tests with pipe or channel flow and use of rotat-
ing discs or cylinders as specimens [229].
7.2. Test Methods Special laboratory investigations of the resis-
tance to stress corrosion cracking may include
Process-Related Corrosion Tests. As men- the use of machinery. In such cases tensile test
tioned above, tests to determine the corrosion specimens are tested under defined mechanical
resistance of materials in industrial corrosive conditions, such as constant stress or constant
media can be performed in the laboratory, in strain rate [127].
pilot plants, and in existing production plants.
With regard to the choice of locations for spec- Standardized Methods. Standardized cor-
imens it should be borne in mind that reactors rosion tests are performed in the laboratory with
and other apparatus may be attacked differently standardized solutions; they are used mainly to
by the liquid and vapor phases of the corrosive determine general corrosion characteristics, as
agent and at the three-phase interface of the liq- well as in fundamental investigations and quality
uid, vapor, and material. As a rule, therefore, control. Various methods [230–235], the choice
material specimens must be exposed at each of of which depends on the type of material con-
these phases. Corrosion testing principles are de- cerned, are used to determine the resistance of
scribed in [221–223]. highly alloyed steels and nickel-based alloys to
The characteristics of individual forms of cor- intergranular corrosion. There is also a standard-
rosion are taken into consideration by provid- ized method for determining resistance to pit-
ing appropriate corrosion specimens. Welded ting and crevice corrosion [236]. The general
coupons having the surface quality of the ma- resistance of various materials to stress corro-
terial used later in practice are sufficient for de- sion cracking (SCC) can likewise be determined
termining uniform corrosion rates and acquir- in test solutions. Depending on the material and
ing general information on the type of local cor- corrodent, the following standards are used:
rosion. Resistance to crevice corrosion can be
determined by using specimens as described in 1) Stainless steels, transgranular SCC: MgCl2
ASTM G 78 [224]. Conditions of heat trans- solution [217], [237]; NaCl solution [242];
fer can be simulated by using hot-wall/cool-wall
Corrosion 725
Figure 107. Stress corrosion cracking specimens

A), C), and E) Typical U-bent specimens; B) Cantilever beam specimen; D) Bent beam specimen, three point loaded; F)
Tuning fork specimen
2) Unalloyed and low-alloy steels: intergranu- performed both on unprotected and on pro-
lar SCC [225]; hydrogen-induced cracking tected (coated) materials, require special meth-
H2 S [238]; ods [243, Parts 1 and 2]. Here it is important
3) Cu materials in NH3 [239]; in NH+4 solution that control specimens be tested simultaneously
[240]; in order to predetermine the corrosive conditions
4) Al materials [241], [242]. at the testing site.
The standard methods also include those used
Atmospheric Corrosion Testing. It is cus-
particularly, but not exclusively, to test anticor-
tomary to perform tests in special climate-
rosion coatings in corrosive atmospheres, e.g.,
chambers in addition to field tests. The tests are
those containing SO2 and Cl− .
used for comparison, but are also valuable for
determining the behavior of anticorrosive films
Field Tests. Field tests include those in
and coatings. The conditions used to obtain the
which specimens are surrounded by aggres-
appropriate atmospheres, constant or alternating
sive soils, atmospheres, or waters (e.g., seawa-
condensed water climates, with and without the
ter). Atmospheric and water tests, which are
726 Corrosion
presence of such additional substances as sulfur pitting – recognizable from the steep increase of
dioxide and salt spray, at various pH values, are the current (Fig. 108) – is forced to occur. After
specified in [244–250]. the rate of pitting corosion has been stabilized
by a further increase of potential the scanning
Electrochemical Measurement. Electro- direction is reversed until the current acquires
chemical methods are used mainly in the lab- values similar to those of the passive current den-
oratory [251–253]. In special cases (potential sity. The potential at which this occurs is known
measurements; corrosion meters) they can also as the pitting passivation potential U pp . Com-
be used in industrial plants. parison of U pp with U corr indicates whether
Electrochemical methods, in contrast to pitting corrosion will occur (U pp < U corr ) or
chemical methods, provide mainly qualitative not (U pp > U corr ) in the corrosion system con-
data on corrosion systems. They are very suit- cerned [256]. The main advantage of this process
able for studying corrosion mechanisms and the is that the repassivation potential U pp is more
influences of parameters, but also for investigat- easily reproduced than the pitting potential U p ,
ing the value and effectiveness of active corro- and that within wide limits it is independent of
sion protection measures. Current density ver- the rate of change of the potential.
sus potential curves (see Chap. 2, Figs. 13, 17)
provide information on the effects of alloy con-
stituents and inhibitors. Quantitative data on loss
of mass rates can be gained by extrapolating the
Tafel lines or by measuring the polarization re-
sistance (see Section 2.3; Figs. 9, 10). The latter
method also forms the basis of a number of com-
mercially available corrosion meters, which are
used to determine corrosion rates and to inves-
tigate the effectiveness of inhibitors.
Depending on the purpose of an investigation,
such tests are performed either at a given poten-
tial ( potentiostatic tests) or at a potential which Figure 108. Determination of susceptibility to pitting cor-
rosion (schematic potentiodynamic current density versus
changes in a defined manner ( potentiodynamic potential curves)
tests). Galvanostatic or galvanodynamic tests are a) U pp < U corr : pitting corrosion susceptibility; b) U pp >
also performed frequently. Besides investigation U corr : no pitting corrosion susceptibility
of the relationship between current density and
potential, simple measurement of the (free) cor-
rosion potential U corr (open loop potential), or
its dependence on time, is a useful way of study- 8. References
ing corrosion systems, for the level at which the
potential of the material settles is very impor- General References
1. H. H. Uhlig: The Corrosion Handbook, J.
tant with regard to the damage suffered. Potential
Wiley & Sons, New York/Chapmann & Hall
measurements are also fundamental, though not
Ltd., London 1948. F. N. Speller: Corrosion,
alone sufficient, in the investigation of contact Causes and Prevention, McGraw-Hill, New
corrosion [254], [255]. Electrochemical meth- York – London 1951. F. Ritter:
ods are also used successfully in the basic in- Korrosionstabellen metallischer Werkstoffe,
vestigation of local corrosion, e.g., crevice and 4th ed., Springer Verlag, Wien 1958. F. Tödt:
pitting corrosion. Korrosion und Korrosionsschutz, 2nd ed., de
A special method for determining the sensi- Gruyter, Berlin 1961. K. Vetter:
tivity of stainless steels to pitting corrosion in Elektrochemische Kinetik, Springer Verlag,
industrial corrodents is the measurement of the Berlin – Göttingen – Heidelberg 1961. F. L.
pitting passivation potential U pp . Here the po- Laque, H. R. Copson: Corrosion Resistance of
tential, which is initially adjusted to the free cor- Metals and Alloys, 2nd ed., Reinhold Publ.,
rosion potential U corr , is slowly increased until, New York 1963. U. R. Evans: Einführung in
at the pitting potential U p (see Section 3.2.1) die Korrosion der Metalle, Verlag Chemie,
Corrosion 727
Weinheim 1965. U. R. Evans: The Corrosion Testing and Materials, Philadelphia 1988.
and Oxidation of Metals; Scientific Principles W. v. Baeckmann, W. Schwenk, W. Prinz:
and Practical Applications, 1st. and 2nd Handbuch des kathodischen
suppl. vols., Edward Arnold Ltd., London Korrosionsschutzes, 3rd ed., VCH
1960, 1968, 1976. H. Kaesche: Die Korrosion Verlagsgesellschaft, Weinheim 1989. P. J.
der Metalle, 2nd ed., Springer Verlag, Gellings: Introduction to Corrosion Prevention
Berlin – Heidelberg – New York 1979. and Control for Engineers, Delft University
Mannesmann-Röhren-Werke, Lexikon der Press, Delft 1976. L. L. Shreir: Corrosion, 2nd
Korrosion, vols. 1 and 2, Düsseldorf 1970. ed., vols. 1 and 2, Newnes-Butterworth,
H. E. Hömig: Metall und Wasser. Eine London – Boston 1976. Corrosion Data
Einführung in die Korrosionskunde, Survey Metals Section, 6th ed., NACE,
Vulkan-Verlag, Essen 1971. H. Gräfen, F. Houston, Texas, 1985. D. Behrens (ed.):
Kahl, A. Rahmel (eds.): 1. Korrosionum: Die DECHEMA Corrosion Handbook, Corrosive
Bedeutung der Korrosion für Planung, Bau Agents and Their Interaction with Materials,
und Betrieb von Anlagen der chemischen und vols. 1 – 5, VCH Verlagsgesellschaft,
petrochemischen Technik sowie in der Weinheim – New York 1987. M. Fischer, K.
Mineralölindustrie, Verlag Chemie, Hauffe, W. Wiederholt: Passivierende Filme
Weinheim 1974. B. J. Monitz, W. I. Pollock und Deckschichten, Springer Verlag, Berlin
(eds.): Process Industries Corrosion, NACE, 1956. K. Hauffe: Oxidation von Metallen und
Houston, Texas, 1986. R. N. Parkins (ed.): Metallegierungen, Springer Verlag, Berlin
Corrosion Processes, Applied Science 1956. O. Kubaschewski, B. E. Hopkins:
Publishers Ltd., London – New York 1982. D. Oxidation of Metals, Butterworth, London
Kuron (ed.): Wasserstoff und Korrosion, 1962. J. Bernard: L‘Oxydation des Metaux,
Bonner Studien Reihe, Verlag I. Kuron, Bonn vols. 1 and 2, Gauthier-Villars, Paris 1962 and
1986. R. Gibala, R. F. Hehemann (eds.): 1964. M. Pfeiffer, M. Thomas: Zunderfeste
Hydrogen Embrittlement and Stress Corrosion Legierungen, Springer Verlag, Berlin 1963. P.
Cracking. Papers presented at a symposium Kofstad: High-Temperature Oxidation of
held at Case Western Reverse University on Metals, J. Wiley, New York 1966. J. C. Scully:
June 1 – 3, 1980, ASM, Ohio 1984. G. Fundamentals of Corrosion, Pergamon Press,
Kortüm: Lehrbuch der Elektrochemie, 5th ed., Oxford 1966. Z. A. Foroulis: High
Verlag Chemie, Weinheim 1972. C. H. Temperature Metallic Corrosion of Sulfur and
Hamann, W. Vielstich: Elektrochemie I, its Compounds, The Electrochemical Society,
Verlag Chemie, Weinheim 1975. Verein New York 1970. H.-J. Engell, A. Rahmel:
Deutscher Eisenhüttenleute (ed.): Prüfung und “Verzunderung von Metallen durch Gase. 50
Untersuchung der Korrosionsbeständigkeit Jahre Tamman’sche Zunderformel,” Korrosion
von Stählen, Verlag Stahleisen, Düsseldorf 23 (1971). A. Rahmel, H. Manenc:
1973. A. Rahmel, W. Schwenk: Korrosion und “Mechanische Eigenschaften und Haftung von
Korrosionsschutz von Stählen, Verlag Chemie, Zunderschichten. Einfluß auf die Oxidation
Weinheim 1977. H. Gräfen et al. in W. J. Bartz, von Metallen,” Korrosion 24 (1973).
Techn. Akademie Esslingen (ed.): Die Praxis
des Korrosionsschutzes, Kontakt und Studium, Specific References
vol. 64, Expert Verlag, Grafenau 1981. 2. DIN 50 900,Korrosion der Metalle. Begriffe,
DIN-Taschenbuch 219:Korrosion und Part 1, Allgemeine Begriffe, Beuth-Verlag,
Korrosionsschutz, Berlin – Köln 1982.
Beurteilung – Prüfung – Schutzmaßnahmen, 3. DIN 50 900,Korrosion der Metalle. Begriffe,
Beuth-Verlag, Berlin – Köln 1987. W. Fischer Part 2, Elektrochemische Begriffe,
(ed.): Korrosionsschutz durch Information und Beuth-Verlag, Berlin – Köln 1984.
Normung, Kommentar zum DIN-Taschenbuch 4. C. Wagner, W. Traud, Z. Elektrochem. Angew.
219, Schriftenreihe der Arbeitsgemeinschaft Phys. Chem. 44 (1938) 391 – 402.
Korrosion e. V., Verlag I. Kuron, Bonn 1988. 5. M. Stern, A. L. Geary, J. Electrochem. Soc.
Annual Book of ASTM Standards 1988, 104 (1957) 56 – 63.
Section 3; Metals Test Methods and Analytical 6. E. Heitz, Werkst. Korros. 19 (1968) 773 – 781.
Procedures, vol. 03.02, Wear and Erosion, 7. E. Heitz, W. Schwenk, Werkst. Korros. 27
Metal Corrosion, American Society for (1976) 241 – 245.
8. U. R. Evans, J. Inst. Met. 30 (1923) 239.
728 Corrosion
9. H. Kaesche, Z. Metallkd. 61 (1970) 94 – 101. 35. R. Kirchheiner, W. Römer: VDM-Report no. 9,

10. U. Gramberg, E.-M. Horn, VDI-Ber. 243 Oct. 1987.
(1975) 75 –92. 36. H. Kaesche, Werkst. Korros. 14 (1963)
11. H. Gräfen, K. Gerischer, E.-M. Horn, Z. 557 – 574.
Werkstofftech. 4 (1973) no. 4, 169 – 186. 37. W. R. Fischer: Zur Lochfraßkorrosion,
12. E.-M. Horn, D. Kuron, H. Gräfen, Z. Dissertation, TH Braunschweig 1964.
Werkstofftech. 8 (1977) 37 – 68. 38. K. Fässler, VDI-Ber. 235 (1975) 51 – 68.
13. E.-M. Horn, VDI-Ber. 235 (1975) 39 – 49. 39. K. Fässler: “Gesichtspunkte der konstruktiven
14. K. Lorenz, G. Medawar, Thyssenforschung 1 Gestaltung chemisch beanspruchter Apparate,”
(1969) no. 3, 97 – 108. in H. Gräfen, F. Kahl, A. Rahmel (eds.): 1.
15. E. Wallis: Einfluß des Molybdängehaltes auf Korrosionum, die Bedeutung der Korrosion für
die Lochkorrosionsbeständigkeit hochlegierter Planung, Bau und Betrieb von Anlagen der
nichtrostender Stähle und chemischen und petrochemischen Technik
Nickel – Chrom – Eisen-Legierungen mit sowie der Mineralölindustrie, Verlag Chemie,
unterschiedlichen Gefügezuständen unter Weinheim 1974, pp. 136 – 165.
Berücksichtigung der Wirksummenrelation 40. R. Münster: “Erscheinungsformen der
Massen-% Cr + 3,3 Massen-% Mo, Korrosion,” in [39] pp. 3 – 27.
Dissertation, TU Clausthal 1988. 41. G. Lennartz, VDI-Ber. 235 (1975) 169 – 182.
16. M. Renner, U. Heubner, M. B. Rockel, E. 42. G. Herbsleb, VDI-Ber. 243 (1975) 103 – 118.
Wallis, Werkst. Korros. 37 (1986) 183 – 190. 43. E.-M. Horn, T. Günther, Chem. Ing. Tech. 41
17. G. Herbsleb, Werkst. Korros. 33 (1982) (1969) no. 18, 991 – 999.
334 – 340. 44. G. Grützner: Über die interkristalline
18. DIN 17 440,issued 07. 85; Korrosion stickstofflegierter 18/10
VdTÜV-Werkstoffblatt 405, issued 12. 87. Chrom-Nickel-Stähle, Dissertation, RWTH
19. VdTÜV-Werkstoffblatt 486, issued 09. 87. Aachen 1971.
20. Stahl-Eisen-Werkstoffblatt des Vereins 45. H. Gräfen, G. Böhm, Z. Metallkd. 51 (1960)
Deutscher Eisenhüttenleute, SEW 400, issued 245 –252.
04. 88. 46. A. Bäumel, E.-M. Horn, H. Gräfen, Proc. Int.
21. VdTÜV-Werkstoffblatt 415, issued 09. 84. Cong. Met. Corros. 5th 1972, 934 – 941.
22. A. Bäumel, E.-M. Horn, G. Siebers, Werkst. 47. A. Kratzer, B. Pieger, H. Tischner, E.-M.
Korros. 23 (1972) no. 11, 973 – 983. Horn: “A Low Carbon Stainless Steel for Use
23. H. Brandis, G. Lennartz, R. Oppenheim, in Nitric Acid at Higher Concentrations and
DECHEMA-Monogr. 78 (1975) 235 – 258. Temperatures,” ICMC, 9th International
24. A. Diebold, H. Weingerl, Werkst. Korros. 25 Congress on Metallic Corrosion, Toronto,
(1974) no. 3, 175 – 179. Canada, June 3 – 7, 1984.
25. J. C. Carlen, B. Kwarnbäck, Werkst. Korros. 48. E.-M. Horn, H. Kohl, Werkst. Korros. 37
25 (1974) no. 9, 653 – 658. (1986) 57 –69.
26. W. Stewen, H. Jörgens, M. Remke, M. 49. E.-M. Horn, A. Kügler, Z. Werkstofftech. 8
Litzkendorf, Glückauf 121 (1985) no. 13, (1977) 362 – 370, 410 – 417.
1030 – 1033. 50. H. J. Rocha, DEW-Tech. Ber. 2 (1962) no. 1,
27. VdTÜV-Werkstoffblatt 421, issued 16 – 24.
02. 82/03. 84/09. 86. 51. Mannesmann-Röhren-Werke: Lexikon der
28. VdTÜV-Werkstoffblatt 473, issued 06. 85.
Korrosion, vol. 1, Düsseldorf 1970, p. 55.
29. M. B. Rockel, M. Renner, Werkst. Korros. 35
52. I. Class, H. Gräfen, Werkst. Korros. 11 (1960)
(1984) 537 – 542.
no. 9, 529 – 547.
30. Nickel Topics 34 (1981) no. 4, 15.
53. G. Herbsleb, Werkst. Korros. 19 (1968)
31. J. C. Crum, E. L. Hibner, R. W. Ross, Jr.,
406 – 412.
Mater. Perform. 20 (1981) no. 2, 9 – 13.
54. Publication H-2007 and H-2019 of Cabot
32. Sandvik Steel AB: Sandvik Sanicro 28 –
Wrought Products Division, now Haynes
References and booked orders for the process
International, 1983/1984.
industry, Oct. 1985.
55. E. Scheil, I. Class, H. Gräfen, DE 1 210 566,
33. Avesta Technical Information: Avesta 254
1961, US 3 203 792, 1964.
SMO – Referenzen und Anwendungsgebiete,
56. R. B. Leonard, Corrosion (Houston) 25
issued 02. 1982.
(1969) no. 5, 222 – 228.
34. W. Heimann, VDI-Ber. 674 (1988) 41 – 63.
Corrosion 729
57. R. W. Kirchner, W. L. Silence, Mater. Prot. 80. E. Wendler-Kalsch, Werkst. Korros. 31 (1980)
Perform. 10 (1971) no. 1, 11 – 15. 534 –542.
58. R. W. Kirchner, F. G. Hodge, Werkst. Korros. 81. W. Schwenk: “Einflußgrößen bei der
24 (1973) no. 12, 1042 – 1049. Korrosion von Stählen unter Rißbildung mit
59. Kh. G. Schmitt-Thomas, G. Fenzel, besonderer Berücksichtigung der
Maschinenschaden 38 (1965) 94 – 97. mechanischen Belastungsparameter,”
60. E. Fot, Schweiz. Arch. 30 (1964) 329 – 344, Mannesmann – Forschungsbericht, no. 944,
384 – 398. 1983.
61. E. Kauczor, Metall (Berlin) 20 (1966) 82. H. Diekmann et al., Stahl Eisen 103 (1983)
1165 – 1168. no. 18, 895 – 901.
62. R. Heidersbach, Corrosion (Houston) 24 83. R. Münster, H. Gräfen, Arch. Eisenhüttenwes.
(1968) 38 –44. 36 (1965) 227 – 284.
63. “Quaterly Report: Clarification of De-alloying 84. W. Rädeker, B. N. Miskra, Werkst. Korros. 21
Phenomena,” Corrosion (Houston) 26 (1970) (1970) 691 – 698.
445 –447. 85. H. Gräfen, Mitt. Ver. Großkesselbesitzer 73
64. W. B. Brooks, Corrosion (Houston) 24 (1968) (1961) 280 – 289.
171. 86. P. Drodten, Rheinstahl-Tech. 10 (1972) no. 3,
65. L. Leontaritis, E.-M. Horn, Werkst. Korros. 31 97 –106.
(1980) 179 – 185. 87. H. Gräfen, D. Kuron, Arch. Eisenhüttenwes.
66. P. Rothenbacher, Corros. Sci. 10 (1970) 36 (1965) 285 – 291.
391 – 400. 88. K. Bohnenkamp, Arch. Eisenhüttenwes. 39
67. H. G. Feller, Z. Metallkd. 58 (1967) 875 – 885. (1968) 361 – 368.
68. E. E. Langenegger, F. P. A. Robinson, 89. E. Wendler-Kalsch, Corros. Sci. 23 (1983)
Corrosion (Houston) 25 (1969) 59 – 66. no. 6, 601 – 612.
69. G. Schikorr: “Häufige Korrosionsschäden an 90. K. J. Kessler, E. Wendler-Kalsch, Werkst.
Metallen und ihre Vermeidung,” in Korros. 28 (1977) 78 – 85.
Landesgewerbeamt Baden-Württemberg (ed.): 91. K. Matsukura, K. Sato: “Effects of
Schriften zur Gewerbeförderung, vol. 3, Verlag Metallurgical Factors of Low Carbon Steel
K. Wittwer, Stuttgart. Sheets on Stress Corrosion Cracking in
70. F. Tödt: Korrosion und Korrosionsschutz, 2nd Methanol Solutions,” Tetsu to Hagane 63
ed., De Gruyter, Berlin 1961, p. 418. (1977) no. 6, 1016 – 1025.
71. D. G. Evans, P. W. Jeffrey: “Exfoliation 92. E. Wendler-Kalsch: “Korrosion und
Corrosion of AlZnMg Alloys,” in R. W. Spannungsrißkorrosion niedriglegierter Stähle
Staehle, B. F. Brown, J. Kruger, A. Agrawal in Methanol, (Project-no. G 6.1/7),” FEKKs
(eds.): Localized Corrosion, International Symposium, Lahnstein 1987.
Corrosion Conference Series, Nat. Assoc. of 93. B. E. Wilde: Stress Corrosion Cracking of
Corrosion Eng., Houston, Texas 1974, ASTM A 517, Steel in Liquid Ammonia:
pp. 614 – 622. Environmental Factors, National Association
72. H. Weingerl, H. Straube, R. Blöch, Werkst. of Corrosion Engineers, vol. 37, no. 3 (1981).
94. H. Gräfen et al., Werkst. Korros. 36 (1985)
Korros. 27 (1976) 69 – 77.
203 – 215.
73. E. Schürmann, H.-J. Voss, Arch.
95. L. Lunde: “Ammonia Plant Safety,” AIChE 24
Eisenhüttenwes. 48 (1977) 129 – 132.
(1984) 154; Symp. on Safety in Ammonia
74. A. Diebold, H. Weingerl, Werkst. Korros. 28
Plants and Related Facilities AIChE, Denver,
(1977) 240 – 243.
CO, August 29 – 31, 1983, report no.
75. A. Bäumel, Schweißen Schneiden 27 (1975)
iFE/KR/E-83/007.
227 – 230.
96. K. Fäßler, H. Spähn: “Grundlagen der
76. A. Bäumel, Werkst. Korros. 27 (1976)
Spannungsrißkorrosion unlegierter Stähle in
687 – 693.
flüssigem Ammoniak – Einflußgrößen und
77. W. Schwarz, W. Simon, Ber. Bunsenges. Phys.
Gegenmaßnahmen,” Essen, VGB-Konf.
Chem. 67 (1963) 108 – 117.
Werkstoffe, 205 – 228 (1989).
78. K. Gerischer, Z. Metallkd. 46 (1955) 661.
97. A. Heuser, H. Spähn, G. H. Wagner,
79. R. N. Parkins: 5th Symp. Linepipe Research,
Materialprüfung 31 (1989) no. 3, 73 – 79.
Amer. Gas Ass. Cat. No. L 30 174, Report U,
98. M. Kowaka, S. Nagata, Boshoku Gijutsu 21
Houston 1974.
(1972) no. 4, 165 – 171.
730 Corrosion
99. H. Gräfen, H. Schlecker: “CO–CO2 –H2 O,” 124. K. Risch, Z. Werkstofftech. 17 (1986) 6 – 17.
GWF Gas Wasserfach Gas Erdgas 126 (1985) 125. H. Spähn, Z. Phys. Chem. (Leipzig) 234
no. 4, 195 –204. (1967) 1 – 25.
100. G. Schmitt:, GWF Gas Wasserfach Gas 126. K. Wellinger, K. Lehr, Mitt. VGB 49 (1969)
Erdgas 122 (1981) no. 2, 49 – 54. 190 –201; Tech. Wiss. Berichte MPA-Stuttgart
101. G. Schmitt, H. Schlerkmann: Met. Corros. (1969) no. 69-02.
Proc. Int. Congr. Met. Corros. 8th, Mainz 127. DIN 50 922 (Oct. 1985), Korrosion und
1981, vol. 1, p. 426. Metalle. Untersuchung der Beständigkeit von
102. H. Gräfen, Werkst. Korros. 23 (1972) metallischen Werkstoffen gegen
247 – 254. Spannungsrißkorrosion.
103. M. O. Speidel in A. J. Sedriks: Corrosion of 128. C. Wagner, Z. Phys. Chem. Abt. B 21 (1933)
Stainless Steels, Wiley & Sons, New York 25 – 41; Z. Phys. Chem. Abt. B 32 (1936)
1979, p. 173. 447 – 462.
104. H. Spähn, G. H. Wagner, U. Steinhoff, TÜ 14 129. E. Houdremont, G. Bandel, Arch.
(1973) no. 10, 292 – 299. Eisenhüttenwes. 11 (1937/38) 131 – 138.
105. L. Logan, J. Res. Nat. Bur. Stand. (U.S.) 56 130. S. Mrowec, T. Welec, T. Werber, Oxid. Met. 1
(1956) R.P. 2662, 159. (1969) 93 – 120.
106. A. Beerwald, H. Gröber, Z. Aluminium 1940, 131. A. Rahmel, VDI-Ber. 235 (1975) 145 – 154.
502 –510. K. Matthaes, Korrosion 9 (1958) 132. A. Preece in: High-Temperature Steels and
5 – 21. Alloys for Gas Turbines, London 1952, (Spec.
107. H. Gräfen, Werkst. Korros. 16 (1965) Rep. Iron Steel Inst. no. 43), pp. 149 – 152.
876 – 879. 133. K. Wickert, Nickel Ber. 24 (1966) 177 – 186.
108. H. Gräfen, H. Spähn, Chem. Ing. Tech. 39 134. A. Rahmel in H. R. Johnson, D. J. Littler
(1967) 138 – 146. (eds.): The Mechanism of Corrosion by Fuel
109. E.-M. Horn, H. Schlecker: unpublished results. Impurities, Plenum Press, New York 1963,
110. W. Dahl, H. Stoffels, H. Hengstenberg, pp. 556 – 570.
C. Düren, Stahl Eisen 87 (1967) 125 – 136. 135. U. Jäkel, W. Schwenk, Werkst. Korros. 26
111. I. Class, Werkst. Korros. 6 (1955) 237 – 245. (1975) 521 – 529. A. Rahmel, E.
112. W. Hofmann, W. Rauls, Arch. Eisenhüttenwes. Tarar-Moisescu, Werkst. Korros. 26 (1975)
32 (1961) 169 – 171. W. Hofmann, W. Rauls, 513 – 520.
Arch. Eisenhüttenwes. 34 (1963) 925 – 934. 136. V. Cihal: “Corrosion Mechanism in Ammonia
113. G. Enterlein, M. Kesten, D. Schlegel, K. F. Synthesis Equipment,” First International
Windgassen, Z. Werkstofftech. 13 (1982) Congress on Metallic Corrosion, London
290 – 297. 1962, pp. 591 – 596.
114. H. Gräfen, T. Günther, Z. Werkstofftech. 10 137. U. Jäkel, W. Schwenk, Werkst. Korros. 22
(1979) no. 11, 373 – 390. (1971) 1 – 7.
115. H. Spähn, G. H. Wagner, U. Steinhoff, TÜ 14 138. V. van Rossum, Chem. Ing. Tech. 25 (1953)
(1973) no. 9, 260 – 264. 481 – 487.
116. H. Böhm, Schweiz. Arch. 33 (1967) 339 – 363. 139. L. Raichle, Chem. Ing. Tech. 28 (1956)
117. C. Bosch: Nobel lecture, 21. 5. 1932 in 203 – 213.
Stockholm, VDI Z. 77 (1933) 305 – 317; 140. Mannesmann-Röhrenwerke, Düsseldorf:
Chem. Fabr. 6 (1933) 127 – 142. Lexikon der Korrosion, vol. 1, pp. 133 – 134.
118. I. Class, Stahl Eisen 80 (1960) 1117 – 1135. 141. C. G. Stevens, J. Board, Br. Corros. J. 4
119. API Refining Department: Steels for Hydrogen (1969) 80 –85.
Service at Elevated Temperatures and 142. D. Goodison, R. J. Harris, P. Goldenbaum,
Pressures in Petroleum Refineries and Brit. Corros. J. 4 (1969) 293 – 300.
Petrochemical Plants, API Publication 941, 143. H. Pfeiffer, G. Sommer, Werkst. Korros. 13
May 1983 (Copyright 1967 by G. A. Nelson). (1962) 667 – 677.
120. H. Spähn, VDI-Ber. 235 (1975) 103 – 115. 144. O. Kubaschewski, B. E. Hopkins: Oxidation of
121. U. Gramberg, T. Günther, H. Palla, Werkst. Metals, Butterworths, London 1962.
Korros. 26 (1975) 461 – 464. 145. J. Möller, Metall 26 (1972) 820 – 825.
122. H. Spähn, Metalloberfläche 16 (1962) 146. J. Möller, Ind. Anz. 96 (1974) no. 38,
267 – 272. 856 – 857.
123. H. Spähn, Metalloberfläche 16 (1962) 147. U. Richter, Schweißtechnik (Vienna) 7 (1975)
335 – 340. 116 –120.
Corrosion 731
148. DIN 8553 (April 1970): 171. H. Gräfen, U. Gramberg, H. Schindler, Werkst.
Verbindungsschweißen plattierter Stähle. Korros. 30 (1979) 297 – 307.
149. U. Richter, Schweißen & Schneiden 25 (1973) 172. A. H. Dietzel: Emaillierung, Springer Verlag,
218 –220. Berlin –Heidelberg – New York 1981.
150. J. Chene, P. Luginbühl, Tech. Rundsch. Sulzer 173. R. Lorentz: “Korrosion von Chemieemail
2 (1973) 73 – 78. durch wäßrigneutrale Medien,” Mitteilungen
151. W. Ruckdeschel, Schweißtechnik (Zürich) 63 des Vereins Deutscher Emailfachleute e.V.,
(1973) 229 – 241. vol. 34/5, (1986) 65 –76.
152. B. Bouaifi, J. Krohn, U. Draugelates, 174. H. Scharbach: “Glas- und Glaskeramikemail
DECHEMA-Monogr. 103 (1986) 165 – 175. für den technischen Einsatz,” Swiss Chem. 5
153. B. Bouaifi, I. Graf, U. Draugelates, Prakt. (1983) 55 –60.
Metallogr. 25 (1988) no. 11, 543 – 554. 175. Pfaudler-Werke AG, Schwetzingen, Printed
154. D. Fuchs, H. Preisendanz, P. Schüler, publication FCP5M 12/87.
DEW-Tech. Ber. 13 (1973) 137 – 142. 176. Literature supplied by Pfaudler-Werke AG,
155. Pfaudler-Werke AG, Data Sheet 249-1: Schwetzingen, at ACHEMA 1988 in Frankfurt.
“Resista-Clad, ein Verfahren, das Metalle 177. E. Kreisel, E. Protogerakis: “Thermisches
dauerhaft verbindet.” Spritzen in
156. The Pfaudler Company, Data-Sheet Chemieapparate-Maschinenbau-Anlagen,
DS49-300-1: “Resista-Clad, Weld-Bonded Werkstoffe, Anwendungen,” Chem. Ing. Tech.
Cladding Process,” 1984. 59 (1987) no. 2, 118 – 122.
157. The Pfaudler Company, Data-Sheet 178. Sigri GmbH, Meitingen, Printed publication
DS49-301-1: “Resista-Clad, Physical & 853 01 10, 1983.
Chemical Performance Data,” 1985. 179. K. H. Möbius: “Füllstoffhaltige elektrisch
158. M. X. Cerny, Power Eng. (1987) no. 8, 36 – 37. leitfähige Kunststoffe,” Kunststoffe 78 (1988)
159. W. Burckhardt, Technik 26 (1971) 697 – 704; no. 1, 53 – 58.
27 (1972) 563 – 570, 528 – 531; 30 (1975) 180. A. Malliaris, D. T. Turner: “Influence of
239 – 245. Particle Size on the Electrical Resistivity of
160. L. L. Shreir, Ind. Finish (London) 8 (1955) Compacted Mixtures of Polymeric and
261 – 267, 389 – 400. Metallic Powders,” J. Appl. Phys. 42 (1971)
161. L. Winkler, Metall (Berlin) 31 (1977) no. 2, 614 – 618.
506 – 509. 181. H. Schindler, H. Gräfen, Chem. Ing. Tech. 57
162. J. Wurm, DECHEMA-Monogr. 76 (1974) (1985) no. 7, 597 – 602.
1486 – 1504, 81 – 89. 182. H. Gräfen: “Fortschritte beim Einsatz
163. A. W. Berger, CAV (1980) 82 – 84. organischer Werkstoffe im Korrosionsschutz,”
164. K. Breitwieser, R. Engelmann, VDI-Ber. 670 (1988) 451 – 468.
Maschinenmarkt 85 (1979) 393 – 400. 183. E. Oelke: “Kunststoffe in Chemieanlagen,”
165. W. Paatsch, Metall (Berlin) 30 (1976) VDI-Gesellschaft Kunststofftechnik,
332 – 336. VDI-Verlag GmbH, Düsseldorf 1986,
166. H. Gräfen, VDI-Ber. 624 (1986) 273. pp. 167 – 183.
167. H. Gräfen: “Werkstoffe des 184. T. Hasky in: “Oberflächenschutz mit
Chemieanlagenbaus, Stand der Entwicklung,” organischen Werkstoffen im Behälter-,
in 50 Jahre Werkstofftechnik an der Fakultät Apparate- und Rohrleitungsbau,”
für Maschinenwesen, Colloquy at the VDI-Gesellschaft Werkstofftechnik,
Technische Universität München (1989) VDI-Verlag GmbH, Düsseldorf 1980,
pp. 38 – 63. pp. 101 – 129.
168. K. Kreisel, E. Protogerakis, 185. E. Schacht: “Erfahrungen mit Gummierungen
DECHEMA-Monogr. 103 (1986) 191 – 205. und Beschichtungen in Anlagen zur
169. H. Schindler: “Nichtmetallische Werkstoffe Rauchgasentschwefelung,” VDI-Ber. 674
für die Chemietechnik,” Fortschritte der (1988) 263 – 281.
Verfahrenstechnik, vol. 15, VDI-Verlag 186. A. Swozil, G. Ullmann, Chem. Ing. Tech. 52
GmbH, Düsseldorf 1977, pp. 445 – 459. (1980) no. 4, 292 – 298.
170. H. Schindler: “Nichtmetallische Werkstoffe 187. J. E. Niesse: “Innovations in Organic Linings,”
für die Chemietechnik,” Fortschritte der Chem. Eng. Prog. 82 (1986) no. 6, 55 – 62.
Verfahrenstechnik, vol. 18, VDI-Verlag 188. G. Dexheimer, H. Schindler, internal report,
GmbH, Düsseldorf 1980, pp. 439 – 456. Bayer AG, 1989.
732 Corrosion
189. “Bekaplast-Säureschutzverkleidung,” 214. M. J. Humphries, R. N. Parkins, Corros. Sci. 7

company brochure, Steuler Industriewerke, (1967) 745 – 761.
Höhr-Grenzhausen. 215. H. Gräfen et al., Werkst. Korros. 22 (1971)
190. H. R. Rottkämer in: [7] , 169 – 184. 16 – 31.
191. J. I. Bregmann: Corrosion Inhibitors, The 216. J. B. Cotton, Werkst. Korros. 11 (1960)
Macmillan Comp., New York 1963. 152 – 155.
192. H. J. Rother: “Die Praxis des 217. Verein Deutscher Eisenhüttenleute (ed.):
Korrosionsschutzes,” Corrosion Inhibitors, Prüfung und Untersuchung der
The Maxmillan Comp., New York 1963, Korrosionsbeständigkeit von Stählen, Verlag
pp. 250 – 266. Stahleisen, Düsseldorf 1973.
193. H. Fischer, Werkst. Korros. 23 (1972) 218. DIN-Taschenbuch 219,see general references.
445 – 465. 219. Annual Book of ASTM Standards 1988, see
194. K. Risch, Werkst. Korros. 25 (1974) 727 – 734. general references.
195. E. Rabald, Werkst. Korros. 5 (1954) 368 – 392. 220. H. Gräfen, G. Herbsleb, in: [39] , pp. 55 – 69.
221. DIN 50 905:Korrosion der Metalle.
196. Corrosion Inhibition, Proceedings of the Int.
Korrosionsuntersuchungen Part 1 Grundsätze;
Conference on Corrosion Inhibition, NACE
Part 2 Korrosionsgrößen bei gleichmäßiger
Houston 1988
Flächenkorrosion; Part 3 Korrosionsgrößen bei
197. D. Kuron, H.-J. Rother, R. Holm, S. Storp,
ungleichmäßiger und örtlicher Korrosion ohne
Werkst. Korros. 37 (1986) 83 – 93.
mechanische Belastung; Part 4 Durchführung
198. M. N. Desai, Werkst. Korros. 23 (1972)
von chemischen Korrosionsversuchen ohne
483 – 487.
199. M. N. Desai, Werkst. Korros. 24 (1973) mechanische Belastung in Flüssigkeiten im
707 – 716. Laboratorium (1987).
222. ASTM G 4-84:Standard Method for
200. J. C. Kora, S. C. Makwana, K. C. Koshel, N. K.
Conducting Corrosion Coupon Tests in Plant
Patel, Werkst. Korros. 25 (1974) 753 – 756.
Equipment (1984).
201. M. Brooke, Chem. Eng. 12 (1954) 230 – 234.
223. ASTM G 31-72:Standard Practice for
202. D. Kuron, H. J. Rother, H. Gräfen, Werkst.
Laboratory Immersion Corrosion Testing of
Korros. 32 (1981) 409 – 421.
Metals (1985).
203. G. Schmitt, B. Olbertz, Werkst. Korros. 29 224. ASTM G 78-83:Standard Guide for Crevice
(1978) 451 – 456. G. Schmitt, B. Olbertz, Corrosion Testing of Iron-Base and
Werkst. Korros. 35 (1984) 99 – 106. G. Nickel-Base Stainless Alloys in Seawater and
Schmitt, B. Olbertz, K. H. Kurtz, Werkst. other Chloride Containing Aqueous
Korros. 35 (1984) 107 – 110. Environments (1983).
204. H. Gräfen, G. Herbsleb, F. Paulekat, W. 225. DIN 50 915:Prüfung von unlegierten und
Schwenk, Werkst. Korros. 22 (1971) 16 – 31. niedriglegierten Stählen auf Beständigkeit
205. E.-M. Horn, R. Kilian, H. Stiepel, H. Gräfen, gegen interkristalline Spannungsrißkorrosion
Werkst. Korros. 23 (1972) 967 – 973. (1985).
206. J.-W. Kühn, V. Burgsdorff, H. Richter in 226. ASTM G 30-79:Standard Practice for Making
W. v. Baeckmann, W. Schwenk (eds.): and Using U-Bend Stress-Corrosion
Handbuch des kathodischen Test-Specimens (1984).
Korrosionsschutzes, Verlag Chemie, 227. ASTM G 38-73:Standard Practice for Making
Weinheim 1971, pp. 342 – 354. and Using C-Ring Stress-Corrosion Test
207. H. Gräfen, F. Paulekat in: W. v. Baeckmann, Specimens (1984).
W. Schwenk, W. Prinz, see general references. 228. K. Risch, Werkst. Korros. 36 (1985) 55 – 63.
208. W. von Baeckmann, Chem. Ztg. Chem. Appar. 229. DIN 50 920:Korrosion der Metalle.
87 (1963) 395 – 404. Korrosionsuntersuchungen in strömenden
209. U. Heinzelmann in: [206] , pp. 330 – 341. Flüssigkeiten. Part 1 Allgemeines (1985).
210. W. P. Banks, J. P. Sudbury, Corrosion 230. DIN 50 914:Prüfung nichtrostender Stähle auf
(Houston) 19 (1963) 300 – 307. Beständigkeit gegen interkristalline Korrosion.
211. J. M. Stammen, Mater. Proc. 7 (1968) no. 12, Kupfersulfat-Schwefelsäure-Verfahren.
33 – 35. Strauß-Test (1984).
212. F. Paulekat, H. Gräfen, D. Kuron, Werkst. 231. Stahl-Eisen-Prüfblatt 1877: Prüfung der
Korrosion 33 (1982) 254 – 262. Beständigkeit hochlegierter,
213. D. Kuron, H. Gräfen, Chem. Ing. Tech. 60 korrosionsbeständiger Werkstoffe gegen
(1988) 604 – 612. interkristalline Korrosion, VDEh (1979).
Corrosion 733
232. DIN 50 921:Korrosion der Metalle, Prüfung 243. DIN 50 917:Korrosion der Metalle.
nichtrostender austenitischer Stähle auf Naturversuche. Freibewitterung (1979).
Beständigkeit gegen örtliche Korrosion in 244. DIN 50 017:Klimate und ihre technische
stark oxidierenden Säuren. Korrosionsversuch Anwendung. Kondenswasser-Prüfklimate
in Salpetersäure durch Messung des (1982).
Massenverlustes (Prüfung nach Huey) (1984). 245. DIN 50 018:Korrosionsprüfungen.
233. ASTM A 262-86:Standard Practices for Beanspruchung im
Detecting Susceptibility to Intergranular Kondenswasser-Wechselklima mit
Attack in Austenitic Stainless Steels (1986). schwefeldioxidhaltiger Atmosphäre (1978).
234. Euronorm 114-72. 246. DIN 50 021:Korrosionsprüfungen.
235. ASTM G 28-85:Standard Test Methods of Sprühnebelprü-fungen mit verschiedenen
Detecting Susceptibility to Intergranular Natriumchloridlösungen (1975).
Attack in Wrought, Nickel-Rich, 247. ASTM B 117-85:Standard Method of Salt
Chromium-Bearing Alloys (1985). Spray (Fog) Testing (1985).
236. ASTM G 48-76:Standard Test Methods for 248. ASTM G 87-84:Standard Practice for
Pitting and Crevice Corrosion Resistance of Conducting Moist SO2 Tests (1984).
Stainless Steels and Related Alloys by the Use 249. ASTM G 91-86:Standard Practice for
of Ferric Chloride Solution (1980). Monitoring Atmospheric SO2 Using the
237. ASTM G 36-87:Standard Practice for Sulfation Plate Technique (1986).
Evaluating Stress-Corrosion-Cracking 250. ASTM G 85-85:Standard Practice for
Resistance of Metals and Alloys in a Boiling Modified Salt Spray (Fog) Testing (1985).
Magnesium Chloride Solution (1987). 251. DIN 50 918:Korrosion der Metalle.
238. NACE Standard TM-01-077.
Elektrochemische Korrosionsuntersuchungen
239. DIN 50 916:Prüfung von Kupferlegierungen.
(1978).
Spannungsrißkorrosionsversuche mit
252. ASTM G 3-74:Standard Practice for
Ammoniak. Part 1 Prüfung von Rohren,
Conventions Applicable to Electrochemical
Stangen und Profilen (1976); Part 2 Prüfung
Measurements in Corrosion Testing (1981).
von Bauteilen (1985).
240. ASTM G 37-85:Standard Test Method for Use 253. ASTM G 5-87:Standard Reference Test
of Mattsson’s Solution of pH 7.2 to Evaluate Method for Making Potentiostatic and
the Stress-Corrosion Cracking Susceptibility Potentiodynamic Anodic Polarization
of Copper-Zinc Alloys (1985). Measurements (1987).
241. ASTM G 47-79:Standard Test Method for 254. DIN 50 919:Korrosion der Metalle.
Determining Susceptibility to Stress-Corrosion Korrosionsuntersuchungen der
Cracking of High-Strength Aluminum Alloy Kontaktkorrosion in Elektrolytlösungen
Products (1984). (1984).
242. ASTM G 44-88:Standard Practice for 255. ASTM G 71-81:Standard Guide for
Evaluating Stress Corrosion Cracking Conducting and Evaluating Galvanic
Resistance of Metals and Alloys by Alternate Corrosion Tests in Electrolytes (1986).
Immersion in 3.5 % Sodium Chloride Solution 256. D. Kuron, H. Gräfen, Z. Werkstofftechn. 8
(1988). (1977) 182 – 191.
Abrasion and Erosion 735
Abrasion and Erosion

Klaus Schneemann, Hüls AG, Marl, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . . . . 735 5.1. Sliding Wear, Elastic Rolling Wear,

2. Types of Wear and Wear Mechanisms 735 and Oscillation Wear . . . . . . ..... 752
3. Behavior of Materials . . . . . . . . . . . 742 5.2. Abrasion Wear . . . . . . . . . . ..... 753
3.1. Metals . . . . . . . . . . . . . . . . . . . . . 743 5.3. Damage by Particle Erosion . ..... 754
3.2. Plastics and Elastomers . . . . . . . . . 747
5.4. Solid Particles-Free Erosion . ..... 756
3.3. Ceramics . . . . . . . . . . . . . . . . . . . 749
4. Surface Treatment and Coatings . . . 749 5.5. Damage Caused
5. Practical Examples of Abrasion and by Erosion – Corrosion . . . . . . . . . . 757
Erosion Damage . . . . . . . . . . . . . . 751 6. References . . . . . . . . . . . . . . . . . . 759
1. Introduction Wear, friction, and lubrication are described

under the term tribology as the science of the
Practical experience with industrial equipment, study, industrial application, and modification
machinery, and plant has shown that components of the phenomena and processes occurring be-
have only limited service lives. Damage and ul- tween surfaces which are acting against each
timate failure of the component can occur as a other and moving relative to one another; this
result of changes in the material that originate at includes boundary surface interactions between
the surface, even if the components are designed solids, and between solids and their gaseous or
such that long-term action of the forces alone liquid surroundings. Since at least two compo-
causes neither fracture nor undue deformation. nents of a system are involved in wear, it is not
If the reactions responsible for the damage a pure material characteristic, but only a sys-
are of electrochemical or predominantly chemi- tem characteristic. Wear itself is generally un-
cal nature, the term corrosion is normally used, derstood as progressive loss of material from the
whereas mechanical damage to the surface of surface of a solid body caused by mechanical
the component is defined as wear. Attempts to action, i.e., contact and relative motion with a
avoid a loss of material due to wear, or at least solid, liquid, or gaseous phase.
to reduce the loss, concentrate on making the af-
fected surface more resistant to wear. This can
be achieved by mechanical, thermal, or thermo- 2. Types of Wear and Wear
chemical treatment of the surface or by applying Mechanisms
or depositing metallic coatings. Under some cir-
cumstances the wear conditions can be changed The treatment of wear must take the diversity
by design measures so that the danger for the of tribological processes into account, and this
affected component surface is eliminated or re- requires precise analysis of the loads and of the
duced to a tolerable level. appearance of the damage. It is usual to sub-
With few exceptions (e.g., running-in of bear- divide the large number of wear processes into
ings), wear in engineering means an undesired types of wear and wear mechanisms, in which
change that causes very high costs every year; different mechanisms have to be allocated to one
in a highly developed, industrialized country this and the same type of wear.
can amount to ca. 1 – 2 % of the gross national The kinematic conditions and the types of
product [1]. materials involved in the wear determine the
Plant construction typical of the chemical in- types of wear, such as sliding wear, elastic
dustry plays an insignificant role, and wear is rolling wear, impact wear, and shock wear.
correctly known as “the problem child of me- Oscillating wear stress, or oscillation wear,
chanical engineering” [2]. is caused by oscillating sliding and by oscillat-
736 Abrasion and Erosion
Table 1. Classifaction of types of wear (based on DIN 50 320)
ing sliding parts when rolling or even on im- More often the material is removed by cut-
pact. Wear mechanisms characterize the ener- ting; so-called microchips are obtained. In duc-
getic and material interactions between the in- tile materials these two processes are predom-
dividual elements of a wear system. DIN 50 320 inant, but in relatively brittle materials micro-
differentiates between adhesion, abrasion, sur- particles break away and microgouging occurs.
face destruction, and tribochemical reaction as Depending on the number of components in-
the principle mechanisms (Table 1) [3]. volved, a distinction is made between two-body
and three-body abrasion wear. Sliding, shock,
Adhesion. If the micro-roughnesses on the and rolling are possible types of wear, see Ta-
“clean” surfaces of two solid bodies are in con- ble 2 [5].
tact with each other, high surface pressures Oscillating mechanical loads in the surface of
are generated locally; relative movements cause a solid can lead to surface destruction by mate-
cold welding which can lead to separation of ma- rial fatigue. This appears as formation and prop-
terial. Material transfer, scales, and shear dim- agation of cracks, and may lead to separation of
ples are typical wear patterns. material particles.
Tribological stress in the system can lead
Abrasion. When two bodies of different to tribochemical reactions in addition to purely
hardnesses slide against each other, abrasion physical processes. As a result layers can appear
causes the softer surface of the base body to on or between the touching surfaces. In general
be scratched by the harder counter body. This these wear mechanisms do not act in pure form
harder body can be a micro-roughness of the in practice; they usually occur in combinations.
counter body or a wear particle that has already According to [4] the relative proportions of
been removed. The penetration of the harder microplowing and microcutting can be deter-
counter body and the relative movement pro- mined from the profile of a wear groove (Fig. 2).
duce wear grooves or furrows in the softer body, The so-called f ab value is defined by
for which reason it is also called furrow wear
Av − (A1 +A2 )
(Fig. 1). If the softer material is plastically de- fab =
Av
formed and is displaced to the furrow edges, the
process is called microplowing. Material is not so that for the two extreme cases, pure mi-
removed in a single event but by the simulta- croplowing and pure microcutting, f ab becomes
neous action of many abrasive particles or by 0 and 1, respectively.
repeated furrowing by one particle [4].
Figure 2. Profile of a wear groove
The linear wear intensity W l/s is defined as

∆h
Wl/s =
s
where ∆h represents the reduction of thickness
of the worn component and s is the wear path.
Using the f ab value allows the wear intensity to
Figure 1. Mechanisms of material damage in furrow wear
A) Microplowing; B) Microcutting; C) Microfatigue; D) be expressed as
Microgouging p
Wl/s =ϕfab ·
Hdef
738
Table 2. Comparison of the characteristics of abrasive sliding, abrasive impact, and three-body abrasive wear
Abrasion and Erosion

where p is the surface pressure, H def is the tion of the ratio HVdef /f ab in accordance with
hardness of the wearing material in the strain- the above equation. For different materials with
hardened state, and ϕ is the form factor. The the same hardness, the wear resistance increases
f ab value is a function of the effective surface with increasing strain-hardening capability; see
deformation caused by the abrading particles, Figure 4 [4].
the ductility of the worn material, and the ma- This assumes that in the test method the wear
terial’s strain-hardening behavior [6]. The value takes place at the so-called upper shelf of the
decreases with increasing ductility, increasing wear characteristic. In the treatment of wear
strain-hardening capability, and decreasing sur- problems, Wahl was the first to draw atten-
face deformation. tion to the connection between abrasive particle
hardness and wear [7]. He found that at a certain
value of the particle hardness the wear increases
sharply, and at higher values remains virtually
constant; see Figure 5.
Note, however, that the pure furrowing de-
scribed here occurs in tests with bonded parti-
cles, a condition which occurs relatively rarely
in practical situations. More typical is the case
where unbonded, loose particles are carried over
the surface of the component, and additional
rolling motion is also possible.
With increasing particle mobility, the wear
caused by loose particles represents the transi-
tion from abrasive sliding wear to erosion (abra-
sive – erosive attack).
Erosion. Erosion phenomena are caused by

flow, in which the flowing fluid itself is erosive
or the fluid carries particles that are unable to
follow the filaments of flow at surface irregu-
larities. In this case a shock component is often
superimposed on the plowing mechanism; this
causes local deformation and destruction.
If the fluid is a gas, tribochemical reactions
with the solid are only possible at fairly high
temperatures where the ablation mechanism can
act through the processes of sublimation, vapor-
ization, or fusion.
Figure 3. Dependence of the abrasive wear resistance of Pure liquid erosion occurs relatively rarely
metallic materials on the hardness of the material (A) and because even at high flow velocities the forces
on the ratio of the particle hardness to the factor f ab (B), acting are hardly sufficient to cause removal of
measured by the abrasive paper method, (SiC, 80 grain, material; exceptions to this are additional corro-
p = 3.54 MPa)
sive elements and the involvement of cavitation.
According to the above equation, a high wear
resistance means a small f ab value and a high Cavitation. Since the term cavitation is used
material hardness in the strain-hardened state. to describe the processes occurring in the liquid
According to this model, hardness alone often and also the resulting damage to the material sur-
fails to provide a reliable assessment of the ex- face, the latter is often called cavitational erosion
pected wear resistance. to avoid confusion. These processes are caused
Figure 3 A shows the wear resistance 1/W l/s by the formation and subsequent collapse of va-
as a function of hardness for various metals, por or gas bubbles in liquids. When the pressure
and Figure 3 B shows the resistance as a func- falls, dissolved gases evolve from small gaseous
Figure 4. Schematic representation of the abrasive wear resistance in the upper shelf and the wear mechanisms plotted versus
the material hardness
LIVE GRAPH
Click here to view
uated by the interposed liquid layer [8]. Damage
is therefore only caused by bubbles which col-
lapse directly at or close to the surface.
Figure 5. Lower and upper shelf wear characteristic (abra-

sive paper method, 80 grain, p = 0.37 MPa)
nuclei, or evaporation takes place if the pressure

falls locally below the vapor pressure. In regions
of higher pressure in the liquid the bubbles im-
plode. If this implosion takes place directly at the
Figure 6. Dependence of drop impingement wear (wear
surface of the component, the cyclic, locally con- depth per centimeter impinging liquid column) on the im-
fined compressive stresses finally lead to micro- pact velocity for various materials
scopic fatigue phenomena. This resembles the a) Glass; b) Aluminum; c) Polyurethane; d) Sintered alu-
behavior of materials under vibratory stress. If mina
the vapor bubbles formed do not implode di- If the pressure differences are caused solely
rectly at the surface the shock intensity is atten- by flow, the resulting process is called flow cav-
itation. However, vibrations of sufficiently high During hydraulic transport the particles fol-
frequency can initiate vibrational cavitation. low the streamlines of the fluid better than in
The material damage described can take pneumatic transport due to the smaller differ-
place by purely mechanical means, but in prac- ence in densities. Sliding jet wear is always
tice it is often considerably intensified by super- present in horizontal pipeline transport due to
imposed corrosion stress. the influence of gravity.
Comparable damage can occur through the Where changes in direction of flow occur,
repeated impact of drops or liquid jets at high (e.g., at pipe bends) the particles, due to their
velocity. After the deformability has become ex- higher density, are pressed to an increasing ex-
hausted in tough materials, initial cracks appear; tent against the surface, where they have an ero-
these develop into breaks and progress to deep sive action (Fig. 7) [10].
fissuring. This wear, known as drop impinge- The wear increases distinctly with increasing
ment, depends on the impact velocity (Fig. 6) velocity and can be described by the empirically
and the angle of impact [9]. determined expression
In chemical technology and process engi-
neering, the most important instances of erosion W (α) =C v n(α)
are those where the fluid contains solid parti-
cles. If the fluid is a liquid this type of wear where α is the angle of impact, C is a constant
is called hydroabrasive wear or scouring wear; that depends on the material and the abrasive, v is
with gaseous fluids it is called jet wear. In both the velocity, and n is a velocity exponent which
types of wear, plowing is active as the essen- depends on the material, the abrasive, and the
tial mechanism, and with steeper angles of im- angle. This equation is also valid for jet wear, in
pact there is an additional component causing which material is removed by impacting and/or
destruction of the material. Tribochemical reac- plowing particles in a carrier gas. Because of the
tions also occur. large number of forms which occur in practice
During hydraulic transport of solids in it is necessary to distinguish between the sliding
pipelines, the flow path lines near the surface jet, in which the particle slides over the surface
travel essentially parallel to the surface. The ero- of the workpiece, and the impact jet, in which the
sive effect of the particles is generally slight pro- particle strikes perpendicularly; all intermediate
vided that the flow remains undisturbed. Flow forms of jet (0◦ ≤ α ≤ 90◦ ) are called inclined
separation at irregularities causes turbulence, jets.
which can force the particles against the wall
and produce erosion. Typical irregularities in
pipelines are the protruding roots of welds. Fur-
thermore, in turbulent flow more collisions be-
tween particles occur, leading to impacts with
the enclosing walls.
Figure 8. Energy balance for the impact, without breakage,

of a hard particle on a ductile metal surface
The basic process in jet wear is the impact of

a particle against the surface at some arbitrary
Figure 7. Path of motion of hydraulically transported parti- angle. About 90 % of the kinetic energy of the
cles of various densities and diameters (calculated for water particle is converted into plastic deformation and
at 18 ◦ C and a flow rate of 2 m/s) heat (Fig. 8) [11]. The main energy conversion
takes place in the softer body [12].
Estimates give values of a few thousand Soft, ductile materials exhibit higher wear un-
megapascals [13] for the pressures occurring on der furrowing conditions. At α = 0◦ , the vertical
impact and of microseconds [14] for the impact component of the force theoretically approaches
times (Fig. 9). The fatigue mechanism is domi- zero, so after a maximum the wear should also
nant where the impact is predominantly perpen- approach zero, but this situation does not actu-
dicular, while at shallow incident jet angles the ally occur in practice (Fig. 10) [15].
particle has a plowing action on the surface un-
der the influence of a normal force component Erosion – Corrosion. Under certain corro-
[15]. These result in different requirements for sive conditions many metals form covering lay-
the material involved: ers. If these are sufficiently dense they act as
protective films against corrosive removal of
1) Very hard materials are best for withstanding material. An example of this is the protective
plowing processes layer of iron oxide formed in unalloyed or low-
2) Impact processes cause little damage if the alloy boiler tubes. Erosion – corrosion is under-
energy can be absorbed elastically or plasti- stood as the combined action of mechanical sur-
cally. face removal and corrosion. With some soft and
LIVE GRAPH
loose layers the shear forces obtained with pure
Click here to view flowing liquids at medium flow velocities are
sufficient to damage the protective layer with-
out the involvement of abrasive solid particles.
Where drop impingement or cavitation are in-
volved the mechanical removal of material is
understandable. On the other hand, diffusion-
controlled corrosion inhibition may be nullified
in flowing fluids as a result of saturation of the
boundary layer [16]. The resulting purely chem-
ical removal of material therefore no longer cor-
responds to the usual term of erosion – corrosion
and is now called flow-induced corrosion [17].
Figure 9. Variation of the calculated impact force of a sphere

(diameter 1 mm, velocity 100 m/s) with time for: 3. Behavior of Materials
a) C60H; b) St 37; c) Rubber
The many outward forms assumed by wear
LIVE GRAPH mechanisms make it necessary to design the
Click here to view
component to be resistant to wear, at least on
the surface under attack. This can be accom-
plished by selecting a suitable base material or
by modifying the surface by mechanical, ther-
mal, or thermochemical treatment or by apply-
ing protective coverings of other materials [18].
Adequate wear resistance of a component is nor-
mally only one of several criteria in the require-
ment profile. Adequate strength, toughness, cor-
rosion resistance, and other properties, such as
ease of repair, are requirements which must also
be met. Economic criteria also have to be con-
Figure 10. Influence of the jet angle on the wear rate
a) Rubber; b) St 37; c) C60H
sidered. In general, theoretical considerations
and laboratory tests do not lead to a quick so-
Since hard materials normally have low duc- lution, and in most cases the final suitability is
tility, wear is low at small angles, but fragments proved under operational conditions. Wear prob-
are removed easily with perpendicular impact. lems can often be overcome by changes in de-
sign or in the process technology. Metals, plas- the loading of the material is confined to the sur-
tics, ceramics, and protective coatings or layers face region, and in abrasive wear a penetration
are compared below purely from the aspect of process occurs that is similar to the hardness
material technology. tests. Unlike hardness tests, an additional tan-
gential force component also has to be taken into
account in the case of wear, which initiates ef-
3.1. Metals fects such as increase in temperature (possibly
associated with phase changes), reaction layer
There is still no comprehensive correlation avail- formation, and strain hardening by plastic de-
able between wear and hardness of materials. formation, and can therefore lead to permanent
Depending on the wear mechanism, other prop- changes in the tribological system.
erties, such as the state of the material’s mi- LIVE GRAPH
crostructure, also play a significant role. Because Click here to view
of the simplicity of the hardness test it is, how-

ever, useful to know which wear processes de-
pend essentially on hardness alone. In any case,
Figure 12. Dependence of wear intensity on the hardness

of the abrasive particles for particle furrowing for various
materials
It is usual to subdivide furrow wear into:

1) counterbody furrowing, in which the miner-
alogical grains are fixed on the surface of the
counterbody (e.g., a grinding wheel), and
2) particle furrowing, in which the wear is
caused by freely moving particles.
In trials both types show a similar dependence
Figure 11. Dependence of wear intensity on the hardness of of the wear rate on the hardness of the attacking
the abrasive particles for counterbody furrowing for various particle (lower shelf/upper shelf characteristic);
materials (abrasive paper method, p = 0.1 MPa, v = 0.25 m/s)
a) Rubber; b) Polystyrene; c) Cast basalt; d) Steel St 37; see Figs. 11 [19] and 12 [20].
e) C60H; f) Hard metal G4; g) Hard metal H2 For steels an increase in wear resistance is
observed with increasing hardness, whereby in-
LIVE GRAPH
Click here to view
Figure 13. Wear resistance of cast iron towards particle furrowing (wear pot method, quartz sand)
a) Martensitic cast iron alloyed with Cr and Ni; b) Unalloyed and low-alloy pearlitic cast iron; c) Steels with 0.15 – 0.5 % C
and gray cast iron with lamellar or spheroidal graphite
LIVE GRAPH
Click here to view
Figure 14. Linear relationship between wear resistance and hardness in the upper shelf region (abrasive paper method, corun-
dum, 180 grain, p = 0.94 MPa)
creasing the hardness by alloying elements has hibit a linear relationship between resistance and
a greater effect than increasing the hardness by material hardness (Fig. 14) [22].
heat treatment.
With cast iron the wear resistance also tends Jet Wear. Materials in chemical plants are
to increase with increasing hardness. The maxi- usually transported through pipelines and con-
mum resistance values increase in the following verted in enclosing containers. Compressors and
order: gray cast iron with lamellar or spheroidal fans are used as the conveying units when
graphite, pearlitic cast iron, and martensitic cast gaseous materials are transported, while pumps
iron (Fig. 13) [21]. are normally used for liquids. The resulting wear
In the upper shelf region and in the presence phenomena are therefore associated with the
of normal abrasive particles, all pure metals ex- type of flow involved, and the various types of
wear are covered by the term erosion.
Even at very high velocities pure gases are (Table 3) which relates predominantly to steel
only capable of damaging the enclosing solid and cast iron.
body when the temperature is high enough
to lead to thermally induced reactions. Prob- Wear with Liquids. The forces that
lems with gas conveying are therefore only to particle-free liquids exert on metal surface are so
be expected when entrained solid particles are low at the usual flow velocities of a few meters
present. In jet wear the material is elastically or per second that they do not cause any removal of
elastically/plastically deformed by impact of the material. According to Heil, no erosion effects
particles against the surface. could be detected with plain carbon steel, even
Apart from particle velocity the most impor- at 60 m/s, in a test method similar to that with
tant factor in jet wear is the jet angle: brittle met- the rotating disc [26]. Damage caused by liquid
als exhibit increasing wear with increasing an- flow alone is therefore relatively rare in practice.
gle of impact, with a maximum at 90◦ ; whereas The situation is different if, for example, a liquid
with tough metals, wear increases up to an an- under high pressure emerges with high velocity
gle of 15◦ – 40◦ , after which the loss decreases into a space of lower pressure; it may have an
at steeper angles. The ductility and strain hard- erosive action on the metal at the exit point.
ening at the surface are thought to be responsible This applies to an even greater extent if the fluid
for this behavior (Fig. 15) [23]. forms dense protective layers with the metal.
If these layers are removed mechanically, they
LIVE GRAPH must be reformed, otherwise erosion will act in
Click here to view
combination with corrosion, which is known as
erosion – corrosion. This situation occurs very
frequently in practice as many metals can only
be used, for example, with water because a thin,
usually oxidic layer protects the metal against
corrosive attack. Table 4 gives guide values for
maximum permissible flow velocities for pure
water and, for comparison, for the more aggres-
sive seawater [27].
Since technical pure liquids usually contain
very fine solid particles, it is often difficult in
practice to differentiate between pure fluid ero-
sion and so-called hydro-abrasive wear. As with
jet wear, the number, hardness, and velocity of
entrained particles determine the extent to which
the protective covering layer is removed and the
extent of the pure metal wear. If mechanical
Figure 15. Impact jet and sliding jet components in jet wear
stressing due to entrained particles is predom-
a) Experimental curve for cast iron (2.8 % C, 21 % Cr); inant then hardness and strength are of decisive
b) Experimental curve for St 37; c) Impact jet component importance for metals, as shown in Figure 16 for
for cast iron; d) Impact jet component for St 37; e) Sliding copper alloys [28].
jet component for cast iron; f) Sliding jet component for St
37
Cavitation and Drop Impingement. Ac-
The relationship between wear resistance and cording to Grein all materials succumb to the
material hardness known from abrasion is valid exceptionally high mechanical stress occurring
only at small jet angles because of the compa- during cavitation if the intensity is sufficiently
rable wear mechanisms. According to Bitter high [29]. In soft materials such as aluminum,
[24], abrasion is dominant with the sliding jet cavitation erosion appears in the form of plas-
and surface destruction with the impacting jet. tic indentations caused by single implosions.
For the first-named conditions Wahl [25] With higher strength metals the damage starts
gives an appraisal of working characteristics by roughening of the surface after a certain in-
cubation time; as the destruction progresses the
Table 3. Performance properties of wear resistant materials
Material Tensile strength, MPa Fracture strain, % Wear resistance
Low-alloy austenitic manganese steel 600 15 very low

Austenitic manganese hard steel 550 50 medium
Unalloyed steels 420 20 extremely low
High-strength low-alloy steels 600 18 extremely low
Pearlitic steels 500 – 600 12 extremely low
Martensitic steels 500 – 600 15 – 20 medium
Ledeburitic steels 600 2 high
Heat-treated 66 (gray cast iron) 250 < 0.5 very low
Heat-treated 666 (nodular iron) 500 3 low
Pearlitic white cast iron 250 < 0.5 high
Martensitic white cast iron 350 < 0.5 very high
High-chromium white cast iron 500 < 0.5 very high
Co – Cr – W – C alloy 500 < 0.5 very high
Hard metal 500 < 0.5 extremely high
interconnected holes eventually form a spongy soft, or very brittle, grain boundaries reduce the
structure. resistance.
Table 4. Maximum permissible flow rates for pure water and sea-
water
Material Flow rate, m/s
Pure water Seawater
Aluminum 1.2 – 1.5 1.0

Copper 1.8 1.0
Copper + As 2.1 1.0
Copper + Fe 4.0 1.5
CuZn28Sn 2.0 – 2.4 1.5 – 2.0
Al bronze ca. 3.0 ca. 2.0
CuNi10Fe 5.0 2.4
CuNi30Fe 6.0 4.5
Steel 3–6 2–5
Nickel alloys 30 15 – 25
Plastics 6–8 6–8
The following factors increase the resistance

to cavition erosion:
1) High corrosion resistance
Figure 16. Maximum tolerable flow rates (water) as a func- 2) Homogeneity
tion of material hardness for various copper alloys 3) Ductility
4) Compressive residual stress
In general, the strength and the fatigue 5) High strain-hardening capability
strength are the most important material param- 6) Smooth surface
eters for resistance to cavitation; hardness is 7) Fine-grained structure
therefore often used as a measure. With simi- 8) Fine-grained hard inclusions
lar microstructures, the metal with the higher 9) High content of hard components
hardness has the more favorable behavior, and 10) Layer structure
where different metals have the same hardness, 11) Wrought structure
the resistance improves with increasing tough-
ness. As cavitation attack takes place locally, the while the following reduce the resistance:
behavior is determined by the structural consti-
tution to a greater extent with this type of erosion 1) Low corrosion resistance
than with others. A homogeneous, fine-grained 2) Heterogeneity
microstructure is required; soft inclusions and 3) Brittleness
4) Tensile residual stress
5) Low strain-hardening capability LIVE GRAPH

Click here to view
6) Rough surface
7) Coarse-grained structure
8) Coarse-grained hard inclusions
9) High content of soft components
10) Dendritic structure
11) Cast structure
The data provided by Piltz [30] and Rein-
gans [31] can be used as guides for the selection
of materials.
As with other types of erosion, the superpo-
sition of a corrosion process also has to be taken
into account where damage by cavitation occurs.
Removal of material by corrosion after destruc-
tion of protective covering layers often repre-
sents the more intensive attack, and the corrosion
resistance of the material is then the dominant
property.
A comparable stress occurs with drop im-
pingement, characterized by repeated, short-
time liquid impacts. The comments made above
about cavitation also apply here to the material
behavior.
LIVE GRAPH
Click here to view
Figure 18. Wear relative to St 37 as a function of impact

angle for various materials (abrasive: quartz sand, particle
size 0.2 – 1.5 mm, HV = 1250)
Since residual stresses counteract the external

loading of the material they can increase resis-
tance to destruction perceptibly. In this sense,
strain hardening has a similar effect to carbur-
ization and nitriding [32].
3.2. Plastics and Elastomers
Figure 17. Relationship between wear and the reciprocal The relationship between wear and surface hard-
product of tensile strength S and fracture strain ε for poly- ness obtained for metals would predict a com-
mers paratively poor behavior for polymers. However,
1) Poly(methyl methacrylate); 2) Low-density polyethy- their special structural features give rise to prop-
lene; 3) Polystyrene; 4) Polyoxymethylene; 5) Polyamide
66; 6) Polypropylene; 7) Epoxy resin; 8) Polytetraflu- erties that can play a special role in wear.
oroethylene; 9) PMMA – acrylonitrile copolymer; 10) The viscoelastic deformation behavior is
Polyester; 11) Polychlorotrifluoroethylene; 12) Polycar- characterized by time-, temperature- and
bonate; 13) Polyamide 11; 14) ABS; 15) Poly(phenylene velocity-dependent deformation processes. Rel-
oxide); 16) Polysulfone; 17) Poly(vinyl chloride); 18)
Poly(vinylidene chloride) atively low levels of hardness and strength,
high plasticity, low thermal conductivity, and
Next Page

Table 5. Jet wear of polymers and metals
Material Hardness Abrasive * Relative wear W /W St37
Steel T 80 H 590 HV II 0.109

Polyurethane 18 Shore D II 0.143
Poly(vinyl chloride) 5 Shore D II 0.143
Polyurethane 34 Shore D II 0.403
Rubber 17 Shore D II 0.57
Steel St 37 122 HV I 1.0
Low-pressure polyethylene 60 Shore D I 1.06
Steel St 34 124 HV I 1.07
Polyamide 6, Grilon R 50 62 Shore D I 1.33
Polyamide 6, Grilon R 70 64 Shore D I 1.33
Copper 99 HV I 1.36
High-pressure polyethylene 42 Shore D II 1.4
Low-pressure polyethylene 58 Shore D II 1.4
Polyamide 11, Rilsan Besvo 71 Shore D I 1.81
Low-pressure polyethylene 58 Shore D I 2.0
Low-pressure polyethylene 60 Shore D II 2.0
Polyamide 6, Ultramid 70 Shore D I 2.21
Aluminum 39 HV II 2.68
Brass 150 HV I 2.76
Aluminum 29 HV II 3.23
Polyamide 11 69 Shore D I 3.31
Resitex 89 Shore D II 8.2
Glass 6 – 7 Mohs II 9.7
Lead 4 HV II 10.5
Plexiglas 85 Shore D II 10.75
Pertinax 92 Shore D II 18.5
Epoxy resin with glass fiber 86 Shore D II 19.5
Epoxy resin with hardener and quartz powder 84 Shore D II 31
* Abrasive I: sand, HV = 5000 MPa, particle size ≤ 0.9 mm; Abrasive II: sand, HV = 7200 – 8100 MPa, particle size 0.3 – 0.5 mm
high thermal expansion are effects of the weak Due to their material properties, polymers
secondary bonding forces between the macro- have proved successful where streams of small
molecules and their coiled structures. particles cause impact stress in addition to slid-
In particular, the low tendency to adhesion ing wear, i.e., with abrasive impact wear and
gives polymers their good slip characteristics with erosive attack. Although polymers gener-
with steels as the sliding partners – in the ab- ally have poor resistance to abrasive sliding at-
sence of additional abrasive particles – because tack, their ductility, especially of elastomers,
of the low frictional forces involved, and the leads to a behavior superior to that of met-
slip system is characterized by additional emer- als when the impacting component is dominant
gency running properties. Polyamide and PTFE (Fig. 18) [36]. Their behavior therefore differs
occupy the prime positions here as they possess significantly depending on the angle of impact.
good cohesive linkage properties compared with The material becomes heated due to internal fric-
other unreinforced polymers [33], [34]. tion, which can lead to complete failure at high
If abrasive sliding stress is present, the de- jet intensities.
pendence on hardness known for metals can- The preferred elastomers include the
not really be depicted in the same way. It polyurethanes and synthetic rubbers because
has been demonstrated that polymers exhibit a of their outstanding resistance to wear. In
good relationship between wear resistance and polyurethanes, greater resistance is found in the
crack propagation energy, or even between wear hardness range 70 – 95 Shore A, whereas normal
and the product of tensile strength and fracture grades of rubber reach their optimum between
strain; see Figure 17 [35]. 50 and 70 Shore A [37]. It is not possible to
Previous Page
separate the influencing factors systematically hardness and melting point, but they are much
with respect to tribological behavior because of more brittle than the oxides and are only used
the large number of additives, types of rubber, in isolated instances as wearing bodies. Silicon
and applications (see Table 5) [38], [39]. carbide is characterized by its low thermal ex-
If, for rubber and C 60 H steel, the amount of pansion and high thermal conductivity and has
wear relative to St 37 steel is plotted versus the proved to be more resistant to thermal shock
impact angle and the hardness of the jet material than oxides. Zirconia is tougher than alumina; its
then, according to [40], it is possible to show the modulus of elasticity is only about half as large
very different wear behavior of these two mate- and is comparable with that of steel. Zirconia is
rials (Fig. 19). therefore very suitable for compound structures
with steel. At present the applications of ceramic
sintered materials in chemical plant construction
3.3. Ceramics are slide rings, pump parts, and slide bearings.
Ceramic materials have gained increasing im-
portance over the last few decades; in addition
to corrosion resistance and suitability for high
4. Surface Treatment and Coatings
temperatures the resistance to wear is the im-
The fact that wear starts at the surface of the
portant property of these materials. The above-
workpiece suggests that only the tribologically
mentioned properties of the sintered body can be
stressed surface should be strengthened instead
varied over a wide range by adjusting the pow-
of making the entire component out of wear-
dered raw material.
resistant material. It should be borne in mind
The nonmetallic, mechanically resistant ma-
that the base material has to fulfill other, for ex-
terials which are constituents of the ceramic ma-
ample, load-bearing functions as well as surface
terials can be subdivided into oxidic and nonoxi-
stressing, i.e., the surface which has been made
dic materials [41]. High melting points and hard-
wear-resistant must not interfere unduly with the
nesses are the outstanding properties, as shown
component.
in Table 6.
If the material involved can be hardened then
Table 6. Hard materials various methods can be used to harden the sur-
Material mp, ◦ C , g/cm3 Vickers hard-
face to a certain depth by structural transforma-
ness HV0.2 tion, making it resistant to wear. These include
induction, flame hardening, HF impulse, elec-
Oxides
Al2 O3 2050 3.9 2300 tron, and laser jet methods. In case hardening,
ZrO2 2700 5.7 1100 a steel which originally cannot be hardened is
TiO2 1860 4.2 1000 made hardenable by inward diffusion of carbon,
Carbides
TiC 3150 4.9 3200 sometimes also with nitrogen; hardening is then
TaC 3780 14.5 1790 carried out by rapid quenching. The hardness
WC 2600 15.7 2080
SiC 2180 3.2 3000 achieved is governed essentially by the contents
B4 C 2450 2.5 3500 of dissolved C and N; the usual depths of appli-
Nitrides
TiN 2950 5.2 2450
cation are 0.5 to 2 mm.
TaN 3090 13.8 3230 Nitride layers are produced after treatment
Si3 N4 1900 3.2 1400 in a salt bath or in a gas atmosphere by inward
diffusion, usually below 600 ◦ C. Unlike trans-
BN (cubic) 3000 * 3.48 8000
Borides
TiB2 2900 4.4 3480 formation hardening, which is effected by lattice
ZrB2 2990 6.0 2200
Carbon
distortion as a result of embedded carbon atoms,
Diamond 3750 3.5 8000 – 10 000 nitriding and boriding provide the surface with
an exceptional increase in hardness by the for-
* Sublimes.
mation of an intermetallic bonding layer. These
bonding layers also increase the general corro-
Alumina is the most important oxidic sion resistance, but they are so thin that they can
abrasion-resistant material. Metal carbides are break by mechanical point loading.
in some ways superior to oxides with respect to
Figure 19. Dependence of jet wear on the jet angle and the hardness of the impinging mineral
Hardfacing, on the other hand, is a thick tance is required. Where flat or rotationally sym-
layer process. By means of various welding tech- metrical surfaces have to be coated over large
niques, wear resistant alloys in rod, wire, or areas, automatic or fully-mechanized welding is
powder form build strong metallurgical bonds much cheaper than manual welding [42].
in the fused state with the surface, which is also Sheet metal plating by roll-bonded or explo-
fused. Mixing should be kept as low as possible. sion plating is not always as effective as weld
There is an exceptionally large variety of addi- plating with respect to adhesion. As the plating
tives available on the market and, among other material must be very plastically deformable to
things, the requirement for mechanical worka- achieve an intimate bond with the supporting
bility must be taken into account. Most filler material, highly wear resistant and high-strength
metals are alloyed on an Fe-base, but Ni or Co materials are unsuitable for the purpose. Never-
can also be the main constituents where high- theless, this method is widely used in chemical
temperature and/or additional corrosion resis- technology because to a large extent corrosion
stresses are superimposed on the wear processes. Typical materials and applications for vac-
The selection of highly corrosion resistant alloys uum plasma spraying are:
applied to mechanically heavily stressed base
bodies provides satisfactory solutions to the ma- 1) M – Cr – Al – Y alloys for protection against
jority of problems in the construction of vessels corrosion by hot gases
and pipes [43]. 2) Carbides (WC, Co – Cr3 C2 , NiCr – TiC –
Thermal spraying can cause even greater NbC) for protection against abrasive wear and
adhesion problems than those of the above- erosion
mentioned coating methods. Unlike hardfacing, 3) Oxides and refractory metals for the forma-
after the coating additive has been fused in a tion of thick protective coatings [44]
flame, arc, or plasma it is projected against the The use of chemical vapor deposition (CVD)
cold or only slightly heated base. Adhesion to and physical vapor deposition (PVD) for form-
the surface and the density of the layer itself can ing coatings of carbides, borides, nitrides, and
differ greatly depending on the intensity of the oxides has increased. The CVD method has been
spraying and the possibility of reaction with the furthest developed for the deposition of TiC,
surrounding medium on the way to the base ma- TiN, CrC, WC, and Al2 O3 [45–48].
terial. From a micrograph it can be seen that, Surface treatment and coating of metals
depending on the process used, the layers have are discussed in more detail in → Corrosion,
a particular structure caused by agglomeration Chap. 5. and in → Metals, Surface Treatment.
of many fine globules of molten material, which
become deformed on impact and leave a visible
porosity in the composite material.
The most important groups of materials for 5. Practical Examples of Abrasion
wire flame spraying and arc spraying are and Erosion Damage
1) Low- and high-alloy steels
Chemical industry with its manifold process
2) Bronzes, nonferrous metals such as nickel,
steps involves conveying products from vessels
copper, zinc, Monel metal, brass, aluminum
or tanks through pipelines to other vessels where
Powder flame spraying is a versatile method new products are produced by chemical reac-
of thermal coating and also handles tions, and then to still further apparatuses where
the solutions or mixture of products are sepa-
1) Special steel alloys with embedded mechani-
rated from one another. The process steps also
cally resistant materials
include mechanical processing such as com-
2) Ceramics with fairly high melting points
minution, kneading, and granulating. Produc-
3) So-called self-flowing Cr – Ni – B – Si alloys
tion of large quantities requires a continuous
which, after the actual spraying process –
material flow. This can be achieved most easily
without any adhesion layer – are submitted in
with fluid phases which are transported in con-
a second operation to subsequent treatment at
veying units. Erosion and abrasion are therefore
about 1100 ◦ C (liquid-phase sintering); this
the predominant types of wear in the main chem-
produces virtually pore-free layers with good
ical plant components, while sliding wear, elas-
adhesion characteristics.
tic rolling wear, and oscillation wear are found
Substantially higher temperatures are more in drives and machinery.
reached in the plasma process, so protective Transport velocities remain within defined
layers can be produced from high-melting ox- limits and material flows are relatively constant,
ides, carbides, and borides. The higher thermal so characteristic wear data which have been
energy and higher velocity produce improved determined under realistic conditions are quite
homogeneity and adhesive strength. readily transferable. Wear, as a form of damage,
The quality of this method is improved by the does not play a dominant part in chemical plants.
use of an inert atmosphere under reduced pres- Nevertheless, it does occur and the following ex-
sure. Individual alloying elements are not burnt amples give an impression of the diversity.
off, oxide and nitride formation is suppressed,
and adhesion and layer structure is improved.
5.1. Sliding Wear, Elastic Rolling Wear, and for increasing the pressure of the transported
and Oscillation Wear medium. Its roller bearings are highly stressed
parts with a limited life. This can be shortened
The pulsation in gases which have been com- considerably if axial shocks are transmitted from
pressed in reciprocating compressors must be the flowing liquid as a result of large numbers of
adequately damped before the gases are trans- stops and starts, i.e., predominantly discontinu-
ferred to heat exchangers for cooling. This ous operation. This is often indicated by running
damping was not sufficient in the case of oxygen tracks displaced towards the edges (Fig. 22).
compression described here, so that the baffles
were continuously striking against the support-
ing spacer tubes; they deformed them increas-
ingly and caused sliding wear to the tubes seated
tightly against them (Fig. 20).
Figure 22. Surface destruction of a ball-bearing inner race

as a result of intermittent axial overloading
Predominantly transient stressing (radial im-

Figure 20. Sliding wear on copper tubes of a heat exchanger
pacts) occurred at the piston of an oxygen com-
for oxygen pressor where the surface of a stuffing box cham-
ber ring showed tribochemical reaction zones
Instances of damage caused by sliding oc- as a result of heating in contact with oxygen
cur quite frequently in piston machines. In the (Fig. 23). Because of the danger of spontaneous
rotary compressor shown (Roots type) for am- ignition of metals in the presence of compressed
monia compression the damage occurred after oxygen any processes involving friction in such
approximately 60 000 h operation (Fig. 21). machines must be treated with great caution.
Figure 21. Sliding wear damage on the rotary piston of a

Roots compressor for ammonia Figure 23. Tribochemical reaction and surface destruction
on the brass piston of an oxygen compressor
The centrifugal pump is the most important
hydraulic machine for setting a fluid in motion
5.2. Abrasion Wear
Where abrasive impact wear occurs in hammer

mills, such as those used for comminution of raw
coal in power stations, continuous replacement
of plain plates of unalloyed steel is preferred to
the application of sustantially more expensive
materials with only moderately improved ser-
vice lives.
Three-body abrasive wear occurs relatively
frequently in machines used for process engi-
neering as the materials processed often contain
additives with abrasive properties. This is par-
ticularly true for the large number of barrel ex- Figure 25. Impact ribs (18 % Cr steel) of a wet comminution
truders used for kneading and milling processes. mill eroded by water containing carbon black
It is found, for example, in the draining of un- The screw housings which enclose the screw
vulcanized rubber, in which the moisture con- shafts are exposed to high stresses, similar to
tent is reduced from 60 to 10 % under a pres- those in the screw combs of the extruders. The
sure of 6 – 8 MPa. Screw elements made of 13 % product, which is processed under high pres-
Cr steel withstood these conditions for several sures, stresses the surface to an exceptional ex-
years without any signs of wear. However, when tent, especially in the so-called kneading zones
the unvulcanized rubber contains carbon black of worm extruders. If glass fibers or glass balls
the service life of screws made of X 40 Cr 13 are added to the product (in this case, polypropy-
is only about one year, even after hard-facing lene), even wear-protecting layers (60 % Ni,
with Hastelloy C (16 % Cr, 16 % Mo, remainder 18 % Co, 13 % Cr, 2 % Mo, 1 % C) applied by
Ni), Figure 24. This carbon black can be pro- centrifugal casting have only limited service life
cessed, for example, in a wet comminution mill: (Fig. 26). A suitable method of coating with ap-
1.5 t/h carbon black is ground with 30 t/h water at propriate protective material should be selected
3000 rpm between a stator and a rotor adjusted to to suit the type of stressing.
a gap of approximately 0.4 mm. Both parts have
impact ribs with special profiling and various
flow diverters. In this case the most economi-
cal solution was again to design the elements as
wearing parts made of 18 % Cr steel and replace
them after 7000 – 10 000 h operation (Fig. 25).
Figure 26. Abrasive wear caused by glass-fiber-containing

polypropylene on the high-alloy protective coating (60 %
Ni, 18 % Co, 2 % Mo, 1 % C) of a screw housing
Permanent magnet pumps with no seals are

being used increasingly for the sake of imission
Figure 24. Three-body abrasive wear, caused by carbon protection. The medium to be transported, in this
black, on a draining screw, hard-faced with Hastelloy C, case liquefied petroleum gas, flows through a
used for unvulcanized rubber gap of less than 1 mm around the non-contact
internal rotor, which is fitted with permanent
magnets. Magnetite particles (Fe3 O4 ) originat-

ing from the pipeline adhere to the outer surface
of the internal rotor and cause permanent slid-
ing abrasion at the isolation shell and the rotor,
(Fig. 27); finally, this causes the entire pump sys-
tem to leak.
Figure 28. Hydroabrasive wear caused by a liquid contain-

ing carbon black in an unalloyed steel pipe as a result of
turbulences behind a weld
High mechanical stressing occurs when dis-

persions of plastics are atomized at high pres-
sure. Under some circumstances the acceleration
Figure 27. Abrasive wear on the inner rotor of a canned in a cone leading to the jet hole (a few tenths of
pump caused by adhering magnetite particles a millimeter in diameter) and passage through
the hole can change the geometry of a jet in a
very short time by erosion. This can affect hard
5.3. Damage by Particle Erosion metals and oxide ceramics as well as steel. Due
to the forces of acceleration produced in cen-
Abrasive wear is found predominantly in con- trifugal pumps, they are particularly liable to
veying equipment, but in pipelines and appara- hydroabrasive wear. Corrosion-resistant pumps
tus erosive wear is more typical, and is caused by made of cast CrNi (1.4408) had to be replaced af-
tribological stressing during the flow of fluids, ter only 6 months’ operating time; this was due to
usually with the involvement of solid particles. the erosion damage shown in Figure 29 because
Unlike the welded joints in apparatus, the butt the sharp-edged CuBi catalyst suspended in the
welds in pipelines can normally only be made aqueous solution had almost eroded through the
from the outside. Depending on geometrical fac- pump cover.
tors (e.g., edge misalignment, difference in wall
thickness) and the welding method, weld seam
roots are often produced which have a very con-
siderable sag. This can cause a great reduction
in the flow cross section and also, depending
on the flow conditions, marked turbulences be-
hind the roots. Figure 28 shows a section of a
pipe made of St 35.8 (unalloyed steel) in which
the carbon black content in a liquid mixture of
organic compounds caused a breach in the wall
after 15 months’ operating time as a result of hy-
droabrasion. The wall retained its original thick-
ness only a few centimeters behind the point of
turbulence, which illustrates the effect of the an- Figure 29. Pump cover (18-8 CrNi cast) eroded by sharp-
edged catalyst particles in the liquid
gle of incidence of the particle on the surface.
Even a ducted-wheel pump made of G-X3
CrNiMoCu 24 6 (Noridur 9.4460) hardly lasted
any longer, but the tempered and quenched cast
alloy G-X170 CrMo 25 2 (Niroloy NL 262) had role here – and the protective layer and the tube
a service life of several years. elbow are worn away in a very restricted area,
When solid particles are carried in a gas as if with a milling cutter (Fig. 31).
stream and not in a guided liquid stream, any
changes in flow direction are very important as,
due to the large difference in density, the solid
particles are pressed with high force on to the
tube surface which guides the flow. The veloci-
ties of the transported gas may be very high and
then, as a result of intensive sliding jet wear at
localized points, lead to short term, but usually
accelerated, loss of wall thickness and to rupture
of the tube bends.
An example of this is provided by bends from
tube furnaces for the production, for example, of
ethylene. Because of the high operating temper-
atures of over 900 ◦ C, the required creep strength Figure 31. Tube elbow of a waste heat boiler whose pro-
and oxidation resistance are usually obtained by tective coating has been worn away in a restricted area by
using high-alloy materials (e.g., 30 % Cr, 30 % inclined jet wear, which ultimately penetrated the tube
Ni) and considerably increasing the wall thick-
ness at the bends. Figure 30 shows localized
penetration of this type. The wear stressing oc-
curs during repeated decoking with superheated
steam.
Figure 32. Plasma-coated protective shell of a steam super-

heater tube, damaged by impact jet wear at ca. 1000 ◦ C
Superimposition of flow and transient stress-

ing by particles in the gas flow, which is charac-
Figure 30. Bend in a tube furnace for ethylene production, teristic of impact wear and inclined jet wear, is
worn by sliding jet wear (material: CrNi 30/30 alloy) not found to any great extent in chemical plants
A comparable situation occurs in waste heat but does occur in power stations. It affects the
boilers that utilize the high temperature of syn- first contact heating surfaces where the ash par-
thesis gas (CO, H2 ) produced in an oil gasifica- ticles, at temperatures up to 1000 ◦ C rising at
tion plant for generating steam. Condensing and ca. 10 m/s with the flue gas, lead to impact jet
solidifying particles of slag often form a dense wear. These tubes, which are under high steam
and tightly adhering coating in the gas-carrying pressure, are therefore usually protected with
tubes, with the result that over a long period the heat-resistant wear-protecting half shells. In the
system provides its own protection against jet case described, comparative tests have shown
wear on the heat-resistant, low-alloy steels used. that high-alloy austenitic alloys (with 25 % Cr,
When there are changes in the mode of opera- 20 % Ni, and Si) last longer than high-chromium
tion, this protective action often fails locally – ferritic steels that have been plasma coated with
the gas velocity apparently plays an important an oxide layer (Fig. 32). It is assumed that metal-
lurgical changes and chemical reactions caused if the heating is carried out with incompletely
by the high temperature combine with the purely dried steam at 2 MPa (Fig. 34).
mechanical stressing to form the complex out-
ward appearance.
However, if the wear-induced break occurs
in steam tubes, the expanding steam escaping at
high velocity causes erosion on adjacent tubes.
Although in this case there are again solid par-
ticles entrained in the flue gas, microscopic ob-
servation of the affected surface shows that, un-
like the situation with particle jet wear, there is
an ripple structure, typical of steam jet action
(Fig. 33).
Figure 34. Steam-heated high-pressure pipe showing liquid

erosion damage due to condensate carried with the steam
Rotary compressors include liquid ring

pumps, in which a rotor eccentric to the hous-
ing opens and closes chambers of different sizes
with the aid of a liquid ring; they are used as
compressors and vacuum pumps. Under some
circumstances cavitation of spontaneously va-
porizing liquid can lead to damage to the ro-
tor at the narrowest gap between the rotor and
the housing, as in the example shown in Fig-
Figure 33. Scanning electron micrograph of the surface of
a steam tube (material: 12 % Cr steel) damaged by a steam
ure 35, where the rotor is made of nodular cast
jet iron GGG 42. The different resistance to cavita-
tional stressing can be seen clearly on the sur-
face, where the harder iron phosphide eutectic is
largely retained, while the iron matrix has been
5.4. Solid Particles-Free Erosion worn away (Fig. 36). There is also the possibil-
ity that a certain corrosive component has con-
Heat transfer systems are one of the basic re- tributed to the damage, so this may be a case of
quirements of thermal process technology. De- cavitation corrosion.
pending on the purpose of the heat exchange, the
terms evaporator, liquefier or condenser, super-
heater, boiler, and many others, are also used.
If the flows of material taking part in the heat
transfer are separated from one another by walls,
the process is called indirect heat exchange. In
general, the flow conditions and prevailing ther-
mal conditions are sufficiently defined and main-
tained, so only in critical cases does mechanical
damage occur by erosion alone.
Liquid erosion damage is to be expected if
heating steam contains a proportion of conden-
sate – again dependent on the angle of incidence.
When compared with austenitic steels, steam-
Figure 35. Cavitation damage on a cast iron pump rotor
heated, high-pressure pipes made of low-alloy
ferritic steel prove to be insufficiently resistant
impingement of droplets at a water content of ap-

proximately 8 % at room temperature (Fig. 38).
Figure 36. Micrograph of the rotor shown in Figure 35; al-

though the iron matrix has been removed by cavitation, the
more resistant iron phosphide eutectic remained unaffected
Figure 38. Impingement attack on a steam turbine blade (X
20 Cr 13)
A type of drop impingement can also lead to

purely mechanical damage and deformation on
such parts where a liquid-filled gap, in this case
between parts of a canned motor pump made of
steel 1.4408, is submitted to transient stressing
in the axial direction with simultaneous oscillat-
ing radial movement without contact between
the metal surfaces (Fig. 39).
Figure 37. Cavitation erosion in a steel (St. 35.8) heat ex-

changer tube due to excessive heating
Comparable conditions also caused the dam-

age shown in the following examples. Damage
occurred only in the region of the gas inlet of
a shell-and-tube heat exchanger in which the
tubes carry water in closed circuit for cooling.
This was because local vaporization of the water
followed immediately by collapse of the vapor
bubbles led to deep holes, while immediately Figure 39. Surface destruction of the case (18-8 CrNi steel)
after the gas inlet point the existing protective of a canned motor pump
layer remained completely undamaged on the The reason for this unusual type of stress-
unalloyed steel. The weakening visible in the ing was incorrect assembly in which the jointed
micrograph resembles that of pitting corrosion, parts had not been correctly secured.
and clearly the already broken protective layer
remains electrochemically active so that a corro-
sive removal mechanism is superimposed. The 5.5. Damage Caused by
hammering effect of the micro jet becomes ob- Erosion – Corrosion
vious from Figure 37. In steam turbines even a
chromium steel X 20 Cr 13 with otherwise good The chemical resistance of many metals to elec-
resistance properties is permanently damaged by trolytes is achieved because the reaction prod-
ucts adhere to the surface, hindering ionic trans-
port that controls the electrochemical dissolu- umn made of 15 Mo 3 (DN 300). The high veloc-
tion process. Guide values can therefore be pro- ity together with the slightly corrosive medium
vided, for example, for the maximum velocity is entirely responsible for the loss in wall thick-
of drinking water up to which certain copper al- ness (Fig. 41).
loys, steels, and titanium retain their protective
coatings, and only when the measured values
are exceeded is removal of the protective layer
to be expected. In many cases unalloyed steel
and cooling water operating under defined flow
conditions represent the most economical solu-
tion for heat exchangers in the chemical indus-
try. Even then, the alternating actions of erosion
and corrosion can cause significant damage due
to the design and the associated changes in flow
direction, although with smooth flow it is pos-
sible to maintain a protective covering layer for
many years.
Cases of this type of damage can be clearly Figure 41. Erosion – corrosion due to turbulence of the liq-
demonstrated in heat exchangers from a CO con- uid caused by the reduction in diameter of a pipe (nominal
version process in which the gas preheats the re- diameter 300 mm, 15 Mo 5)
circulating water (nominal pressure 6.4 MPa) to
Occasionally the free fall of a corrosive liquid
a maximum of 220 ◦ C: excessive water veloci-
is also sufficient to remove protective layers and
ties through perforated impact plates, at changes
promote the corrosion process, as can be seen
in direction, and at tube openings through baffles
in a melting apparatus for dodecanedioic acid
prevented the formation of a complete protective
(Fig. 42).
layer; this led to progressive wear through liquid
erosion accelerated by electrolytic dissolution of
the metal (Fig. 40). It was possible to eliminate
this type of erosion on the internal surfaces of
vessels completely and permanently when they
were spray-coated with stainless Cr – Ni steel.
Figure 42. Erosion – corrosion caused by dripping molten

acid (material: 18-8 CrNi steel)
Crystalline acid with a moisture content of

10 – 20 % is fed through a filling hopper and
melted by heating tubes made of 18-8 CrNi steel,
Figure 40. Due to the high flow velocity of the cooling wa- and the vapor produced is driven off. This dam-
ter, the protective layer was removed from heat exchanger age, a combination of erosion and corrosion,
tubes (St. 35.8) and sheets (St. 37), leading to intensive ero- occurred at the region of highest temperature.
sion – corrosion
The complex stress profile of the extruder screw
Loss of material by preferential erosion – may also be demonstrated with the example of
corrosion caused by the flow conditions can be a kneader for unvulcanized rubber, in which, as
seen at a product outlet connection of a wash col- a result of a localized escape of fumaric acid
and very small quantities of water, serious dam- 4. K. H. Zum Gahr: “Grundlagen des
age occurred within one day due to superim- Verschleißes,” in: Metallische und
posed erosion and corrosion of a kneading ele- nichtmetallische Werkstoffe und ihre
ment made of quenched and tempered ionitrided Verarbeitungsverfahren im Vergleich, part III,
chromium steel X 35 CrMo 17 (Fig. 43). VDI-Ber. 600.3 (1987) 29 – 56.
5. H. Uetz, K. Sommer:
“Abrasiv-Gleitverschleiß,” in: H. Uetz (ed.):
Abrasion und Erosion, Carl Hanser Verlag,
München – Wien 1986, pp. 108 – 157.
6. K. H. Zum Gahr: “Einfluß des Makroaufbaus
von Stahl/Polymer-Faserverbundwerkstoffen
auf den Abrasivverschleiß,” Z. Werkstofftech.
16 (1985) 297 – 305.
7. H. Wahl: “Verschleißprobleme im
Braunkohlenbergbau,” Braunkohle Wärme
Energie 3 (1951) 75 – 87.
8. R. Schulmeister: “Zur Untersuchung der
Werkstoffzerstörung durch Kavitation und
Korrosion mit Ultraschall-Koppelschwingern,”
Figure 43. Superposition of erosion and corrosion in a Metalloberfläche 21 (1967) no. 1, 17 – 25.
kneading element of a rubber extruder (material: X 35 CrMo 9. H. Rieger: Kavitation und Tropfenschlag,
17, ionitrided) Werkstofftechnische Verlagsgesellschaft,
Karlsruhe 1977.
10. H. Brauer, E. Kriegel: “Probleme des
Conclusion. In chemical plants the prob- Verschleißes von Rohrleitungen beim
lems of wear play a significantly smaller role pneumatischen und hydraulischen
than those of errosion. Damage in the component Feststofftransport,” Maschinenmarkt 71
equipment and pipelines is met relatively rarely, (1965) no. 68, 140 – 151.
although abrasion and erosion can occasionally 11. J. M. Hutchings: “Some Comments on the
be very detrimental to the potential availabil- Theoretical Treatment of Erosive Particle
ity of the plant components at risk. However, Impacts,” Proc. 5th Int. Conf. on Erosion by
it is a different question with machines and con- Solid and Liquid Impact, Cambridge 1979.
veying units, in which exceptionally high wear 12. G. Gommel: Stoßuntersuchungen
stresses can sometimes result from the influence Stahlkugel/Stahlplatte im Zusammenhang mit
of high flow velocities and high accelerations at Strahlmittelzertrümmerung und
housing walls, and especially at sliding seal el- Strahlverschleiß, Dissertation, TH Stuttgart
1966.
ements. The manufacturing industries make use
13. J. S. Rinehard, J. Pearson: Behavior of Metals
of the most modern materials technology to con-
Under Impulsive Load, American Society of
trol these problems. Nevertheless, design mea- Metals, Cleveland 1954.
sures also have to be chosen so that components 14. K. Wellinger, H. Uetz: “Strahlverschleiß,”
which are exposed to particular stresses and have Tech. Rundsch., 8 (1958) 1 – 8.
limited service lives are designed as easily re- 15. J. Föhl: “Strahl- und Spülverschleiß,” in: K. H.
placeable wearing parts. Zum Gahr (ed.): Reibung und Verschleiß,
Deutsche Gesellschaft für Metallkunde,
Oberursel 1983, pp. 157 – 176.
6. References 16. H.-G. Heitmann, W. Kastner:
“Erosionskorrosion in
1. BMFT-Report: Damit Rost und Verschleiß Wasser-Dampf-Kreisläufen – Ursachen und
nicht Milliarden fressen, BMFT, Bonn 1984. Gegenmaßnahmen, VGB Kraftwerkstech. 62
2. B. Genath: “Der Verschleiß ist das Sorgenkind (1982) 211 –219.
im Maschinenbau,” VDI-Nachr. 52 (1971) 17. H. Tischner: “Korrosionserscheinungen in
no. 47, 1, 6, 7. strömenden Medien am Beispiel von
3. DIN 50 320:Dec. 1979. Chemiepumpen,” Chem. Ing. Tech. 62 (1989)
no. 3, 220 – 228.
18. C. Razim, C. Düll, W. Räuchle: “Über die der Basis von Modellrechnungen sowie
Beeinflussung der Bauteil-Grundeigenschaften experimentellen Ergebnissen,” Fortschr. Ber.
durch Verschleißschutzschichten,” VDI-Ber. VDI Z. Reihe 5 96 (1985).
333 (1979) 11 – 22. 35. J. K. Lancaster: “Abrasive Wear of Polymers,”
19. K. Wellinger, H. Uetz: “Gleitverschleiß, Wear 14 (1969) 223 – 239.
Spülverschleiß, Strahlverschleiß unter der 36. K. Wellinger, H. Uetz, G. Gommel:
Wirkung von körnigen Stoffen,” “Verschleiß durch Wirkung von körnigen
VDI-Forschungsh. 449, ed. B(1955) no. 21. mineralischen Stoffen,” Materialprüfung 9
20. M. Y. Gürleyik: (1967) no. 5, 153 – 160.
Gleitverschleißuntersuchungen an Metallen 37. H.-D. Ruprecht: “Elastomere-Polyurethane,”
und nichtmetallischen Hartstoffen unter in: H. Uetz (ed.): Abrasion und Erosion, Carl
Wirkung körniger Gegenstoffe, Dissertation, Hanser Verlag, München – Wien 1986,
TH Stuttgart 1967. pp. 438 – 450.
21. F. Henke: “Niedrig- und hochlegierter 38. H. P. Lachmann: “Elastomere-Gummi,” in H.
verschleiß-fester Vergütungsstahlguß,” Uetz (ed.): Abrasion und Erosion, Carl Hanser
Gießerei-Prax. 1975, no. 23/24, 377 – 407. Verlag, München – Wien 1986, pp. 451 – 465.
22. M. M. Krushchov, M. A. Babichev: 39. H. Brauer, E. Kriegel: “Untersuchungen über
“Experimental Fundaments of Abrasive Wear den Verschleiß von Kunststoffen und
Theory,” Russ. Eng. J. (Engl. Transl.) (1964) Metallen,” Chem. Ing. Techn. 35 (1963)
no. 6, pp. 43 – 48. 697 – 707.
23. H. Uetz, K. J. Groß: “Strahlverschleiß,” in: H.
40. K. Wellinger, H. Uetz: “Verschleiß durch
Uetz (ed.): Abrasion und Erosion, Carl Hanser
körnige mineralische Stoffe,” Aufbereit. Tech.
Verlag, München – Wien 1986, pp. 236 – 278.
4 (1963) 193 – 204, 319 – 335.
24. J. G. A. Bitter: “A Study of Erosion
41. E. Dörre: “Nichtmetallische Hartstoffe,” in H.
Phenomena,” Part I: Wear 6 (1963) 5 – 21; Part
Uetz (ed.): Abrasion und Erosion, Carl Hanser
II: Wear 6 (1963) 69 – 190.
25. W. Wahl: “Unterschiedliche Verlag, München – Wien 1986, pp. 451 – 465.
Werkstoffbewährung bei abrasiv 42. W. Wahl, I. Kretschmer, J. Wabnegger:
beanspruchten Bauteilen,” VDI-Ber. 600.3 “Auftragschweißen,” in H. Uetz (ed.):
(1987) 245 – 286. Abrasion und Erosion, Carl Hanser Verlag,
26. K. Heil: Erosionskorrosion an unlegierten München – Wien 1986, pp. 374 –394.
Eisenwerkstoffen in schnellströmenden 43. H. Gräfen: “Beschichtungen in der
Wässern, Dissertation, TH Darmstadt 1979. Chemietechnik,” in: Beschichtungen für
27. D. Kuron: “Korrosion durch Kühlwasser und Hochleistungs-Bauteile, VDI-Ber. 624
Schutzmaßnahmen,” in W. J. Bartz (ed.): Die (1986) 273 – 296.
Praxis des Korrosionsschutzes, Expert Verlag, 44. H.-M. Höhle: “Thermische Spritzverfahren,”
Grafenau 1981. in: Beschichtungen für
28. H. Sick: “Die Erosionsbeständigkeit von Hochleistungs-Bauteile, VDI-Ber. 624 (1986)
Kupferwerkstoffen gegenüber strömendem 71 – 83.
Wasser,” Werkst. Korros. 23 (1972) no. 1, 45. F. Wendl: “Aktuelle Trends bei der
12 – 18. Oberflächenbehandlung von Werkzeugen in
29. H. Grein: “Kavitation – eine Übersicht,” Sulzer der Kunststoffverarbeitung,” Thyssen Edelstahl
Forschungsh. 1974, 87 – 112. Tech. Ber. 15 (1989) no. 2, 110 – 125.
30. H. H. Piltz: Werkstoffzerstörung durch 46. H.-A. Mathesius: “Herstellen von
Kavitation, VDI-Verlag, Düsseldorf 1966. verschleißfesten Schichten mit Hilfe von
31. W. J. Rheingans: “Cavitation in Hydraulic CVD-Verfahren,” in: Beschichtungen für
Turbines,” Symp. on Erosion and Cavitation, Hochleistungs-Bauteile, VDI-Ber. 624 (1986)
ASTM Spec. Tech. Publ. 307 (1962) 17 – 31. 37 – 48.
32. K. H. Habig: Verschleiß und Härte von 47. H. Weiß: “Elektrochemische Beschichtung
Werkstoffen, Carl Hanser Verlag, München – und Sonderverfahren der Oberflächentechnik,”
Wien 1980, p. 215. Thyssen Edelstahl Tech. Ber. 15 (1989) no. 2,
33. H. Uetz, J. Wiedemeyer: Tribologie der 85 – 114.
Polymere, Carl Hanser Verlag, München – 48. H. Simon, M. Thoma: Angewandte
Wien 1985. Oberflächentechnik für metallische Werkstoffe,
34. J. Wiedemeyer: “Deutung des tribologischen
Carl Hanser Verlag, München – Wien 1985.
Verhaltens ungeschmierter Thermoplaste auf
Mechanical Properties and Testing of Metallic Materials 761
Mechanical Properties and Testing of Metallic Materials

Ali Fatemi, The University of Toledo, Toledo, Ohio 43606, United States
1. Introduction . . . . . . . . . . . . . . . 762 2.4.1. Direct Shear Stress and Test . . . . . . 770

1.1. Concepts of Stress and Strain . . . . 762 2.4.2. Torsional Shear Stress and Test . . . . 770
1.1.1. Stress . . . . . . . . . . . . . . . . . . . . 762 2.5. Hardness Tests . . . . . . . . . . . . . . 771
1.1.2. Strain . . . . . . . . . . . . . . . . . . . . 762 2.5.1. Rockwell Hardness Test . . . . . . . . . 771
1.2. Elastic Deformation and Properties 763 2.5.2. Brinell Hardness Test . . . . . . . . . . 772
1.2.1. Young’s Modulus . . . . . . . . . . . . . 763 2.5.3. Vickers Hardness Test . . . . . . . . . . 773
1.2.2. Shear Modulus . . . . . . . . . . . . . . 763 2.5.4. Knoop Hardness Test . . . . . . . . . . 773
1.2.3. Poisson’s Ratio . . . . . . . . . . . . . . 763 2.5.5. Correlation of Hardness with Strength 773
1.2.4. Relation Between Elastic Constants . 763 2.6. Impact Testing . . . . . . . . . . . . . . 773
1.3. Plasticity and Flow . . . . . . . . . . . 764 2.6.1. Notched Bar Impact Test . . . . . . . . 773
2. Mechanical Testing . . . . . . . . . . . 764 2.6.2. Dynamic Tear Test . . . . . . . . . . . . 774
2.1. Tensile Test . . . . . . . . . . . . . . . . 764 2.7. Creep Test . . . . . . . . . . . . . . . . . 775
2.1.1. Significance and Use . . . . . . . . . . . 764 2.8. Stress Relaxation Tests . . . . . . . . 776
2.1.2. Apparatus and Specimen . . . . . . . . 764 3. Fatigue Loading . . . . . . . . . . . . . 777
2.1.3. Stress – Strain Diagram . . . . . . . . . 765 3.1. Principles and Terminology . . . . . 777
2.1.4. Strength Properties . . . . . . . . . . . . 765 3.1.1. Fatigue Phenomena . . . . . . . . . . . 777
2.1.5. Ductility . . . . . . . . . . . . . . . . . . 766 3.1.2. Fatigue Fracture Surfaces . . . . . . . . 777
2.1.6. Toughness and Resilience . . . . . . . 766 3.1.3. Fatigue Behavior . . . . . . . . . . . . . 777
2.1.7. True Stress – True Strain Diagram . . 767 3.2. Cyclic Stress-Controlled Fatigue . . 778
2.1.8. Strain-Rate Sensitivity . . . . . . . . . . 768 3.2.1. Stress – Life Curves . . . . . . . . . . . 778
2.1.9. Temperature Effects . . . . . . . . . . . 768 3.2.2. Fatigue Tests . . . . . . . . . . . . . . . . 778
2.2. Compression Test . . . . . . . . . . . . 768 3.2.3. Mean Stress Effects . . . . . . . . . . . 779
2.3. Bend and Flexure . . . . . . . . . . . . 769 4. Fracture Mechanics . . . . . . . . . . 780
2.3.1. Elastic Bending Stress and Deflection 769 4.1. Principles and Terminology . . . . . 780
2.3.2. Bend and Flexure Test . . . . . . . . . . 769 4.2. Fracture Toughness . . . . . . . . . . 780
2.4. Shear and Torsion . . . . . . . . . . . 770 5. References . . . . . . . . . . . . . . . . . 783
Symbols: K strain-rate constant

Kc fracture toughness
a crack length
K Ic plane-strain fracture toughness
A cross-sectional area
l length
A0 initial cross-sectional area
l0 initial gauge length
Af final cross-sectional area
lf final gauge length
C distance to neutral surface in beam bend-
∆l change in length
ing
m strain-rate sensitivity
d diameter
M bending moment
D indenter diameter
n strain-hardening exponent
E elastic (Young’s) modulus
N number of cycles
f function
r radius
F force or load
R stress ratio
F max maximum load
S shear strength
G shear modulus or modulus of rigidity
t thickness, indentation depth, time
h0 initial height
∆t time increment
hf final height
T torque
I moment of inertia
v displacement
K stress intensity factor, strength coefficient
762 Mechanical Properties and Testing of Metallic Materials
V shear force normal (or axial) stress σ. There are two general
w width types of normal stress: tensile and compressive.
Y dimensionless parameter A pulling force produces tensile normal stress,
γ shear strain whereas a pushing force produces compressive
γ max maximum shear strain normal stress. When the load acts parallel to the
δ max maximum deflection area, the resulting stress is referred to as shear
ε normal (axial) strain stress τ .
εe elastic normal strain In SI units, stress is measured in newtons per
εeng engineering strain square meter or pascals.
εp plastic normal strain
εtrue true strain
ε̇ creep rate 1.1.2. Strain
ε̇true true strain rate
∆ε strain increment When stresses are applied to a body, they cause
µ Poisson’s ratio deformation of the body and result in changes in
σ normal (axial) stress dimensions or distortion; the body is then said
σa alternating stress or stress amplitude to be strained. Strains resulting from changes in
σ eng engineering stress dimension are normal strains ε, whereas strains
σf fracture stress resulting from distortion of the body are shear
σ fat fatigue strength for σ m = 0 strains γ. A normal strain is, by definition, the
σm mean stress axial deformation (elongation or contraction)
σ max maximum stress per unit length
σ min minimum stress ∆l
σ true true stress ε= (2)
l
σu ultimate tensile strength
where ∆l is the change in length and l is the
σ ys yield strength
length. A normal strain resulting from elonga-
∆σ stress range
tion is called a tensile strain, and a normal strain
τ shear stress
resulting from contraction is called a compres-
τ ave average shear stress
sive strain.
τ max maximum shear stress
A change in the shape of a body is caused
Φ displacement angle or angle of twist
by the application of shearing stresses. Shearing
stresses cause relative displacement of the up-
per and lower surfaces of the body, as shown in
1. Introduction Figure 1. The angular change between the two
perpendicular lines is defined as the shear strain
1.1. Concepts of Stress and Strain γ. Strain is a nondimensional quantity, but it is
frequently expressed in meters per meter or in
1.1.1. Stress percent.
Stress σ is defined as the force divided by the

cross-sectional area on which the force acts
F
σ= (1)
A
where F is the force and A is the area. It repre-
sents the intensity of the reaction force at any
point in the body as imposed by service loads,
assembly conditions, fabrication, and thermal
changes. Figure 1. Distortion of a body as a result of the application
If the imposed load is perpendicular to the of shear stress.
area over which it acts, the resulting stress is a —- undeformed; – – – deformed
1.2. Elastic Deformation and Properties 1.2.2. Shear Modulus
Elastic deformation is a temporary deformation Shear stress and strain are related through:
that is fully recoverable when the load is re-
moved. The amount of elastic deformation that a τ =Gγ (4)
metal can undergo is small because metal atoms
are displaced from their original positions dur- where G is a material property called the shear
ing elastic deformation, but not to the extent that modulus, sometimes referred to as the modu-
they take up new positions. lus of rigidity. The shear modulus represents the
slope of the linear elastic region of the shear
stress – strain diagram, as shown in Figure 3. For
1.2.1. Young’s Modulus many metals, G is ca. 0.4 E.
If a long steel wire is pulled by an increasing

load, the length of the wire increases propor-
tionately with the load. The relationship bet-
ween stress resulting from the load (σ = F/A)
and strain resulting from elongation of the wire
(ε = ∆ l/l ) is given by Hooke’s law:
σ=Eε (3)
where the proportionality constant E is a ma-

terial property, called the elastic modulus or
Young’s modulus. This value represents the stiff-
ness of the material (its resistance to elastic
strain), and for most typical metals its magnitude Figure 3. Elastic shear stress – strain diagram
is in the range of 45 – 410 GPa. A stress – strain
diagram representative of elastic deformation 1.2.3. Poisson’s Ratio
for loading and unloading is shown in Figure 2.
When a uniaxial tensile force is applied to a rod
or bar, it results in extension (or contraction in
the case of a compressive force). Existing si-
multaneously with this elongation, however, is
a lateral or transverse contraction (or extension
for a compressive force) in the directions normal
to the applied stress. The ratio of the magnitude
of the transverse change per unit length (trans-
verse strain) to the magnitude of the longitudi-
nal change in length per unit length (longitudinal
strain) is called Poisson’s ratio µ:
|Lateralstrain|
µ= (5)
|Longitudinalstrain|
Figure 2. Elastic axial stress – strain diagram Poisson’s ratio is a material elastic property and
for typical metals is on the order of 0.3.
As expected, imposition of a compressive
stress also evokes elastic behavior. However,
stress – strain characteristics and Young’s mod- 1.2.4. Relation Between Elastic Constants
ulus are virtually the same for both tensile and
compressive stresses in the elastic range. The three elastic constants (E, G, and µ) in linear
elasticity are related to each other by the equa-
tion:
E
G= (6)
2 (1+µ)
Therefore, if two of the elastic constants are

given or measured, the third can be calculated.
Typical values of elastic constants for metallic
materials are given in Table 1.
Table 1. Elastic constants for some common metallic materials
Material Young’s Shear modulus Poisson’s

modulus E, G, 103 MPa ratio µ
103 MPa
Aluminum 71 26 0.34
Brass 110 41 0.34
Copper 128 48 0.34
Iron 207 80 0.29
Magnesium 45 17 0.29
Nickel 200 77 0.30 Figure 4. Plastic deformation preceded by elastic deforma-
Silver 83 30 0.37 tion
Titanium 113 43 0.32
2. Mechanical Testing
1.3. Plasticity and Flow The mechanical properties of materials deter-

mine their characteristics and behavior under
Many materials undergo permanent or nonre- applied service forces or loads. Specifically, the
coverable deformation when stressed beyond mechanical behavior of a material characterizes
a certain level. This is called plastic deforma- its response (or deformation) when subjected
tion; it remains in the material after the load or to an applied load. Important mechanical prop-
stress has been removed. Plastic deformation re- erties include stiffness, strength, ductility, and
sults from permanent displacement of atoms or hardness. In this chapter, several tests that are
molecules from their original positions in the lat- used to determine these properties are discussed.
tice. This displacement is due to the breaking of
bonds between atoms or molecules and the net
movement of large numbers of them relative to 2.1. Tensile Test
one another.
A constant load of sufficient magnitude ap- 2.1.1. Significance and Use
plied to a material results in continuously in-
creasing deformation; this phenomenon is called The tensile test (or pull test) provides informa-
flow. tion on the strength and ductility of materials
Figure 4 illustrates the idea of plastic defor- under a uniaxial tensile stress condition. The
mation. If the material is stressed to σ 1 and then results of this test are often used to evaluate
released, the strain returns to zero (elastic be- the mechanical properties of materials and to
havior). However, when the material is stressed compare materials. Details of tensile testing are
to level σ 2 and then released, the material recov- given in ASTM E8M-89 [1].
ers to the extent (ε − εp ), where εp is the plastic
strain remaining after the load or stress has been
removed. Therefore, for stress levels beyond the 2.1.2. Apparatus and Specimen
elastic limit, the total strain is composed of elas-
tic, εe , and plastic, εp , portions: A typical setup for a tensile test is shown in
Figure 5. A typical specimen has a diameter
ε=εe +εp (7) of 12.5 mm and a gauge length of 62.5 mm as
shown in Figure 6 [1]. The ends of the speci- εeng =

Changeinlength ∆l
= (9)
men are screwed into a pair of grips, which are Initiallength l0
part of the tensile testing machine (Fig. 5). The A typical engineering stress – strain diagram for
grips are then pulled apart, often by mechanical a mild steel is shown in Figure 7, which is di-
means. The load on the specimen is recorded vided into two distinct regions of elastic defor-
continuously by means of a load cell, which is mation and plastic deformation.
often a calibrated stiff spring. Extension of the
gauge section is measured by an extensometer,
which is anchored to the specimen gauge section
at the start of the test. Raw data are recorded in
terms of load and extension.
Figure 7. Engineering stress – strain diagram for a mild

steel
Stretching of the metal in the elastic portion

of the stress – strain curve (the initial linear por-
tion) is fully recoverable when the load is re-
moved. At higher forces the material behaves in
a plastic manner. Plastic deformation is perma-
Figure 5. Schematic of a tension test setup nent; upon removal of the load, only the elas-
a) Specimen; b) Grips; c) Load cell; d) Extensometer; tic deformation (which is often very small com-
e) Moving crosshead pared to the plastic deformation) is recovered.
The plastic region is the nonlinear portion of the
stress – strain diagram.
2.1.4. Strength Properties
The proportional limit is the limit within which

Hooke’s law (Eq. 3) applies; it is shown in Fig-
ure 7. Young’s modulus E is determined from
Figure 6. Typical round tension test specimen [1]
the slope of this linear portion of the curve and
measures the stiffness of a material (see Sec-
tion 1.2.1).
The stress level at which plastic deformation
2.1.3. Stress – Strain Diagram begins is referred to as the yield point. At this
point the material undergoes rather rapid and ex-
Load versus gauge extension data are converted tensive plastic deformation with little accompa-
to engineering stress σ eng and engineering strain nying increase in load. Since the transition from
εeng as follows: elastic to plastic behavior is usually gradual, ac-
Load F curate assessment of the yield point is often dif-
σeng = = (8)
Initialarea A0 ficult. Therefore, the yield strength is generally
found by an offset method. A line parallel to the a material has sustained at fracture. A mate-
initial linear elastic line is drawn from an offset rial that undergoes very little deformation before
point (typically at a strain of 0.002). The inter- rupture is said to be brittle, whereas one that un-
section of this line with the stress – strain curve dergoes a large amount of plastic deformation
determines the yield strength for the material, before rupture is said to be ductile. Engineering
as shown in Figure 7. The yield strength of a stress – strain curves for a brittle and a ductile
metal is a measure of its resistance to plastic de- metal are shown in Figure 9.
formation and is probably the most important
mechanical property used in design.
The ultimate tensile strength is the max-
imum strength reached in the engineering
stress – strain curve, as shown in Figure 7. Even
though the ultimate tensile strength is relatively
unimportant for selection or fabrication of mate-
rials, its value is often reported in handbooks be-
cause it is easy to measure and some of the other
material mechanical properties that are more dif-
ficult to measure, can be estimated from it. All
deformation up to this point in the stress – strain
curve is uniform throughout the specimen gauge
section. However, at this maximum stress, defor-
mation does not remain uniform, and one region Figure 9. Engineering stress – strain curves for a ductile
and a brittle material
starts deforming more than others (a large local
decrease in cross section). This phenomenon is Ductility is expressed by two measures: per-
called necking and is prominent in ductile mate- cent elongation and percent reduction in area.
rials. Figure 8 shows a schematic representation Percent elongation describes the amount that the
of this local deformation. specimen stretches before fracture and is calcu-
lated from
lf −l0
%elongation = ×100 (10)
l0
where l 0 is the initial gauge length and l f is the
final gauge length. The percent reduction in area
describes the amount of thinning that the speci-
men undergoes during the test and can be deter-
Figure 8. Necking during tension testing mined from the following equation:
A0 −Af
As soon as a localized neck begins to form, %reductioninarea = ×100 (11)
A0
a drop in the force occurs due to the decrease
in the cross-sectional area at this point. With the where A0 is the initial gauge area and Af is the
onset of necking, the stress distribution changes final gauge area. Both percent elongation and
from uniaxial to triaxial. percent reduction in area also give an index of
After the neck has developed, further plas- metal quality. If defects such as porosity and in-
tic deformation is constrained to its vicinity and clusions are present, decreases in percent elon-
fracture ultimately occurs at this point. The frac- gation and percent reduction in area are often
ture or rupture strength corresponds to the stress observed.
at fracture, as shown in Figure 7. Tensile properties for some metallic engi-
neering materials are listed in Table 2 [2].
2.1.5. Ductility 2.1.6. Toughness and Resilience

Ductility is another important mechanical prop- Toughness is a measure of the ability of a ma-
erty; it measures the amount of deformation that terial to absorb energy before fracturing and
Table 2. Tensile properties for some metallic materials [2]
Material Treatment Yield strength σ ys , Ultimate tensile Elongation, % Reduction in

MPa strength σ u , MPa area, %
Steel alloys
1015 as-rolled 315 420 39 61
1050 as-rolled 415 725 20 40
1080 as-rolled 585 965 12 17
4340 Q + T ∗ (205 ◦ C) 1675 1875 10 38
4340 Q + T ∗ (650 ◦ C) 855 965 19 60
301 annealed plate 275 725 55
403 annealed bar 275 515 35
Aluminum alloys
2024 T3 345 485 18
2024 T6, T651 395 475 10
7075 T6 505 570 11
7075 T73 415 505 11
Titanium alloys
Ti – 5Al – 2.5Sn annealed 805 860 16 40
Ti – 6Al – 4V annealed 925 995 14 30
∗ Quenched and tempered
is given by the area under the engineering of toughness and resilience is shown in Fig-
stress – strain curve. Toughness is particularly ure 10.
important for materials subjected to dynamic
or impact loads, such as automobile bumpers,
shock absorbers, and airplane landing gear. Un- 2.1.7. True Stress – True Strain Diagram
der dynamic loads, toughness is determined by
means of an impact test in which a certain load In the engineering stress – strain diagram
is applied suddenly to a specimen (see Section (Fig. 7), engineering stress decreases beyond the
2.6). ultimate tensile strength, which seems to indi-
cate that the material is becoming weaker. How-
ever, in reality the material’s strength increases.
The reason for the decrease of stress in the engi-
neering stress – strain curve is that the calculated
stress is based on the original cross-sectional
area, whereas the area actually changes continu-
ally with plastic deformation. Calculation of the
true values of stress σ true and strain εtrue are
based on the instantaneous area and length of
the specimen as follows:
Load F
σtrue = = (12)
Trueareaatthetime A
l
dl l A0
εtrue = = ln = ln (13)
l0 l0 A
Figure 10. Schematic representation of toughness and re- l0
silience
True and engineering stress and strain are related
Resilience is a measure of a material’s ability by the following equations:
to absorb energy in the elastic range. The modu-
lus of resilience is given by the area under the lin- σtrue =σeng (1+εeng ) (14)
ear portion of the uniaxial stress – strain curve. εtrue = ln (1+εeng ) (15)
A high-resilience material has high strength and
low elastic modulus. A schematic representation The true stress – strain curve is compared to the
engineering stress – strain curve in Figure 11. As
can be seen from the figure, the true stress nec- 2.1.8. Strain-Rate Sensitivity
essary to sustain increasing strain continues to
increase after necking. An increase in loading rate (strain rate) usually
results in an increase in flow stress of the mate-
rial and is often adequately represented by the
following empirical equation:
σtrue =K (ε̇true )m (17)
where ε̇true is the true strain rate (dεtrue /dt), m is

the strain-rate sensitivity, and K is a constant.
The value of m varies between zero (indicating
a strain-rate-insensitive material) and unity (in-
dicating a highly strain-rate-sensitive material).
Strain-rate sensitivity generally increases with
increasing temperature. The effect of strain rate
on the tensile properties of a mild steel at room
temperature is shown in Figure 13 [3].
Figure 11. Comparison of true and engineering
stress – strain diagrams LIVE GRAPH
Click here to view
The true stress – strain curve is important in

certain instances involving high plastic deforma-
tion of ductile materials, for example, in metal
forming. If log σ true is plotted against log εtrue ,
a straight line is obtained, as shown in Fig-
ure 12. The equation of this line is given by
σtrue =Kεn
true (16)
where K is a material property called the

strength coefficient and n is the strain-hardening Figure 13. Effect of strain rate on tensile properties of a
exponent, which gives a measure of the mate- mild steel [3]
rial’s work-hardening behavior. The higher the a) Ultimate tensile strength; b) Total elongation; c) Yield
strength
strain-hardening exponent, the more difficult the
material is to work (deform), i.e., higher stress
is necessary for a given strain.
2.1.9. Temperature Effects
In general, tensile properties are significantly af-

fected by temperature. The modulus of elastic-
ity, yield strength, and ultimate tensile strength
all decrease with increasing temperature. How-
ever, the ductility of the material, as measured by
percent elongation or percent reduction in area,
generally increases with increasing temperature.
2.2. Compression Test
Figure 12. Plot of log σ true versus log εtrue Compressive properties are used in the analysis
of structures subjected to compressive loads or
bending loads that result in compressive normal
stresses, as well as in processes involving large the bottom, and maximum deflection at the free
compressive deformations such as metal work- end of the beam. For the simply supported con-
ing (e.g., rolling of steel). Mechanical properties figuration (Fig. 14 B), maximum stress and de-
obtained from a compression test generally inflection occur at the middle of the beam, with
clude Young’s modulus, yield strength, and com- tension on the bottom and compression on top.
pressive strength. These properties are obtained Note that the equations given in Figure 14 ap-
by a test conducted in a manner similar to the ply when the load magnitude is such that only
tensile test, except that the test specimen used elastic deformation results.
is often in the form of a solid circular cylin-
der and the force is compressive. The resulting
stress – strain behavior in the plastic region is
similar to its tensile counterpart, but no necking
occurs and the mode of fracture is different from
that for tension.
Equations (8) and (9) are also used for cal-
culating the compressive stress and strain. In a
compression test, the specimen contracts along
the load direction; therefore, the final length l f is
smaller than the initial length l 0 in Equation (9),
resulting in a compressive strain that is negative.
In compression testing, the specimen geometry
and loading should be such that the specimen
does not buckle; otherwise, failure may occur
by instability rather than by crushing. Details of
compression testing are given in ASTM E9-89 a
[4]
2.3. Bend and Flexure

2.3.1. Elastic Bending Stress and Deflection
The stress in an elastically deformed beam or bar

can be calculated by using the flexure formula
MC
σ= (18)
I
where M is the applied bending moment, C is the
distance from the neutral plane (the plane with Figure 14. Maximum stress σ max and maximum deflec-
zero stress) to the point at which the stress is be- tion δ max in selected beams
ing calculated, and I is the moment of inertia for a) Cantilever beam with end load; b) Simple supports with
center load
the beam cross section. The value of the bend-
ing moment M depends on the magnitude of the
2.3.2. Bend and Flexure Test
applied load, the length of the beam, and the lo-
cation of the supports. The moment of inertia I
The bend test is a method of evaluating the duc-
is a geometrical property of the cross section.
tility of a material, as evidenced by its ability
The maximum stress σ max and deflection δ max
to resist cracking during bending. Because the
for two common beam geometries and support
loading in such a test consists of both elastic
configurations are shown in Figure 14.
and plastic deformation (particularly in ductile
For the cantilever beam (Fig. 14 A), maxi-
materials), the flexure and deflection equations
mum stress occurs at the supported end of the
given in Section 2.3.1 cannot be used.
beam, with tension on top and compression on
In a bend test, the test specimen is a bar shear stress that the rivet, bolt, or pin experi-
with either rectangular or circular cross section. ences. Rivets, bolts, or pins that resist shearing
Bending forces are usually applied through one forces at a single cross section are called single-
of the three arrangements shown in Figure 15 shear joints, and those resisting shearing forces
[5]. Bending is continued to a specified angle of at two cross sections are called double-shear
bend and inside radius of curvature. If complete joints, as illustrated in Figure 16. The average
fracture does not occur, the convex surface of shearing stress for each condition is also given
the bar is examined for cracks, and the number in Figure 16.
and size of the cracks can be used as the crite-
rion for failure. Therefore, the bend test does not
provide a quantitative method of evaluating the
ductility of a material. Details of the bend test
can be found in ASTM E290-87 [5].
Figure 16. Single- and double-shear joints

a) Single; b) Double
The shear strength of a joint is determined

by a shear test in which the joint is usually sub-
jected to double-shear loading (Fig. 16 B). The
load required to fracture the joint is determined,
and the shear strength is calculated from
Figure 15. Bend test arrangements [5]
Fmax Fmax 2Fmax
S= = = (20)
2A 2 (πd2 /4) πd2
where S is the maximum shear strength, F max

2.4. Shear and Torsion is the maximum load in the test, and d is the
2.4.1. Direct Shear Stress and Test diameter of the joint.
Mechanical joints, such as rivets, bolts, and pins,

often experience direct shearing stress, which
is defined as the shearing force divided by the 2.4.2. Torsional Shear Stress and Test
cross-sectional area of the rivet, bolt, or pin:
A torque applied to a circular bar results in twist-
V ing of the bar, as shown in Figure 17. Point A on
τave = (19)
A the circular bar moves to point A when a torque
where V is the shear force and A is the cross- T is applied. Details of shear testing are given in
sectional area. Equation (19) gives the average ASTM B 565-87 [6].
Hardness tests measure the resistance to pen-

etration of the surface of a material by an in-
denter with a force applied to it. The hard-
ness of materials depends on the type of bind-
ing forces between atoms, ions, or molecules
and, like strength, increases with the magnitude
of these forces. Because indentation occurs by
plastic deformation in metals and alloys, hard-
Figure 17. Torsion of a solid bar
ness is inherently related to the material’s plastic
A shear strain is produced that varies linearly resistance and, therefore, to its yield strength and
with the radius of the bar. The maximum shear wear resistance.
strain γ max occurs on the lateral surface and is A hard indenter (such as hardened steel, tung-
given by sten carbide, or diamond) of a standard shape
(either round or pointed) is pressed into the sur-
Φd face of the material under a known force. The
γmax = (21)
2l resulting area or depth of indentation is mea-
where d is the diameter, Φ is the displacement sured, which in turn is related to the hardness
angle, and l is the length. number. This process is shown schematically in
For elastic twisting, the displacement angle Figure 18.
Φ, which is referred to as the angle of twist, can
be calculated from
32T l
Φ= (22)
πd4 G
In elastic twisting, the shear stress also varies
linearly with the radius. The maximum shear
stress τ max occurs on the lateral surface and is Figure 18. Hardness test
given by
16T
τmax = (23) Depending on the material tested and the type
πd3
of test, various combinations of load and inden-
The shear stress and strain are related by the ters are used. The most common methods of
shear modulus G discussed in Section 1.2.2. hardness testing for metals are the Rockwell,
A torsional test is analogous to a tensile test in Brinell, Vickers, and Knoop methods. Table 3
that shear stress τ is plotted against shear strain summarizes the type of indenters and types of
γ. The slope of the initial linear portion is the impressions associated with these four common
shear modulus G (Fig. 3), which is related to hardness tests.
Young’s modulus and Poisson’s ratio by Equa-
tion (6), discussed in Section 1.2.4. Because of
this relationship, if Young’s modulus and Pois- 2.5.1. Rockwell Hardness Test
son’s ratio are determined from a tensile test, a The Rockwell hardness test is widely used; it has
torsional test is not required to determine G. scales (Rockwell A, Rockwell B, etc.) for differ-
ent hardness ranges. A small-diameter steel ball
is used as the indenter for soft materials, and
2.5. Hardness Tests a diamond cone for hard materials. The depth
of penetration is measured automatically by the
Hardness tests are probably the most frequently testing machine and converted to a Rockwell
performed mechanical tests because they are hardness number. Therefore, each measurement
nondestructive and usually no special specimen requires only a few seconds. The Rockwell scale
need be prepared. is designated by an R with appropriate scale let-
ter as a subscript (i. e., RB indicates Rockwell
Table 3. Hardness tests [7]
B). For each scale, hardness values range up to with a special microscope. A schematic of the
100. Details of the Rockwell hardness test are Brinell hardness test is shown in Figure 19.
given in ASTM E18-89 a [8]. The Brinell hardness number is defined as
the load divided by the surface area of the in-
dentation and is calculated from the following
2.5.2. Brinell Hardness Test equation:
In the Brinell hardness test, a single scale covers F F

BHN = √ = (24)
a wide range of material hardness. A hard spher- π
D D− D2 −d2 πDt
2
ical indenter (10 mm in diameter) is forced into
the surface of the metal (a 500 kg load is used where F is the applied load in kilogram-force;
for softer metals such as copper and aluminum; and D is the diameter of the indenter, d the di-
a 3000 kg load for hard metals such as steel, ameter of the impression, and t the indentation
iron, and alloys). The Brinell hardness number depth – all in millimeters. This hardness testing
(BHN) is a function of both the magnitude of method is relatively insensitive to irregularities
the load and the diameter of the resulting inden- in the material surface because the impression
tation. The diameter of indentation is measured left by the indenter is large. Details of the Brinell
hardness test are given in ASTM E10-84 [9].
2.5.3. Vickers Hardness Test For example, a strong linear correlation exists
between the Brinell hardness number and the
The Vickers hardness test is termed a microhard- ultimate tensile strength σ u of steel, as follows:
ness test because it forms a small indentation
of microstructural dimensions. A small diamond σu = 3.45BHN (25)
pyramid is pressed into the surface of the speci-
men, and the diagonal of the square impression where tensile strength is given in megapascals.
is measured. Based on this measurement, the Figure 20 shows the conversion among Brinell,
Vickers hardness number (VHN) is read from Vickers, and Rockwell tests, as well as the cor-
a chart. Because a small indentation is made, relation between the hardness numbers and ul-
Vickers hardness testing is often used for mea- timate tensile strength; conversion tables are
surements of small regions, for example, in as- given in ASTM E140-88 [13].
sessing the relative hardness of various phases LIVE GRAPH
in multiphase alloys. A microscope is required Click here to view
to obtain the measurement. Details of the Vick-

ers hardness test can be found in ASTM E92-82
[10].
Figure 19. Schematic of the Brinell hardness test Figure 20. Correlation of hardness with tensile strength
and conversion among Brinell, Vickers, and Rockwell tests
[12]
2.5.4. Knoop Hardness Test
The Knoop test is also a microhardness test, and 2.6. Impact Testing
the resulting impression requires measurement
under a microscope. A skewed diamond inden- Impact tests measure a material’s resistance to
ter is used in this test, and the Knoop hardness failure under an impact load. The ability of the
number (KHN) is calculated as the force divided material to resist an impact load without failure
by the projected indentation area. The Knoop is also referred to as toughness. This resistance
hardness scale is approximately equivalent to the to failure by fracture is particularly important for
Vickers hardness scale. The Knoop hardness test notched components. Two common methods of
is often used in measuring the microhardness of impact testing are the notched bar impact test
small areas of metallic material microstructures and the dynamic tear test.
and for brittle materials such as ceramics. Details
of the Knoop hardness test are given in ASTM
E384-84 [11]. 2.6.1. Notched Bar Impact Test
The notched bar impact test is the most com-

2.5.5. Correlation of Hardness with Strength mon laboratory test to measure impact energy. A
Charpy V-notch specimen, shown in Figure 21,
Since hardness and tensile strength are both indi-
is often used. The Charpy V-notch specimen is
cators of a metal’s resistance to plastic deforma-
placed in an impact testing machine, as shown
tion, a strong correlation exists between them.
in Figure 22 [14]. A heavy pendulum is reserved at fracture. Therefore, the absorbed en-
leased from a known height h0 . After striking ergy is low. The temperature at which the ma-
and breaking the specimen, the pendulum stops terial changes behavior from ductile to brittle
at a lower, final height hf . If the mass of the is called the transition temperature. The transi-
pendulum and its initial and final elevations are tion temperature can fall between ca. −100 and
known, the energy absorbed by the fracture can +100 ◦ C, depending on the alloy and the test con-
be determined. The energy is usually expressed ditions. Figure 23 shows the effect of tempera-
in joules. In general, materials that have both ture on the impact energy of a typical material.
high strength and high ductility have large im- Details of the notched bar impact test can be
pact energies (or high toughness). found in ASTM E23-88 [15].
Figure 21. Charpy V-notch specimen
Figure 23. Effect of temperature on impact energy
Figure 24. Dynamic tear test specimen and supports
2.6.2. Dynamic Tear Test
The dynamic tear test is conducted to determine

the resistance of a metallic material to rapid pro-
gressive fracture. This resistance is measured as
dynamic tear energy, which is the total energy
required to fracture a dynamic tear specimen.
Figure 22. Standard Charpy impact test machine [14] A single-edge notched beam specimen is
a) Hammer; b) Scale; c) Pointer; d) Starting position; e) End used as the dynamic tear specimen and is simply
of swing; f) Anvil; g) Specimen
supported on its ends, as shown in Figure 24.
The specimen is then impact loaded in the
The impact energy of a material is usually middle by a pendulum or drop weight. The total
very sensitive to temperature. At high tempera- energy during separation of the specimen as it
ture, the material behaves in a ductile manner, fractures is measured as the dynamic tear energy
and a large absorbed energy is required for frac- for the material tested. Details of dynamic tear
ture. At low temperature, the material behaves testing can be found in ASTM E604-83 [16].
in a brittle manner, and little deformation is ob-
2.7. Creep Test
Permanent deformation of materials at elevated

temperature when subjected to a constant ex-
ternally applied load or stress below the yield
strength is called creep. In metallic materials,
this phenomenon usually occurs at temperatures
of about 40 % of the melting point. The creep test
measures the resistance of a material to deforma-
tion under a static load at high temperature. A
cylindrical specimen is placed in a furnace, and
a constant stress or load is applied while a con-
stant temperature is maintained. As soon as the
constant load or stress is applied the specimen
undergoes a small elastic strain. After this ini-
tial instantaneous elastic deformation, the strain
increases with time, as shown in Figure 25. The
creep curve has three distinct stages. Stage I is
the primary stage, during which the strain rate
(dε/dt) decreases, which indicates that the ma-
terial is experiencing an increase in hardness.
The second stage is the linear region, which in-
dicates a constant strain rate and is referred to
as the steady-state region. This stage of creep
usually has the longest duration. The slope of
the steady-state region of the creep curve is the
creep rate ε̇:
Figure 26. A) Variation of creep curve with stress; B) Vari-
ation of creep curve with temperature
∆ε
ε̇= (26)
∆t
In stage III, the strain rate increases due to the To predict the expected lifetime of a compo-
increase in true stress as a result of a reduction in nent for a given combination of stress and tem-
cross-sectional area (necking), until failure oc- perature, stress rupture curves are often plotted.
curs. This failure is called rupture, and the time These curves are obtained from a series of creep
required for failure to occur is the rupture time. tests by plotting the logarithm of the stress versus
The creep rate of a material is a function of both the logarithm of rupture life (Fig. 27). Details of
the applied stress level and the test temperature. the creep test can be found in ASTM E139-83
Figure 26 shows the variation of the creep curve [17].
with stress and temperature.
Figure 27. Stress rupture curves

Figure 25. Typical creep curve of strain versus time at
constant load or stress and constant elevated temperature
Figure 28. Stress relaxation test

A) At constant strain rate; B) At constant load rate
2.8. Stress Relaxation Tests Relaxed stress, which is the initial stress mi-
nus the remaining stress at a given time, is then
Stress relaxation refers to the time-dependent plotted against time (Fig. 29). The absolute value
decrease in stress under a constant constraint of the slope of the stress relaxation curve at a
and environment. Stress relaxation test data are given time gives the relaxation rate. Stress re-
often necessary for the design of mechanically laxation testing is described in ASTM E328-86
fastened joints such as bolted and riveted assem- [18].
blies, and shrink-fit components, for which per-
manent tightness is of major concern.
Stress relaxation tests for a material can be
conducted under tension, compression, bend-
ing, or torsion loads. In general, a specimen is
subjected to an increasing load until a prede-
termined strain is reached. The time at which
this initial strain is attained is taken as the refer-
ence (zero) time. Then, while the predetermined
strain is held constant, the stress during the test
is monitored continuously. This procedure un-
der constant strain rate as well as constant load
rate is shown in Figure 28 [18].
Figure 29. Typical relaxation curve
3. Fatigue Loading whereas the final fracture region usually exhibits

a rough surface. In addition, the crack growth
3.1. Principles and Terminology region generally contains line markings referred
to as “beach marks”, which result from different
3.1.1. Fatigue Phenomena periods of crack extension and various positions
of the crack front during its growth. The size of
In many applications and service conditions, the crack growth region, compared to the final
metallic components and parts are subjected to fracture region, depends mainly on the magni-
repetitive or cyclic stresses. Repeated stress usu- tude of the cyclic stress and the material tough-
ally arises in moving parts that rotate, bend, or ness. As the magnitude of stress decreases or
vibrate. Under cyclic stress, the material usu- toughness increases, the size of the crack growth
ally fails at a stress level far below its maximum region on the fracture surface increases. In con-
static strength (yield strength or ultimate tensile trast to the gross deformation observed in a ten-
strength). Failures that occur under repeated or sile failure for a ductile material (i.e., necking;
cyclic stress are called fatigue fractures. see Section 2.1.4), typical fatigue fractures do
not exhibit gross plastic deformation. Therefore,
fatigue failures are often characterized as brittle
3.1.2. Fatigue Fracture Surfaces failures, even for ductile materials.
A typical fatigue failure usually originates at a
point of stress concentration. Stress concentra- 3.1.3. Fatigue Behavior
tions generally result from either geometrical
discontinuities in a part (e.g., keyways, holes, The applied stress history can be completely ran-
and fillets) or metallurgical defects (e.g., inclu- dom or simple and repetitive. Examples of a ran-
sions and voids). Once a fatigue crack has nucle- dom history and a simple sinusoidal history are
ated, the effect of stress concentration increases given in Figure 31.
and the crack grows during, and as a result of,
cyclic stress. The crack growth rate is primarily
a function of the magnitude, and frequency of
the cyclic stress. As the crack grows, the stressed
area decreases in size, which results in increased
magnitude of the stress, leading ultimately to
rapid fracture of the remaining area. Figure 30
is a schematic representation of this process for
a typical fatigue failure in rotating bending.
Figure 30. Schematic of a typical fatigue failure process in

rotating bending Figure 31. Cyclic variation of stress with time
a) Crack nucleation; b) Crack growth region; c) Final frac- A) Random history; B) Sinusoidal history
ture region
The applied cyclic stress can be axial, flexural
As can be seen in Figure 30, the fracture sur- (bending), or torsional. The standard stress vari-
face has three distinct regions: (1) the crack nu- ables in fatigue loading are shown in Figure 31 B
cleation site or sites, (2) the crack growth region, and are defined as follows:
and (3) the final fracture region. Since the crack
surfaces are pressed together repeatedly during Stressrange = ∆σ=σmax −σmin (27)
crack growth, the crack growth region is smooth,
∆σ σmax −σmin [21]. As Figure 32 indicates, the higher the stress

Stressamplitude = σa = = (28)
2 2 amplitude, the smaller is the number of cycles
σmax +σmin to failure. For steel, leveling off occurs in the
Meanstress = σm = (29) S – N curve with no decrease in fatigue strength
2
σmin as the number of cycles increases. The stress
Stressratio = R= (30) level at which the S – N curve becomes hori-
σmax
zontal is called the fatigue limit or endurance
For completely reversed stressing the mean limit. The endurance limit is the stress below
stress σ m is zero, and R = −1. which fatigue failure does not occur. Ferrous
Depending on the number of cycles that a part materials usually have S – N curves exhibiting
must withstand during its intended lifetime, the an endurance limit. For steel, the fatigue limit
fatigue behavior can be classified into low-cycle is estimated to be about half the ultimate tensile
or high-cycle regimes. The strain – life approach strength. For materials such as the aluminum al-
is generally used to characterize the low-cycle loy in Figure 32, the S – N curve continues to
(typically less than 105 cycles) fatigue of ma- decline and such materials do not have an en-
terials, whereas the stress – life approach (see durance limit.
Section 3.2.1) is often used for high-cycle fa-
tigue applications. Cyclic plasticity is an impor-
tant consideration in the treatment of low-cycle
fatigue, whereas strain is primarily elastic in the LIVE GRAPH
high-cycle fatigue regime. Click here to view
The strain – life approach or strain-controlled

fatigue is mainly used to evaluate the fatigue
life of notched parts because significant plastic
strains usually exist at the root of a notch. In this
approach, the fatigue life of the notched part is
related to the life of a small smooth specimen
cycled to the same strain level as the material at
the root of the notch. Further details of strain-
controlled low-cycle fatigue testing are given in
ASTM E606-80 [19].
The treatment of material fatigue behavior
in this section covers only stress-controlled,
constant-amplitude cyclic loading, shown in Figure 32. Typical S – N curves for a steel and an aluminum
Figure 31 B. For treatment of variable amplitude alloy [21]
or random loading and strain-controlled fatigue,
see [20].
3.2. Cyclic Stress-Controlled Fatigue

3.2.2. Fatigue Tests
3.2.1. Stress – Life Curves
The rotating bending fatigue test is the most
Traditionally, the stress – life method has been commonly used small-scale test, in which the
widely used in design against fatigue. A series smooth polished specimen is subjected to alter-
of tests are performed under stress-controlled nating compression and tension stresses of equal
conditions by using smooth polished specimens. magnitude while it rotates. The apparatus is de-
The data from these tests are then plotted in the picted schematically in Figure 33 [20]. A dead
form of a stress – life (S – N) curve in which the weight W produces a uniform bending moment
stress causing failure is plotted against the num- over the test section of the specimen as it rotates.
ber of cycles to failure. Figure 32 shows typical The stress is then calculated from the flexure for-
S – N curves for a steel and an aluminum alloy mula (see Section 2.3.1).
Figure 33. Schematic of rotating bending fatigue test ma-

chine [20]
a) Motor; b) Flexible coupling; c) Main bearings; d) Load
bearings; e) Test piece
This type of test, however, cannot be used to

simulate loading conditions with a mean stress
(i.e., R = −1) because in rotating bending, the
loading is completely reversed (R = −1). There-
fore, for fatigue testing with a mean stress,
an axially loaded specimen, shown in Fig- Figure 35. Effect of mean stress on fatigue life
ure 34, is often used [2]. Pulsating tension or
tension – compression axial stress is provided by As can be seen from Figure 35, cyclic life
means of a hydraulic or mechanical actuator. A decreases with increasing mean stress level at a
standard procedure for constant amplitude axial given alternating stress σ a . To account for the ef-
fatigue testing is given in ASTM E466-82 [22]. fect of mean stress on long-life fatigue strength,
one of the following empirical relations is gen-
erally used:

σm
Goodman : σa =σfat 1− (31)
σu
2
σm
Gerber : σa =σfat 1− (32)
σu
where σ fat and σ a are fatigue strengths for

the conditions σ m = 0 and σ m = 0, respectively.
These equations are shown graphically in Fig-
ure 36. Most experimental data fall between the
two lines plotted in Figure 36. Therefore, the
Goodman relation is a more conservative cri-
terion of mean stress.
Figure 34. Axial fatigue loading [2]

a) Specimen; b) Grips; c) Load cell; d) Moving actuator
3.2.3. Mean Stress Effects
Mean stress can substantially influence a mate-

rial’s fatigue behavior. In general, tensile mean
stresses (σ m > 0) are detrimental to fatigue
behavior, whereas compressive mean stresses
(σ m < 0) are beneficial. Typical S – N diagrams Figure 36. Relations for mean stress effects
with differing mean stress levels are shown in a) Goodman; b) Gerber
Figure 35.
4. Fracture Mechanics These equations indicate that the stresses at

a given point near the crack tip are dependent
4.1. Principles and Terminology only on K, which is a stress field parameter, de-
fined as the stress intensity factor, that depends
Fracture mechanics is used to study the behavior on crack geometry, configuration, and loading.
of components and structures containing cracks The general form of K is given as
or other flaws. If the geometry and size of the
√
crack or flaw are known, the fracture strength of K =σY πa (36)
the part or structure can be evaluated by applying
the principles of fracture mechanics. where σ is the nominal applied stress, a is crack
Figure 37 shows the three modes of loading length, and Y is a dimensionless parameter that
under which a crack can extend. Mode I, the depends on specimen and crack geometry. Typ-
opening or tensile mode, is the most common. ical mode I stress intensity expressions for sev-
Mode II is the sliding or shear mode, and mode eral common specimen configurations, shown
III, the tearing or antiplane mode. in Figure 39, are as follows [20]: for a center-
cracked plate in tension (Fig. 39 A),
√ - F
KI =σ πa· sec (πa/w), where σ = (37)
wt
for a single-edge cracked plate in tension
(Fig. 39 B),
a a 2
√
KI =σ πa 1.12 − 0.231 +10.55 −
w w
Figure 37. Crack extension modes a 3 a 4

A) Mode I; B) Mode II; C) Mode III 21.72 +30.39 ,
w w
Stresses in the vicinity of the crack tip, shown F
where σ = (38)
in Figure 38, are given by wt
K and for a single-edge cracked beam in pure

σy = √ f1 (θ) (33) bending (Fig. 39 C),
2πr
K a a 2
σx = √ f2 (θ) (34) √
2πr KI =σ πa 1.12 − 1.40 +7.33 −
w w
K
τxy = √ f3 (θ) (35)
2πr a 3 a 4
13.08 +14.0 ,
where θ and r are geometric parameters, defined w w
in Figure 38, and f 1 (θ), f 2 (θ), and f 3 (θ) are func- where σ = 6M/tw2 (39)
tions of θ.
The subscript I in these equations denotes mode
I (opening or tensile mode) loading. Stress inten-
sity factor expressions for other common crack
geometry and loadings can be found in [2], [20].
4.2. Fracture Toughness
Fracture toughness is the critical value of the

stress intensity factor and refers to the condi-
tion in which a crack extends in a rapid (unsta-
ble) manner. Fracture toughness can therefore be
Figure 38. Stresses in the vicinity of a crack tip considered the limiting value of the stress inten-
sity factor and is designated K c . If the fracture
toughness and the size and geometry of the crack exists, the fracture resistance can actually de-
in a material are known, the fracture stress σ f can crease. Also, the fracture toughness of metals
be calculated from depends on strain rate and environmental condi-
tions such as temperature and corrosion. In gen-
Kc eral, as temperature decreases, fracture tough-
σf = √ (40)
Y πa ness usually decreases, whereas yield strength
In general, the interaction of material properties generally increases.
(i.e., K c ), design stress, and crack size controls Table 4. Values of K Ic for some metallic materials [23]
the fracture condition in a cracked component.
If any two of these three parameters are known, Material K Ic , MPa · m1/2 Yield strength
σ ys , MPa
the third can be calculated from Equation (40).
Steel
4340 99 860
4340 60 1515
52100 14 2070
Aluminum
2024 26 455
7075 24 495
7178 33 490
Titanium
Ti–6Al–4V 115 910
Ti–6Al–4V 55 1035
Figure 39. Several common crack configurations

A) Center-cracked plate in tension; B) Single-edge cracked
plate in tension; C) Single-edge cracked beam in pure bend-
ing Figure 40. Variation of fracture toughness with thickness
Although fracture toughness can be consid-
ered a material property, its value depends on Fracture Toughness Testing Because K Ic
thickness. In general, a material can exhibit represents a lower limiting value of fracture
ductile behavior in a thin sheet, whereas the toughness it can be considered an important ma-
same material may fracture in a brittle manner terial property. By using this property, a relation-
in a thick plate. The thicker the material, the ship between failure stress and crack or defect
lower is the fracture toughness, as shown in Fig- size can be obtained (Eq. 40).
ure 40. As thickness increases, K c approaches Different specimen configurations can be
an asymptotic minimum value called the plane- used for K Ic testing. Acceptable specimen
strain fracture toughness, denoted by K Ic . Val- configurations for K Ic testing according to
ues of K Ic for several metallic materials are the ASTM standard are the bend, arc-shaped,
given in Table 4 [23]. compact, and disk-shaped compact specimens
In general, the fracture toughness of metals (Fig. 41) [24].
and alloys decreases as yield strength increases. The crack length a is nominally equal to the
Therefore, even though the fracture resistance thickness, which is usually half of the width w.
of a component may be increased by choosing For a valid plane-strain fracture toughness test,
a higher strength material, if a crack (or flaw)
Figure 41. Configurations of K Ic test specimens [24]

A) Bend specimen; B) Compact specimen; C) Arc-shaped specimen; D) Disk-shaped compact specimen
the specimen thickness and crack length should in Figure 42, type I. However, if a maximum
satisfy the following criteria: load precedes F 5 and exceeds it, this maximum
2 load is F Q (types II and III in Fig. 42). Once
KIc
thicknesstandcracklengtha≥2.5
σys
(41) F Q has been determined according to this pro-
cedure, K Q is calculated from it. For the com-
The test sample is usually fatigue loaded to ex- pact tension specimen (Fig. 41 B), K Q is given
tend the machined notch for a sharp initial crack. by [24]
A clip gauge is then placed at the crack mouth
in order to monitor crack displacement as the FQ a
KQ = √ f (42)
specimen is loaded. Typical load – displacement t w w
plots are shown in Figure 42 [24].
To determine a valid K Ic value, the follow- where
ing procedure is used [24]: the secant 0F 5 is a
f = (43)
drawn through the origin of the test plot with w

a slope that is 5 % lower than the tangent line a
(2+ w ) a −13.32 a2 +14.76 a3 −5.6 a4
0.886+4.64 w
w2 w3 w4
0A (see Fig. 42). If the load at every point on
a 3/2
the load – displacement that precedes F 5 is lower 1− w
than F 5 , then F 5 = F Q . This situation is shown
Similar K Q expressions for other specimen ge- 8. In [1], Designation E18-89a: Standard Test
ometries are given in [24]. If K Q satisfies Equa- Methods for Rockwell Hardness and Rockwell
tion (41), then K Q = K Ic . Otherwise, a thicker or Superficial Hardness of Metallic Materials.
more deeply cracked specimen should be used. 9. In [1], Designation E10-84: Standard Test
For further details, see [24]. Method for Brinell Hardness of Metallic
Materials.
10. In [1], Designation E92-82: Standard Test
Method for Vickers Hardness of Materials.
Method for Microhardness of Materials.
12. R. A. Flinn, P. K. Trojan: Engineering
Materials and Their Applications, 3 rd ed.,
Houghton Mifflin Co., 1986, p. 84.
13. In [1], Designation E140-88: Standard
Hardness Conversion Tables for Metals.
14. H. W. Hayden, W. G. Moffatt, J. Wulff: The
Structure and Properties of Materials, vol. III,
Wiley Interscience, New York 1965, p. 13.
Methods for Notched Bar Impact Testing of
Figure 42. Load – displacement plots in a K Ic test [24] Metallic Materials.
Method for Dynamic Tear Testing of Metallic
Materials.
5. References 17. In [1], Designation E139-83: Standard Practice
1. Annual Book of ASTM Standards, vol. 3.01, for Conducting Creep, Creep – Rupture and
1989, Designation E8M-89: Standard Test Stress – Rupture Tests of Metallic Materials.
Methods for Tension Testing of Metallic 18. In [1], Designation E328-86: Standard
Materials. Methods for Stress Relaxation Tests for
2. R. W. Hertzberg: Deformation and Fracture Materials and Structures.
Mechanics of Engineering Materials, 3 rd ed., 19. In [1], Designation E606-80: Standard
Wiley Interscience, New York 1989, p. 21. Recommended Practice for Constant
3. M. J. Manjoine: “Influence of Rate of Strain Amplitude Low-Cycle Fatigue Testing.
and Temperature on Yield Stresses of Mild 20. H. O. Fuch, R. I. Stephens: Metal Fatigue in
Steel,” J. Appl. Mech. 66 (1944) A211-A218. Engineering, Wiley Interscience, New York
4. In [1], Designation E9-89a: Standard Test 1980.
Methods for Compression Testing of Metallic 21. H. W. Hayden, W. G. Moffatt, J. Wulff: The
Materials at Room Temperature. Structure and Properties of Materials, vol. III,
5. In [1], Designation E290 – 87: Standard Test Wiley Interscience, New York 1965, p. 15.
Method for Semi-Guided Bend Test for 22. In [1], Designation E466-82: Standard Practice
Ductility of Metallic Materials. for Conducting Constant Amplitude Fatigue
6. In [1], Designation B565-87: Standard Method Tests of Metallic Materials.
for Shear Testing of Aluminum and 23. J. E. Shigley, C. R. Mischke: Mechanical
Aluminum-Alloy Rivets and Cold-Heading Engineering Design, 5th ed., McGraw-Hill,
Wire and Rods. New York 1989, p. 224.
7. H. W. Hayden, W. G. Moffatt, J. Wulff: The 24. In [1], Designation E399-83: Standard Test
Structure and Properties of Materials, vol. Method for Plane-Strain Fracture Toughness
III, Wiley Interscience, New York 1965, p. 12. of Metallic Materials.
Mechanical Wear → Abrasion and Erosion

Nondestructive Testing 785
Nondestructive Testing
Kanji Ono, Department of Materials Science and Engineering, University of California, Los Angeles,
California 90024, United States
1. Introduction . . . . . . . . . . . . . . 785 2.4.4. Acoustic Emission Monitoring . . . 804

2. Methods of Nondestructive Testing 786 2.5. Penetrant Methods . . . . . . . . . . 805
2.1. Material Identification . . . . . . . . 786 2.6. Magnetics and Electromagnetics . 806
2.2. Radiography . . . . . . . . . . . . . . 788 2.6.1. Magnetic Particle Inspection . . . . . 806
2.2.1. Radiation . . . . . . . . . . . . . . . . . 788 2.6.2. Magnetic Leakage Field Inspection . 808
2.2.2. Attenuation . . . . . . . . . . . . . . . . 788 2.6.3. Other Magnetic Inspection Methods 808
2.2.3. Imaging . . . . . . . . . . . . . . . . . . 790 2.6.4. Eddy-Current Inspection . . . . . . . 808
2.2.4. Recording Images . . . . . . . . . . . 790 2.6.5. Microwave Inspection . . . . . . . . . 811
2.2.5. Screens . . . . . . . . . . . . . . . . . . 792 2.7. Thermal and Optical Methods . . 812
2.2.6. Radiographic Quality . . . . . . . . . 792 2.7.1. Thermal Inspection . . . . . . . . . . . 812
2.2.7. Radiographic Practices . . . . . . . . 793 2.7.2. Visual and Optical Inspection . . . . 812
2.2.8. Radiographic Interpretation . . . . . 794
2.7.3. Optical Holography . . . . . . . . . . 813
2.2.9. Other Techniques . . . . . . . . . . . . 794
2.8. Leak Testing . . . . . . . . . . . . . . 813
2.2.10. Radiation Safety . . . . . . . . . . . . 795
2.8.1. Pressurized Gas Leaks . . . . . . . . . 814
2.3. Ultrasonics . . . . . . . . . . . . . . . 795
2.8.2. Pressurized Liquid Leaks . . . . . . . 814
2.3.1. Waves . . . . . . . . . . . . . . . . . . . 796
2.3.2. Generation and Detection . . . . . . . 797 2.8.3. Vacuum System Leaks . . . . . . . . . 815
2.3.3. Inspection Methods . . . . . . . . . . 800 3. Uses . . . . . . . . . . . . . . . . . . . . 815
2.3.4. Display Methods . . . . . . . . . . . . 800 3.1. Metallic Pressure Vessels
2.3.5. Interpretation . . . . . . . . . . . . . . 801 and Piping . . . . . . . . . . . . . . . . 815
2.3.6. Inspection Standards . . . . . . . . . . 802 3.2. Composite Pressure Vessels and
2.4. Acoustic Emission . . . . . . . . . . . 803 Piping . . . . . . . . . . . . . . . . . . . 816
2.4.1. Detection . . . . . . . . . . . . . . . . . 803 3.3. Weldments . . . . . . . . . . . . . . . 817
2.4.2. Material Behavior . . . . . . . . . . . 803 3.4. Other Uses . . . . . . . . . . . . . . . . 817
2.4.3. Source Location . . . . . . . . . . . . . 804 4. References . . . . . . . . . . . . . . . . 818
1. Introduction higher efficiency and the material capability is

exploited to its fullest extent. For example, a
Nondestructive testing of materials has become bonded joint of composite materials is a desir-
an indispensable part of modern industry. Be- able design approach, yet no nondestructive test-
ginning with the oil and whiting method, a fore- ing method is available to assure the strength of
runner of the penetrant testing method used for the joint.
crack detection, a variety of tests – based on nu- This article provides brief summaries of
merous physical principles – have been devel- widely used methods of nondestructive testing,
oped. At the start, the primary task was to find covering basic concepts, techniques in common
flaws and discontinuities. With the advent of use, and examples of industrial applications.
fracture mechanics, the measurement of flaw di- Less well developed but promising methods are
mensions became more urgent. Increasing use of also introduced. Because the field of nondestruc-
fiber-reinforced plastics in the past decade has tive testing is broad, all methods of importance to
posed new challenges in material characteriza- the chemical industry are included, but those ap-
tion. plicable primarily to the aerospace, nuclear, and
Techniques of nondestructive evaluation have steel industries are covered only incidentally.
made substantial advances. However, many Two major problems, corrosion and crack-
problems still remain because the current de- ing, confront nondestructive test engineers in
sign of components and structures demands the chemical and petroleum industries. Fer-
786 Nondestructive Testing
rous and corrosion-resistant nonferrous alloys gen results in hydrogen-induced cracking, and
used in vessels and piping are often subjected fluid flow produces erosion damage. High-tem-
to chloride- and hydrogen-containing environ- perature environments in furnaces and reactors
ments. Hydrogen-induced cracking and stress cause creep and oxidation, leading to wall thin-
corrosion cracking are found frequently. Crack- ning and cracking. The nature and origin of the
ing of welds from residual stress or poor weld flaws listed here are discussed in [1], [2].
quality is another persistent problem during ser- Detailed information on nondestructive test-
vice. Many vessels and pipes are constructed ing can be found in introductory texts [3], [4],
from carbon steel, and general corrosion from training guides [6], handbooks [7, vols. 1 – 6],
long-term service must be monitored. In addi- codes and standards [8–10], and a series of
tion, fiber-reinforced plastic components require monographs and conference proceedings [11],
special attention because traditional nondestruc- [12–15]. Several journals and a newsletter are
tive testing methods cannot adequately evaluate published in English [16], and publications in
their reliability. other languages are also available. More than a
Nondestructive testing attempts to discover dozen national societies for nondestructive test-
indications of discontinuities and abnormal con- ing, such as the American Society for Nonde-
ditions in materials and structures. If an indica- structive Testing (ASNT), the British Institute
tion is found to be beyond an acceptable limit, it for Nondestructive Testing (BINDT), Deutsche
is a flaw and the material (or structure) must be Gesellschaft für Zerstörungsfreie Prüfung e. V.
repaired or rejected. A very small gas hole in a (DGZfP), and the Japanese Society for Non-
weld is innocuous and can be allowed to remain. destructive Inspection (JSNDI), exist world-
Beyond a certain size, however, it is no longer wide, and the International Institute of Welding
tolerated, while cracks of any size are typically (IIW) and the International Standards Organiza-
rejected. Flaws and discontinuities are treated as tion (ISO) are active in establishing standards.
interchangeable because the size limits are set by The Institut für Zerstörungsfreie Prüfverfahren
design considerations. (IZfP; Saarbrücken, Federal Republic of Ger-
Flaws are introduced at three stages. The many) and the Electric Power Research Institute
first is during primary manufacturing. Shrinkage (EPRI) NDT Center are research institutes ded-
cavities, inclusions, cracks, blowholes, and other icated to studies of nondestructive testing.
faults occur in castings. Flaws in forgings may
be traced to ingots that contain segregations,
pipes (shrinkage cavities), inclusions and, hy- 2. Methods of Nondestructive Testing
drogen-induced cracks or hydrogen flakes. Dur-
ing forging, forging bursts (internal tears), sur- 2.1. Material Identification
face flaws (such as cold shuts, laps, folds, and
seams), burning, and decarburization are often To verify that an alloy is within specified com-
the result of improper setup and control. Rolling position limits, quantitative chemical analysis is
and drawing of ingots and billets generate flaws the only answer. However, a system of rapid
similar to those of the forging process. In addi- identification of metals and alloys is useful in
tion, lamination and chevron defects may occur. confirming the alloy type or in sorting mixed lots
The second stage is fabrication into structures, of alloys. Several techniques are used singly or in
in which welding is the most important process. combination. The basic technique is to use mass
Because the fusion of metals is induced, many density (specific gravity) for preliminary group-
flaws are also introduced. These include gas ing into light (Al, Mg, Ti), medium (steel, Cu,
porosity, slag entrapment, incomplete fusion, in- Ni, Zn), heavy (Pb, Mo, Ag), and very heavy (W,
complete penetration, and cracks. In addition, Ta, Pt) alloys. Some alloys have distinct colors,
surface flaws such as undercut, mismatch, and but most have a white or grayish white color.
underfill occur. The third stage of flaw genera-
tion is during service. Overloading and fatigue X-Ray Fluorescent Analysis. Each element
loading produce cracks, and corrosion leads to generates characteristic X-rays at several spe-
pitting, general reduction of wall thickness, and cific energy levels when it is irradiated with elec-
stress corrosion cracking. Exposure to hydro- tromagnetic radiation having a higher energy
spectrum. Characteristic X-ray energies range Hardness Testing. Hardness testing is not
from 1 keV for sodium to 118 keV for uranium strictly nondestructive because an indenter is
K radiation, and from 1 keV for zinc to 17 keV forced into the surface of a test piece. The re-
for uranium L radiation. Fluorescent X-rays are sulting indentation is, however, often sufficiently
detected with an energy-discriminating propor- small to be left on a finished product. The inden-
tional counter or solid-state detector and are ter is a ball, cone, or pyramid made of hardened
electronically processed to identify the chemi- steel or diamond. Constant force is applied on
cal composition of an alloy sample. Because of the indenter, and the diameter, length, or depth
the high absorption of low-energy X-rays, only of the indentation is used as a measure of ma-
the surface of the sample can be analyzed. terial hardness. The Brinell, Rockwell, Vickers,
Radioactive isotopes are often used as the and Knoop hardness tests are commonly em-
source of radiation for exciting fluorescent X- ployed [19] (see also → Mechanical Properties
rays. An isotope source of 1 – 100 millicuries and Testing of Metallic Materials). Because each
(mCi) can be small and portable. Some sources alloy has a certain hardness range, knowing the
must be replaced periodically. Regular X-ray hardness aids in material identification. Hard-
sources or small, air-cooled X-ray tubes can also ness measurement is also a nondestructive test
be used. For X-ray energy analysis, a solid-state method for the yield and tensile strength of duc-
detector commonly used in a scanning electron tile alloys based on empirical correlations. In
microscope (SEM) for elemental detection can brittle ceramic materials, cracks emanate from
be employed, but such a detector requires con- the corners of a Vickers hardness indentation.
stant cooling with liquid nitrogen. Another limi- The length of these cracks has been found to
tation arises from the resolution of the X-ray en- be related to the fracture toughness of ceramics.
ergy analyzer; elements lighter than aluminum Thus, nearly nondestructive determination of ce-
cannot be evaluated. In the electron microprobe ramic fracture toughness can be conducted.
analyzer, energetic electrons are used to gener-
ate fluorescent X-rays; a high-resolution energy Electrical and Magnetic Testing. Electri-
spectrum analyzer is employed, which is capa- cal resistivity can be used to classify metals and
ble of detecting an element as light as boron. alloys and the state of heat treatment of many
Small samples can be analyzed in an SEM or alloys. One technique involves use of a four-
microprobe. point probe with four equally spaced tips. The
probe passes a direct current (I dc ) between the
Chemical Spot Testing. Chemical spot test- two outermost tips and measures the potential
ing utilizes chemical color reactions, which are (V t ) between two inner tips. For samples whose
carried out on a sample, on filter paper, or on a thickness is more than three times the distance
spot plate. A test kit consists of about 100 solu- between two tips (S t ), the electrical resistivity
tions. Carbon steels, for example, can be iden- (e ) is
tified by placing a drop of 50 % nitric acid on a e = 2πSt Vt /Idc
fresh surface. After 5 min, the spot is rinsed with
water; a brown spot indicates carbon steel. See Another technique uses the eddy-current prin-
[17] for a listing of solutions and identification ciple (see Section 2.6.4). A probe containing
tests. a coil(s) is placed on the surface of a sample.
Changes in coil impedance are analyzed and in-
Spark Testing. The spark testing technique dicated as electrical conductivity (the inverse of
classifies ferrous alloys according to their chem- resistivity) values on the analyzer output device,
ical composition by visual examination of the for example, a digital readout.
sparks thrown off when a sample is held against The magnetic properties of alloys can be
a high-speed grinding wheel. The test is fast checked with a hand magnet to classify them
and economical, yet an experienced operator can as strongly magnetic, weakly magnetic, or non-
identify a variety of alloys with reasonable ac- magnetic. Austenitic stainless steels and some
curacy [1], [2], [18]. nickel alloys are weakly magnetic or nonmag-
netic, depending on cold working and heat treat-
ment. The eddy-current instrument for electrical
conductivity testing can also be used for quanti- are decelerated at the target, a continuous spec-
tative evaluation of magnetic permeability. trum of X-ray photons is produced, having en-
Heated and cold electrodes are brought in ergies lower than that of the electrons. The peak
contact with the surface to evaluate the thermo- X-ray intensity occurs at about one-third of the
electric properties of a sample [9, E 977]. This maximum photon energy. At photon energies of
is useful in sorting alloys by comparative mea- less than 118 keV, characteristic X-rays are also
surements. produced and their energies are specified by the
target element. A common choice of target mate-
Composite Phase Testing. In fiber-rein- rial is tungsten, but copper, iron, and cobalt are
forced plastic composites, the amount of fiber also used. Tubes are used to generate X-rays,
reinforcement is an important material variable. with tube voltages up to 1000 kV. These consist
Destructive testing for fiber content uses acid basically of a diode with a filament for electron
digestion and ignition techniques to eliminate emission (cathode) and a target (anode), between
the resin matrix. Ultrasonic velocity has been which an accelerating potential is applied. The
shown to depend on fiber content, although few cathode has a focusing cup to control the size
dedicated instruments are in use. An instrument of the electron beam. The anode is fluid cooled,
based on elastostatic principles has also been and the target is usually tilted to direct the X-rays
developed [38]; it can determine the fiber con- generated. The vacuum envelope is made partly
tent and the porosity fraction from differential of glass or ceramic for electrical insulation and
compressibility measurements (i.e., measuring has a thin beryllium X-ray window.
the thickness of a sample under different static Higher energy X-rays are generated by us-
loading conditions) together with destructive ing an electron linear accelerator (a linac). Elec-
calibration procedures. When the density and tron energies of 1 – 30 MeV can be obtained
composition of matrix and fiber phases differ, with commercial equipment, which employs mi-
as in the case of a resin matrix with glass fibers, crowave power to accelerate electrons in a series
X- or gamma-ray absorption can be used to of cylindrical cavities. Betatrons, as well as Van
determine the fiber content. de Graaff and resonant transformers, have also
been utilized, but they are larger and less conve-
nient than linacs.
2.2. Radiography Gamma rays are produced by radioisotopes
such as cobalt-60 and cesium-137. Although ra-
Radiography utilizes the differential attenuation dioisotope sources require radiation shielding
of penetrating radiation to find internal flaws and safe handling equipment, no power supply
such as porosity and compositional changes, as is needed. This results in portability, but the ra-
well as variations in thickness and cracks. X- diation intensity is low and long exposure times
rays, gamma-rays, and neutrons are used and are common. Radioisotopes (e.g., 60 Co) are also
are imaged by photographic films, fluoroscopic a convenient source of the high-energy radiation
screens, and more recently, electronic imaging needed to penetrate thicker test pieces.
devices. Thickness changes of 1 – 2 % and flaw Neutrons are produced by nuclear reactors,
sizes of a few tenths of a millimeter can typically deuterium accelerators, or isotopes such as
be detected. This method examines a large vol- californium-252. Because of the capability of
ume of material simultaneously, and most welds neutrons to detect explosives, neutron radiog-
are radiographed routinely. However, radiation raphy is used by the military. Industrial applica-
safety measures must be rigorously enforced. tions are uncommon.
For details, see [7, vol. 3], [20], and more than
20 ASTM standards [9].
2.2.2. Attenuation
2.2.1. Radiation Both X-rays and gamma rays are attenuated in a

substance by absorption and scattering. At lower
X-rays are generated when high-energy elec- energy levels, an incoming photon is absorbed
trons strike a metallic target. When the electrons by ionization of an atom (photoelectric effect).
This effect decreases with increasing photon en- copper alloys, photoelectric absorption is domi-
ergy E p as E −3.5
p , except when the energy cor- nant at a photon energy of less than 100 keV. In
responds to the electronic binding energy, at light metals (aluminum alloys), this range shifts
which point absorption increases greatly. Such to less than 40 – 50 keV. The atomic attenua-
increases are called absorption edges. Another tion coefficient increases with atomic number.
absorption process, in which the photon energy The exponential attenuation equation is valid
is used to create an electron – positron pair, oc- when the photon energy spectrum remains un-
curs above 1 MeV. Scattering of a photon by an affected by passage through the material. This
electron occurs either coherently without chang- condition exists when a collimator is used in
ing the kinetic energy (Rayleigh scattering) or front of the radiation detector to exclude scat-
incoherently with loss of the photon energy and tered radiation (i.e., the so-called narrow-beam
changes in photon direction (Compton scatter- geometry). Here, all scattered photons are as-
ing). Figure 1 shows changes in attenuation for sumed to be absorbed. In conventional radio-
several materials as a function of energy. graphs, scattered photons reach the recording
medium; this condition is known as broad-beam
LIVE GRAPH geometry. The broad-beam attenuation coeffi-
Click here to view cient is smaller than the narrow-beam attenua-
tion coefficient and depends on the photon en-
ergy spectrum and the penetration depth. Pub-
lished data on attenuation coefficients are based
on the narrow-beam geometry. When estimating
radiographic exposures, narrow-beam data may
result in inaccuracy, especially with low-energy
X-rays and thick test pieces.
The radiation intensity I B in the broad-beam
geometry is expressed as
IB = I0 B exp (−µa x)
where B is the buildup factor, which is equal to
the ratio of the total intensity (direct beam plus
scattered beam) to the direct-beam intensity. The
buildup factor increases with increasing thick-
ness of the test piece, and the rate of increase of
B is higher for lower energy radiation (see Fig. 2
for B in steel).
When X-rays are generated at the target of
an X-ray tube, the energy spectrum contains
the low-energy portions. As the beam passes
Figure 1. Absorption coefficient µa versus energy for var-
through the tube window, higher proportions of
ious materials low-energy X-rays are absorbed, hardening the
spectrum. This spectrum change is quantified
Radiation intensity I decreases exponentially by equivalent filtration with a thickness of alu-
with the thickness x of a uniform material: minum and is called inherent filtration. When
harder (higher average X-ray energy) radiation
I =I0 exp (−µa x) =I0 exp (−Na σa x)
is required, a filter is inserted into the beam path.
where I 0 is the incident intensity, µa the lin- After electromagnetic radiation is emitted
ear attenuation coefficient, N a the number of from the source, the beam spreads as it trav-
atoms per unit volume, and σ a the atomic at- els. As the distance from the source increases,
tenuation coefficient. When µa is divided by the same radiation intensity is distributed over
mass density , the mass attenuation coeffi- a larger area and the intensity varies inversely
cient (µa /) is obtained to express attenuation with the square of the distance. If the intensity
per unit areal weight. In steels and nickel or is I 1 at a distance x 1 , the intensity I 2 at x 2 is
LIVE GRAPH
Click here to view The finite spot size of X- and gamma-ray
sources produces regions of partial shadow at the
edges of an object. These are known as penum-
bra and result in a geometric unsharpness U g ,
given by
Ug =Fs (xi −xo ) /xo
where F s is the source spot size (see Fig. 3). Ge-

ometric unsharpness and image distortion are re-
duced by using a larger source-to-object distance
x o . Increasing x o , however, reduces the radiation
intensity, and the exposure time must therefore
be increased.
Figure 2. Buildup factor as a function of thickness
I2 =I1 (x1 /x2 )2
which is called the inverse-square law.
2.2.3. Imaging
Radiographic images are formed in analogy to

geometric optics because of straight-line prop-
agation of X and gamma rays. A point source Figure 3. Geometrical unsharpness in radiography
of radiation is generally used. However, the X-
and gamma-ray sources are finite in size, typi-
cally ranging from 0.5 to 5 mm. When an image 2.2.4. Recording Images
(or shadow) of an object at the source-to-object
distance x o is formed at the source-to-image dis- The most common method of recording radio-
tance x i , the image is enlarged by a factor x i /x o . graphic images is the use of X-ray films. Films
This enlargement factor is nearly unity in con- make a permanent record of images of large ar-
ventional radiography because the film is placed eas. These have a thin emulsion coating on both
immediately behind the object or test piece. By sides of a film base or a thin clear plastic support.
using a microfocus X-ray tube with a source size The emulsion is typically 25 µm thick and con-
of 1 – 10 µm, a ten- to hundredfold magnifica- tains a microscopic suspension of silver halide
tion can be realized in microradiography (X-ray grains. Both X-ray and gamma-ray energy cause
microscopy) applications. Here, a test piece is a latent image to form. A visible image is re-
placed near the source and the film is further vealed by a developer that converts the exposed
away. silver halide to metallic silver. The image is then
Image distortion occurs when a two- fixed by washing off unexposed halide grains
dimensional object is imaged on a nonparallel and drying. Most X-ray films are for direct expo-
image plane. A three-dimensional object always sure to X-rays. Some are used with fluorescent
gives a distorted image because the enlargement screens and are more sensitive to visible light
factor is not constant over the object. emitted by the screens.
The exposure of a film causes an inherent the range 4.75 – 5.15 to obtain high contrast and
unsharpness, which results from the scatter- densities of 2 – 4. This film has a narrow latitude.
ing of secondary electrons in the film emul- LIVE GRAPH
sion. Typical values of inherent unsharpness are Click here to view
0.01 – 0.05 mm for 100 – 250-kV X-rays.

Darkening of a film is measured as density D
by transmitting light through it. The density is
defined as
D= log (I0 /It )
where I 0 is the intensity of the incident light

and I t is that of transmitted light. Only 1 % of
light is transmitted at a density of 2, and 0.01 %
at D = 4. Since low values of D give low sen-
sitivity and high values make viewing difficult,
standard procedures restrict D values. Valid den- Figure 4. Characteristic curves for films
sity ranges for single and composite viewings For a given range of densities on the char-
are 1.5 – 4 and 2 – 4, respectively. For D > 2, a acteristic curve, the average slope Gav can be
high-intensity illuminator is required. The den- defined. A change in density ∆ D for a given
sity of an exposed film is dictated by exposure, exposure time is related as
film characteristics, and film development con-
ditions. Exposure is the product of the radiation ∆D= −0.43Gav µa ∆x/B
intensity and the time of exposure. In radiog-
raphy, relative exposure is generally used, with where µa is the attenuation coefficient for the ra-
a certain exposure condition including X-ray diation used, ∆ x is the change in thickness, and
source, energy, filters, source-to-film distance, B is the buildup factor. A change in D of more
film type, and developing condition, being set than 0.006 is required for a perceptible density
as reference. change, so the minimum thickness change that
The characteristic curve, also known as the H can be detected radiographically is expressed as
and D curve after Hurter and Driffield, ex-
− (2.3 × 0.006) B/µa Gav
presses the relation between the relative expo-
sure applied to a film and the resulting density. That is, higher attenuation coefficients, obtained
The relative exposure is plotted on a logarithmic with low-energy radiation, and steeper slopes
scale. Figure 4 shows examples of such curves, of the characteristic curve increase radiographic
which are useful for determining suitable expo- sensitivity. The buildup factor, on the other hand,
sure conditions and comparing the speed and decreases the sensitivity due to non-image-
contrast of various film types. Speed describes forming scattered radiation. Both B and µa in-
how fast a particular density can be produced. In crease with decreasing radiation energy, but µa
Figure 4, type 1 has the lowest speed and type 4 is affected much more than B.
the highest. High-speed film tends to have coarse The shape of characteristic curves is affected
grains, whereas low-speed film has fine grains. by the development time: film contrast increases
Such graininess results from clustering of indi- with development time, which also gives some
vidual silver halide grains. Film contrast, also increase in speed. The energy spectrum of the
called film gradient, is the difference in density radiation also affects the speed. The character-
due to a change in exposure and is expressed by istic curve is shifted to the higher exposure side
the slope G of the characteristic curve. A higher as the radiation energy increases from less than
contrast gives a larger difference in density for 100 kV to several hundred kV or more.
the same variation in exposure, allowing better For a given combination of radiation source,
resolving of details, but the range of usable ex- source-to-film distance, material to be radio-
posure conditions is narrow. For type 1 film in graphed, type of film, and film development
Figure 4, the log of relative exposure must be in technique, a radiographic exposure chart for a
particular density can be prepared. When the the phosphor gives rise to screen unsharpness,
thickness of a test piece varies within the area of reducing image definition on the film. Typi-
coverage, a latitude chart may be used to help de- cal values of screen unsharpness for commer-
termine the correct exposure. The latitude chart cially available screens are 0.1 – 0.4 mm. An-
is similar to the exposure chart except that a band other drawback of fluorescent screens is the ap-
corresponding to a range of densities is given pearance of screen mottle on the finished radio-
(Fig. 5). graph. This arises from statistical variations in
LIVE GRAPH
Click here to view fluorescence and appears as a larger scale grain-
iness.
2.2.6. Radiographic Quality
Image quality is influenced by many variables

that contribute to radiographic contrast and im-
age clarity. Superior contrast is obtained by a
large change in thickness ∆ x, lower radiation
energy, less scattered radiation, exposure in the
high-film-gradient region, adequate film devel-
opment, and use of films with high gradients.
Figure 5. Latitude chart for type 2 film
Good image clarity results from low total un-
sharpness, which is defined as the square-root
of the sum of the squares of geometrical, in-
2.2.5. Screens herent, and screen unsharpnesses. Motion un-
sharpness also arises due to movement of the
Lead foil screens are commonly used in direct test piece. Typical values of total unsharpness
contact with films to produce an intensifying ac- with good film techniques for 100-kV X-rays
tion at as low as 90 kV, depending on the thick- are 0.05 mm; 200-kV X-rays, 0.10 mm; 400-
ness of the material and the foil. The intensi- kV X-rays, 0.20 mm; iridium-192 gamma rays,
fication arises through emission of secondary 0.25 mm; and cobalt-60 gamma rays, 0.50 mm.
electrons by the lead upon X-ray photon bom- Practical indicators of image quality are
bardment. Higher energy radiation gives greater known as penetrameters or image quality indi-
intensification. A screen in front of the film also cators. One ASTM design [9, E 1025] is based
filters out scattered radiation arising from the test on rectangular or round sheets with thickness T
piece and improves radiographic quality. Lead of 0.13 – 1.3 mm, having holes of size 1 T , 2 T ,
screens, 0.13 mm thick, are generally used in and 4 T (1 T and 2 T for round penetrameters).
front and back for radiography of 6-mm-thick A penetrameter whose thickness corresponds to
(or more) steel with sources of more than 135 kV. 2 % of that of the test piece is generally used. An-
For higher energy radiation (e.g., 60 Co) 0.25- other type of penetrameter [9, E 477] employs a
mm-thick lead screens are used. The rear screen set of six wires of different sizes. The penetram-
also protects the film from backscattered radia- eter material is the same as that of the test piece.
tion. For this purpose, a lead sheet is used in the The penetrameter is placed directly on the test
back of the film holder as well. Other screen ma- piece, facing the source and remote from the area
terials include copper, gold, tantalum, and lead of inspection. Image quality is usually expressed
oxide. as the size of the smallest penetrameter feature,
Fluorescent screens are used only when the such as hole size or wire diameter, that is clearly
exposure would be extremely long without them. visible in the processed radiograph. The mini-
They are employed in combination with film mum acceptable quality level corresponds to the
optimized for high sensitivity to emitted light. visibility of a 2 T hole with a 2 % thickness pene-
The screens are coated with phosphors such as trameter. This quality level is expressed as 2-2 T.
CaWO4 and ZnCdS and can produce 2 – 25-fold Equivalent penetrameter
√ sensitivity (in percent)
√
intensification. However, light scattering within is defined as 100 T h/x 2, where x is the test
piece thickness, T is the penetrameter thickness, internal holes or openings can be reduced by us-
and h is the hole size. Other measures of equiv- ing lead masks that cover the holes or openings
alent sensitivity are also used. and by surrounding the test piece with metal-
lic shot or a liquid absorber. Backscatter from
objects behind a film (away from the source) is
eliminated by a lead screen or sheet. A colli-
mator is placed near the source and reduces the
beam size to cover only the test piece, thus elim-
inating spurious scattering.
Figure 6. Three methods of equalizing radiographic density

a) Radiation source; b) Film; c) Solid cradle; d) Liquid ab-
sorber; e) Shims
2.2.7. Radiographic Practices

The positions of the radiation source, the test
piece, and the film are chosen to best reveal ex-
pected flaws with minimum geometrical distor-
tion. In the case of cracklike flaws, the X- or
gamma-ray beam must be oriented parallel to
the flaw. The orientation matters little for void- Figure 7. Radiographic inspection
A) Single-wall and B) Double-wall radiographic technique
like flaws, but the size or shape of the image a) Radiation source; b) Beam; c) Pipe; d) Film
will change unless the beam passes normal to
the plane of the flaw.
Flat test pieces can best be radiographed by
Scattered radiation decreases radiographic
a normally incident beam with films below the
sensitivity. Scattering from wall reflections and
test pieces. Curved plates can be inspected sim- 2.2.8. Radiographic Interpretation
ilarly, but minimum distortion is achieved with
the source at the center of the radius of curva- The radiographic appearance of the types of flaw
ture. Inspection of a cylindrical test piece re- usually found in castings and weldments has
quires section-equalizing techniques with a solid been compiled in volumes of reference radio-
cradle, liquid absorber, or shim stocks (Fig. 6). graphs, which are graded according to flaw size
Double-film techniques with films of different and severity. The ASTM has produced 12 vol-
speed, and multiple exposures with different umes of reference radiographs [9]. Radiographic
radiation energies can be employed instead of acceptance criteria are defined from these refer-
these section-equalizing techniques. Overexpo- ence radiographs, permitting acceptable limits
sure of the outer portion of the radiographic of flaw types, sizes, and densities. Linear-type
image can be corrected either by exposing a flaws, such as cracks and incomplete fusion, are
film of lower sensitivity or by using lower en- prohibited regardless of size in most criteria [8].
ergy radiation. Tubular sections are inspected Of the service-induced flaws, corrosion in a
by single- or double-wall techniques (Fig. 7). flat or tubular section can be detected because
Single-wall techniques use an external radia- the loss of material results in dark areas in the
tion source and the film inside the cavity. Al- radiograph. In contrast, tight cracks from stress
ternatively, the source is placed inside the cav- corrosion and hydrogen effects are difficult to
ity and the film on the outside. For the latter, detect. Similarly, short fatigue cracks are hard
a panoramic X-ray source that emits radiation to locate.
360◦ around its axis may be used. Single-wall
techniques usually take a single image through a
wall or weld and provide good radiographic sen-
sitivity. Double-wall, double-image techniques
are used when single-wall techniques are dif-
ficult to employ, e.g., for small cross sections
(< 9 cm). These produce radiographs on which
the images of both walls are recorded and are
also applied to the inspection of diagonally op-
posed corner welds in rectangular box sections.
Circumferential butt welds can be inspected with
the offset or corona techniques (Fig. 8). For
smaller diameters, two images can be exposed,
but the single-image technique gives a better ra-
diograph for large-diameter pipes.
Inspection of complex shapes requires mul-

Figure 8. Corona (offset) radiographic technique
tiple exposures with different viewing direc- a) Pipe; b) Offset angle; c) Radiation beam; d) Weld; e) Im-
tions. Combinations of the above-mentioned ages of weld; f) Film
techniques are chosen to reduce the image to a
simple shape for easy interpretation. Welds are
usually inspected to reveal flaws in weld met- 2.2.9. Other Techniques
als and in heat-affected zones. A beam direc-
tion normal to the surface of the weld is used. Computerized tomography, developed for med-
For T-joints or lap joints, the beam direction is ical applications, can also be used in inspec-
inclined to both sides of the weld joint. When tion of lightweight composites. Conventional to-
two adjacent welds are made, two beam direc- mography equipment is expensive and as yet
tions are usually required, but the images may impractical for routine commercial use. Film-
be recorded on a single film. based tomography may, however, become a use-
ful method in the future [21].
past decade because of improvements in elec-

tronic image processing. However, they are five
to ten times less sensitive to cracks and are used
mainly in electronic component inspection and
airport baggage screening [9, E 1000].
Microfocus X-ray tubes can readily provide
a magnification of two to ten times because of
their small spot size (ca. 10 µm). Although their
low X-ray output requires long exposure times or
use of an electronic image intensifier (combining
the real-time fluoroscopic and image-processing
equipment), a microfocus unit allows the inspec-
tion of small flaws in ceramics and composites.
Inspection of thick sections requires high-
energy radiation sources. Steel sections up to
5 cm can be radiographed with medium energy
X-rays (250 – 400 kV) or iridium-192, and up to
10 cm, with 1-MV X-rays or cobalt-60. Higher
energy radiation improves radiographic sensi-
tivity for thick sections, but requires specialized
equipment.
2.2.10. Radiation Safety
Exposure to radiation is harmful to health and

must be strictly controlled. Radiation safety is
practiced by adhering to established procedures
of handling radiation equipment and radioactive
materials, by incorporating adequate shielding
design and safety interlock systems, by thor-
oughly educating personnel about safe practices,
by monitoring radiation levels of the working en-
vironment, and by enforcing the limit on allow-
able exposure. Proper licensing requirements
must be maintained.
2.3. Ultrasonics
Ultrasonic testing uses high-frequency mechan-
ical (elastic) waves in the range of 20 kHz to
50 MHz. Elastic waves are reflected and re-
fracted at interfaces where elastic moduli and
density are discontinuous. Cracks, voids, non-
metallic inclusions, and back surfaces reflect
incident waves. By sending a pulse and re-
Figure 9. Ultrasonic waves ceiving its reflection, the presence and location
A) Compressive wave; B) Shear wave; C) Surface wave; D) of flaws can be defined in analogy to radar.
Symmetrical plate wave; E) Asymmetrical plate wave
This is the pulse-echo technique. When lami-
Real-time radiographic inspection tech- nations, disbonding, and other flaws are present,
niques have advanced substantially within the the intensity of transmitted waves is attenuated.
By measuring the intensity on the back sur- The velocity V c of plane compressional
face, the through-transmission technique detects waves in an isotropic medium is given by
flaws via attenuation. When the material under -
inspection is uniform, the time of transit of elas- Vc = (λ+2µ) /
tic waves through the material can be converted
to the thickness by determining the wave veloc- where λ and µ are Lamé constants and is mass
ity on a calibration sample. This time-of-flight density. Similarly, the shear wave velocity V s is
technique is used in thickness meters. Time-of- -
Vs = µ/
flight and attenuation measurements on samples
of known thickness are used to characterize ma- Wavelength is equal to wave velocity V divided
terial properties, such as grain size of metals or by frequency f . For steels, V c ≈ 6 mm/µs, and
fiber and void content in composites. for f = 1 MHz, λu ≈ 6 mm; for water, V c ≈
The ability to locate and measure internal 1.5 mm/µs and λu ≈ 1.5 mm. Table 1 lists typi-
flaws, the ability to internally inspect three- cal values of V for various materials.
dimensional objects from a single surface, and
nonhazardous operation are advantages of ultra- Table 1. Typical ultrasonic velocities
sonic testing. Disadvantages include the com- Material V c , mm/µs V s , mm/µs
plexity in interpreting some results and the dif-
Carbon steels 5.94 3.24
ficulty of inspecting parts with rough surfaces, 304 stainless steel 5.64 3.07
irregular or small shapes, or near surface flaws. Cast iron 3.5 – 5.6 2.2 – 3.2
Operator training requirements are also higher Inconel 5.82 3.02
than for most other nondestructive testing meth- Brass (70/30) 3.83 2.05
Titanium (pure) 6.10 3.12
ods; see [9], [22] for further details. Glass 5.77 3.43
Poly(methyl methacrylate) 2.67 1.12
(Plexiglas)
2.3.1. Waves
By measuring wave velocities, the elastic
Elastic waves travel with characteristic veloc-
constants, Young’s modulus E, and Poisson’s ra-
ity in a gas, liquid, or solid. In gases and liq-
tio ν, can be found:
uids, only compressive waves exist; i.e., the
medium is alternately compressed or rarefied. . /
Vs2 3 (Vc /Vs )2 −4
Waves travel parallel to the direction of com- E=
pression and rarefaction; hence, they are also (Vc /Vs )2 −1
called longitudinal waves. In solids, compres- (Vc /Vs )2 −2
ν=
sive waves and shear waves are present. In shear 2 (Vc /Vs )2 −2
or transverse waves, elastic displacement occurs
perpendicular to the direction of wave propaga- Surface (or Rayleigh) waves are also used in ul-
tion. These waves are shown schematically in trasonic testing. These travel along the surface
Figure 9 A and B. Here, the distance between with approximately 90 % of the shear wave ve-
two points of the same phase is the wavelength locity. The wave energy is concentrated within
λu . about one wavelength of the surface, as shown in
Most ultrasonic testing utilizes frequencies Figure 7 C. Rayleigh waves follow curved sur-
of 1 – 25 MHz. Higher frequencies allow bet- faces and corners, but are reflected when the ra-
ter spatial resolution due to the shorter wave- tio of the radius of curvature r to the wavelength
length. However, more attenuation occurs above λu is less than 1.6. About half the wave energy
10 MHz in steels as the wavelength approaches is reflected for r/λu < 0.6. In comparison to bulk
the grain size. In highly attenuating fiber- waves (compressive and shear), Rayleigh waves
reinforced composites, frequencies of 1 MHz or are attenuated less and are well suited to inspect-
lower are commonly used. In most structural ing parts that have complex contours.
steels and wrought alloys, attenuation is low, and Lamb waves (plate waves) propagate in
ultrasonic testing has good penetrating power to sheets and plates in which the wavelength and
depths of 1 – 10 m. thickness are of the same order of magnitude.
Symmetric and asymmetric modes of propaga- and higher intensity waves are produced for
tion exist (Fig. 7 D and E). These waves have shear waves refracted at 35 – 60◦ . Partly due to
different phase and group velocities, each depen- geometrical considerations, 45◦ and 60◦ shear
dent on frequency and thickness. Until recently, wave transmission paths are most commonly
the application of Lamb waves to ultrasonic test- used. For thin sections, 70◦ shear waves are also
ing has been limited due to their complex prop- employed.
agation characteristics.
When ultrasonic waves are normally incident
on a plane interface of two materials, 1 and 2,
part of the wave energy is transmitted through
the interface, and the remainder is reflected. The
ratio of transmitted energy to incident wave en-
ergy, known as the transmission coefficient T i ,
is expressed in terms of the acoustic impedance
Z, the product of mass density and wave velocity
(Z = V c ):
Ti = 4Z1 Z2 / (Z1 +Z2 )2

= 41 2 Vc1 Vc2 / (1 Vc1 +2 Vc2 )2
Figure 10. Mode conversion of ultrasonic waves
The reflection coefficient Ri = 1 − T i . At an inter- Useful depth of inspection is determined by
face of water and steel, T i = 0.12 and Ri = 0.88; the attenuation of ultrasonic waves. The acoustic
that is, nearly 90 % of the wave energy is re- pressure decreases exponentially with depth, as
flected. in the case of X-rays. However, the attenuation of
When a plane wave is obliquely incident ultrasonic waves is usually expressed in decibels
on an interface, both compressional and shear per meter (dB/m). General ranges of inspection
waves are reflected or refracted regardless of the are up to 1 – 10 m in steels, in nickel, titanium
nature of the incident wave. This is known as and magnesium alloys with fine microstructures,
mode conversion, and the angles of reflection and in all aluminum alloys; these have attenua-
and refraction are defined by Snell’s law (see tion rates of 0.1 – 1 dB/m. Most cast metals have
Fig. 10): a lower inspection range of 0.1 – 1 m. Stainless
sinθc1 sinθs1 sinθc2 sinθs2 steel weldments and fiber-reinforced composites
= = = have high attenuation, and the inspection range
Vc1 Vs1 Vc2 Vs2
extends to less than 0.1 m.
For water (1) and steel (2) with an incident an- In highly attenuating materials such as cast
gle θc1 of less than 45◦ , compressional waves nonferrous materials and fiber-reinforced com-
in water are reflected at θc1 ; refracted compres- posites, the wave velocities are frequency depen-
sional and shear waves exit from the interface at dent. This dispersion affects waveforms as they
θc2 and θs2 . Note that no shear wave exists in propagate because higher frequency contents are
liquids. The angle attenuated.
θc1 = sin−1 (Vc1 /Vc2 ) = 14.5◦
2.3.2. Generation and Detection
is called the first critical angle because θc2 be-
comes 90◦ and the compressional waves in steel Ultrasonic waves are generated and detected by
no longer exist for higher values of θc1 . The sec- using a transducer element that converts elec-
ond critical angle is at sin−1 (V c1 /V s2 ) = 27.4◦ , trical signals to mechanical ones and vice versa
above which no shear wave is observed in steel [23]. A thin disk of piezoelectric crystal or po-
and total reflection occurs. Between the first and larized ceramic is used. Quartz, lithium sulfate,
second critical angles, only shear waves are re- and lithium niobate are used as single-crystal el-
fracted in steel. This is advantageous because in- ements, whereas lead zirconate – titanate is the
terpretation is easier with only one wave mode, most common ceramic element. The transducer
element is enclosed in a protective casing with duce a train of short pulses or tone bursts (up to
a thin ceramic or plastic faceplate and an atten- ten oscillations). These are repeated 50 to 2000
uative backing such as a tungsten – epoxy mix- times per second. A short pulse contains a wide
ture (see Fig. 11 A). The backing is needed to spectrum of frequencies, while the frequency
dampen the resonance of the transducer element spectrum of a tone burst is centered at its base
and to broaden the frequency response. The cas- frequency. When the search unit is excited with
ing also acts as an electrical shield. A thicker a pulse (or tone burst), the frequency spectrum
faceplate (a delay tip) may be used to separate of the ultrasonic wave output is the product of
the front-surface signal from the large excitation the frequency spectra of the input pulse (or tone
pulse. The frequency characteristics of the pack- burst) and the search unit.
aged transducer or search unit are dictated pri-
marily by the thickness resonance of the trans-
ducer element, which occurs when the thickness
equals one-half of the wavelength, causing con-
structive interference of waves reflected at the
surface.
Figure 12. Ultrasonic waveforms and their frequency spec-

tra
A) Narrow band; B) Broad band
The waveform of the output can be obtained

from the frequency spectrum by inverse Fourier
transform. This waveform W 0 can also be ex-
pressed as the convolution of the input waveform
W i and the input response W s :

W0 (t) = Wi (t−τ ) Ws (τ ) dτ
where W s is the characteristic waveform for

an infinitely short pulse (delta-function shape).
Typical waveforms and the frequency spectra
of narrow-band and broad-band search units
are shown in Figure 12. High peak voltages
(300 – 500 V) are needed for a short pulse be-
cause only part of the pulse energy is used. This
Figure 11. Typical ultrasonic search units often leads to the failure of thin, high-frequency
A) Straight-beam unit; B) Angle-beam unit transducer elements. With a tone burst, the base
a) Case; b) Epoxy potting; c) Tungsten-loaded backing; frequency must be matched to the nominal res-
d) Electrical connections; e) Cable connector; f) Transducer
element; g) Faceplate; h) Plastic wedge onance frequency of the search unit. Since the
tone burst is limited in bandwidth, the peak volt-
To generate ultrasonic pulses with a search age can be much lower to obtain the same ul-
unit, an electronic pulse generator is used to pro- trasonic energy output. Alternatively, a much
stronger wave can be generated with a tone burst temperature or with rough surfaces, for which
than with a short pulse for a given applied volt- noncontact generation is desirable for ease of
age. use. Commercially available units can be used
The sound field immediately in front of the up to 3 MHz. A strong magnetic field is required,
faceplate is basically a plane wave, but the in- and a special powering unit must be used. Non-
tensity varies depending on the position and dis- magnetic test pieces lower the efficiency. Limits
tance from the search unit because of diffraction in the frequency range of operation and lower
effects. This region is known as the near field, signal-to-noise ratios are some of the disadvan-
which extends to a distance N x given by tages.
By using the principle of refraction, ultra-
Nx =Dt2 /4λu sonic search units can be designed to generate
where Dt is the diameter of the transducer el- angle beams. A plastic wedge is housed with a
ement. For flaw detection, the near field is dif- transducer element as shown in Figure 11 B. The
ficult to use because of the intensity variation direction of the beam is valid for a specified ma-
(near-field effect). Near-field effects in the mate- terial. Surface wave search units are also made
rial under inspection can be eliminated by plac- with the same design concept.
ing a delay tip between it and the search unit, In the pulse-echo mode, the same search unit
whereby the near-field effect is confined to the is used for generation and detection of ultrasonic
delay tip. The region beyond N x is known as waves. Dual-element search units are also used
the far field and a spherical wave propagates as which house separate transducer elements for
shown in Figure 13. No diffraction fringe oc- detection and generation. Two separate search
curs, and the wave intensity decreases with the units are employed for the through-transmission
square of the distance. The spread ϕ of the far- mode, in which one is dedicated for receiving
field sound beam is dictated by λu /Dt and is the ultrasonic waves. Received ultrasonic waves
given by produce low-level electrical signals. Electronic
amplifiers with low noise levels (even for a wide
ϕ= 2sin−1 (1.22λu /Dt ) bandwidth of 0.1 – 50 MHz) are used to pro-
vide good signal-to-noise ratios. When a single
For example, ϕ = 44◦ in steel at 1 MHz with search unit is used for transmission and receiv-
Dt = 19 mm. For the same Dt at 5 MHz, ϕ de- ing, an input protection circuit is required and
creases to 8.7◦ . A smaller value of Dt allows the input amplifier must be capable of rapid re-
flaws to be more accurately located at short discovery from an overload due to the excitation
tances, but this advantage is lost as the beam pulse.
spreads with increased penetration. A higher fre- The sound beam can be focused by means of
quency beam spreads less for a given value of Dt an acoustic lens attached to the front surface of
or allows the use of a smaller Dt . the transducer. This requires a water path bet-
ween the lens and the test piece. Transducers
can be spherically focused to a spot or cylin-
drically to a line. For the latter, a rectangular
transducer element is used. Spherical focusing
achieves the same for pipe and tubing inspec-
tion. Both can increase near-surface resolution
without increasing the transducer frequency. Fo-
cusing also reduces the effects of surface rough-
Figure 13. Near- and far-field regions ness and contour.
Focal distance is given in water path length.
For special laboratory studies, ultrasonic Path length in a solid is converted to an equiva-
pulses can be generated by means of the ther- lent path length in water by multiplying by the
moelastic effect with a strong laser beam. Elec- ratio of sound velocities. Focal distance should
tromagnetic transducers allow noncontact gen- then be equal to (water path) + (solid path) ×
eration and detection. They are suited for auto- (sound velocity in solid) ÷ (sound velocity in
mated inspection of pipes and plates at elevated
water). Search units of various focal distances for such a display, but recent equipment can store
(typically, 1 – 25-cm water path) are available. the scan position and ultrasonic data from 107 –
108 locations in digital form. Real-time or post-
test analysis of the stored data provides detailed
color displays.
Wheel-type search units consist of a station-
ary transducer element, a liquid path inside a
rubber tire, and a rolling wheel to provide contin-
uous contact with a test piece. The transducer el-
ement can be placed for straight-beam or angle-
beam inspection. The wheel unit can be station-
ary and a test piece moved past it, or it may be
moved over a fixed test piece.
Figure 14. Ultrasonic inspection of pipes A search unit can be fitted with a squirter,
a nozzle through which water streams out un-
der pressure, which provides a column of wa-
ter for a sound beam to reach the test piece.
2.3.3. Inspection Methods
The squirter technique can be combined with
robotics. This combination eliminates the size
When a search unit is placed directly over the limitation of immersion testing, can be adapted
surface of a part under test in contact inspec- to complex contours, and is suited for automatic
tion, a thin layer of liquid couplant is used to operation. Another method, known as the bub-
provide a low loss path for wave transmission. bler method, uses a small tank with overflowing
Water, oils, glycerol, greases, and resins are used water. A search unit is placed in this tank, and a
as couplants. Certain soft rubbers have been spe- test piece is moved over it.
cially formulated to provide dry coupling of a
search unit. In immersion inspection, the part
under inspection and the search unit are placed
in a tank of water. Here, a water path exists in
place of a couplant layer. A search unit is usually
fitted with a waterproof connector and attached
to a manipulator. It is usually set manually but
is increasingly used under computer control.
In conventional immersion inspection, the
search unit and the test piece are placed in a
water-filled tank. The search unit is connected
via a manipulator and an extension tube to an
electromechanical scanning device (or a probe
manipulator bridge). The basic scanning de-
vice provides X – Y movements of prearranged Figure 15. A-scan display for pulse-echo technique
scanning patterns. Advanced units add computer a) Front reflection; b) Flaw echo; c) Back reflection
control that adapts to the shape of a test piece.
Turntables and roller drives allow efficient scan-
ning of round disks and cylindrical test pieces. A 2.3.4. Display Methods
rotating reflector inside a tube can be used to re-
Results of ultrasonic testing are commonly pre-
flect the ultrasonic beam of an immersion search
sented in A-scan, B-scan, and C-scan and, more
unit toward the tube wall, allowing the inspec-
recently, with reconstructed images. The A-scan
tion of thickness changes or flaws by means of
presentation is a plot of amplitude versus time,
normal or shear beams (Fig. 14) [24]. Scanning
as shown in Figure 15. Front reflection, back re-
is synchronized with ultrasonic data acquisition,
flection, and a flaw echo are indicated on the time
and flaw indications are displayed at correspond-
axis, which corresponds to depth. The height of
ing locations. An X – Y recorder has been used
the flaw echo is related to the size of the flaw. In
the absence of a flaw, an A-scan over a longer

period also shows the ultrasonic attenuation of
the test piece. Multiple back reflections, whose
heights decrease exponentially, are detected.
The B-scan presentation is used to display
the depth and length of a flaw. The transducer
is moved along the front surface, as shown in
Figure 16. When a flaw echo exceeds a prede-
termined threshold, an indication is recorded on
the display along with indications of the front-
and back-surface signals. Convenient visual ob-
servation is possible with manual scanning and
a storage oscilloscope. Mechanized scanning al-
lows more accurate determination of the position
of a flaw.
Figure 17. A) Pulse-echo technique; B) C-scan display
In specialized inspection systems, A-scan

records are accumulated along with location data
during a more complex mechanical scanning
of various shapes. For tubular products, helical
scanning is used, either internally or externally.
For pressure vessels, remote-controlled crawlers
are used. Industrial robots are used on contoured
Figure 16. A) Pulse-echo technique; B) B-scan display
surfaces. Three-dimensional images of flawed
The C-scan presentation is most useful in regions can be reconstructed from these data,
identifying defective areas in a plane view of and different perspectives of flaw images can
a test piece. The transducer is moved back and be obtained. A reconstructed view of flaws in
forth over the front surface (Fig. 17). When a a weld is shown in Figure 18. In both recon-
flaw echo above a threshold is present, it is structed imaging and C-scan displays, the use of
recorded on an X – Y recorder, which is also color enhances visual perception.
scanned synchronously. The use of several elec-
tronic timing gates, each sensing the flaw echo
over a specified time interval, enables scanning 2.3.5. Interpretation
for flaws at predetermined depth ranges. Newer
inspection systems are usually equipped with Echo intensity in an A-scan display depends on
a computer that controls scanning, ultrasonic the size, shape, and distance of the flaw. For disks
data acquisition (in digitized form), and dis- of various sizes in water, the intensity of the echo
play. These allow data storage, display of C-scan varies as shown in Figure 19 [22]. The reduction
records at different depths, and a variety of imin echo intensity results from attenuation and
age processing. For example, flaws at different spreading of the beam. Compensation for this
depths can be displayed in different colors. reduction is provided by a distance – amplitude
Next Page
correction (DAC) circuit in most ultrasonic in- may not produce a flaw echo if the reflected
struments. By comparing the echo intensities of beam is directed away from the search unit. In
flaws with those of flat-bottom holes in reference this case, the loss of back reflection indicates the
blocks, flaw sizes can be estimated. Another ap- presence of a flaw. Scattering from slags, inclu-
proach is to use the ratio of echo intensity to sions, and large grain structures also results in
the back-surface reflection as an indicator of an the loss of back reflection.
unacceptable flaw. An echo intensity equal to The large grain structures of anisotropic ma-
50 % of the back reflection is one such rejection terials (e.g., stainless steel or brass) produce
criterion. beam scattering, which is indicated as random
echoes between the front and back reflections.
These are called grass and make the discrimi-
nation of small flaw echoes difficult. Spurious
reflections are also produced by fillets. A choice
of suitable inspection position is important for
complex geometries.
2.3.6. Inspection Standards
Ultrasonic inspection is performed under spec-

ified procedures established by national bod-
ies, such as the ASTM, DIN, and JIS. They
require the use of standard reference blocks,
Figure 18. Reconstructed image of weld flaws which may be of different sizes prepared
LIVE GRAPH
from different alloys, containing holes, slots,
Click here to view or notches. Two types of standard blocks are
widely used. One type is the area – amplitude
or distance – amplitude block, including ASTM
E 127 blocks. Each of the ASTM blocks is
51 mm in diameter and has a 19-mm-deep flat-
bottom hole. The size of the holes varies from
0.40 to 6.4 mm in diameter, and the distance
from the surface to the bottom of the hole varies
from 3.2 to 152 mm. By changing the hole size at
a given distance, these blocks can be used to re-
late the amplitude of the flaw signal to the area of
a flaw, and to check the linearity and sensitivity
of a pulse-echo inspection system. For a given
hole size at various depths, distance – amplitude
Figure 19. Distance – echo amplitude – flaw size diagram blocks can evaluate variations of echo amplitude
with distance for straight-beam inspection in a
The shape of the echo depends on the shape, given material. These blocks must be made from
orientation, and sound-reflecting characteristics the same material as the test piece in order to es-
of an interface. Smooth metal – air interfaces that timate flaw sizes at various depths. However, a
are normal to the beam produce sharp echoes. set of blocks can be used as reference blocks for
Curved or rough interfaces (pores, cracks, lami- performance calibration of a test system.
nations) produce broadened echoes. Changing Another reference block is known as the IIW
the beam orientation and the position of the type. It is a nearly rectangular steel plate (25×
search unit often provides clues to flaw shape 100×360 mm) with a curved edge of radius
and orientation. Loss of back reflection is an- 100 mm at one end. The block has a notch, a slot,
other factor in flaw size estimation. This is due and large and small holes (50 and 1.5 mm diam-
to the reflection of a sound beam by a flaw, which eter), which are used together with the curved
Previous Page
edge to determine the sensitivity, propagation ultrasonic testing. One type enhances the sen-
angle and beam spread of angle-beam search sitivity by using the resonance of a transducer
units. The IIW block can also be used for simple element, which is usually a piezoelectric disk.
sensitivity evaluation of straight-beam units. A These are resonant or narrow-band sensors and
miniature version based on the same concept is are most commonly employed in acoustic emis-
also used. sion testing. The second type has a broadened
frequency response and uses a backing material
behind a transducer element; its construction is
2.4. Acoustic Emission essentially identical to that of ultrasonic sensors.
For specialized high-fidelity capture of signal
Acoustic emission (AE) refers to transient elas- waveforms, a conical piezoelectric element with
tic waves generated from localized sources matched backing and a capacitive sensor can be
within a material or structure. Such transient used.
waves originate at, for example, cracks, de- Acoustic emission activity is measured by
fective welds, and yielding regions in metals the rate of burst-type emissions (AE event
and at delaminations, fibers, and matrix frac- count rates) and by the averaged signal inten-
tures in composite materials. Sensitive ultra- sity of continuous-type emissions (e.g., root-
sonic sensors detect acoustic emission signals, mean-square voltages of amplified signals). The
from which the location and activity level of cumulative number or rate of oscillations that
the source can be evaluated. Acoustic emission cross a predetermined threshold value (called
requires the application of a stimulus to a test AE counts or AE count rates), some measures
piece. In pressure vessels and piping, hydrostatic of signal energy, the duration of burst-type sig-
pressurization is usually employed to activate nals, and the distribution of peak amplitudes are
acoustic emission sources. Acoustic emission also employed.
has become the inspection method of choice for
fiberglass-reinforced composite vessels and pip-
ing and, more recently, for metallic vessels, in- 2.4.2. Material Behavior
cluding industrial gas transport trailers and rail-
road tank cars; see [7, vol. 5], [25], [26]. Plastic deformation of most structural alloys
emits acoustic emission that reaches a maxi-
mum near the yield stress and diminishes with
2.4.1. Detection work hardening. The composition, microstruc-
ture, and heat treatment of alloys affect acous-
In acoustic emission testing, signals in the ul- tic emission behavior. Cold-worked metals pro-
trasonic frequency range of 30 kHz to 2 MHz duce hardly any acoustic emission because AE
are usually detected. Airborne noise interferes phenomena are irreversible; therefore, acoustic
with AE measurements at lower frequencies, emission is absent until previously applied stress
and signal attenuation makes the higher fre- levels are exceeded. Some alloys (e.g., austenitic
quency range difficult to use. In composite test- stainless steels and 2219 aluminum alloy) have
ing, the 30 – 150-kHz range is common, and the inherently low acoustic emission activity during
100-kHz to 1-MHz range is used for metals. plastic deformation. Stressing of various types of
Both burst-type (pulselike) and continuous-type composite materials produces very high levels of
(random noise) signals are generated. Burst- acoustic emission. Matrix cracking is dominant
type emissions arise from distinct events in- at low stress. Glass-fiber fracture and delamina-
volving the release of elastic energy, such as tion generate intense signals at higher stress.
crack advances, fiber fracture, and delamina- Subcritical crack growth emits acoustic emis-
tion. Continuous-type emissions are produced sion at increasing rates as the crack nears crit-
by many overlapping events and are observed icality. Some ductile cracks and fatigue crack
from plastic deformation of metals. growth have lower acoustic emission activity.
Sensors used for acoustic emission detection Such cracks can still be located by detecting
are 40 – 60 dB more sensitive than those used for secondary AE sources, such as crack face in-
terference and crushing of corrosion and oxida-
tion products. Decohesion and fracture of non- 2.4.3. Source Location

metallic inclusions are also prominent sources
of acoustic emission. Acoustic emission monitoring utilizes the struc-
ture under test to discover flaws. Acoustic
emission signals emitted from the flaws travel
through the structure to sensors mounted on its
surface. When the structure is hot, a waveg-
uide is used to mount a sensor. The flaws are
located by analyzing the signals received. Two
general approaches are employed in flaw loca-
tion. The zone location method uses multiple
sensors. The flaw is presumed to exist within
the zone that belongs to the sensor receiving the
strongest AE signals. This method is suitable
for locating leaks that produce continuous emis-
sions and flaws in highly attenuating media, such
as fiber-reinforced plastics, but is also used in
testing metal vessels. Typical results are shown
in Figure 20 [27]. The discrete source location
method also employs multiple sensors, but uses
triangulation techniques based on the exact dif-
ferences in time between the arrival of a given
event at different sensors. It provides more accu-
rate positions of acoustic emission sources. This
approach requires an AE signal to reach at least
two (linear location) or three (planar location)
sensors. Attenuation of the signals must be low
to avoid the use of an excessive number of sen-
sors and signal processing channels. Most metal
vessels and piping can be inspected by this ap-
proach. An example is shown in Figure 21 [28].
Figure 20. Zone location results from pressurization test of 2.4.4. Acoustic Emission Monitoring
a hydrocracker reactor
Sensor 20 indicates a significant flaw requiring immediate Acoustic emission testing of metallic pres-
inspection; sensors 17 – 19 and 21 – 24 show flaws that re- sure vessels is conducted by using one of the
quire follow-up evaluation
source location methods. The vessels are pres-
surized according to applicable code specifica-
tions. Sources of emissions are usually crack
Other important acoustic emission sources growth, yielding, delamination, corrosion ef-
include corrosion (gas evolution), stress cor- fects (corrosion product cracking or spalling, lo-
rosion (cracking), martensitic transformation, cal yielding of thinned sections), stress corrosion
solidification (hot cracking), oxidation (oxide cracking, and embrittlement. Most weld defects
cracking and spalling), gas and fluid leakage, also exhibit acoustic emission when stressed.
and welding processes (metal and slag crack- When metals are ductile, AE activity is low and
ing, transformation, and contamination). Mag- AE test results should be evaluated carefully.
netization of steels produces magnetoacoustic Once the metals have been embrittled by the
emission, which can be used to evaluate heat environment or by low temperature, even early
treatment and residual stress. stages of stressing activate AE sources. In fact,
acoustic emission is the best method for detect-
ing hydrogen-induced cracking and stress cor-
rosion cracking. The flaws located are usually
confirmed by other nondestructive test methods.

In small, thick-walled metallic vessels, the use
of acoustic emission examination alone has been
approved in lieu of ultrasonics or radiography [8,
Sect. VIII]. Highway gas-trailer tube testing can
be performed with acoustic emission instead of
the formerly used hydrostatic recertification pro-
cess. Many chemical and petrochemical vessels,
including tank cars and tank trailers, are moni-
tored by acoustic emission during and between
service without being emptied, thus minimizing
the length of plant shutdown [39].
Composite vessels and piping are monitored
with acoustic emission. This is one of the most
successful AE applications (see Section 3.2).
Figure 22. Steps of penetrant testing

A) Penetrant application; B) Surface Cleaning; C) Applica-
tion of Developer; D) Inspection
Figure 21. Discrete source location from pipe subjected to Emulsifiers are used only for postemulsifiable penetrants.
sour gas solution
X marks the sensor position; dots indicate located acoustic Penetrant testing consists of (1) surface
emissions sources on an X – Y plot preparation, (2) penetration, (3) penetrant re-
moval, (4) development, and (5) inspection; see
Figure 22. Initial cleaning of the surface re-
2.5. Penetrant Methods moves oil, grease, dirt, surface coatings, rust,
scale, and other foreign objects that give rise to
Inspection with liquid penetrants relies on the false indications or interfere with wetting by a
capillary action of a surface-wetting fluid and penetrant. Chemical etching may be required to
provides a reliable method for locating minute eliminate a cold-worked layer. A film of liquid
surface flaws down to micron sizes. Surface penetrant is applied to cover the surface to be
cracks, laps, porosity, shrinkage areas, lamina- inspected. The film remains on the surface for a
tions, and other discontinuities can be detected penetration (dwell) period specified for the pen-
as long as they are open to the surface. The shape, etrant used. Excess penetrant remaining on the
size, and composition of the test piece have no surface is then removed, leaving penetrant that
effect, but materials with rough or porous sur- has seeped into discontinuities. For postemul-
faces cannot be inspected; see [1], [2], [7, vol. sifiable penetrants, application of emulsifier is
2]. required before removal. A developing agent is
applied to cover the surface in a thin coating. The Inspection of high-strength steels and
developer draws penetrant out of the disconti- titanium- or nickel-based alloys with penetrants
nuities and broadens the apparent width of the requires special attention to the sulfur and chlo-
visible indications. The test piece is then viewed rine content of all materials used. These ele-
under suitable lighting, either in white light for ments should be kept below 1 %. Some pene-
visible-dye penetrants or ultraviolet (black) light trants are shock sensitive in the presence of liq-
with darkened background for fluorescent pen- uid oxygen. Special penetrants must be used if
etrants. the surface will come in contact with liquid oxy-
Fluorescent and visible-dye penetrants are gen. Another limitation of penetrant systems is
made with water-washable, postemulsifiable, that most penetrants cannot be used much above
or solvent-removable fluids. Different levels of ambient temperature because they may be baked
flaw detection sensitivity are available with any onto the surface and lose efficiency. A crayon
combination, but visible-dye penetrant systems penetrant system has been developed for high-
are less sensitive than fluorescent ones. Water- temperature use up to 270 ◦ C.
washable penetrants contain emulsifiers and can
be removed by water. This requires careful wash-
ing so that penetrants in flaws are not removed. 2.6. Magnetics and Electromagnetics
Postemulsifiable penetrants require application
of emulsifier following a penetrant dwell period. 2.6.1. Magnetic Particle Inspection
Excess penetrants become washable with wa-
ter and are rinsed off. Penetrant in the flaws Magnetic particles become attached to the sur-
remains water insoluble, providing excellent face and to some subsurface discontinuities
retention capability. Although postemulsifiable when a ferromagnetic test piece is magnetized.
penetrants are more expensive, they provide The particles (e.g., iron or soft ferrite), which
greater sensitivity and can reveal hairline cracks have high permeability and low coersive force,
and shallow discontinuities. Solvent-removable are coated with colored or fluorescent pigments
penetrants are used for limited, special applica- for increased visibility. They are applied as dry
tions because the use of solvent is labor inten- particles or as suspensions in water or oil. Mag-
sive and in some locations requires an extensive netic leakage fields of a discontinuity collect
pollution abatement system. Minimum facili- the particles, indicating its location, size, and
ties are needed especially for solvent-removable, shape by color contrast or fluorescence. Non-
visible-dye penetrants, which are convenient for magnetic materials cannot be tested with this
use in remote locations. method. Such materials include austenitic stain-
Reference photographs of typical flaw indi- less steels and many heat-resistant nickel alloys;
cations are available to establish inspection cri- see [1], [2], [7, vol. 6], [9, E 709].
teria [9, E 433]. The smallest flaws that can be In the continuous method, magnetization is
detected by penetrant inspection with a laser and applied continuously while the magnetic parti-
a photodetector are cracks of ca. 1-µm width. cles are administered. Because the high current
Reliable visual inspection of 25-µm cracks can used causes heating, it is used for only a short
be made. Most inspection has been done by time during which the magnetic particles must
the human eye, but automated scanning equip- be applied. In the residual method, a pulse mag-
ment has increased inspection speed substan- netization is applied, after which magnetic par-
tially for quantity inspection of identical or sim- ticles are brought in contact with the test piece.
ilarly shaped parts [29]. The residual method can be used when the test
The quality of penetrant inspection systems piece has adequate remanence to retain a leak-
can be monitored by the use of cracked-block age field for attracting magnetic particles. Most
comparators or suitable materials with known structural steels fall into this category, but low-
flaws. A number of comparators have been de- carbon steels and soft magnetic materials require
veloped, including cracked chrome-plate panels, the use of the continuous method.
fractured glass panels, unglazed ceramic disks, Magnetic leakage fields are formed when a
and nickel – copper laminates. Quenched alu- discontinuity lies normal to the applied magnetic
minum plates are the best known example.
field. The direction of magnetization must be se- a current can be passed parallel to the crack
lected to reveal expected flaws. Several methods (Fig. 24 B). For short hollow cylinders, electrical
of magnetization are used: (1) the flow of direct current may be passed through a central conduc-
or alternating current through a test piece, and tor.
(2) the placement of a test piece within the mag-
netic field of a magnetizing coil or yoke. Because
of the eddy-current effect (see Section 2.6.4),
an a.c.-induced magnetic field concentrates near
the outer surface and is used for surface flaw de-
tection.
Figure 24. Circular magnetization methods

A) Current passing through a sample (head-shot); B) Cur-
rent passing locally through two plods
The levels of magnetization of ferrous mate-

Figure 23. Longitudinal magnetization methods rials must be of the order of 1 T (10 000 gauss).
A) Encircling coil; B) Between magnetic pole pieces; C) Typical ferromagnetic materials have a relative
Magnetic yoke
permeability of more than 240. For direct, cir-
To detect a transverse or circumferential flaw cular magnetization, the required magnetization
(e.g., a weld crack in a butt-welded pipe joint) a can be achieved by 200 – 350 A per linear cen-
longitudinal magnetic field is necessary. To pro- timeter in diameter. For longitudinal magneti-
duce the required field, a magnetizing coil can zation of a short test piece having a length-to-
be wound over the pipe (Fig. 23 A), the pipe can diameter ratio (L/D) of 2 – 15, the number of
be placed between two pole pieces of a magnet required ampere-turns is 45 000/(L/D).
(Fig. 23 B), or the two poles of a magnetizing Interpretation of magnetic particle indica-
yoke (a C-shaped electromagnet with flexible tions requires the ability to reject irrelevant in-
poles) can be placed across the flaw (Fig. 23 C). dications. Reference photographs of indications
The test piece can also be placed inside a sta- on steel castings have been compiled and can be
tionary magnetizing coil. To reveal a longitudi- used to establish acceptance and rejection crite-
nal flaw (e.g., an axial crack in a welded pipe) ria.
the magnetic field must exist circumferentially. Variations of magnetic particle testing have
This can be induced by diametrically applying been developed. The magnetic rubber method
a magnetizing yoke. Alternatively, a high cur- polymerizes in situ a liquid rubber containing
rent can be passed axially parallel to the flaw to magnetic particles. During curing, the particles
produce a circular magnetic field (Fig. 24 A). By concentrate in the region of a leakage field. This
using two plod contacts placed along the weld, allows the inspection of recessed areas (e.g., bolt
holes) and makes a permanent record. Magnetic magnetic field is removed). The latter require
printing and painting are also useful. These em- high-sensitivity probes such as flux-gate mag-
ploy magnetic tape and paint for recording and netometers. Magnetic leakage field methods are
indication. used extensively in the inspection of tubular
shapes. Excitation fields and sensing probes can
be placed on the outside or inside to search for
2.6.2. Magnetic Leakage Field Inspection axial and transverse flaws. For internal inspec-
tion, a drive section, a magnetizing and sensing
Magnetic leakage fields from a surface of sub- section, and a recording or data output section
surface flaw can be detected and measured by are combined into a form of inspection “pig,”
Hall-effect probes, magnetic diodes, moving which is universally jointed to permit movement
coils, and magnetometers. Leakage fields can through bent tubes. For smaller diameter tubes
in principle provide quantitative information on (< 5-cm inside diameter), permanent magnets
the flaw. The leakage fields have tangential and can be employed for magnetization. Flaws such
perpendicular components, and their distribu- as pitting, holes, splits, hydrogen damage, and
tion for simple flaw shapes has been calcu- cracks in heat exchangers, pipelines, and chem-
lated. Added to the leakage fields are large, but ical plant tubing can be inspected by using this
slowly varying bias magnetic fields. Most mate- method.
rials, however, have nonlinear magnetic proper-
ties that vary with processing conditions. Thus,
estimation of flaw size and shape is difficult ex- 2.6.3. Other Magnetic Inspection Methods
cept by methods that use reference flaws for
comparison; see [7, vol. 4], [30]. The magnetic properties of a ferromagnetic ma-
Hall-effect probes are made with submillime- terial, such as initial permeability, saturation in-
ter dimensions and have high sensitivity. Some duction, coersive force, and remanence, are af-
have a built-in amplifier and a sensing element fected by its metallurgical history. Of these, per-
as small as 100×25 µm. The probe size must not meability and coersive force are most often used
be much larger than the dimensions of the leak- for material characterization (i.e., hardness, heat
age field. Two probes are often used to cancel treatment, alloy content, and grain structure).
the effect of bias fields. Magnetic diodes work Applications include sorting of steel, ferrite con-
similarly to Hall-effect probes. A moving coil tent determination in stainless steel welds and
probe senses the rate of change of magnetic flux castings, and detection of ferromagnetic impu-
lines through the coil. The coil is moved uni- rities [31].
formly over the surface of the sample. It must The magnetic Barkhausen effect and magne-
be small to achieve as high a sensitivity as Hall- toacoustic emission originate from the motion
effect probes. of magnetic domain boundaries [32]. These are
A flux-gate magnetometer or a Förster probe also suited for material characterization and de-
utilizes the nonlinear magnetic hysteresis of a tection of residual stresses.
ferrite core, on which two coils are wound [3,
pp. 328 – 332]. The primary coil of the probe 2.6.4. Eddy-Current Inspection
is excited at a carrier frequency, and the sec-
ond harmonics in the secondary coil are de- A changing electromagnetic field induces eddy
tected. The output is sensitive to the magnetic currents in an electrical conductor. The eddy cur-
field acting on the ferrite core and has a sen- rents create a secondary electromagnetic field,
sitivity hundreds of times greater than that of which is detected through its effects on the pri-
Hall-effect probes. Nuclear magnetic resonance mary exciting coil or by means of a separate
magnetometers are also very sensitive. Because sensor. In nonmagnetic materials or ferromag-
they use microwave frequencies, these are con- netic materials that are magnetized to more than
fined to specialized studies. 98 % saturation, the electrical conductivity of the
Applications of magnetic leakage fields use materials is the primary property controlling the
either continuous field excitation or residual secondary field. In unsaturated magnetic mate-
leakage fields (fields existing after the applied rials, magnetic permeability has a larger effect
on the secondary field. Moreover, the permeabil- into an encircling coil, the coil impedance Z c
ity of a material is sensitive to a variety of ma- varies from A (no rod) to B (a fill factor or ra-
terial properties, including heat treatment, cold tio of rod area to coil area of 0.49), C (0.64),
working, composition, and magnetization level. and D (0.81) through E (1.0). Both the mag-
Eddy-current testing of ferromagnetic materials nitude Z c and the phase angle (tan−1 2 π f L/R)
has been hampered by this variation in perme- vary with changing rod diameter Dr along the
ability and by the difficulty of applying fields dashed lines. The value given for the curve of
high enough to achieve saturation. This method the unit fill factor is the ratio of the frequency f
can measure a combination of electrical conduc- to the characteristic frequency f c and is equal to
tivity and magnetic permeability, as well as any
parameter or discontinuity that affects these two f /fc =f µr σe Dr2 /5066
properties. Consequently, the detection of heat
treatment and hardness changes and the sorting where σ e is given in µΩ−1 cm−1 and Dr in mm.
of dissimilar alloys can be performed. The de- Thus, when σ e varies, Z c changes along the solid
tection of corrosion and flaws in tubular prod- curve. These variations in Z c can be measured
ucts has been an important application of this by detecting the voltage and current in the coil.
method; see [7, vol. 4], [28]. This example gives the basis for an absolute
Eddy-current testing can be carried out with- (single) coil inspection method for variations in
out direct contact, and signal processing is en- rod diameter. The same method can be used to
tirely electronic. Thus, an automated inspection inspect variations in alloy composition or heat
system can achieve high inspection rates. treatment for constant-diameter rods and longi-
Because of the eddy current, externally ap- tudinal flaws in such rods. These flaws lower
plied electromagnetic fields are attenuated in the effective conductivity of the rod in the direc-
a conductor. At the skin depth Ds , the field tion of the eddy currents. A basically identical
strength decreases to 1/e, where method can inspect the diameter and thickness
of tubing by means of an encircling coil.
-
Ds = 1/ πf µm σe For practical instruments, two coils are used
in a bridge circuit to detect small differences. A
where f is the frequency, µm the magnetic per- reference rod is placed in one coil, and the other
meability, and σ e the electrical conductivity. coil is used to inspect a rod or tubing. Another
In terms of the electrical resistivity (e = 1/σ e ) approach is to use one coil for excitation and
in µΩ · cm, and the relative permeability µr the other for sensing. These coils are usually in-
(which is unity for nonmagnetic materials, and ductively coupled, but they are separated for the
200 – 800 in structural steels), Ds (in mm) can remote field eddy-current techniques. Differen-
be expressed as tial sensing methods can also be used for the
- coupled-coil approach [33].
Ds = 50 e /f µr Inspection frequencies of 200 Hz to 6 MHz
Typical values of Ds are given in Figure 25 as a are used in eddy-current testing. Lower frequen-
function of frequency. cies have greater penetration depth, but the sensi-
The basic element of an eddy-current instru- tivity to flaws and speed of inspection decrease.
ment is an inductor or a coil. When its inductance For surface flaw inspection of nonferrous alloys,
is L 0 and its resistance is R, the coil impedance frequencies in the megahertz range can be used.
Z c is given by Ferromagnetic materials require lower frequen-
cies because of the poor penetration (high µr ).
2
A single coil or a set of coils can be used as
Zc = (2πf L0 )2 +R2
a probe to be placed over the flat surface of a
Z c is affected by a conductor in proximity, and conductor. This arrangement is used to measure
such changes are usually plotted in a normalized conductivity by first calibrating the instrument
impedance plane representation (Fig. 26). The with electrical conductivity standards of known
abscissa is the resistive component (R/2 π f L 0 ), values. The frequency is chosen so that the thick-
and the ordinate is the inductive component ness of test pieces and standards is at least 2.6
(2 π f L/2 π f L 0 ). When a solid rod is inserted times the skin depth. For conductivity measure-
LIVE GRAPH
Click here to view
Figure 25. Skin depth versus frequency for various metallic materials
a) Hastelloy; b) Inconel; c) 300 stainless steels; d) 400 stainless steels, titanium; e) Zirconium, Monel; f) Nickel – silver (20 Ni);
g) Lead; h) Brass (30 Zn); i) Aluminum alloys; j) Copper (pure); k) Carbon steel; l) Alloy steel; m) Iron (pure)
ments, the coil-to-metal distance (lift-off) is kept tubular products, only the weld is typically ex-
constant or compensated. amined.
Changes in lift-off can be measured while A coil can be placed inside a tube (Fig. 27 C).
the conductivity effect is kept negligible by con- The internal coil can be concentric, the same
trolling the frequency. This allows measurement type as an encircling coil, for exciting and sens-
of thickness for nonconductive coatings on con- ing circumferential eddy currents. Two concen-
ductive materials. The thickness of sheet materi- tric coils can be used as an exciter and a sensor,
als can be measured by adjusting the frequency each of which may be placed inside or outside.
so that it is of the same order as the skin depth When one is outside and the other inside, this
Ds . is a transmission technique and the sensor is af-
The encircling coil technique passes a tube fected only by those electromagnetic fields that
lengthwise through a coil energized at one have passed through the wall. The two coils can
or more frequencies (Fig. 27 A). The electrical also be located inside or outside. This reflection
impedance of the coil is modified by the prox- technique is suited for detecting primarily inner
imity of the tube, the tube dimensions, electri- or outer surface flaws.
cal conductivity, saturating magnetic field, mag- A smaller probe can be used to scan helically
netic permeability, and metallurgical or mechan- the inner or outer surface of a tube. These rotat-
ical discontinuities in the tube. Encircling coils ing probe techniques are suitable for detecting
are used for small-diameter tubing (< 8 cm) be- corrosion and cracks in tubing (Fig. 27 D).
cause the sensitivity to flaws deteriorates for Reference standards for flaws are required to
larger diameter tubes. set eddy-current test conditions. Samples with
A probe with one or more sensors in close actual flaws and those with drilled holes and
proximity to a test piece is used in the probe tech- machined notches of known size are employed.
nique (Fig. 27 B). The probe is generally small Notches are milled, filed, or electrodischarge
and examines only a limited area. For welded machined on the outer or inner surface.
For magnetic materials, a saturation magnetic to detect chemical changes, voids, and discon-
field is applied to reduce the permeability and tinuities in ceramics, polymers, and fiberglass-
its variation. For tubular products, an encircling reinforced composites; and to gauge thickness.
saturation coil is employed. Permanent magnets For conductive materials, skin depth is very low
and U-shaped electromagnets are used in other and most of the incident wave is reflected. Only
instances. reflection techniques can be used for metals.
For nonconductive materials, transmission, re-
LIVE GRAPH flection, and standing-wave techniques are used.
Click here to view
The techniques can employ different modes of
microwave generation. Frequency may be fixed,
swept, or pulse modulated. Continuous waves or
pulsed waves are generated [7, vol. 4].
Figure 26. Normalized coil impedance plot of inductive

versus resistive components for variations in frequency or
conductivity (solid lines for fill factors of 1, 0.81, 0.64, . . .)
and diameter (dashed lines for f/f c = 2, 3, 4, 6, and 10) of a
nonmagnetic solid cylinder
For eddy-current inspection of small surface

Figure 27. Examples of inspection coil arrangement
flaws, various probe designs have been devel- A) Encircling coil; B) Probe coil (with or without core); C)
oped. These typically have a ferrite core and Inside coil (with or without core); D) Probe coil (rotating
concentrate electromagnetic fields to a gap in probe or tube)
the core. The gap is placed on the surface of Basic transmission techniques use a mi-
a test piece, which increases the flaw detection crowave generator, two antennas for transmit-
sensitivity. ting and receiving, and a phase-sensitive detec-
tor or peak-amplitude detector. With the phase-
sensitive detector, the in-phase and out-of-phase
2.6.5. Microwave Inspection (quadrature) components can be determined for
a fixed-frequency system. Attenuation and phase
Microwaves are electromagnetic radiation with change may be used to determine the moisture
frequencies of 300 MHz to 300 GHz. For nonde- content, dimensional changes, and property vari-
structive testing, frequencies of 1 – 20 GHz are ation of dielectric materials. The presence of
generally employed. By measuring attenuation local anomalies can also be detected. By us-
and reflection, this method can be used to ana- ing a pulse-modulated transmission and a peak-
lyze the moisture content of dielectric materials; amplitude detector, the velocity of propagation
can be measured. This is useful in evaluating with some methods. Massive changes in thermal
polymerization, esterification, distillation, vul- conductivity from thermal fatigue cracking, de-
canization, and evaporation in polymers. lamination, and stress corrosion cracking may
Reflection techniques use one antenna. When be detected by using coatings of liquid crystals
a metal backing exists or a reflector is placed be- and heat-sensitive substances and applying cer-
hind a dielectric sample, property measurements tain heat flow patterns [1], [2].
similar to those made with transmission tech- Noncontact thermography utilizes IR radia-
niques can be achieved. Instruments for dielec- tion emitted by the surfaces of a test piece. The
tric property determination are referred to as mi- principle used is similar to radiation pyrome-
crowave dielectrometers. Both fixed-frequency try, but modern thermographic cameras can ob-
and swept-frequency (also known as frequency- tain false-color images of the surface, with each
modulated, FM) reflection techniques are also color representing a narrow range of temper-
used to detect delaminations (if a detectable air ature having intervals as small as 0.1 ◦ C. In-
gap exists), inclusions, voids, and other three- frared optics are also available to image mi-
dimensional anomalies in dielectric materials. croscopic areas. Thermographic cameras can be
Since microwaves are reflected at an inter- employed to evaluate the temperature distribu-
face, standing waves are produced when paral- tion of a component in service. When an abnor-
lel interfaces or reflectors exist; for example, the mal condition exists, such an examination can
front and back faces of a plastic plate. The pat- reveal it. Transient heat flow can also disclose
terns of standing waves are used for distance an anomaly in thermal conductivity that may re-
measurements and thickness gauging. sult from delamination and unbonding. Temper-
Moisture measurements are perhaps the most ature changes on the surface can be induced by
widely used application of microwaves. Water an external heat source. Higher temperatures are
has a high dielectric loss compared to most other observed where the section thickness has been
dielectric materials, and its content can be deter- reduced by corrosion. This method is applicable
mined by sensing dielectric constants with trans- to inspection of piping.
mission or reflection techniques. Transmission Another method of inducing a temperature
techniques may be employed at high water lev- differential is to apply mechanical vibration.
els (50 – 85 %). Reflection measurements with a This is known as vibrothermography [40] and
resonant cavity can achieve high sensitivity over can be applied to flaw detection in composite
a narrower range of moisture content. materials subjected to fatigue loading.
Another use of microwaves occurs in eddy- A scanning high-power laser can be com-
current inspection. In contrast to the usual fre- bined with an IR detector. The unbonding of a
quencies up to 10 MHz, a ceramic crystal res- coated layer can be revealed because the temper-
onator is used in a sensor, extending the fre- ature of the coating at the irradiated unbonded
quency to several gigahertz. Resolution of sur- spot rises more than that at well-bonded regions.
face flaws is greatly improved. Photoacoustic spectrometry employs modulated
laser beams, irradiating mainly particulate mat-
ter. Thermal excitation leads to detectable emis-
2.7. Thermal and Optical Methods sion of acoustic waves. This method has been
used in evaluating ceramic powders and chemi-
2.7.1. Thermal Inspection cals.
Heat flow and temperature changes are de-

tected to locate flaws and abnormal heat distri- 2.7.2. Visual and Optical Inspection
bution. Temperature can be measured by many
types of substances and devices such as heat- Evaluating the surface of a structure with the
sensitive paints, papers, and phosphors; liq- human eye is generally the first step in any
uid crystals; thermocouples; thermistors; and nondestructive inspection [42]. Visual inspec-
bolometers. These have been used in limited ap- tion is facilitated by using a magnifier, a
plications because direct contact is required and borescope, a fiberscope, or a videoscope. Video
only point-by-point measurements are possible technology has also become an integral part
of this method for examination and record- of the test piece can be observed and measured.
ing of images. Borescopes and fiberscopes are With no part of the optical system or test piece
used for remote viewing. Borescopes are low- position changed, the test piece is irradiated with
magnification devices with a rigid tube support the same reference beam and an inspector views
for optical lenses. Their length may be extensi- it through the hologram. Interference patterns
ble. Fiberscopes are made with a bundle of flexi- are seen with optical fringes surrounding anoma-
ble optical fibers and provide magnification up to lies where the test piece has moved short dis-
200×. These are available in diameters as small tances. In a double-exposure technique, the sur-
as 0.35 mm and are often combined with a video face of the test piece is slightly distorted between
camera. Videoscopes employ a small image sen- exposures, which are recorded on a single holo-
sor, which is typically a charge-coupled device graphic film, thereby producing a holographic
consisting of many light-sensitive elements. The fringe pattern. Another method utilizes the in-
image is sent electronically to a video moni- terfering holographic image effects of vibrating
tor. Videoscopes provide higher resolution and test surfaces.
greater depth of field than fiberscopes. Images
from fiberscopes and videoscopes are displayed
on a monitor screen and recorded on a video
recorder.
Long-distance microscopes have a large
working distance, up to a few hundred times
that of conventional microscopes. This allows
the examination of small objects 1 – 2 m away
with 5-µm resolution.
By using a laser as the light source and
scanning rapidly over a surface, transmitted, re-
flected or scattered light can be used to charac-
terize the surface by imaging the flaws and dis-
continuities and by measuring the surface rough-
ness. Diffraction of light scattered from certain
kinds of surfaces (e.g., weave patterns) can be
used to detect unacceptable surface patterns.
Optical interferometry is used to obtain Figure 28. Basic holography setup
surface profiles via interference fringes [44]. A) Recording hologram; B) Reconstructing image
Noncontact displacement measurements can a) Laser; b) Laser beam; c) Beam splitter; d) Reference
beam; e) Mirrors; f) Spatial filters; g) Photographic plate;
be made with a resolution of 10 nm. Two- h) Test piece; i) Virtual image of test piece
dimensional surface profiles are also obtained
by laser speckle reflectometry [43], which is em- These methods are used to inspect brazed or
ployed mainly for measurement of roughness. adhesively bonded honeycomb-sandwich struc-
tures, coatings, and tires for lack of bonding, de-
lamination, and other flaws. They are also use-
2.7.3. Optical Holography [41] ful in vibration analysis of rotating and vibrating
components.
Optical holography utilizes coherent monochro-
matic light from a laser. First, both the amplitude
and the phase of coherent light from a test piece 2.8. Leak Testing
are recorded on a film or plate along with the
reference beam (Fig. 28 A). Three-dimensional Leak testing detects the leakage of a liquid or
images are formed from the holographic film or gas from an internally pressurized vessel or the
plate when it is irradiated with the same type of leakage of a gas into a vacuum vessel. The lo-
light (Fig. 28 B). The regenerated image can then cation of a leak, the amount of leakage, or both
be used as a three-dimensional template against can be determined. A number of methods have
which any deviations in the shape or dimensions
been developed with different sensitivities and gases. The human nose detects very low lev-
detection principles [1], [2], [7, vol. 1]. els of odorous gases but quickly becomes in-
sensitive. A halogen-sensitive detector uses a
diode that ionizes halogen atoms and detects
2.8.1. Pressurized Gas Leaks the ionic current. Air is drawn into the diode
through a sniffing probe. If a vessel does not
Two approaches are used to detect leaks in pres- contain halogens, a tracer gas containing halo-
surized gas systems. The amount of gas lost is gen compounds can be mixed with the gas in
determined by the measurement of weight or the vessel for leak detection. Combustible gas
pressure. Both methods are insensitive, and leak and sulfur hexafluoride gas detectors are simi-
location is not possible. If two vessels are avail- lar to the halogen detector. Common uses of the
able, a differential pressure gauge can be used to halogen and combustible gas detectors are for
increase the sensitivity of the pressure-gauging air-conditioner maintenance and in unventilated,
method. enclosed areas where leaked gases accumulate.
The other approach is to detect the escap- Leaked gas can react chemically with a coat-
ing gas; many techniques are available for this. ing or tape placed on the surface of a vessel to
Acoustic methods rely on sound or ultrasound change its color. Ammonia is generally used for
generated by turbulent flow through a leak. If this method. Another type of gas detector works
the leak is large, audible sounds are emitted. like a thermocouple vacuum gauge and a Pirani
Stethoscopes can be used for smaller leaks. gauge [45]. Gases with a different thermal con-
Still smaller leaks can be detected with ultra- ductivity (e.g., hydrogen) can be sensed relative
sonic probes, which operate for airborne ultra- to air by this method.
sound in the range of 30 – 45 kHz. Airborne ul- Mass spectrometers detect the distribution of
trasound can be detected from as far away as atomic or molecular weights of different com-
30 m and works well for overhead gas pipelines. ponents of a gas. Helium mass spectrometers
Parabolic sound collectors are useful. With low are most commonly used in leak detection. Ei-
background noise, turbulent leaks on the order ther a sniffing probe is used to draw leaked
of 1 mPa · m3 s−1 can be detected. An acoustic gas from a helium-filled vessel (Fig. 29 A) or an
emission sensor (30 – 100 kHz) can be coupled evacuated enclosure may be used to collect the
directly to the leaking vessel. By using multiple leakage from a helium-filled vessel (Fig. 29 B).
AE sensors, a leak can be located. This method When a vessel can be evacuated (even partially),
is effective in leak detection especially in buried it can be placed in an enclosure filled with
gas pipelines. helium (Fig. 29 C). This is the most sensitive
Bubble testing is applied to small vessels that method, and a sensitivity of nPa · m3 s−1 is often
can be immersed in a liquid. Oils and glycerol are achieved.
more sensitive to leaks than water, and reduced
pressure above the liquid is also helpful. Bubble-
forming solutions are applied to the surface of 2.8.2. Pressurized Liquid Leaks
larger or fixed-pressure vessels and piping. Soap
solutions can be used for simple tasks, but spe- Liquid leaks are visually detectable if leak rates
cially formulated solutions have been developed are high. Dye penetrants may be introduced into
for more consistent bubbling. Sensitivity on the a vessel and procedures for penetrant testing ap-
order of 10−2 mPa · m3 s−1 and qualitative esti- plied on the outside of the vessel. As in the de-
mates of leak size are feasible. tection of chemically reactive gases, the vessel
Flow detection is applicable to a vessel if it surface can be coated with pH-sensitive paint,
can be placed in a larger enclosure with an ori- paste or tape, and color changes can be mon-
fice. The flow of leaking gas from the orifice itored. Liquid level loss monitoring is simple
is measured by using a flow meter. Leaks of and is used commonly for underground tanks.
1 µPa · m3 s−1 can be detected. The liquid-containing tank can be pressurized
Specific-gas detectors are used to respond to and sealed, and the pressure drop monitored.
halogens, combustible and odorous gases, gases Acoustic methods are also useful when tur-
that cause chemical reactions, and certain other bulent flow occurs. Acoustic emission tech-
niques are used to detect leaks through valves, the system is enclosed in a container filled with
steam condensate lines, and flat-bottomed tanks. helium.
Metal and plastic pipelines are monitored for In testing high-vacuum systems, virtual leaks
leaks by means of multiple acoustic emission may be a substantial source of leakage. These in-
sensors during hydrostatic testing. volve gradual desorption of gases from surfaces
or components within a vacuum system.
3. Uses
3.1. Metallic Pressure Vessels and Piping
Pressure vessels are constructed in various sizes
and shapes, but invariably these are manufac-
tured and inspected according to the Ameri-
can Society of Mechanical Engineers (ASME)
Boiler and Pressure Vessel Code [8]. Section
V of the ASME code establishes methods of
nondestructive testing and covers visual, radio-
graphic, ultrasonic, acoustic emission, magnetic
particle, penetrant, and eddy-current methods.
The code specifies inspection methods and
acceptance criteria for plates, forgings, and
tubes, before and during fabrication, and for ves-
sels and piping after fabrication. The most likely
locations of flaws are at various weldments (see
Section 3.3).
Acoustic emission testing is used to local-
ize defective areas during initial hydrotesting. It
is also employed for in-service inspection and
continuous monitoring, in which process flu-
ids are used for pressurization. Results indicate
the locations of active AE sources, which are
Figure 29. Helium leak testing graded according to their severity. The severity
a) Helium source; b) Mass spectrometer; c) System un- of the source is classified according to the av-
der test (helium filled); d) System under test (evacu- erage energy of the most energetic emissions,
ated); e) Evacuated enclosure; f) Helium-filled enclosure; energy release rates, number of AE events dur-
g) Probe; h) Vacuum pump
ing a load hold period, number of events dur-
ing a load increase, number of high-amplitude
events, etc. These provide real-time indications
2.8.3. Vacuum System Leaks
of defective areas of the pressure vessel being
tested and allow prevention of catastrophic fail-
Vacuum systems are normally tested in the vac-
ure of the vessel. The defective areas identified
uum condition. Most vacuum-sealing systems
are then inspected by using other test methods.
are not suited for internal pressurization, and
Acoustic emission testing is applied on various
container walls may not withstand pressure re-
types of vessels, including ammonia spheres and
versal. Helium mass spectrometers are generally
tanks, hydroformer reactors, and catalytic crack-
used for leak detection. Vacuum pressure gauges
ing units [8, Section V], [34].
and halogen detectors may also be used. The
Surface examination for cracks, corrosion,
vacuum system is connected to the helium de-
and contamination relies mainly on visual meth-
tector, and a stream of helium gas is directed at
ods, which are used for all welds not internally
a suspect area. To determine the total leak rate,
tested after a hydrotest. Magnetic particle and
penetrant methods are also applied for crack de- this, the maximum operating pressure within the
tection. For surface inspection of vessel interi- previous year must be known. Acoustic emis-
ors, plant shutdown is required. sion instrumentation should have a sufficient
Generally, radiographic and ultrasonic meth- number of channels to localize sources by us-
ods are used for internal flaw detection. Both ing the zone location method; that is, many
X- and gamma-ray sources are used in radiog- AE sensors are installed to completely cover
raphy. Access to the vessel interior is often dif- the vessel with the corresponding zone marked
ficult, which limits the use of radiography. For around each sensor. Acoustic emission activi-
heavy steel sections (> 10 cm), field inspection ties of flaws within each zone are detected, and
becomes difficult because high-energy sources the zone represents the approximate position
are needed. Ultrasonic methods, especially with of these flaws. High-frequency (100 – 200 kHz)
shear waves, are widely used for weld inspec- sensors are used for zone location. Two or more
tion. Thickness measurement using the normal low-frequency (25 – 75 kHz) sensors are used to
beam is commonly practiced for corrosion mon- evaluate the adequacy of coverage of the high-
itoring. Those areas having a high corrosion rate frequency sensors. If a low-frequency sensor
or history of attack are inspected thoroughly. detects acoustic emission whereas none of the
high-frequency sensors do, the latter must be re-
located. Sensors are positioned to detect struc-
3.2. Composite Pressure Vessels and tural flaws at critical sections of the test vessel,
Piping such as high-stress areas, geometrical discon-
tinuities, nozzles, manways, repaired regions,
The performance of fiber-reinforced plastic ves- support rings, and visible flaws.
sels and piping has been poor, and many fail- Pressurization of a vessel during AE testing
ures have been recorded. Apart from acoustic proceeds in steps, with pressure hold periods.
emission, no satisfactory test exists for determin- For atmospheric vessels, the pressure is held at
ing the structural adequacy of fiber-reinforced 50, 75, 87.5, and 100 % of the test pressure.
plastic equipment. Radiography is difficult be- Pressure vessels are stressed with 10 % incre-
cause resins have low absorption coefficients. ments, with depressure increments (also 10 %)
Fiber-reinforced plastics are anisotropic, and ul- above 30 % of the test pressure. A test is termi-
trasonic attenuation is very high, making pulse- nated whenever a rapid increase in AE activity
echo techniques hard to use. In addition, the vari- indicates an impending failure. Acoustic emis-
ous types of life-limiting flaws are quite different sion data from the high-frequency sensors are
and some of them are not amenable to conven- used for evaluation, whereas the low-frequency
tional ultrasonic inspection. Fiber fracture and sensors generally detect acoustic emission from
fiber – matrix debonding are difficult to detect significant flaws. Detected flaws are graded ac-
with ultrasonics. cording to using several criteria, including emis-
The use of acoustic emission for testing fiber- sions during pressure hold periods, felicity ratio
reinforced plastic vessels and piping has been (the ratio of the load at the onset of significant
highly successful, and standard test procedures emissions to the maximum prior pressure), to-
have been established [9, E 1067], [28], [35], tal AE counts, high-amplitude events, and long-
[36]. Test vessels and piping are pressurized up duration events. Emissions during hold indicate
to 150 % of the maximum allowable working continuing permanent damage and lack of struc-
pressure. The procedures are designed to locate tural integrity. For in-service vessels, the felicity
substantial flaws, which are then evaluated by ratio criterion (when it is less than 0.95) is an
other techniques such as ultrasonic testing (de- important measure of previous damage. High-
lamination) or visual (resin loss) and penetrant amplitude events indicate structural (fiber) dam-
(matrix cracking) inspection. A vessel (or pip- age, especially in new vessels. Long-duration
ing) to be tested can be new, in-service, or re- events are characterized by measured area of
paired, and different steps are specified for at- the rectified signal envelope (MARSE), which
mospheric, vacuum, and pressurized vessels. A is an indicator of combined signal and ampli-
vessel that has been in service must be precon- tude duration. Large MARSE values result from
ditioned by reducing the operating pressure; for
delamination, adhesive bond failure, and crack placed on the base metal surface at the edge of
growth. the weld. The sound beam is directed into the
weld by angling the search unit at ca. 15◦ . The
scanning of the search unit is parallel to the weld.
3.3. Weldments Magnetic particle testing and penetrant test-
ing are used mainly for surface-breaking flaws
Nondestructive testing methods used for com- (also for subsurface flaws in magnetic particle
pleted fusion weldments include (1) visual in- testing). These methods are relatively inexpen-
spection, (2) radiography, (3) ultrasonic pulse sive but can reveal even fine cracks with clarity.
echo, (4) magnetic particle and leakage field test- In magnetic particle testing, the magnetic field
ing, (5) liquid penetrant testing, (6) leak testing, is applied in two mutually perpendicular direc-
and (7) acoustic emission testing. tions.
For many noncritical welds, integrity is as- Leak testing of welded vessels uses a tracer
sured mainly by visual inspection to look for gas under pressure or vacuum. Welds are tested
cracks, bead thickness, bead contour, undercut, for leak location or for leak rate. Acoustic emis-
overlap, and spatter. For critical welds, both sion tests for large-scale structures can narrow
faces and root surfaces are examined, especially the areas of inspection by locating sources of
for cracks, undercut, root penetration, and un- acoustic emission. Typically, the structure is
filled craters. These are tested further by radio- stressed by pressurization while AE sensors are
graphy and ultrasonics for internal flaws. mounted in arrays on the surface of the structure.
Radiography is commonly used for detect- When the applied stress exceeds the previously
ing porosity, slag entrapment, and inclusions. applied stress level, acoustic emission activities
A round or oval dark spot represents the im- increase rapidly. The positions of such activi-
age of a pore. Slag inclusions appear along the ties are identified by triangulation or the zone-
weld edge as irregular or continuous dark lines, location method. Often, the source of acoustic
whereas tungsten inclusions give rise to single or emission is localized to specific weld regions
clustered light spots. Cracks are sometimes visi- which are inspected further by ultrasonic and
ble in radiographs as dark narrow irregular lines, radiographic methods.
but the lack of any radiographic image of cracks
does not assure their absence. Radiography may
be unable to detect incomplete fusion and in- 3.4. Other Uses
complete penetration because of their small ef-
fects on X-ray absorption. They appear as very Polymeric materials are adversely affected by
narrow dark lines. improper curing, inclusions, porosity, environ-
Ultrasonic pulse-echo techniques are used ef- mental degradation, machining and impact dam-
fectively for the detection and location of pla- age, and fretting. These are detected by spe-
nar defects such as laminations, unbonded areas, cialized application of various nondestructive
cracks, hidden surfaces, and other flaws. They testing methods. Ultrasonic propagation charac-
are also used to reveal a lack of root penetra- teristics are used to reveal anisotropy of elas-
tion, porosity, and unbonded sidewalls of fusion tic moduli, film and fiber orientation, struc-
zones. Ultrasonic testing and radiography are tural relaxation, glass transition, degree of cross-
complementary techniques, and both are used linking, and state of cure in polymers.
for inspection of critical welds. When no access Dielectric measurements are used to monitor
to the opposite side of the weldment is available, the curing process [37]. In situ radio-frequency
ultrasonic testing is the only option for internal impedance is determined for this purpose. Mi-
flaw inspection. crowave transmission and reflection methods are
Shear wave beams are generally used in weld used for flaw detection (cracks, voids, inclu-
inspection. To detect longitudinal flaws (along sions) and for monitoring moisture, thickness,
the weld), the search unit is moved along a and cure. Optical techniques are employed to
zigzag scanning path either with sharp changes measure the state of mechanical strain in trans-
in direction or with right-angle changes. To de- parent polymers (photoelasticity). This is used
tect transverse flaws in welds, the search unit is
widely in studying stress concentration effects 5. Nondestructive Testing,“A Survey,” NASA

in model components. SP-5113, NASA, Washington D.C. 1973.
Thermographic techniques are useful in test- 6. Nondestructive Testing Study Guides, “Basic
ing polymers because they have low thermal Magnetic Particle Testing, Penetrant Testing,
conductivities. Infrared spectroscopy provides Eddy-Current Testing and Radiography
information on molecular structure and has also (1983),” General Dynamics, Convair Div.,
been used to measure stress concentration ef- 1977 – 1983.
fects near crack tips. 7. Nondestructive Testing Handbook, 2nd ed.,
Radiography of polymers requires low- vol. 1, “Leak Testing,” 1982; vol. 2, “Liquid
Penetrant Tests,” 1982; vol. 3,
energy (ca. 20 kV) radiation because polymers
“Radiography,” 1985; vol. 4,
have low absorbance. To enhance contrast, high
“Electromagnetic Methods,” 1987; vol. 5,
atomic number penetrants are used. Test pieces “Acoustic Emission Testing,” 1987; vol. 6,
are immersed in fluids such as tetrabromoethane “Magnetic Particle Testing,” 1989, ASNT,
and diiodobutane. This is only beneficial for Columbus, Ohio.
surface-breaking flaws. Although difficult to 8. ASME Boiler and Pressure Vessel Code,
use, neutron radiography is effective for poly- ASME, New York 1989.
mers. 9. 1989 Annual Book of ASTM Standards,
Paper and paperboard products require spe- vol. 3.03, “Nondestructive Testing,” ASTM,
cial testing methods during production. Radia- Philadelphia 1989.
tion thickness gauging with beta emitters (85 Kr 10. Redi-Reference Guide, “An Issue of Materials
and 90 Sr) is used for the measurement of ba- Evaluation,” published yearly by ASNT,
sis weight (areal weight). For determining ash Columbus, Ohio.
in paper due to fillers and coating minerals, the 11. R. S. Sharpe (ed.): Research Techniques in
attenuation and fluorescence of low-energy pho- Nondestructive Testing, vol. 1 1970, vol. 2
tons (4 – 5 keV) are used. 1973, vol. 3 1977, vol. 4 1980, vol. 5 1981,
Various on-line optical methods are em- vol. 6 1982, vol. 7 1984, vol. 8 1985, Academic
ployed in determining opacity, surface rough- Press, London.
ness, color, and reflectance. Infrared absorption 12. D. O. Thomson, D. E. Chimenti (eds.):
in the 1.95-µm region is used for moisture mea- Quantitative NDE, vol. 1 – 7, Plenum
Publishing, New York(1982 – 1988).
surement. For heavyweight paper, moisture is
13. Proc. World Conference on Nondestructive
measured by microwave methods.
Evaluation, 11th, Las Vegas, Nov. 1985. J.
The mechanical properties of a paper can be Boogard, G. M. van Dijk (eds.):
probed by means of ultrasonic wave propaga- Non-Destructive Testing (Proc. World
tion. An online caliper system obtains the thick- Conference on Nondestructive Evaluation),
ness and ultrasonic propagation data and the re- Elsevier, Amsterdam 1989.
sults are correlated to the mechanical strength of 14. 17th Symposium on Nondestructive
the paper. Evaluation, San Antonio, April 1989.
15. J. M. Farley, R. W. Nichols (eds.):
Nondestructive Testing, vol. 1 – 4, Pergamon
4. References Press, Oxford 1988.
16. Materials Evaluation; NDT International;
1. Metals Handbook, “Inspection and Quality Research in Nondestructive Evaluation; Brit. J.
Control,” 8th ed., vol. 11, Amer. Soc. Metals, Nondestructive Testing; Soviet J.
Metals Park, Ohio 1976. Nondestructive Testing; NTIAC Newsletter.
2. Metals Handbook, “Nondestructive 17. F. Feigl, U. Anger: Spot Tests in Inorganic
Evaluation and Quality Control,” 9th ed., Analysis, 6th ed., Elsevier, Amsterdam 1972.
vol. 17, ASM International, Metals Park, Ohio 18. G. Tschorn: Spark Atlas of Steels, Macmillan
1989. Publ. Co., New York 1963.
3. D. E. Bray, R. K. Stanley: Nondestructive 19. A. R. Fee, R. Sagabache, E. L. Tabolski,
Evaluation, McGraw-Hill, New York 1989. Metals Handbook, “Hardness Testing,” 9th
4. R. Halmshaw: Nondestructive Testing, ed., vol. 8, ASM International, Metals Park
Arnold, London 1987. 1985, pp. 69 – 113.
20. R. Halmshaw: Industrial Radiography-Theory 35. Recommended Practice for Acoustic Emission
and Practice, Applied Science Pub., Testing of Fiberglass Reinforced Plastic
Englewood, NJ 1982. Tanks/Vessels, Soc. Plastics Industry, New
21. R. A. Armistead, R. N. Yancey, Mater. Eval. York 1982.
47 (1989) 487 – 491. B. D. Hansche, Mater. 36. T. J. Fowler, Chem. Proc. (Chicago) March
Eval. 47 (1989) 741 – 745. 1984, 24 – 27.
22. J. Krautkrämer, H. Krautkrämer: Ultrasonic 37. F. I. Mopsik et al., Mater. Eval. 47 (1989)
Testing of Materials, 3rd ed., Springer Verlag, 448 – 453.
Berlin 1983. 38. C. A. Salvado, Proc. Design and
23. M. G. Silk: Ultrasonic Transducers for Manufacturing of Advanced Composites,
Nondestructive Testing, A. Hilger, Bristol ASM International, Metals Park 1989,
1984. pp. 111 – 119.
24. C. Broere et al., in [15], vol. 4, pp. 2424 – 2432. 39. T. J. Fowler, J. A. Blessing, P. J. Conlisk,
25. Progress in Acoustic Emission, (a) I (1982), AECM-3 (Third Int. Symp. Acoustic Emission
(b) II (1984), (c) III (1986), (d) IV (1988), from Composite Materials, Paris 1989),
Japan Soc. Non-Destructive Inspection, Tokyo. ASNT, Columbus 1989, pp. 16 – 27.
26. Many articles in J. Acoustic Emission, 40. S. S. Russell, E. G. Henneke, NDT Int. 17
vols. 1 – 9 (1982 – 1990). (1984) 19 – 25.
27. R. K. Miller et al., J. Acoustic Emission 8 41. J. W. Wagner, in [22], pp. 405 – 431.
(1989) 25 – 29. 42. R. C. Anderson, Inspection of Methods: Visual
28. R. Davies, in [25, (c)], pp. 9 – 25. Examination, vol. 1, ASM, Metals Park, Ohio
29. K. Göbbels, G. Ferrano, in [15] vol. 4, p. 2763. 1983.
30. W. Lord (ed.): Electromagnetic Methods of 43. E. P. Chiang in C. P. Grover (ed.): Optical
Nondestructive Testing, Gordon and Breach, Testing and Metrology, vol. 661, SPIE
New York 1985. International Soc. Optical Eng., Bellingham
31. D. C. Jiles, NDT Int. 21 (1988) 311 – 319. 1986, pp. 249 – 261.
32. K. Ono, in [25, (c)]pp. 200 – 212. 44. R. Jones, C. Wykes, Holographic and Speckle
33. V. S. Cecco, F. L. Sharp, NDT Int. 22 (1989) Interferometry, Cambridge University Press,
217 – 221. Cambridge 1983.
34. T. J. Fowler, in [25, (c)]pp. 150 – 162. 45. In [7, vol. 1], pp. 346 – 368.
On-Line Monitoring of Chemical Reactions 821
On-Line Monitoring of Chemical Reactions

Wolf-Dieter Hergeth, Wacker Polymer Systems, Burghausen, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . . 823 6. Particle Size Analysis . . . . . . . . . 848

2. Reaction Calorimetry . . . . . . . . . 825 6.1. Scattering Techniques . . . . . . . . . 848
2.1. Introduction . . . . . . . . . . . . . . . 825 6.1.1. Turbidimetry . . . . . . . . . . . . . . . . 848
2.2. Heat Flow Balance and Principles of 6.1.2. Angular Static Light Scattering . . . . 849
Measurement . . . . . . . . . . . . . . . 826 6.1.3. Dynamic Light Scattering . . . . . . . 849
2.2.1. Heat Flow Balance . . . . . . . . . . . . 826 6.1.4. Other Optical Techniques . . . . . . . . 850
2.2.2. Basic Modes of Operation . . . . . . . 828 6.2. Separation Techniques . . . . . . . . 850
2.3. Applications and Instrumentation . 829 7. Chromatography . . . . . . . . . . . . 851
3. Ultrasonic Methods . . . . . . . . . . . 830 7.1. Introduction . . . . . . . . . . . . . . . 851
3.1. Introduction . . . . . . . . . . . . . . . 830 7.2. GC Hardware Components . . . . . 852
3.2. Theory . . . . . . . . . . . . . . . . . . . 830 7.3. Applications of Gas
3.3. Applications . . . . . . . . . . . . . . . 832 Chromatography . . . . . . . . . . . . 854
4. Dielectric Spectroscopy . . . . . . . . 833 7.4. Other Chromatographic Techniques 855
4.1. Theory and Mechanisms . . . . . . . 833
8. Electroanalytical Methods . . . . . . 855
4.2. Instrumentation and Applications . 835
8.1. Introduction . . . . . . . . . . . . . . . 855
5. Optical Spectroscopy . . . . . . . . . . 837
8.2. Conductometry . . . . . . . . . . . . . 855
5.1. Introduction . . . . . . . . . . . . . . . 837
8.3. Potentiometry . . . . . . . . . . . . . . 856
5.2. Instrumentation for Reaction
Monitoring . . . . . . . . . . . . . . . . 837 8.4. Amperometry, Voltammetry, and
5.3. Applications of Optical Coulometry . . . . . . . . . . . . . . . . 857
Spectroscopy . . . . . . . . . . . . . . . 839 9. Miscellaneous Methods . . . . . . . . 858
5.3.1. UV – VIS Spectrocopy . . . . . . . . . 839 9.1. Mass Spectrometry . . . . . . . . . . . 858
5.3.2. NIR Spectroscopy . . . . . . . . . . . . 839 9.2. Densimetry and Dilatometry . . . . . 859
5.3.3. IR Spectroscopy . . . . . . . . . . . . . 842 9.3. Rheometry . . . . . . . . . . . . . . . . 861
5.3.4. Raman Spectroscopy . . . . . . . . . . 844 9.4. NMR Spectroscopy . . . . . . . . . . . 862
5.3.5. Fluorescence . . . . . . . . . . . . . . . . 847 10. References . . . . . . . . . . . . . . . . . 862
Abbreviations FOQELS fiber-optic quasi elastic light scatter-

ing
AOTF acousto-optic tunable filter
FRA frequency response analyzer
APM acoustic plate mode
FT Fourier transform
ATR attenuated total reflection
FTIR Fourier transform infrared
CCD charge-coupled device
HT Hadamard transform
CHDF capillary hydrodynamic fractionation
HDC hydrodynamic chromatography
CID charge-injection device
IR infrared
DGEBA diglicidyl ether of bisphenol A
LEC liquid exclusion chromatography
DGEBF diglicidyl ether of bisphenol F
LED light-emitting diode
DDM diaminodiphenylmethane
NIR near infrared
DLS dynamic light scattering
NMR nuclear magnetic resonance
DWS diffusing wave spectroscopy
PCS photon correlation spectroscopy
EWA evanescent wave absorption
PS power source
FFF field flow fractionation
QELS quasi-elastic light scattering
FID free induction decay
QCM quartz crystal microbalance
FIR far infrared
RIM reaction injection molding
FOCS fiber-optic chemical sensor
SAW surface acoustic wave
FODLS fiber-optic dynamic light scattering
SEC size exclusion chromatography
822 On-Line Monitoring of Chemical Reactions
SERS surface-enhanced Raman scattering n refractive index

SH shear-horizontal nm refractive index of medium
SLS static light scattering np refractive index of particle
SRS stimulated Raman scattering Nν stirrer speed
UV ultraviolet p pressure
P polarization
p0 pressure amplitude
Symbols
pbubble bubble pressure
A absorbance (extinction), instrument pgel gel point
constant ph hydrostatic pressure
AR reactor wall heat exchange area px pressure amplitude at distance x
aη Kuhn – Mark – Houwink exponent P0 power number
B instrument constant q scattering vector
c concentration Qacc accumulated heat
C0 equivalent capacitance of free space Qcal heat generated by calibration heaters
ci concentration of component i Qel heat generated by electrical heaters
cp,cool specific heat capacity of coolant Qfeed heat generated by material feed
cp,k specific heat capacity of kth reactor feed Qi sources and sinks of heat
cp,liq specific heat capacity of jacket liquid Qloss heat losses
Cp,mixture heat capacity of reaction mixture Qosc heat of forced temperature oscillations
Cp,tot heat capacity of filled reactor Qr heat of reaction
d distance, path length Qreflux heat flow over reflux condensor
D diffusion coefficient, dielectric dis- Qstir heat input due to stirring
placement Qtrans heat transfer through reactor wall
dp particle diameter R reflection coefficient, tube diameter
d stir stirrer diameter r radius
E electric field rh hydrodynamic radius
f res resonance frequency Rj reaction rate of jth reaction
f frequency, particle size distribution t time
function T transmission coefficient, temperature
g contraction factor δT amplitude of temperature oscillations
G shear modulus, distribution function T1 outer reactor wall temperature
g1 electric field autocorrelation function T2 inner reactor wall temperature
g2 light intensity autocorrelation function T cool,in coolant temperature (inflow)
G conductance T cool,out coolant temperature (outflow)
h depth Tg glass transition temperature
∆H r,j reaction enthalpy of jth reaction TJ reactor jacket temperature
I electrical current, light intensity T J,in jacket temperature (inflow)
I0 incident light (radiation) intensity T J,out jacket temperature (outflow)
Id detected light intensity Tk temperature of kth reactor feed
Il light intensity at distance l T osc period of tube oscillations
K bulk modulus, scattering coefficient T osc,cal period of tube oscillations filled with
Kη Kuhn – Mark – Houwink parameter calibration liquid
l (optical) path length, distance TR reactor temperature
kQ heat transfer coefficient u sound velocity
Kb Boltzmann constant U electrical voltage
m refractive index ratio u0 sound velocity of reference component
mk mass of component k U0 initial electrical voltage
mcool mass of coolant (∆u/∆c)i sound velocity-concentration coeffi-
mliq mass of jacket liquid cient i
Mw weight-average molecular mass ul,liq longitudinal sound velocity of liquids
M w,crit critical weight-average molecular mass ul,sol longitudinal sound velocity of solids
umix sound velocity of a mixture start density at reaction start

utr,liq transversal sound velocity of liquids σ dc dc conductivity
utr,sol transversal sound velocity of solids τ oscillation period, relaxation time, op-
Ux electrical voltage at distance x tical transmittance (turbidity)
V volume ω oscillation (angular) frequency
V excess excess volume ω max frequency at loss maximum
Vi volume of component i
Vr volume of reaction mixture
V total total volume
x distance 1. Introduction
xr monomer conversion
Xr calorimetric conversion The terms “on-line monitoring” and “process
Y complex admittance analytical chemistry” are often used synony-
Z acoustic impedance, complex mously. They are gaining increasing attention
impedance and importance in both industry and academia.
Z real component of complex impedance The extent of agreement between the two terms
Z imaginary component of complex is indeed very broad in that they provide suffi-
impedance ciently accurate and immediate information on
α sound attenuation variables that describe the state of a chemical
αliq sound attenuation in liquids reaction.
β adiabatic compressibility On-line monitoring of reactions encompasses
δ loss angle on-stream and on-reactor application of analyt-
ε decadic extinction coefficient ical methods to monitor the chemical composi-
ε∗ dielectric permittivity tion of a reaction mixture, to identify process-
ε0 free space dielectric permittivity related chemical species, and to quantify the
ε∞ high frequency dielectric permittivity concentration of reaction ingredients, products
ε storage component of dielectric permit- and byproducts. In addition to revealing the state
tivity of the reactor, on-line analysis of physical pa-
ε loss component of dielectric permittiv- rameters (temperature, pressure, level, density,
ity viscosity, etc.) may also reflect the extent of a
ε∗ dipolar dipolar reorientation contribution to chemical reaction.
ε∗ Process analytical chemistry comprises ap-
γ surface tension plications which supply relevant process infor-
Γ decay constant mation of interest “in-time”: The time for sam-
η (bulk) viscosity pling and analysis is very short compared to the
η0 viscosity of dispersion medium overall reaction time and thus allows adequate
ηs shear viscosity monitoring and efficient control of the reaction.
ηv volume viscosity The utilization of the analytical data for control
ϕ wave phase, volume fraction strategies makes process analytical chemistry an
ϕr phase shift between temperature oscil- essential integral part of process engineering and
lations control systems (see also → Process Develop-
Λ conductivity ment).
λ wave length Process analytical methods may be classified
λexc excitation wave length as off-line, at-line, on-line, or in-line with re-
λm medium light wave length spect to sampling, sample transport, and analy-
λQ heat conductivity sis itself (Table 1) [1]. There is no clear-cut line
ν frequency (of light), average velocity between the different classes, and the bound-
θ scattering angle aries are even moving: “Some of today’s off-
density line techniques may become tomorrow’s on-line
cal density of calibration liquid techniques” [2]. An increasing number of off-
end density at reaction completion line techniques have been converted into on-
mix density of reaction mixture line methods by automated, robot-assisted with-
Table 1. Classes of process analyzers (adapted from [1])
Process analyzer Sampling Sample transport Analysis
Off-line manual to remote or centralized laboratory automated/manual

At-line discontinuous/manual to local analytical equipment automated/manual quick check
On-line automated integrated automated
In-line integrated no transport automated
Noninvasive no contact no transport automated
drawal of samples from the reactor or from by- In most cases, purchasing and installation
pass or process streams and feeding them into costs of on-line and in-line analytical instru-
off-line instruments. ments exceed those of off-line equipment, but
On-line monitoring and control of chemical as soon as the measurements required exceed
reactions contributes to: a certain (relatively small) number per day, on-
– Guaranteeing and improving product quality line analysis becomes superior to off-line analy-
and consistancy (i.e., repeatability of prod- sis (Fig. 1). However, the real savings of on-line
uct properties within narrow specification reaction monitoring are due to improved process
ranges) efficiency, lower raw materials consumption and
– Increasing the efficiency of the process waste generation, and, most important, the abil-
– Ensuring safe reactor operation by monitor- ity to manufacture high-quality products.
ing process and reactor parameters Several issues have to be addressed when de-
– Understanding fundamentals of the reaction signing an on-line analysis application [1], [3–
itself 8]:
– Saving time for analysis and sample trans- – Information necessary to monitor and con-
port trol the process (physical parameters, chem-
– Reducing emissions by avoiding sample ical composition, etc.)
withdrawal and transport – Frequency of measurements with respect to
– Reducing costs for labor, raw materials, off- the time scale of the reaction
spec products, and process waste – Average values, typical fluctuations, dy-
namic ranges and expected extremes of prop-
erties
– Type, precision, and response time of sensors
– Robustness of sensors and simplicity of in-
stallation
– Full automation and minimum maintenance
of equipment
– Number (combination) of sensors and loca-
tion of measurement
– Proper sampling and, if required, sample
conditioning
– Form of data output and further handling of
information
– Compatibility with process control system
– Safety precautions and possible hazards
– Costs of instrumentation and availability of
Figure 1. Total costs for on-line and off-line process anal-
trained personnel
yses (including instrument costs, labor costs, energy, mate- Demands on performance characteristics of
rial, etc.) on-line analytical techniques differ for academic
A) Costs for purchase of off-line instruments; B) Costs for
purchase and installation of line equipment research applications, process development and
pilot plant operation, and monitoring of indus-
Table 2. Relative importance of various performance characteristics of on-line analyses in academic research, process development, and
industry [9]
Characteristics Academic research Process development Manufacturing
High accuracy +++ +++ +++

Good reproducibility +++ +++ +++
Good selectivity +++ +++ +++
Good sensitivity +++ +++ +++
Extended linearity ++ +++ +++
Good stability ++ +++ +++
Robustness ++ +++ +++
High analysis frequency ++ +++ +/+++∗
Short time delay of result ++ ++ +++
Low price +++ ++ +
Multi-analyte analysis +++ +++ +
Ease of use + +++ +++
Ease of validation + ++ +++
High flexibility + +++ +
Ease of implementation + +++ ++
Low maintenance + +++ +++
∗
Process-dependent. +++ Very important, ++ important, + not very important.
trial manufacturing processes, as summarized in rate of reaction. This allows easy access to ba-
Table 2 (see also → Plant and Process Safety; sic kinetic and thermodynamic data of chemical
→ Process Development). reactions.
With reaction calorimetry, rates of reaction
or conversion of reactants can be determined
2. Reaction Calorimetry quasi-instantaneously and continuously with a
high degree of resolution. This makes reaction
2.1. Introduction calorimetry an ideal tool for real-time feed-
back control of chemical composition during the
The majority of chemical processes are accom- course of reaction.
panied by temperature changes of the reaction Reaction calorimetry not only provides quan-
mixture owing to release or consumption of heat titative information on the chemical process it-
in the course of the reaction. Heat evolution is a self (e.g., heat of reaction, reaction rate, conver-
definite, reproducible, and directly measurable sion) but also on reactor parameters necessary
characteristic of a chemical reaction. This en- for safe reactor operation and process design:
ables one to monitor the extent of a reaction – Global reaction kinetics
by measuring temperature or heat flux changes – Heat production rates
(see [10–21] for introduction, overviews, appli- – Necessary cooling power
cations, and related subjects). – Reactant accumulation
Reaction calorimetry is noninvasive, rapid, – Adiabatic temperature rise to avoid runaway
accurate, robust, and, as it is based on tempera- reactions
ture measurements, relatively easy to carry out. – Heat-transfer coefficients for scale-up
Temperatures can be measured directly within
the reaction mixture (reactor interior), at the re- However, reaction calorimetry is a nonselec-
actor/exterior interface (reactor wall), or in the tive method. It is impossible to distinguish bet-
heating/cooling liquid of the reactor jacket. ween parallel chemical reactions with heat gen-
An advantage of reaction calorimetry is that eration and simultaneous enthalpic processes
the heat of reaction Qr derived from tempera- within the system such as phase transitions, crys-
ture measurements is directly proportionalto the tallization, mixing, and dissolution.
2.2. Heat Flow Balance and Principles of Feeding of material into the reactor with a
Measurement mass flow rate dmk / dt (and also withdrawal of
material from the reactor) leads to a heat flux
2.2.1. Heat Flow Balance dQfeed / dt

The basis for reaction calorimetry is the energy Q̇feed = ṁk cp,k (Tk − TR ) (4)
k
balance around the reactor. Sources and sinks
of heat Qi which contribute to the overall heat where cp,k is the specific heat capacity of the kth
flux balance (Eq. 1) are shown schematically in reactor feed and T k its temperature.
Figure 2: The heat input by stirring the (viscous) reac-
tion mixture Qstir is given by
Q̇stir = P0 Nν3 d5stir mix (5)
where P0 is the power number, N v the stirrer

speed, d stir the diameter of the stirrer, and mix
the density of the reaction mixture.
The energy balance of the reactor is also influ-
enced by heat losses to the surroundings Qloss
(e.g., by conduction or radiation). It is impor-
tant to identify and quantify all possible sources
of heat losses around a reactor because heat
losses might be significantly larger (2 – 5 times)
than Qacc , Qstir , or Qfeed . In most cases, heat
losses must be determined by separate experi-
Figure 2. Schematic of a reaction calorimeter
ments prior to the reaction or without a running

reaction.
Q̇i = 0 (1) Additional heat can be removed by the inser-
i tion of reflux condensers into the reactor. The
The quantity of interest in reaction calorimetry heat flow over the reflux condenser can be cal-
is the heat flux Qr generated by chemical reac- culated according to Equation (6)
tions within the reactor
Q̇reflux = ṁcool cp,cool Tcool,in − Tcool,out (6)

Q̇r = VR rj (−∆Hr,j ) (2) where ṁcool is the coolant mass flow through the
j
condenser, cp,cool is the specific heat capacity of
where V R is the volume of the reaction mixture, the coolant, and T cool,in − T cool,out the temper-
rj the rate of reaction j, and ∆H r,j the reaction ature difference across the condenser.
enthalpy of reaction j. For calibration purposes (see below), heat
Different rates of heat generation within the may also be generated by additional heaters
reactor and heat flow out of or into the reac-
tor lead to temperature changes of the reaction Q̇cal = U I (7)
mixture. This accumulated heat Qacc is a ma-
where U and I are the voltage and current of the
jor cause of uncertainty and error in quantitative
electrical heater, respectively.
analysis of reaction calorimetry data because it
The quantity that is actually measured in a
depends on the derivative of the reactor temper-
calorimetric experiment is the heat flux through
ature T R
the reactor wall to the cooling/heating system
Qtrans . There are two main methods to deter-
Q̇acc = Cp,tot ṪR (3)
mine Qtrans : heat flux calorimetry and heat bal-
where Cp,tot is the heat capacity of the filled ance calorimetry.
reactor (reactor plus reaction mixture).
Heat Flux Calorimetry. In heat flux Reichert [22], [23] developed an elegant
calorimetry, the generated heat is measured by method to overcome the problem of varia-
means of the temperature difference between tions in k Q AR , known as temperature oscilla-
reactor and jacket. The heat transfer between tion calorimetry. A small sinusoidal temperature
reactor interior and jacket medium Qtrans de- change is added to the overall temperature/time
pends on the overall heat transfer coefficient k Q characteristic of the reactor via the jacket liquid
through the wall, the heat exchange area of the or a calibration heater. These forced temperature
reactor wall AR that is actually in contact with oscillations
the reaction mixture (“wet area”), and the dif-
ference between reactor temperature and mean Q̇osc ∼ (1 + sin (ωt)) (9)
jacket fluid temperature T̄ J

create temperature oscillations of the reactor
Q̇trans = kQ · AR T̄J − TR (8) with amplitude δT R and frequency ω = 2π/τ ,
Typically, the temperature difference is suffi- where τ is the oscillation period. Decoupling
ciently large for heat flux calorimetry to be very and separate determination of oscillating and
sensitive. nonoscillating terms in the energy balance equa-
Advantages of heat flux calorimetry are its tion allows the simultaneous on-line calculation
(i) high sensitivity because of the (relatively of the rate of reaction as well as the heat transfer
large) temperature difference between reaction value of the reactor k Q AR :
medium and jacket fluid, (ii) fast response and δTR sin ϕr
high accuracy, and (iii) its independence on the kQ · AR = − ω Cp,mixture (10)
δTJ − δTR cos ϕr
flow rate of the jacket medium.
The reactor area for heat exchange with the where ϕr is the phase shift between the oscil-
jacket AR is almost constant for batch reactions. lations, and δT J the amplitude of temperature
There can be some variation in AR as a result of oscillations of the jacket liquid.
density changes of the medium during the course One- or Two-Point Calibration. In the case
of the reaction. In semibatch reactions, AR is no of a constant heat transfer coefficient during the
longer a constant. Feeding of reaction compo- reaction the heat transfer value k Q AR can be de-
nents into the reactor leads to an increase of its termined by calibration before the start of the
filling level. If the feeding rates are known their reaction.
influence on AR can be taken into account. Several commercially available calorimeters
A major problem in heat flux calorimetry is apply a two-point calibration. The first calibra-
the determination of the exact k Q value. The tion must be carried out before the reaction run
overall heat transfer coefficient may change con- starts to determine an initial value of k Q AR . A
siderably during the course of the reaction be- second calibration after completion of the re-
cause it depends on, for example, the mixture’s action in combination with the assumption of a
viscosity and density, the stirring rate (hydrody- linear behavior between start and end calibration
namics of the reactor), and heat transfer through allows one to back-interpolate the reaction data
the reactor/jacket interface (influence of film for- after the end of the reaction.
mation or reactor fouling). Hence, k Q AR must However, the reactor/jacket interlayer is
be calibrated separately in a typical heat flux prone to film formation and precipitation of reac-
calorimetry experiment. Several variations are tion products or byproducts, and the viscosity of
proposed in the literature and offered by instru- the reaction mixture may change dramatically in
ment manufacturers: a short time interval, all of which can alter k Q by
Continuous calibration during the reaction orders of magnitude at a certain time (not contin-
can be achieved by application of well-defined uously). Hence, interpolation is inaccurate, and
heat pulses produced by a calibration heater. The even pre- and post-calibration of k Q by separate
reactor heat measured with these pulses enables experiments may lead to erroneous results.
one to quantify the heat of reaction. However, Absolute Heat Flux Calibration. Absolute
the hot surface of the calibration heater may also heat flux calorimetry (ChemiSens AB, Lund,
cause problems with temperature-sensitive sam- Sweden) relys on the fact that the thermal con-
ples (e.g., product degradation, film formation). ductivity λQ within the reactor wall is constant
throughout the reaction, in contrast to the over- 0.05 K in heat flux calorimetry for the same res-
all heat transfer coefficient k Q through the wall olution). Under typical conditions, energy reso-
(wall + interlayers). Calorimeter calibration can lution in heat balance calorimetry is on the or-
be carried out by utilizing the temperature gra- der of 2 W, compared with 0.5 W in heat flux
dient (T 1 − T 2 )/d (see Fig. 3). Thus, the heat calorimetry.
flux can be calculated according to
Heat Compensation Calorimetry. In heat
λQ
kQ · AR (TJ − TR ) = AR (T1 − T2 ) (11) compensation calorimetry, both the vessel tem-
d
perature T R and the jacket-fluid temperature T J
are fixed with T J < T R . Heat from an additional
electrical heater Qel is supplied to the mixture
to maintain the temperature T R of the reactants.
After the reaction has been started and a heat
Qr released, the electrical power Qel is reduced
to hold T R constant. This reduction in Qel is
equal to the reaction heat Qr under the condition
that k Q AR and the heat losses Qloss are constant
throughout the reaction.
As in heat flux calorimetry, the unknown and
changing quantity k Q AR requires calibration of
Figure 3. Absolut Heat Flux Calorimetry: Schematic of re-
actor wall temperature gradient (reproduced by permission
the calorimeter. The hot surface of the electrical
of ChemiSens AB, Lund, Sweden) heater is prone to the formation of films, coat-
ings, precipitates, and hot spots.
Note that the immediate vicinity of the reac-
tor wall to both sides (i.e., reaction mixture and
jacket liquid) may behave like an additional thin 2.2.2. Basic Modes of Operation
film characterized by other distinct heat transfer
resistances. From a thermodynamic point of view, three ba-
sic modes of operation in heat flux calorimetry
Heat Balance Calorimetry. An alternative can be distinguished: adiabatic, isoperibolic, and
approach for measuring the heat generated isothermal calorimetry.
within the reactor is to determine the total heat
balance of the cooling/heating liquid circulating Adiabatic Reaction Calorimetry. An adia-
through the jacket: batic reaction calorimeter is characterized by
thermal insulation of the reaction mixture from
Q̇trans = ṁliq cp,liq TJ,in − TJ,out (12) the surroundings. As a result, the heat released
during the reaction is stored within the reaction
where cp,liq is the specific heat capacity of the
mixture. Thus, the temperature gradient of the
jacket liquid. In this case, Qtrans is independent
reaction mixture directly reflects the ongoing re-
of both heat exchange area and heat transfer co-
action, and the total heat balance is simply given
efficient. However, it depends on the circulation
by (cf. Eq. 13):
rate ṁliq of the jacket liquid. Heat losses at the
outer jacket wall directly influence the heat bal-
Q̇r = CR,tot ṪR (13)
ance of the circulating liquid.
Heat balance calorimetry is relatively slow In practice, thermal insulation of the reaction
and insensitive compared to heat flux calorime- mixture can be achieved either by means of an
try because of the small temperature difference infinitely large thermal resistance between mix-
T J,in − T J,out . This also leads to stricter require- ture and surroundings (e.g., Dewar calorimeter
ments with respect to the accuracy of temper- with evacuated reactor jacket) or by continu-
ature measurements. To achieve 0.5 W resolu- ously matching the jacket temperature to that
tion, it is necessary to measure the temperature of the mixture such that there is no heat transfer
with an accuracy of about 0.001 K (compared to through the reactor/jacket wall (T J (t) = T R (t)).
A major disadvantage of adiabatic reaction surface area to volume compared to bench-scale

calorimetry is the interdependence of mass bal- reactors and calorimeters; hence, their heat-
ance and heat balance via the reaction rate, removal capacity is limited. To achieve a max-
which requires an adequate kinetic model for imum production rate in industrial-scale reac-
data analysis. tors, the reaction rate should be matched to the
heat-removal capacity throughout the reaction.
Isothermal Reaction Calorimetry. In On-line reaction calorimetry provides some of
isothermal reaction calorimetry, the reaction the data necessary for a desired reaction run and
mixture temperature T R is held constant, for safe reactor operation (e.g., heat release rates,
example, by adjusting the temperature of the heat losses, reaction rate, conversion).
jacket fluid T J or by controlling the power of Reaction calorimetry has been used to mon-
a compensation heater. In practice, it is very itor polymerization reactions and crystalliza-
difficult to keep the reactor strictly isothermal tion processes [28–30]. Strategies for on-line
because of the nonzero heat transfer resistance control of reactions on the basis of calorimet-
of the reactor wall and deviations and delays in ric measurements during the course of the re-
power control. Thus, heat accumulation must be action have been described [31–33]. Reaction
taken into account in the isothermal heat balance calorimetry is the method of choice for studying
thermal runaway reactions [34]. The application
Q̇r = kQ AR TR − T̄J + Cp,total ṪR (14) of calorimetry to investigating the kinetics of
reactive blending and reactive extrusion is dis-
cussed in [35], and the application of adiabatic
Isoperibolic reaction calorimetry is oppo- temperature rise for monitoring reaction injec-
site to isothermal calorimetry in the sense that tion molding (RIM) in [36].
the jacket temperature T J is held constant in-
stead of the reactor temperature T R . As a conse-
quence, T R changes during the reaction. Heat
is both accumulated in the reaction mixture
and transferred to the jacket liquid. Hence, the
heat balance can be described as in isothermal
calorimetry (see Eq. 14).
2.3. Applications and Instrumentation

The heat of reaction Qr (t) can be calculated ac-
cording to Equation 1 if all contributions Qi to
the overall heat balance of the reactor are mea-
sured or known. If only one exothermic chemi-
cal reaction proceeds in the vessel, the reaction
rate is given by Equation 2, and the actual rel-
ative calorimetric conversion X r (t) is given by
Equation 15
t
Qr (t) dt Figure 4. Reaction calorimeter RM-2S for heat flow and
0
Xr (t) = (15) heat balance measurements (reproduced by permission of

t,final
ChemiSens AB, Lund, Sweden)
Qr (t) dt
0
Most instrument suppliers (e.g., Mettler-
On-line calorimetry has been used by chemical Toledo, ChemiSens, HEL) offer computer-
companies to monitor the extent of reactions for controlled calorimeters that can be run in differ-
several decades [24–27]. Industrial-scale reac- ent modes (Figure 4). The nonselectivity of re-
tors have a relatively low ratio of heat-exchange
action calorimetry in monitoring complex reac- In most applications, ultrasound is gener-

tions (e.g., reactions in which parallel processes ated by piezoelectric transducers. Because of
occur, copolymerizations, etc.) can be over- the reversibility of the piezoelectric effect, the
come by combining calorimetry with other on- transducers can act both as emitters and re-
line methods to obtain additional information. ceivers of ultrasonic waves. Depending on the
These methods include density, pressure, gas requirements of the application, a wide vari-
chromatography, dielectric spectroscopy, and ety of readily available and cost effective piezo-
infrared and Raman spectroscopy (Fig. 5). electric materials can be utilized as transducers
(e.g., quartz, lithium niobate, barium titanate,
poly(vinylidene fluoride), zinc oxide).
Ultrasonic sensors and ultrasonic systems for
materials characterization, process monitoring,
and applications in chemistry are reviewed in
[41–48].
3.2. Theory
A planar elastic ultrasonic wave can be described
by its complex alternating pressure p(x,t) as a
function of time t and distance x (Eq. 16)
. x /
p (x, t) = p0 exp iω t − · exp [−αx] (16)
u
where ω = 2πf (f = frequency), p0 is the pressure
amplitude, and u and α are the velocity and atten-
uation of sound in matter. The frequency of ultra-
sound waves is in the range of 20 kHz to about
1 GHz with corresponding wavelengths on the
order of 1.6 cm to 0.3 µm in air (u ≈ 330 m/s),
6 cm to 1.2 µm in liquids (u ≈ 1200 m/s), and
Figure 5. Reaction calorimeter RC1 equipped with React 20 cm to 4 µm in solids (u ≈ 4000 m/s).
IR infrared Spectrometer (ASI Applied Systems) for simul-
taneous on-line calorimetry and infrared analysis (courtery Both u and α strongly depend on the mate-
of Mettler-Toledo GmbH, Analytical) rial’s state and properties. In solids, the longitu-
dinal and transverse sound velocities ul,sol and
utr,sol are related to the bulk modulus K, the
Calorimetric data of chemical reactions have
shear modulus G, and the density according to
also been determined by differential scanning
calorimetry [37–40]. K + 4
G G
u2l,sol = 3
and u2tr,sol = (17)

The longitudinal ultrasonic velocity in liquids

3. Ultrasonic Methods ul,liq depends on both the adiabatic compress-
ibility β of the liquid and its density (Eq. 18).
3.1. Introduction
1
u2l,liq = (18)
The propagation of ultrasound in matter is a β
physical effect that is receiving increasing at- Ultrasonic shear waves in liquids (utr,liq ) do not
tention for on-line monitoring of chemical pro- propagate significantly. They are strongly damp-
cesses. Ultrasonic methods are easy to use, ened, and therefore not of technical importance.
safe, nondestructive, and noninvasive. Signal re- The sound attenuation α of solids and liquids
sponse times on the order of milliseconds allow depends on several loss mechanisms. Intrinsic,
real-time monitoring of fast reactions. viscous, and thermal losses may contribute to
α, as well as scattering and reflection effects at 1 p0 1 U0

interfaces in heterogeneous samples, relaxation α = ln = ln (23)
x px x Ux
processes in polymers, electrokinetic losses in
disperse systems, and structural losses in con-
centrated systems (e.g., pseudoplasticity). Thus,
α is influenced by material properties such as
density, viscosity, thermal conductivity, expan-
sion, and capacity; by the morphology of the
sample (grain size and shape); and by temper-
ature and pressure. It is difficult to derive ana-
lytical expressions for α because of its complex
dependence on these parameters. However, in
simple homogeneous liquid systems, α can be
described as

αliq 2 · π2 4
= ηs + ηv (19)
f 2 · u3 3
where η s and η v are the shear and the volume Figure 6. Schematic of ultrasonic pulse travelling measure-
ments. (The transducer arrangement can also be used in
viscosities of the liquid. Sound is strongly ab- multiple reflection echo mode.)
sorbed at high frequencies (f 2 dependence) and
cannot penetrate deeply into the material.
A third acoustic parameter of importance Measurements of pulse travelling time are
with respect to reaction monitoring is the acous- highly accurate and relatively easy to carry out
tic impedance Z of the material (Eq. 20). compared to sound attenuation measurements.
The frequency of ultrasonic sensors for reac-
Z = ·u (20) tion monitoring is generally in the 1 – 10 MHz
It is typically measured in reflection experi- range. In principle, the accuracy of sound veloc-
ments at interfaces by means of the reflection ity measurements is poor for very low frequen-
coefficient R (Eq. 21). cies (< 100 kHz) and increases with increasing
frequency. However, attenuation does also in-
Z1 − Z2 crease for f 10 MHz, and the distance bet-
R = = 1−T (21)
Z1 + Z2 ween transducers must be shortened for the sig-
where Z 1 and Z 2 are the acoustic impedances of nal to reach the receiver. As a result, the accuracy
the materials on both sides of an interface, and of pulse travelling time measurements also de-
T is the transmission coefficient. teriorates at very high frequencies. Typical de-
A common method for determining acoustic mands on the accuracy of ultrasonic sensors for
properties is to monitor (compressional) sound reaction monitoring are
pulses travelling over a well-defined distance
(Fig. 6). The emitting transducer E generates a ∆u ∆α ∆Z
≤ 10−3 ≈ 0.5 % ≤ 10−3
sound burst of initial amplitude p0 (proportional u α Z
to the applied voltage U 0 ) which travels a dis- These conditions imply time measurements in
tance x in a time ∆t. In multiple-echo mode, ∆t the nanosecond and picosecond range, and of
is the time delay between successive echoes, and amplitude resolutions of 12 bit and higher [41].
x is twice the distance between transducers. The Additionally, temperature control has to be bet-
dampened (and broadened) pulse reaching the ter than ± 0.1 K.
receiving transducer R generates an electrical In addition to u and α, other sound wave char-
voltage Ux proportional to the pressure ampli- acteristics (e.g., wave phase ϕ, resonance fre-
tude px at the receiver. By using this method, quency f res and shift ∆f res ) can be measured
sound velocity and attenuation can simply be in certain ultrasonic sensor applications for ma-
calculated according to Equations 22 and 23. terials characterization and chemical processes
x monitoring [41].
u = (22)
∆t
Next Page
3.3. Applications tic impedance Z via reflection coefficient mea-

surements may reduce the bubble disturbances.
The basic condition for monitoring chemical However, so far, no application of Z determina-
processes by means of ultrasound is that physical tion in reaction monitoring has been described
properties that determine u, α, or Z change dur- in the literature.
ing the course of the reaction (see Eqs. 17 – 20).
In polymer production and modification, curing LIVE GRAPH
Click here to view
and cross-linking reactions, mechanical mod-
uli as well as the mixture’s density, compress-
ibility, viscosity, thermal conductivity, etc. al-
ter dramatically, thus influencing sound atten-
uation and velocity (see Table 3). Hence, those
processes are ideal for application of ultrasound
to detect the extent of reaction. Even electro-
chemical processes can be monitored because
of the sensitivity of ultrasound to the type of ion
and concentration.
Table 3. Ultrasound velocities of monomers and polymers at 20 ◦ C
Substance Monomer Polymer
Butyl acrylate 1233 m/s 1375 m/s

Styrene 1354 m/s 2120 m/s
Vinyl acetate 1150 m/s 1853 m/s
Vinyl chloride 897 m/s 2260 m/s
LIVE GRAPH
Click here to view
LIVE GRAPH
Click here to view
Figure 7. Influence of gas bubbles on ultrasound velocity

measurements during emulsion polymerization
A major advantage of ultrasound (velocity)

measurements in industrial applications is the
capability to plug the sensor directly into the
reacting mixture. They do not necessarily re-
quire a sampling loop. Care should be taken be-
cause plug-in transducers may cause fouling at Figure 8. Ultrasonic velocity (A) and relative ultrasonic ab-
sorption (B), both measured at 1 MHz, as a function of the
their edges or lead to formation of coagula and extent of epoxide ring reaction P for a DGEBA/DDM sys-
films. The disturbing influence of gas bubbles in tem at 70 ◦ C; gel point Pgel = 0.58
the reaction mixture between the transducers is (reprint from [62], with permission from Elsevier Science)
demonstrated in Figure 7. Monitoring of acous-
Previous Page
A simple empirical but useful approach for The dependence of ultrasonic parameters on
describing the sound velocity of multicompo- grain sizes in heterogeneous media enables one
nent reaction mixtures is based on the assump- to determine particle sizes and particle size dis-
tion that each component i of the mixture contributions in latices, emulsions, suspensions, etc.
tributes independently to the sound velocity of even at very high concentrations of the disperse
the mixture umix according to its concentration phase [73–77]. Thus, acoustic spectroscopy (as
ci well as electroacoustic spectroscopy [75], [78])
∆u is developing rapidly as an alternative to light-
umix = u0 + ci (24) scattering methods for particle size analysis in
i
∆c i
dense media.
where u0 is the sound velocity of a ref- Ultrasonic microsensors are used for mate-
erence component (e.g., solvent, dispersion rials characterization and reaction monitoring
medium) whose ultrasonic velocity is either con- [41], [43]. Ultrasonic microsensors based on the
stant throughout the process or changes in a quartz crystal microbalance (QCM) principle
known manner, and ∆u/∆c is the (temperature- are very sensitive for a wide variety of chem-
dependent) sound velocity – concentration coef- ical applications. The high precision and ease of
ficient, which itself may depend on concentra- measurement of the QCM frequency has made
tion. However, higher order terms are neglected it a useful tool for measuring slight changes in
in Equation 24. The influence of component i on mass on the QCM electrode surface. By coating
the sound velocity of component j is also ne- the surface with a sensitive layer, the QCM can
glected. Equation 24 is the basis for on-line con- be used as selective gas or even under-liquid sen-
centration measurements in numerous applica- sor. The determination of contact angles and sur-
tions in chemistry, biochemistry, and the foods face tensions with a QCM is described in [79].
industry. Detergency processes have been monitored in
Ultrasound has been used to monitor chemi- real-time by using a QCM [80]. The use of shear-
cal reactions for more than twenty years [49–52]. horizontal (SH) acoustic plate mode (APM) de-
Ultrasonic on-line monitoring of polymerization vices to monitor cross-linking reactions in poly-
reactions was reported in [53–57]. Crosslinking mer films in real time is described in [81]. Photo-
reactions (curing, gelation) were investigated cross-linking of diacetylene thiol-based mono-
with ultrasound in [52], [58–64]. As an exam- layers on surface acoustic wave sensors (SAW)
ple, the influence of the extent of reaction of the has been monitored in situ [82]. Recent develop-
epoxide ring in a system consisting of the digly- ments include the application of fiber-optic in-
cidyl ether of bisphenol A (DGEBA) and 4,4 - terferometric ultrasound sensors for monitoring
diaminodiphenylmethane (DDM) on the ultra- the cure of epoxy resins [83], [84].
sonic velocity and relative ultrasonic absorption
is shown in Figure 8. Viscoelastic properties of
polymer melts in extruders can be monitored by 4. Dielectric Spectroscopy
in-line determination of ultrasonic parameters,
along with temperature and pressure measure- 4.1. Theory and Mechanisms
ments [35], [51], [65–67].
Ultrasound is sensitive to the local concentra- Dielectric spectroscopy deals with the electrical
tion of oil in emulsions and thus enables mon- response of the polarization P (ω) of matter to
itoring of creaming and flocculation processes the application of an oscillating electric field E
[68], [69]. It is applicable to both dilute and con- (ω)
centrated emulsions.
D (ω) = εo E (ω) + P (ω) = ε∗ (ω) ε0 E (ω) (25)
Ultrasound is not only a tool for monitor-
ing chemical reactions but also one for initiating where D is the dielectric displacement vector,
them. The origin of the enhancement of chem- ω is the angular frequency, and ε∗ and ε0 are
ical reactions by ultrasonication is the intensity the dielectric permittivity and the permittivity
of the cavitation bubbles produced in the soni- of free space, respectively. Several atomic and
cated medium at higher sound intensities [47], molecular mechanisms contribute to the dielec-
[48], [70–72]. tric behavior of matter [85–88]:
LIVE GRAPH
Click here to view
Figure 9. Dielectric relaxation: Dielectric permittivity and dielectric loss as a function of frequency
1) Electronic polarization (i.e., induced dipole ical reaction are orientation polarization of per-
moment due to the displacement of electrons manent dipoles, migration of charges, and inter-
from their equilibrium position with respect facial effects in heterogeneous systems.
to the nucleus) In contrast to electronic and atomic polar-
2) Displacement polarization (atomic, ionic, ization, the orientation of permanent dipoles is
lattice polarization; e.g., induced dipole mo- time-dependent and not always instantaneous. It
ment due to the deflection of ions from their is governed by the (micro) viscosity of the im-
equilibrium positions in molecules) mediate surroundings. In polymeric systems, it
3) Orientation polarization of permanent requires cooperative motion of chains or chain
dipoles present in the system (i.e., align- sequences, too. Dipole relaxation is the strongly
ment to the direction of the external field) temperature dependent reorientation of dipoles
4) Motion of intrinsic and extrinsic charge car- due to thermal fluctuations after the removal of
riers (ions, particles) the external field. As the frequency is scanned,
5) Charge transfer and polarization at elec- various characteristic dipole relaxations accom-
trodes panied by corresponding losses are observed.
6) Interfacial polarization and distortion of the The migration of charges mainly influences
electrical double layers at interfaces in het- the dielectric losses. The (ionic) conductivity
erogeneous systems contribution to the loss factor is inversely pro-
A certain mechanism contributes to the over- portional to the frequency of the external field.
all polarization of the sample if its characteris- Ionic conductivity can be correlated with viscos-
tic relaxation time is faster than the time scale ity, since fluidity is indicated by the ease with
of the external field. Hence, the various polar- which charge carriers can migrate through the
ization mechanisms can be distinguished on the sample.
basis of their different frequency dependencies. The complex dielectric permittivity ε∗ (ω) is
Time scales for resonances of electronic and composed of two parts, a real (or storage) com-
displacement polarization of atoms and ions are ponent ε (ω) in phase, and an imaginary (or loss)
in the femtosecond (10−14 to 10−15 s; UV re- component ε (ω) out of phase with the applied
gion) and picosecond range (10−12 to 10−13 s; oscillating electric field (Eq. 26).
IR region), respectively. Thus, these induced
dipoles contribute instantaneously to the dielec- ε∗ (ω) = ε (ω) + iε (ω) (26)
tric properties of matter typically measured in
where i is (−1). ε (ω) is proportional to the
the frequency range 10−5 to 1011 Hz.
capacitance of the sample, and ε (ω) is influ-
Key phenomena determining the change of
enced both by the material’s conductivity and
dielectric properties during the course of a chem-
by dipolar losses. A sigmoidal change in ε (ω) formalism (e.g., Z vs. Z plots) is particularly
and the appearance of a peak in ε (ω) is indica- helpful in separating bulk and surface phenom-
tive of a relaxation process (Fig. 9) ena (e.g., polarization in the bulk and electrode
polarization).
ε0 − ε∞ ω 2 τ 2
ε (ω) = ε0 − (27)
1 + ω2 τ 2
4.2. Instrumentation and Applications
ε0 − ε∞ ωτ
ε (ω) = (28)
1+ ω2 τ 2 Instrumentation. According to the fre-
where τ is the relaxation time. The loss factor quency of the external electric field, several fre-
tan δ is defined by quency regimes for dielectric experiments can
be distinguished which require different mea-
ε (ω) surement principles [90–92] (Fig. 10).
tanδ (ω) = (29)
ε (ω)
As indicated above, the dielectric permittiv-

ity is not a constant but a function of frequency.
Additionally, ε∗ is strongly influenced by tem-
perature since both the transitional mobility of
charge carriers as well as the reorientational mo-
tion of dipoles are temperature-dependent. For
some cases in the absence of chemical reactions,
the temperature dependence of dielectric prop-
erties can be described in terms of Arrhenius
and Williams – Landel – Ferry (Vogel – Fulcher)
type relations, depending on the nature of the
dipolar motions (single activation and coopera-
tive process, respectively).
In addition to the complex dielectric permit-
tivity, there are several other quantities that can
be alternatively derived from dielectric spectra
[89], [90]. These include the impedance and ad-
mittance (or conductivity), the dielectric mod-
ulus, and the susceptibility. Admittance spec-
tra Y ∗ (ω), the inverse of impedance spectra
Z ∗ (ω) = Z (ω) − iZ (ω) = (Y ∗ (ω))−1 for linear
response, can be calculated from permittivity
data according to Equation 30.
Y ∗ (ω)
ε∗ (ω) = (30)
iωC0
where C 0 is the equivalent capacitance of free

space.
Transformations from one formalism to an-
other can help resolve particular aspects of the Figure 10. Principles of dielectric measurements: A) Fre-
relaxation processes, but no new information can quency response analysis technique; B) Resonance circuit;
be extracted in the linear response regime of the C) standing wave in hollow conductor
material. The impedance spectrum Z ∗ (ω) is of- PS: Power source
ten used for discussion because dielectric data The common instrumentation in the
can be analyzed in terms of equivalent electri- impedance regime from about 10−5 to 108 Hz
cal circuits consisting of resistors and capaci- includes current – voltage measurements in elec-
tors connected in parallel and series. The Z ∗ (ω) trode/sample/electrode sandwich arrangements
of electrical (ratio-arm) bridges, and resonance When van der Waals or other weak interactions
(oscillating) circuits. The main techniques for between molecules are replaced by covalent
dielectric reaction monitoring are (1) the di- bonds during the conversion of low-viscosity
rect ac measurement of amplitude and phase monomers into polymers, the dipole moments of
between voltage and current over a certain fre- molecules and the mechanisms of their Brown-
quency range by using a frequency response ian diffusion change, as does the size of the dif-
analyzer (FRA), and (2) step voltage applica- fusing moieties. The restrictions on the diffusion
tion (or removal) with rapid acquisition of the of dipoles and charge carriers increase [93–98].
current response over time and transformation LIVE GRAPH
Click here to view
of the signal into the frequency domain.
Minimum time intervals for dielectric mea-
surements are on the order of tenths of seconds,
so dielectric spectroscopy in the impedance fre-
quency regime is suitable for on-line monitor-
ing of chemical reactions. Typical accuracies
of measurements achievable in the impedance
frequency regime are about ± 0.05 % for ε ,
± 0.2 % for ε , and better than 10−4 for tan δ.
Dielectric cells for liquids are generally sim-
ple and consist of two concentric cylinders with
the fluid in the space between them. These mea-
surements are of very high precision because of Figure 11. Real and imaginary impedance as a function
the good dimensional stability of the cells. Solid of time with frequency as parameter during the reaction
of the diglycidyl ether of bisphenol F (DGEBF) with 4,4
samples are typically sandwiched between metal methylenedianiline (MDA) at 36 ◦ C [96]
plate electrodes as in a capacitor. Compared to a) Z = 500 Hz; b) Z = 500 Hz; c) Z = 2000 Hz;
liquid cells, solid sample set-ups are quite com- d) Z = 2000 Hz; e) Z = 10 000 Hz; f) Z = 10 000 Hz
plicated because they must take into account for
the sample’s thermal coefficient of expansion. Both the real and the imaginary parts of the di-
The radio regime from about 106 to 1010 Hz electric permittivity can have dipolar and ionic-
requires resonance circuits (low ω) or guided- charge polarization components. At lower fre-
wave techniques (high ω; e.g., standing waves quencies, ε is typically dominated by the mo-
in hollow conductors). bility of ions in the sample, whereas dipolar re-
The typical equipment for the microwave reorientation mobility contributes to ε at higher
gion from 109 to several 1011 Hz is coaxial or frequencies (Eq. 31).
rectangular waveguides. σdc
ε∗ (ω) = ε∗dipolar − i (31)
Propagating wave techniques are utilized in ωε0
the IR and UV – VIS regimes above a few
1011 Hz with Fourier transform technique as the Here σ dc is the dc conductivity due to ever-
method of choice. present ionic impurities [99], [100]. The ionic
mobility (i.e., σ dc ) is a molecular probe for quan-
Applications. Chemical reactions are acces- titatively monitoring viscosity changes during
sible to reaction monitoring by dielectric spec- cure. At short curing times, ε is dominated by
troscopy if they lead to changes in the rate of the dc conductivity. When gelation occurs, the
motion of molecules contributing to the dielec- dc conductivity decreases strongly since the mo-
tric response of the mixture (e.g., rotational or bility of the charge carriers decreases due to net-
vibrational motion of dipoles and translational work formation. Peaks in ε indicate when dipo-
motion of charge carriers). lar reorientation processes contribute to ε .
Many applications of dielectric spectroscopy Dielectric spectroscopy in the 10 to 105 Hz
published so far are for monitoring the cure frequency range with a ratio-arm bridge has been
of resins. Dielectric spectroscopy can detect used to monitor the UV polymerization of a
changes in the polymer cross-link density dur- polymer-stabilized liquid crystal cell containing
ing the course of polymerization (Fig. 11). a mixture of nematic and chiral liquid crystals
together with DSM monomer and photoinitia- spectroscopy in this wavelength range is con-
tor [101]. The authors discuss their results in structed with typical optical elements such as
terms of capacitance units. They have shown mirrors, lenses, gratings, and optical filters. The
that the decreasing loss serves as an excellent incident energy is delivered by light sources.
monitor for changing molecular processes and The long-wavelength end of the electromagnetic
the state of photopolymerization, whereas the spectrum (i.e., millimeter range) requires com-
capacitance itself does not change dramatically pletely different experimental techniques (e.g.,
during the course of the polymerization. Low- hollow conductors for microwave spectrometry)
frequency losses observed at the beginning of as does the short-wavelength end (λ 100 nm)
the reaction are mainly caused by ionic impuri- with special X-ray and γ-ray equipment.
ties. After polymerization, the liquid crystal cell Electronic absorptions determine the spec-
has the dielectric characteristic of a relatively tral features observable in the UV – VIS region.
low loss dielectric. Molecular vibrations, rotations, and combined
In particular, dielectric spectroscopy is the rotational-vibrational transitions of molecules
method of choice for following the curing of can be detected in the near (NIR) to the far (FIR)
polar coatings. In these thin-layer systems, very infrared wavelength range. Spectra can either be
high signal-to-noise ratios can be achieved be- recorded in absorption (UV, VIS, NIR, IR, FIR)
cause their capacitance is inversely proportional or emission (IR, Raman, fluorescence).
to their thickness, like the capacitance in a plate
capacitor as a function of interplate distance.
Dielectric spectroscopy has been also applied 5.2. Instrumentation for Reaction
to disperse systems [102–105]. The relaxation Monitoring
pattern is the dielectric fingerprint of a colloidal
system [106]. Correlations between relaxation Spectroscopy over the entire spectral range of
frequencies and suspension properties such as optical wavelengths has been applied to on-
particle volume fraction, electrolyte concentra- line process monitoring for several decades.
tion, Zeta potential, pH, surface conductivity, The vast majority of applications is based on
particle radius, Debye screening length, degree nondispersive instruments, and light absorption
of ionization, and diffusion coefficient have been or emission is typically measured either at a sin-
developed [107], [108]. These characteristics gle wavelength or by integration over a certain
change during reactions in colloidal systems, (rather small) wavelength range.
and on-line monitoring is possible. Moreover, In absorption spectroscopy, the light is gener-
dielectric spectroscopy is especially valuable for ated by monochromatic light sources (including
studying concentrated and opaque dispersions. lasers) or polychromatic light sources combined
For a latex exhibiting a low-frequency relaxation with optical filters. Tuning of the wavelength to
process, the relaxation time at the loss maxi- characteristic absorptions of certain molecules
mum τ = 1/ω max is proportional to the square enables one to detect substances and to observe
of the particle radius, and inversely proportional the variation of their concentration as a function
to the diffusion coefficient of the electrical dou- of time with high selectivity and sensitivity.
ble layer of counterions up to 30 % total solids In transmission measurements, the funda-
[109]. mental relation between the incident light inten-
sity I 0 , the transmitted light intensity I l , and the
concentration of the analyte c in a cell of optical
5. Optical Spectroscopy length l is given by the Lambert – Beer law:
I0 (ν) 1
log = log = A (ν) = ε (ν) cl (32)
5.1. Introduction Il (ν) τ (ν)
where ε(ν) is the (decadic) extinction coefficient
Optical spectroscopy covers the range of the of the sample at frequency ν, l is the length of the
electromagnetic spectrum from the ultravi- measurement cell, A is the absorbance (extinc-
olet (UV, λ 10 nm) to the infrared (IR, tion), and τ is the transmittance of the sample.
λ < 1 mm). Experimental equipment for optical Monitoring procedures based on this classical
photometric method are still extensively used of an FT instrument is very high because light
because of its simplicity, ruggedness, sensitiv- of all frequencies is recorded simultaneously.
ity, and low cost and maintenance requirements. Depending on the spectral resolution and the
It works best for well-characterized continuous signal-to-noise ratio required, FT spectrometers
material streams but is less advantageous for dy- are suitable for monitoring very fast chemical
namic processes (e.g., some batch operations). processes on the timescale of seconds to min-
The number of substances that can be de- utes. However, they are less rugged than pho-
tected simultaneously by nondispersive instru- tometers or array-detector instruments because
ments in absorption and emission modes is lim- the interferometer is susceptible to vibrations,
ited, and detailed molecular information on the for instance, in a production-plant environment.
species undergoing a reaction is not available. The introduction of fiber optics has been a
These restrictions can be overcome by parallel major step forward in reaction monitoring by op-
installation of several nondispersive instruments tical spectroscopy. Nowadays, most instrument
operating at different wavelengths, or utilization suppliers offer their spectrometers with optional
of dispersive instruments (spectrometers) to ex- fiber optics. Optical fibers connect the remote in-
ploit the whole spectral information. strument with the reactor or process line for on-
With classical dispersive wavelength- line monitoring with the following advantages:
scan spectrometers, data collection is time- – Reduced risk of fire or explosion in produc-
consuming because such an instrument records tion units
the data points of the spectrum consecutively. – Reduced interaction of the delicate spec-
Therefore, dispersive scanning spectrometers trometer with the hostile process environ-
are not suitable for process monitoring. ment
However, the substitution of point detectors – Enhanced accessibility of various measure-
by array detectors in dispersive instruments of- ment points in a process stream or reactor
fers the opportunity to acquire large amounts – Simplified multiplexing
of spectrally and/or spatially resolved data in
extremely short periods of time. Semiconduc-
tor array detectors are characterized by high Table 4. Fiber types and typical optical wavelength range [111]
quantum efficiency, wide dynamic range, fast re-
Fiber type Approximate optical range
sponse, low noise, low power requirement, and
continuously decreasing costs. Array detectors High-purity fused silica 200 – 2000 nm
suffer from either limited resolution or limited Plastics 350 – 1100 nm
Glass 350 – 1800 nm
bandwidth. However, the two-dimensionality Low-OH fused silica 250 – 2700 nm
of some types of array detectors in combina- Zirconium fluoride 2 – 5.5 µm
tion with cross-dispersion enables the complete Chalcogenide 3 – 11 µm
Silver halides 5 – 20 µm
spectrum to be obtained with high resolution.
Since the whole spectrum is available with one
shot of light on the detector, chemical reaction
monitoring on the sub-second timescale is pos- Light may be delivered and collected through
sible. Another advantage of two-dimensional ar- separate single fibers or fiber arrays; alterna-
ray detectors is the ability to record several spectively, fibers can be arranged in integrated fiber
tra simultaneously in different lines of the array bundles in which a light source fiber is sur-
thus enabling multiplexing. Fundamentals and rounded by detector fibers, or in which source
applications of array detectors [charge-transfer and detection fibers are randomly distributed
devices (CCD, CID), photodiode arrays, and within the bundle. A review of the developments
photoconductor arrays] in both absorption and in fiber optic applications in molecular spec-
emission spectroscopy are reviewed in [110]. troscopy is given in [111]. Commonly used fiber
With Fourier transform (FT) spectrome- types are listed in Table 4.
ters, the spectral information is first recorded Recently, the development of fiber-optic
in the time domain as an interferogram and chemical sensors (FOCS) based on evanes-
then Fourier transformed into the frequency cent wave absorption (EWA) spectroscopy has
(wavenumber) domain. The optical throughput experienced much progress and improvement.
FOCSs can be employed for real-time in situ The versatility of UV – VIS spectroscopy in
monitoring by simply immersing them in the process monitoring has been extended by the de-
mixture and establishing a connection between velopment of UV array spectrometers [112].
the fiber, the light source, and the detection sys- Optical fibers for use in the VIS region
tem. They offer fast response times on the order are readily available. Transmission of visible
of seconds with all the advantages of ATR spec- light through optical cables is possible over
troscopy, and considerably improved sensitivity. long distances for remote process monitoring.
Figure 12 shows various instrument/probe/- In the short-wavelength UV, however, the opti-
process vessel configurations for the applica- cal absorption of the fiber core and/or cladding
tion of optical spectroscopy to the monitoring material restricts light throughput. Recently,
of chemical reactions. Spectra can either be evanescent-wave fiber optic absorption sensors
recorded in transmission, reflection, transflec- for use in the UV and VIS regions have been de-
tion, or attenuated total reflection (ATR). Probes scribed [113], [114]. UV reflection spectroscopy
can be directly immersed into the reaction mix- with a fiber optic accessory has been used to
ture, or the spectra can be recorded through win- characterize the cure of bis(maleimide) resins
dows in the reactor or pipe wall. [115], [116].
5.3. Applications of Optical 5.3.2. NIR Spectroscopy

Spectroscopy Absorption bands in the near infrared origi-
nate from electronic transitions of the heavi-
5.3.1. UV – VIS Spectrocopy est atoms and from overtones and combinations
of fundamental vibrations in the IR. In organic
UV – VIS spectroscopy is highly sensitive, but
substances, C – H, N – H, and O – H vibrations
the spectra are less informative because they
give rise to dominant absorptions in the near-
typically consist of a few broad absorption
IR. Therefore, the detection of water was one
peaks. Therefore, UV – VIS spectroscopic re-
of the first on-line applications of NIR spec-
action monitoring is less commonly used than
troscopy. However, water interference may also
other spectroscopic techniques. Typical appli-
complicate NIR spectroscopy of aqueous sam-
cations of UV – VIS spectroscopy include pho-
ples [117]. NIR-active vibration overtones and
tometric gas analysis in transmission gas cells
combinations are characterized by low molar ab-
for the detection of sulfur dioxide, nitrogen ox-
sorptivities and high scattering efficiencies, and
ides, chlorine, mercury vapor, toluene, benzene,
the NIR bands are broad and overlapped.
methane, ethanol, etc. Detection limits are in the
The peculiarities of NIR spectrometry lead to
order of tens of ppm in air [8].
important consequences in practice:
A major advantage of the UV – VIS spectral
region is that water does not absorb considerably 1) Near IR wavelengths are able to penetrate
in the entire VIS region up to the mid-UV, thus into and sometimes even through a sam-
making it attractive for water and wastewater ple, thus enabling measurements on real
analysis. UV – VIS absorption measurements in world samples in the millimeter or centime-
aqueous or other fluid process streams are typi- ter thickness range. Spectra can be recorded
cally performed in transmission or ATR modes. on most types of liquid, solid, powder, or
With ATR probes, even highly opaque mixtures gaseous samples without sample pretreat-
and liquid systems containing strongly scatter- ment. Sample size may vary from tiny bits
ing particulate solids are accessible to process to large chunks.
analysis. 2) NIR spectra contain all the spectral infor-
In disperse systems, light scattering by par- mation necessary for fingerprinting, albeit
ticles accounts for much of the attenuation of buried under broad and strongly overlapped
the incident light. Thus particle size measure- absorption features. In most cases, the spec-
ment by UV – VIS scattering methods is com- tra cannot be interpreted directly, unlike the
mon practice in colloid laboratories and at pro- individual peaks of IR spectra, and calibra-
duction sites. tions and chemometric methods have to be
Figure 12. Instrument probe process vessel configurations for the application of optical spectroscopy to monitoring chemical
reactions
A) Transmission; B) Transflection; C) Reflection; D) Scattering (90 ◦ ); E) Attenuated total reflection (crystal); F) Attenuated
total reflection (single-bounce tip); G) Evanescent-wave fiber optic
FO = fiber optic; L = light source; D = detector
Figure 13. Ceramic transmission NIR probe with variable optical pathlength and diffuse reflectance dipper probe for insertion
into extruder (courtesy of IPF Dresden)
exploited for quantitative analysis. This may process environments. LED spectrometers are
cause problems in NIR reaction monitoring highly sensitive and selective, with fast response
of batch processes with frequently chang- and exceptional dynamic range. So far, they have
ing recipes and reaction regimes because of been applied to on-line monitoring of HF and
the necessity to provide an extensive training H2 S traces in refineries. However, their high
data set for each process [118]. costs are prohibitive for most on-line appli-
cations. Acousto-optic tunable filter (AOTF)
Typical analysis time is on the order of sec- based instruments have been occasionally used
onds or even shorter, with sensitivities down to for on-line analysis. Hadamard transform (HT)
tenths of a percent; hence, NIR is an ideal tool spectrometers have not been described for NIR
for observing fast reactions. Spectra of chemi- on-line applications so far.
cally changing mixtures can be recorded through Typical problems with NIR measurements
quartz glass windows mounted in reactors and are the need to check the calibration of the in-
pipes or by fiber optic immersion probes for strument, since the instrumental response may
diffuse reflectance, attenuated total reflectance change after some time [119], and the sensi-
(ATR), transmission, and transflection measure- tivity of NIR spectra to the sample temper-
ments. The application of cheap silica fibers ature, which complicates training procedures.
allows truly remote sensing with distances up NIR equipment and the application of NIR to
to kilometers between process and spectrome- reaction monitoring are reviewed in [120–124].
ter because of the extremely low attenuation of NIR spectroscopy has been widely used for
quartz in the VIS to NIR range. the characterization of epoxy curing [125] with
NIR equipment suitable for reaction conventional fiber optics [126], [127], evanes-
monitoring includes both holographic grat- cent wave high-index fiber optic sensors [128],
ing/semiconductor array detector instruments and the NIR ATR technique [129]. Other fiber
and Fourier transform spectrometers. Light- optic applications include reaction monitoring
emitting diode (LED) based instruments have in explorative organic synthesis [130], real-time
no moving parts because each wavelength band analysis of light alkenes in high-pressure reac-
is produced by a different diode with precise tors at elevated temperatures [131], remote mon-
wavelength tunability and monochromaticity, itoring of styrene emulsion polymerization in the
thus making the instrument rugged to harsh short-wavelength NIR region [132], and deter-
Figure 14. On-line NIR spectra of a polypropylene/ethylene – vinyl acetate copolymer during blend formation (courtesy of
IPF Dresden)
mination of octane in refinery processes [133]. ture during blend formation with an accu-
A fiber optic coupled AOTF NIR spectrome- racy of about 1 %. With the help of ATR
ter has been described for dryer effluent mon- (Fig. 15) and diffuse reflectance probes the
itoring in a chemical plant [134]. NIR spec- formation of styrene – maleimide copolymer
troscopy has been shown to be suitable for on- (Fig. 16), and the filler concentration in molten,
line detection of reaction completion in a closed- opaque polypropylene/chalk powder compos-
loop hydrogenator in pharmaceutical production ites have been monitored. In the latter appli-
[135]. Diffuse reflectance NIR spectroscopy has cation, the inhomogeneous distribution of filler
been evaluated as an on-line technique for the particles may lead to substantially different
monitoring of powder blending [136–138]. Gas- spectra during the course of extrusion. The scat-
phase real-time monitoring by transmission NIR tering contribution of the particles to the NIR
spectroscopy is described in [139]. A promising spectra has to be corrected before chemomet-
application of remote-sensing NIR spectroscopy ric analysis. Appropriate chemometric calibra-
is the on-line identification and classification of tions models are required in both cases [143–
plastics material [140–142]. 145]. Hansen et al. [146–149] were even able to
Near-infrared spectroscopy is one of the derive rheological properties of ethylene – vinyl
few analytical methods applicable to real-time acetate copolymers from NIR spectra recorded
monitoring of chemical processes in polymer in-line in an extruder via fiber optics.
melts during extrusion. Figure 13 shows a ce-
ramic transmission NIR probe with variable op-
tical pathlength that is adapted to a corotat- 5.3.3. IR Spectroscopy
ing twin-screw extruder and interfaced to an
NIR spectrometer via fiber optic cables. On- Infrared spectroscopy has a long tradition of
line NIR spectra, as shown in Figure 14, pro- use in chemistry, materials science, physics, and
vide the quantitative composition of a polypro- even reaction monitoring [150]. It is one of the
pylene/ethylene – vinyl acetate copolymer mix- standard techniques in most analytical laborato-
ries. The IR region of the spectrum is highly spe-
cific and very sensitive to molecular structures. A major obstacle to industrial IR on-line ap-
Individual peaks can be assigned unequivocally plications is the lack of appropriate fibers trans-
to chemical species and calibrated for analyte parent to IR radiation. The chalcogenide fibers
concentration. The timescale for FTIR spectro- currently used are very expensive and have only
scopic analysis is on the order of seconds. All of limited light throughput and hence do not en-
this makes IR spectroscopy attractive for on-line able remote monitoring. Infrared spectrometers
process monitoring. should be installed close to the process to al-
low the use of automated sampling devices, short
fibers, or optical systems that transmit the light
via mirrors and tubes to the analyzer. The latter
option is shown in Figure 5, in which a “mirror-
arm” is interfaced to an FTIR spectrometer. In
Figure 17, a waterfall spectrum and the corre-
sponding line intensities as a function of time
are shown for the reaction of secondary amines
with paraformaldehyde. In this case, a linear cal-
ibration model makes it possible to examine the
reaction kinetics on-line on a quantitative basis.
In aqueous systems, the strong water ab-
sorption in the IR region may interfere with
spectral features of interest for reaction char-
acterization. Nevertheless, on-line monitoring
of 2-ethylhexyl acrylate/styrene emulsion co-
polymerization with an ZnSe ATR fiber optic
FTIR device has been demonstrated successfully
[151].
Applications of FTIR spectroscopy to poly-
Figure 15. ATR immersion probe adapted to a corotation merization reactions include kinetic studies of
twin-screw extruder (courtesy of Carl Hanser Verlag) laser-induced photopolymerization directly in a
a) ATR immersion probe; b) ZnSe crystal; c) Intermediate spectrometer [152], multiacrylate polymeriza-
plate; d) Melt in the itermeshing zone; e) screw
tion studies with a quartz crystal ATR device
[153], and monitoring of carbocationic poly-
High molar absorptivities in the IR are advan- merization with ATR probes [154], [155]. A
tageous for gas analysis but may present chal- water-cooled mid-infrared chalcogenide fiber-
lenges for liquid analysis because sample layer optic probe with an ZnSe crystal was described
thicknesses (optical pathlengths) would have to for in situ monitoring of an acid-catalyzed es-
be in the micrometer range to transmit IR radia- terification reaction in toluene at 110 ◦ C [156].
tion. This distance is too short for circulation of Cross-linking reactions in various resins have
the reaction mixture, so transmission and trans- been studied by IR spectroscopy [157–159], and
flection measurements cannot be used for pro- FTIR imaging with focal-plane array detection
cess monitoring. [160]. The melt crystallization process of isotac-
The technique of choice is ATR spectroscopy. tic polystyrene was studied by means of in situ
The short penetration depth of the evanescent FTIR spectroscopy [161].
wave is both the strength and a limitation of ATR On-line gas process stream analysis was car-
spectroscopy. ATR crystals are prone to surface ried out by piping the gas through a transmission
fouling and layer build-up, which leads to in- gas cell [162] or by means of photoacoustic gas
terference with the process signals. Additional sensors [163]. Chemical processes in thin films
issues to be considered with respect to on-line and coatings have been investigated by photoa-
applications of ATR are the scratch resistance coustic FTIR spectroscopy [164] and in situ IR
of the crystal; the relatively low light through- ellipsometry [165].
put, which requires sensitive detectors; and the
linearity (or nonlinearity) of calibration.
Figure 16. Formation of styrene – maleimide copolymer monitored with a diffuse reflectance dipper probe (courtesy of Carl
Hanser Verlag)
FA = C-18 fatty amine; PS = polystyrene; SMA = styrene – maleic anhydride copolymer; SMI = styrene – maleimide copolymer
5.3.4. Raman Spectroscopy
Fundamentals. Raman spectroscopy com-

bines some of the advantages of (FT)IR and NIR
spectroscopy without the limitations associated
with these techniques. Nowadays, it is one of the
fastest growing areas of analytical chemistry.
Raman spectroscopy produces well-resolved
spectra of fundamental vibrations comparable to
IR spectroscopy. The interaction probabilities of
light with the molecule for the two techniques
are quite different. Infrared absorption is favored
when a molecule has a permanent dipole which
is modulated by the vibration. Raman scattering
occurs when the molecule is polarizable, with
the polarizability modulated by the vibration.
Thus the intensities of IR and Raman bands of
LIVE GRAPH
Click here to view the same substance are fundamentally different,
and the two methods provide complementary in-
formation about the molecule. Some of the bands
can even be absent in one or the other spectrum.
The Raman line intensity is directly propor-
tional to the number of corresponding oscillators
in the scattering volume and the intensity of the
illuminating radiation. Line intensity changes
primarily reflect concentration changes within
the sample, thus making calibration of the spec-
tra rather simple and straightforward. Raman
Figure 17. Waterfall spectrum (a) and the corresponding
line intensities (b) as a function of time for the reaction
of secondary amines with paraformaldehyde (courtesy of
Mettler-Toledo GmbH, Analytical)
spectroscopy does not require extensive sam- scattering of latices, emulsions, aerosols). Mul-
ple preparation, and Raman spectra can be taken tiple elastic light scattering reduces severely the
from almost all samples without pretreatment. scattering volume from which the light for Ra-
The Raman effect is an extremely weak, in- man spectroscopy is collected. Hence, confocal
elastic scattering process. Typically, only 10−6 illumination and collection optics are essential
to 10−9 of incident photons undergo Raman for efficient sample excitation and signal detec-
scattering, and low-loss optical devices are re- tion. Light scattering affects spectral intensities
quired for proper recording of spectra. In Ra- but not band shapes. With confocal optics, inter-
man spectroscopy, there is always a competitive ference of both the window material and films
mechanism for light emission present, namely, built up on window surfaces with the spectrum is
fluorescence of the sample. In some cases, the much reduced, and spectra can be obtained from
quantum yield of fluorescence outweighs the Ra- samples through colored or opaque sample con-
man scattering efficiency by several orders of tainer walls.
magnitude, and the fluorescence of the sample
completely obscures the Raman spectrum. The Instruments. Dispersive scanning Raman
most convenient way to avoid sample fluores- spectrometers operating in the UV or VIS re-
cence is excitation at longer wavelengths. How- gion are not very suitable for process monitoring
ever, as the excitation wavelength increases, the because of the time required to record a spec-
light scattering intensity decreases according to trum. Additionally, the short wavelength excita-
a λ−4 power law. tion may cause severe sample fluorescence. The
Raman signals of some species are much main advantage of dispersive scanning instru-
more sensitive than the corresponding IR ab- ments is the very high resolution achievable by
sorptions. The ability to measure Raman spec- using double or triple monochromators.
tra of symmetrical diatomic molecules (for in- As in IR spectroscopy, FT Raman spectrom-
stance O2 , N2 , H2 , F2 , Cl2 , Br2 , I2 are not ac- eters are suitable for monitoring even very fast
tive in IR absorption) opens up opportunities chemical processes on the timescale of sec-
in gas analysis. Raman spectroscopy is sensi- onds. For practical and cost reasons, most in-
tive to nonpolar molecular vibrations. Hence, strument manufacturers use the same type of in-
double or triple bonds in monomeric or poly- terferometers in their IR and FT Raman spec-
meric molecules are strong Raman scatterers. trometers. Hence, excitation in FT Raman spec-
Vinyl or diene monomers can easily be iden- troscopy is typically at 1064 nm with Nd:YAG
tified, and their concentrations determined by lasers. Therefore, sample fluorescence is very
means of their double bonds. Therefore, Raman much reduced, but FT Raman spectra of aque-
spectroscopy is an ideal tool for monitoring the ous samples are modified by self-absorption of
disappearance of monomers during the course water in the NIR (i.e., for wavenumbers above
of polymerization, and for detecting residual 2000 cm−1 with excitation at 1064 nm). Pros
monomers in final products. Metal carbonyls in and cons of FT Raman spectroscopy are re-
catalysts and cyanides in plating baths give rise viewed in [167–169].
to strong Raman signals due to their triple bonds. The application of holographic transmis-
Raman spectroscopy can be used to monitor the sion gratings and semiconductor array detec-
quality of diamond or diamond-like carbon and tors (CCD or CID) has led to the rediscovery
to distinguish between isomers [166]. of dispersive Raman spectrometers. The major
Water, with a strong molecular dipole, has an advantage of these instruments is they do not
intense IR absorption, but a very weak Raman re- contain any moving parts and are thus rugged
sponse. Thus water obscures IR spectra, whereas and compact for on-line applications in chemi-
Raman scattering is more or less oblivious to the cal plants. However, the insensitivity of a CCD at
presence of water. Hence, Raman spectroscopy wavelengths above 1050 nm restricts the wave-
can easily be applied to aqueous solutions, emul- length of the incident light. For a CCD-based
sions, latices, and suspensions. Disperse sys- instrument, excitation of the sample has to be
tems scatter light because of refractive index dif- done below 800 nm to obtain the entire spec-
ferences between particles and the surrounding trum up to 3000 cm−1 . Most instruments for
continuous phase (e.g., elastic Rayleigh or Mie reaction monitoring are equipped with recently
developed inexpensive and compact NIR solid- Table 5. Double bond Raman lines
state diode lasers operating between 780 and
850 nm, whereby 785 nm or 840 nm are com- Monomer ν̃(C=C), cm−1
monly used. A review on diode lasers for Raman Vinyl chloride 1607
spectroscopy is given in [170]. Acrylonitrile 1610
In this wavelength range, low-cost silica op- Vinyl sulfonate 1619
N-Methyl acryl amide 1629
tical fibers deliver the laser light to the measure-
Styrene 1631
ment site and return the signal efficiently for re- Methyl acrylate 1635
mote monitoring. Holographic filters integrated 2-Ethylhexyl acrylate 1637
into the probe head remove the Raman signal Butyl acrylate 1638
Diisopropyl fumarate 1638
generated within the excitation optical fiber and Ethyl acrylate 1638
prevent reinjection of elastically scattered laser Butadiene 1639
light into the signal return fiber. Raman spec- Glycidyl methacrylate 1640
trometry with fiber-optic sampling is described Methyl methacrylate 1641
Allyl methacrylate 1641/1648
in [171–174]. Veo Va 9/10∗ 1646
For trends in instrumentation and applica- Vinyl acetate 1648
tions, see [175–179]. Vinyl propionate 1648
Crotonic acid 1658
∗
Applications. Prior to the 1990s, only a few Vinyl esters of versatic acids.
publications deal with Raman reaction moni-
toring. The validity of the method has been In the 1990s, a wealth of publications ap-
demonstrated for the suspension polymeriza- peared on in situ Raman investigations, for
tion of styrene [180] and vinyl chloride [181], instance, of polymerization reactions [188–
the thermal polymerization of styrene [182– 193], epoxy resin cure [194–196], crystalline-
184] and methyl methacrylate [184], the so- state photoreactions [197], fast high-pressure
lution polymerization of methyl methacrylate decomposition reactions [198], hydrolysis of
[185], the γ-initiated polymerization of diacety- acetic anhydride to acetic acid in a hydrother-
lene [186], and the microemulsion polymeriza- mal/supercritical water reactor [199], liquid-
tion of styrene and methyl methacrylate [187]. phase chemistry of aliphatic organic peroxides
The decreasing intensity of the ν(C=C) Ra- [200], crystallization of polymer melts [201], a
man lines of the monomer during the course of PCl3 production process [202], petroleum distil-
the reaction was monitored as a measure of the late quality in pipelines [203], and chlorosilane
extent of conversion to polymer. The positions of stream composition [204]. Chemical reactions
the Raman double bond stretching vibration of have even been monitored in aerosol particles
several monomers are listed in Table 5. Raman by means of Raman spectroscopy [205–208].
spectra recorded during emulsion copolymeri- The study of Raman spectra of adsorbed
zation of styrene and butyl acrylate are shown molecules on surfaces is one of the most promis-
in Figure 18. The ν(C=C) double bond peaks of ing areas in Raman spectroscopy. Molecules ad-
the two monomers cannot be resolved since the sorbed on metal surfaces show enhancement
spectral resolution of the instrument was on the of the scattering efficiency by up to seven or-
same order of magnitude as the difference bet- ders of magnitude [209], [210]. This surface-
ween their peak maxima (ca. 7 cm−1 ). The dou- enhanced Raman scattering (SERS) is ultrasen-
ble bond peak disappears almost completely dur- sitive for detecting numerous adsorbed com-
ing the reaction. Based on the spectral changes pounds by means of their vibrational spectra.
as a result of polymerization, the conversion of Originally, SERS experiments were carried out
the two monomers as a function of time can be with either bare metal surfaces or metal colloids
calculated with an accuracy of about ± 1 %. The mixed with solutions of the sample. Covering the
combination of Raman on-line monitoring and substrates with extremely thin modifying layers
automated spectra evaluation enables chemical enables the construction of chemical sensors for
reactions to be controlled efficiently. remote monitoring [211–214].
Figure 18. Raman spectra recorded during emulsion copolymerization of styrene and butyl acrylate. The spectra were recorded
with a fiber-based instrument equipped with a CCD detector. Laser excitation at 785 nm with an output power of about 90 mW
was performed through a glass window in the reactor wall. The accumulation time for each spectrum was about 15 s. Spectra
were recorded at regular intervals of 1 min. Hence, the instrument meets the requirements for an on-line process monitoring
system.
A nonlinear Raman technique, stimulated action monitoring with fiber-optic fluorescence

Raman scattering (SRS), has been used to mon- sensors coated with fluorescent probe molecules
itor the bulk polymerization of styrene and is an emerging technology. In contrast, fluo-
methyl methacrylate [215]. In contrast to sponta- rescence signals in Raman spectroscopy are a
neous Raman scattering, most compounds show source of disturbance because they originate
only a few Stokes lines in their SRS spectrum. from largely unknown impurities and mask the
As a result, spectral interference of SRS-active more specific Raman signal. The fluorescence
compounds in a reaction mixture is minimized. technique is potentially much cheaper than Ra-
man spectroscopy.
Fluorescence methods have been demon-
5.3.5. Fluorescence strated to be useful in academic research for in
situ monitoring of curing [216–218] and poly-
Fluorescence spectral signals are quite intense merization [219–225]. Polymer colloids have
because of the efficient electronic excitation and been characterized by fluorescence quenching
fluorescent emission process. This enables mea- techniques in order to draw conclusions about
surements down to the nanosecond timescale on the internal particle structure, transport phenom-
small samples with remarkable accuracy. The ena, and particle flocculation of latices [226],
sensitivity is high over a wide concentration [227]. A traditional field for the application
range. The spectral features are rather broad of various fluorescence techniques are micel-
compared to those of other spectroscopic meth- lization behavior, molecular interactions, aggre-
ods. Fluorescent techniques provide informa- gation and clouding phenomena in surfactant
tion on molecular arrangement and dynamics of solutions [228–231]. Optical fluorescence mi-
micro-heterogeneous systems, and on micropo- croscopy is capable of in situ chemical analy-
larity or microvicosity. sis of phase-separating polymer blends [232].
Steady-state fluorescence spectroscopy and Various aspects of latex coalescence and film
fluorescence lifetime measurements have been formation were studied by fluorescence tech-
used for on-line reaction monitoring. Sources niques [233–236]. Various monitoring applica-
of fluorescence can be the reaction components tions of fluorescence-based sensors and fluores-
themselves or a fluorescent probe that is added to cent probes are described in [237–242].
enhance the selectivity of the measurement. Re-
Fluorescence is not commonly used for on- of scatterers, or, in the FT time domain, fluc-
line monitoring of chemical processes outside tuations of the light intensity by correlation
academia. Nevertheless, fuel in the cylinder wall techniques. Thus, quasi-elastic light scattering
oil film of a combustion engine has been detected (QELS), Rayleigh linewidth/spectroscopy, in-
in situ with a fiber-optic laser-induced fluores- tensity correlation spectroscopy, and photon cor-
cence system [243]. relation spectroscopy (PCS) are synonymous
with DLS.
Most of the light scattering techniques re-
6. Particle Size Analysis quire extensive dilution of the extracted sample
to avoid multiple-scattering effects. Automatic
An important characteristic of disperse systems
dilution devices are interfaced to the light scat-
(latices, emulsions, aerosols, suspensions, pow-
tering instrument for on-line applications. Direct
ders) is their particle size distribution. Particle
optical access to the (undiluted) reaction mixture
sizes affect almost all properties of a disperse
became possible with the development of fiber-
system (electrical, optical, rheological, etc.), as
optic probes and instruments.
well as its stability. The evolution of the particle
For general reading see [244–246].
size distribution is a sensitive indicator of the
progress of heterophase reactions, and it deter-
mines the application properties of final reaction
6.1.1. Turbidimetry
products.
In this chapter, the main focus is on process
The turbidimetric experiment is rapid, precise,
particle size measurements in suspensions.
reproducible, and absolute (i.e., no calibration is
required). Spectrophotometers are readily avail-
6.1. Scattering Techniques able. Turbidity gives a measure of the attenua-
tion of light traversing a suspension or aerosol
The scattering of electromagnetic waves (light, of nonabsorbing particles. Turbidimetry may re-
X-rays) and neutrons by particulate matter is quire dilution of the mixture to avoid multiple
a powerful tool for studying particle sizes and scattering effects. The wavelength-dependent
shapes, internal particle morphologies, particle turbidity τ of a (diluted) sample provides infor-
dynamics (even under shear), the structure and mation on particle size and concentration. Tur-
dynamics of concentrated disperse systems, and bidimetric (and nephelometric) measurements at
particle charges. Wave interference yields infor- single wavelengths can be used to determine the
mation on particle sizes and shapes whenever concentration of particulate matter in liquid and
the wavelength is of a comparable order of mag- gaseous process streams. Fraunhofer diffraction
nitude to the size of the scatterer. is used for particles sizes 1 µm.
Neutron and X-ray scattering both rely on the Several publications describe the determina-
availability of corresponding neutron and radi- tion of particle size during emulsion polymer-
ation sources. Hence, their use for on-line size ization by specific turbidity τ /ϕ or turbidity ra-
monitoring is extremely limited. tio measurements [247–249]. For a polydisperse
Particle size determination by light scatter- suspension, the turbidity is related to the poly-
ing techniques is a well established broad field mer volume fraction ϕ according to
of experimental methods. In addition to inelasti-
cally scattered light (Raman and Brillouin scat-
∞
dp np
d2p · K ,
λm nm
f (dp ) ddp
tering), there are two basic approaches that ex- 3 0
τ = ϕ (33)
ploit light scattering data for on-line particle 2
∞
d3p f (dp ) ddp
size analysis: Static light scattering (SLS) and 0
dynamic light scattering (DLS). SLS methods
where K, f , λm , and d p are the scattering coef-
involve measurement of the time-averaged an-
ficient, the size distribution function, the wave-
gular scattering as well as turbidity measure-
length of light in the medium, and the particle
ments (i.e., elastically scattered light). DLS mea-
diameter, respectively. The quantities K and τ
sures the very small frequency shift of scat-
tered light caused by translation and rotation
are functions of both the refractive indices of the 6.1.3. Dynamic Light Scattering
particles np and of the medium nm , and of the
size of particles relative to the wavelength of the Particles suspended in a continuous medium
light d p /λm . K can be calculated from the gen- undergo random Brownian motion. Hence, the
eral Mie theory. If the size distribution function phase of light waves scattered by Brownian par-
f is known, the particle size distribution can be ticles also fluctuates randomly in a time-resolved
estimated from specific turbidity measurements light scattering experiment. Their mutual inter-
at several wavelengths. Despite the complicated ference leads to a net randomly fluctuating scat-
dependence of τ on K and its direct dependence tered light intensity I(t) at the detector. The nor-
on the distributional form f (which is sometimes malized autocorrelation function g2 (t ) of the
unknown), the specific turbidity can yield (1) light intensity as a function of time delay t is
the turbidity average particle diameter and the given by
volume-surface average (i.e., D3,2 ) diameter for 9 :
small and large particles, respectively, for any I (t) · I (t + t )
g2 t = 9 :2 (34)
value of m = np /nm , (2) the weight average diam- I
eter for m < 1.15 and particles that are smaller
than the wavelength of the light, and (3) an esti- with I(t) · I(t + t ) (t → ∞) = I2 , the square
mate of the weight average particle diameter in of the average scattered light intensity. The field
all other (monomodal) cases if a log-normal par- autocorrelation function g1 (t ) can be calculated
ticle size distribution is assumed [248], [249]. if the Siegert relation holds
Turbidimetry has been used to study the co- 2

agulation kinetics of aqueous dispersions [250], g2 t = A + B · g1 t (35)
[251]. Efforts were made to extend the theoret-
ical basis of turbidity to higher concentrations where A and B are instrument-related constants.
[252–254]. For a monodisperse system of Brownian par-
ticles, their diffusion coefficient D can simply
be derived from g1 (t ) according to Equation 36
6.1.2. Angular Static Light Scattering
g1 t = exp −q 2 Dt = exp −Γ t (36)
Angle-dependent static light scattering measure- where Γ is the decay constant. The scattering
ments with goniometers are not very suitable vector q is defined as
for on-line monitoring because of the time re-

quired and on other specific demands. A fast- 4πn θ
q = sin (37)
response multichannel photometer capable of λ 2
on-line monitoring even at moderate concentra-
tions is described in [255]. The scattered light where n, λ, and θ are the refractive index, the
is simultaneously measured at 168 angles. This wavelength of light, and the scattering angle,
static light scattering instrument has a response respectively. The Stokes – Einstein equation re-
time of 100 ms and an angular resolution of 1◦ . lates the diffusion coefficient D to the hydrody-
Static light scattering at a fixed angle is valu- namic radius of the particles r h
able for studying the formation and aggregation kb T
of latex particles during emulsion polymeriza- rh = (38)
6πηD
tions [256].
Several instruments are on the market which where kb , T , and η are the Boltzmann con-
automatically dilute aqueous dispersions to a de- stant, temperature, and viscosity of the disper-
sired (extremely low) concentration and perform sion medium, respectively.
static multiple-angle light scattering. Different For polydisperse systems, the autocorrelation
modes of light scattering (including Frauenhofer function becomes a sum of exponentials with a
diffraction) are typically combined within one distribution function G(Γ )
instrument to enable particle size analysis over
a wide range of sizes.
∞ and makes the method applicable to turbid

g1 t = G (Γ ) exp −Γ t dΓ (39) and concentrated systems. Monomode fibers
0 further suppress multiple scattering effects
[261].
Particle size characteristics and distribution
Particle growth during emulsion polymer-
functions can be derived from measured auto-
ization has been studied by conventional DLS
correlation functions by (1) directly inverting the
[262–266] and fiber-optic DLS [267], [268].
Laplace integral equation (Eq. 39, a mathemati-
cally ill-conditioned problem), or (2) parameter
fits, exponential sampling, regularization tech- 6.1.4. Other Optical Techniques
niques, and histogram analysis.
Some advantages make dynamic light scat- The effect of multiple scattering can be useful for
tering attractive for on-line applications: studying highly concentrated dispersions. The
path of multiply scattered light in the dispersion
1) DLS is an absolute method; no calibration is similar to the path of particles or molecules
over time is necessary. With conventional under the influence of Brownian diffusion [269–
DLS systems, accuracies of ± 1 % for the 272]. The concept of photon migration or diffus-
mean particle diameter can be achieved on a ing wave spectroscopy (DWS) has already been
routine basis within a few minutes of mea- applied to particle size determination.
surement time. Care must be taken in react- Colloidal refractometry is an optical method
ing systems, where either temperature or vis- that measures the refractive index n of a disper-
cosity change during the course of the reac- sion and analyzes it by using Mie theory. This
tion (see Eq. 38). method allows the structure of concentrated dis-
2) Particle properties such as density or refrac- persions to be probed in the undiluted state. The
tive index do not affect the time behavior of measured values of n can provide a measure of
the intensity fluctuations. Thus, the derived the volume average particle size [273].
particle sizes are independent of the chemi-
cal composition of the particles.
3) In the single-scattering regime, diffusion co- 6.2. Separation Techniques
efficients and particles sizes are independent
of particle concentration. This is an advan- Recently, particle separation techniques (chro-
tage over turbidity measurements, for which matography, fractionation) have been developed
exact knowledge of the particle concentra- that are capable of on-line monitoring of parti-
tion is crucial for size calculations. cle size. These methods require fully automated
4) The use of inexpensive fiber-optics allows removal of samples from the reaction mixture,
remote monitoring. dilution, and injection into the instrument.
Size exclusion chromatography (SEC) is ap-
Two approaches are possible for on-line DLS plicable with porous (liquid exclusion chro-
measurements: matography LEC) and nonporous packing of the
column (hydrodynamic chromatography HDC).
1) A device interfaced with the process line Particles are separated because of the depen-
or reactor automatically captures a certain dence of the rate of particle flow through gaps
amount of the mixture and dilutes it suffi- between packing beads on particle size. Larger
ciently to avoid multiple scattering and allow particles are eluted first since they travel through
noise-free measurements [257]. larger gaps with higher flow rates. The main ad-
2) A fiber-optic probe (optode) is directly vantage of SEC methods is that particle size dis-
immersed into the mixture and both il- tributions can be obtained directly without any
luminates the colloidal system and col- assumption regarding the mathematical form of
lects the scattered light (FOQELS: fiber op- the distribution. Calibration of the instruments
tic quasi elastic light scattering; FODLS: with particle size standards is necessary but sim-
fiber optic dynamic light scattering [258– ple. Disadvantages are the limited resolution be-
260]. This backscattering arrangement short- cause of radial dispersion, and relatively long
ens the light path within the dispersion elution times of up to half an hour [274], [275].
Next Page
Much higher resolution than with SEC meth- 7. Chromatography

ods can be achieved by capillary hydrodynamic
fractionation (CHDF) [276] and field-flow frac- 7.1. Introduction
tionation (FFF). The fluid in a CHDF capillary
has a parabolic velocity profile with the greatest Chromatographic methods (especially gas chro-
fluid velocity at the center of the tube and zero matography) are the most widely applied family
velocity at the wall. Particles move radially due of techniques for determining the chemical com-
to their Brownian motion. Larger particles are position of reaction mixtures.
unable to approach the wall as closely as smaller A comprehensive discussion of (gas) chro-
particles. Hence, larger particles travel through matography for on-line monitoring of chemical
the tube faster than smaller particles. This sepa- reactions has been published [287]. Process ap-
ration effect is exclusively a function of particle plications can also be found in [288–291].
size; it is independent of particle density. The The term “process chromatography” almost
efficiency of capillaries for separating particles exclusively refers to the application of gas chro-
depends on the eluent viscosity, the flow rate, matography (GC) to monitor chemical reac-
and the capillary diameter. The optimum parti- tions or process streams. Advantages of GC are
cle size for CHDF analysis is < 1 µm. The main its simplicity, high sensitivity and selectivity,
disadvantage of this method is the possibility and ease of automation. Liquid chromatogra-
of capillary clogging. The CHDF method has phy (LC, including HPLC), supercritical fluid
been used to monitor the evolution of the parti- chromatography (SFC), electrophoresis (EP),
cle size distribution during emulsion [277] and and ion chromatography (IC) are less common
miniemulsion polymerization [278]. in process monitoring because of their higher
Field-flow fractionation (FFF) is a family of maintenance requirements, greater complexity,
chromatography-like elution techniques based and higher costs for purchase and maintenance.
on influencing the rate of particle flow through Because GC (like other chromatographic
a narrow channel by applying an external field methods) is an inherently discontinuous batch-
perpendicular to the flow direction [279–283]. like analytical technique which is applied to con-
The external field separates particles of differ- tinuously monitor a chemical system in a nonbe-
ent sizes by driving them into different localized nign environment, there are distinct differences
laminas (< 10 µm thick) of the parabolic veloc- between laboratory and process instruments, al-
ity profile of the eluent within the fractionation though the basic components of a gas chromato-
channel thus causing their separation. In contrast graph can be found in instruments of both cate-
to CHDF, FFF does not necessarily require cal- gories (Fig. 19) and the basic principles of sep-
ibration of the instrument. Retention times for aration are the same.
particles of different sizes can be calculated di- In contrast to laboratory instruments, pro-
rectly from first principles. cess analyzers have to meet stringent safety and
FFF can be classified according to the type of explosion-proof requirements because of their
applied field into sedimentation, thermal, elec- close vicinity to the product line. The typical
trical, cross-flow, and steric. The most suitable GC process instrument is designed to detect and
external fields for particle size analysis are cross- monitor only one or a few (previously known)
flow and sedimentation fields. The particle sep- components of the reaction mixture so as to con-
aration in cross-flow occurs according to the hy- trol a chemical reaction or process stream. This
drodynamic radius of the particles, whereas their requires special injection valves and column-
effective weight separates particles in a sedimen- switching devices. As in conventional GC, the
tation field. The particle size ranges for cross- amount of sample required for process GC is ex-
flow and sedimentation field FFF are 10 nm to tremely small. Hence, the sampling system must
100 µm and 50 nm to 100 µm, respectively. Re- ensure that the sample is representative of the
cently, FFF (including thermal FFF) has been process to be monitored. Often, a sample con-
used to characterize the size and composition ditioning system is necessary to further process
of core/shell latices [284]. On-line coupling of
FFF with multi-angle laser light scattering is de-
scribed in [285], [286].
Previous Page
Figure 19. Schematic of a process GC analyzer GS: gas supply for carrier, auxiliary, and purge gases; V: valves for presepa-
ration, column switching, and injection; VP/LP: vapor-phase/liquid-phase sampling; SHC: sample handling and conditioning
system; R: reactor; S: separation unit; C: column(s); D: detector; O: thermostatically controlled oven; PC/C/NW: personal
computer/controler/network; W: waste gases
the sample, which may still be reactive, for GC the GC analyzer, the gas storage and delivery
analysis. systems should be equipped with valves that
The nonspecific character of detection based switch atomatically between empty and full con-
exclusively on retention time (i.e., no positive tainers.
identification) makes GC preferably suitable
for process monitoring of continuous processes Sampling. The quality of a GC analysis of a
with small variations in composition. Different reacting mixture is only as good as the quality
molecules may have the same retention time, of the samples withdrawn from it. Because of
confusing quantification of the chromatograms the very small amounts of sample necessary for
and leading to misinterpretation of overlapping GC, it is crucial to withdraw samples that are re-
peaks. Additionally, GC analysis requires time presentative of the mixture. The sampling point
for separation and detection. This time interval (sample probe) should be located at a point in
must be reasonably short compared to both the the bulk of the medium where it is homogeneous
run time of the reaction and the time required to and well mixed so as to obtain the “true” bulk
feed the analytical result into a process controler, composition of the mixture. Close to the walls,
and to influence the reaction. adsorption and deposition phenomena and stag-
nant flow may locally change the overall com-
position.
7.2. GC Hardware Components From an analytical point of view, the best lo-
Carrier Gas. In principle, the same carrier cation for the analyzer would be right next to
and auxiliary gases can be used in both labora- the process line or sampling loop. However, a
tory and process GC analyzers (usually hydro- number of factors and restrictions have to be
gen, helium, argon, synthetic air, or nitrogen, taken into consideration for placing the chro-
depending on the application). Most high-purity matograph relative to the sampling point, e.g., 1)
gases are supplied in containers (e.g., high-pres- space available for installation, 2) maintenance
sure gas cylinders). For an on-line operation of
requirements, 3) safety requirements, 4) access- actions. Since detection is solely based on reten-
ability of sampling point and chromatograph, 5) tion time, all processes that can influence reten-
connection to utilities and supplies (carrier gas, tion times must proceed unaltered to avoid loss
electricity, compressed air), 6) optimization of of calibration under automated operating condi-
instrument lag time versus control cycle time, tions. Constant temperature is usually guaran-
7) minimization of sample transport, 8) reactiv- teed by circulating heated air within the process
ity/stability of the analyte. In most applications, analyzer oven or by using high-mass metal heat
a sample transfer line bridges the distance bet- reservoirs. In some applications, tighter temper-
ween sampling point and analyzer. Length and ature control can be circumvented by an inde-
diameter of the transfer line must be optimized pendent delayed injection of a standard or by
for (high) analyte flow. Pressure drop and tem- adding an internal standard to the carrier gas.
perature changes along the line must be con- Pressure control and programming is domi-
trolled. When the analysis is complete, the sam- nant in process chromatographs, although some
ple is returned to the process by a separate line temperature programmable analyzers and gradi-
or disposed of along with the carrier/purge gas. ent systems have been recently described in the
In many processes, GC samples are taken literature.
at elevated temperature and/or pressure. These
samples may contain unconverted components, Valves and Columns. In contrast to labora-
other reactive ingredients, water vapor, liquids, tory instruments, a process chromatograph is
or solid impurities. Hence, process samples usually designed to monitor only one or just a
must be appropriately conditioned before feed- few components of the reacting system for con-
ing them into the GC analyzer. The sample control purposes. Exceptions include some petro-
ditioning system peforms depressurizing and chemical applications, in which up to several
temperature reduction as well as filtration and hundreds of components are monitored simulta-
removal of liquids (e.g., by vaporization). Its dif- neously. Additionally, the process GC analyzer
ferent elements may be close to the sample point must operate unattended in a rather harsh envi-
(pressure reducer, filter) or close to the analyzer ronment over extended periods of time, but still
(temperature control, flow control). The condi- provide reproducible and stable data. Of special
tioning system ensures that the temperature of importance is a constant sample volume/mass
gaseous samples is held above the dew point to for injection (and volume of standard, if nec-
avoid condensation and that the temperature of essary). Therefore, dedicated valve systems for
liquid samples is well below the boiling point to sample injection and column switching have
avoid bubble formation in the line. been developed [287]. For gaseous samples, the
Sample transfer and conditioning are the sample size is normally defined by the volume of
most time-consuming part of an on-line GC an external sampling loop connected to different
analysis. The lag time between process and anal- valve ports. The injection volume of liquid sam-
ysis is on the order of a few minutes and must ples can be defined by the size of internal grooves
be taken into account in designing reaction con- within the valve or by external sampling loops.
trol systems based on conventional GC. With Sliding, rotary, and diaphragm valves with
microsensor GC systems, timescales on the or- a wide variety of internal pathways and port
der of (milli) seconds for on-line analysis are configurations are commonly used in process
possible. chromatography of gaseous samples. For liq-
uid samples, piston (syringe) valves may also
Analyzer Oven. In contrast to most labo- be applied. Valves are heated externally or in-
ratory instruments, the actual process chro- ternally. Depending on the component(s) of
matograph (i.e., injection system and valves, interest within the complex reaction mixture,
column(s), detector(s), controls) is placed in cutting (mainly heart-cut technique) and other
a single temperature-controlled oven. Temper- column-switching techniques (e.g., backflush-
ature control of better than ± 0.05 K sup- ing) or multicolumn analysis are often combined
presses fluctuations in temperature-sensitive with precolumn separation. The main reason for
processes such as gas flow, mobile-phase diffu- using column-switching techniques in on-line
sion, adsorption/desorption, and chemical inter- process GC is to drastically reduce the total anal-
ysis time and to fully separate the components 7.3. Applications of Gas
of interest from the mixture. In general, the same Chromatography
types of valves are used for injection and column
switching. GC has a long tradition of use for controlling
Traditionally, the use of packed columns pre- processes and process streams in industry. On-
dominates in process GC. As in laboratory GC, line GC is one of the most important tech-
packed columns are being replaced by capillar- niques for monitoring distillation, rectification,
ies in an increasing number of on-line applica- and conversion processes in refineries and chem-
tions. With capillary columns, chromatographic ical and pharmaceutical plant. It is extensively
separation is improved, resolution is higher, applied in catalysis research, development, and
and analysis time is shorter than with packed production to evaluate catalysts and study reac-
columns because of the much simpler flow and tion mechanisms and kinetics. Another field of
diffusion pattern of the analyte. However, cap- use is in metallurgical smelters for gas and sul-
illaries are normally less sensitive, more expen- fur analysis in metals. It is widely utilized as a
sive, and not so easy to use as packed columns. A part of workplace safety systems, e.g., to ensure
major drawback of capillary columns in process air quality in production units, pilot plants, and
applications is their sensitivity to flow, pressure, laboratories.
and especially temperature fluctuations. On-line GC has proved useful for determin-
Columns, their supports, coatings, and packing organic substances in water [292], [293],
ing materials have to withstand possible corro- wastewater analysis [294], and air monitoring
sive action of ingredients of the reaction gas [295–297]. Reports have been published on
mixture and should be inert to reactions with the on-line analysis of petroleum [298], [299]
solute molecules (e.g., by silylation of the col- and gasoline [300–302], the determination of
umn packing material or capillary coatings). The octane numbers with n-alkanes as reference
presence of water vapor and oxygen traces in [303], the on-line monitoring of methyl for-
process gases may also be of relevance to col- mate conversion to methanol and carbon monox-
umn selection. ide [304], Fischer – Tropsch synthesis [305]
and thermolysis/decomposition of organic com-
Detectors in process chromatographs have pounds [306], [307]. The application of gas
to comply with the overall safety, robustness, chromatography (among other techniques) for
and reliability standards of an on-line instru- on-line monitoring of polymerization reactions
ment. The overwhelming majority of GC de- is reviewed in [308]. Gas chromatography of the
tectors utilized in process analyzers are of the reaction mixture [309], [310] and the head space
thermal conductivity (TCD) and flame ioniza- of the reactor [311], [312] can be applied for on-
tion (FID) types because of their ease of use and line determination of residual monomer compo-
sensitivity to the process components of interest. sition in emulsion polymerization.
TCDs are sensitive to changes in the bulk ther- Head-space GC in liquid reaction mixtures is
mal conductivity of the carrier gas in the pres- not straightforward for direct reaction monitor-
ence of the analyte, which gives a concentra- ing because it requires knowledge of the par-
tion-dependent signal, whereas FIDs sense the titioning of each component between the gas
number of certain ionized molecules entering phase above the reaction mixture and the liquid
the flame with a specific flow rate. In some rare mixture, and, especially in multiphase reactions,
cases, photoionization (PID) and flame photo- between the different phases of the reaction mix-
metric (FPD) detectors are applied. ture (e.g., aqueous phase, monomer droplets,
Several methods have been utilized in pro- and polymer particles in an emulsion polymer-
cess GC to convert detector output signals (peak ization). Additionally, the head space should be
areas) into desired analyte concentration values, in thermodynamical equilibrium with the fluid
such as the separate injection of calibration stan- reaction mixture.
dards, the use of internal standards, and calcula- The utilization of (mass) sensors for gas and
tions based on relative response for the different liquid analysis has been reviewed in [313–315],
detector types.
In-line applications of chemical sensors to mon- to abrasion, deactivation, and contamination of

itor polymerization reactions has not been de- the active electrode surfaces. Additionally, the
scribed in the literature so far. Such sensors analytical information of interest must be ex-
should have a very high selectivity so as to de- tracted from the integral signal. Calibration of
tect components well below the percent range in the sensing system is typically necessary at the
a matrix of solvent or solvent vapor (including beginning of a measurement cycle and subse-
water) containing a large number of ingredients, quently in regular intervals. Accumulation of
some of them with a chemical structure com- static electricity within the sensing system and
parable to that of the analyte. Additionally, the on its body must be avoided.
sensors would have to deal with precipitates on
their surfaces.
8.2. Conductometry
Conductometric measurements rely on the ex-
7.4. Other Chromatographic Techniques istence of charges in the medium that are mo-
bile in an applied electrical field (e.g., ions in
Applications of liquid chromatographic systems electrolyte solutions or melts, electrons in met-
to monitoring chemical and biochemical pro- als). In conductometry, no reaction takes place
cesses are described in [316–322]. On-line ion at the electrodes. Electrical conductance of the
chromatography has been used to monitor adipic medium or electrical capacitance of a measure-
acid production [323], trace metal ions [324] and ment cell is the measured quantity. Conductome-
cations [325], and oxides in flue gases [326]. try in solutions and melts is a nonspecific method
Reviews on process ion chromatography can be because all anions and cations contribute to the
found in [327] and [328]. In some rare cases, medium’s conductivity. However, the method is
capillary electrophoresis [329], [330] and super- very robust, precise, sensitive, fast, and does not
critical fluid chromatography [331], [332] have require extensive maintenance.
been described as on-line reaction monitoring Concentration ci and µi of all the ions i
techniques. present in a medium determine its conductivity
Λ (and conductance G)

Λ = kG = kF ci ni µi (40)
8. Electroanalytical Methods i
where ni is the ion valency, F is Faraday’s con-
8.1. Introduction stant, and k a cell constant. This linear relation-
ship between concentration and conductivity is
Electroanalytical methods are based on the in- the basis for concentration measurements in the
teraction of electrical fields with chemical pro- lower concentration range (≤ 0.1 Ω−1 cm−1 ).
cesses or on chemically induced electrical sig- For higher electrolyte concentrations, Equa-
nals on electrodes. The major advantage of elec- tion (1) becomes nonlinear because of ionic
troanalytical methods is the electrical output of interactions. Additionally, polarization effects
the measurement (i.e., electrical current, poten- may occur at the electrodes. The temperature
tial, resistance, or charge), which can directly dependence of the ionic mobility µ leads to an
be processed electronically without any further almost (quasi) linear dependence of Λ on tem-
transformation, in contrast to other monitoring perature in the temperature range common for
techniques. Although the main application for conductivity measurements in electrolyte solu-
electroanalytical techniques is process monitor- tions (0 – 100 ◦ C).
ing in aqueous solutions, they can also be applied Two different principles of conductivity mea-
to nonaqueous and nonliquid systems. surements are in industrial use: 1) two- or four-
In most electroanalytical measurement sys- electrode conductive cells with direct electrode
tems, the sensing electrodes are in direct contact contact to the medium, and 2) inductive, elec-
with the reaction medium and all of its compo- trodeless, and contactless devices.
nents, not only with the species of interest. This Contact electrode cells are applied in nonag-
can lead to cross-sensitivity and poisoning, and gressive media. The cell itself is typically part
of a Wheatstone bridge operating with low- mation, disappearance of particles, phase inver-
frequency alternating current to avoid electrode sions, and particle swelling in heterophase reac-
polarization. Two-electrode cells are in use in tions such as crystallization and emulsion and
the conductance range 10−8 to 10−1 Ω−1 cm−1 , suspension polymerization [334–337].
whereas four-electrode cells are suitable for Most applications of conductometry deal
the higher conductance range of 10−3 to with monitoring of process streams rather than
10 Ω−1 cm−1 . direct reaction monitoring. Typical application
Electrodeless inductive measurements are the fields are drinking water purification and tap
method of choice for highly conductive systems; water monitoring, wastewater treatment, clean-
for aggressive, abrasive, or corrosive media; and ness of ultrapure water in the electronics indus-
for high-temperature applications. The medium try, distillation processes, neutralization and pre-
to be measured is circulated through a loop; two cipitation reactions, concentration monitoring of
transformer coils are attached to the inert wall acids (e.g., in production of concentrated sulfu-
material of the loop pipe (Fig. 20). A generator ric acid), lyes, and salt solutions, and monitoring
supplies alternating voltage to the primary coil. of process streams in dairies and breweries.
The induced alternating voltage at the secondary
coil depends on the conductivity of the solu-
tion circulating through the loop. For contact- 8.3. Potentiometry
less measurements, the medium’s conductance
Potentiometric techniques are characterized by
is typically much higher than 10−1 Ω−1 cm−1 .
the fact that electrode reactions at equilibrium
Inductive devices are less sensitive than elec-
are involved in the potential measurement. In po-
trode cells.
tentiometry, the actual electrical current through
the electrode is zero. The electrode potential can-
not be measured directly but only as a difference
with respect to the potential of another electrode
(reference electrode). Electrode potentials and
the potential difference between two electrodes
can be calculated according to Nernst’s equation
(Eq. 42)

RT ai
Uelectrode ∼ ln (42)
F ai,ref
where R is the gas and F is Faraday’s con-
Figure 20. Schematic of an electrodeless conductivity mea-
surement device G: generator; D: detector; P: primary coil;
stant. The ion activities ai can be activities of
S: secondary coil; ≈: alternating current two different ions within the same solution (re-
dox pair), activities measured with two different
electrodes, or activities at two different concen-
trations or partial pressures.
The elctrical conductivity Λd of a disperse
system is a function of both the volume fraction Ion-Selective Electrodes. The swelling
of the disperse phase ϕ (ϕ 1) and the electrical glass layer of ion-selective electrodes is de-
double layer properties of the particles (surface signed to be sensitive to a certain type of ions and
conductivity Λs , Zeta potential ζ) insensitive to others. This can be achieved by us-
ing membranes containing inorganic salts of the
1
Λd = Λ0 + ΛS (41) ions of interest (e.g., Na+ , K+ , Cu2+ , NH4+ ,
f
Cl− , F− , I− ). Conditioning of the mixture to a
where ΛS is the conductivity of the dispersion certain conductivity and pH level is a prerequi-
medium, Λ0 the conductivity of the dispersion site for ensuring precise concentration measure-
medium and f a form factor accounting for ments with ion-selective electrodes. Hence, the
the shape and the volume of the (nonconduct- use of this type of electrodes for direct (in-line)
ing) particles [333]. Thus, conductivity mea- insertion into a reaction mixture is limited [338],
surements provide information on particle for- [339].
pH measurement is the most important and a reference electrode. Redox potential measure-
most widely used potentiometric technique in ments are highly nonspecific because all redox
aqueous solutions or water-containing systems. couples of a mixture contribute to the potential.
Measurements of pH are crucial for monitoring The redox potential also strongly depends on
processes in the chemical and pharmaceutical in- pH. Thus, the applicability of redox potential
dustries, the food and beverages industry, waste- measurements is mainly limited to determining
treatment plants, environmental protection, and qualitatively, e.g., nitrites in wastewater (deni-
biochemical operations [340]. In particulate sys- trification), cyanides, copper, and chromium in
tems, the pH has a dramatic influence on col- galvanic wastes, or chlorine in public swimming
loidal stability (e.g., cosmetic products, emul- pools.
sion and suspension polymerization). Care must
be taken to take into account temperature varia- Potentiometric Oxygen Analysis. Solid-
tions of the reacting system because of the strong state electrolytes that exhibit ionic conductivity
temperature dependence of electrode potentials. at elevated temperatures (> 500 ◦ C) can also be
pH measurements are easily performed with used for potentiometric measurements. Porous
standard glass electrodes. For process appli- ZrO2 membranes covered with platinum grids
cations, the most common pH-sensitive mem- have been used to determine oxygen in gases
branes consist of lithium glasses. Other alkali potentiometrically. Different oxygen concen-
metal glasses are prone to increased hydrolysis trations on the two sides lead to a potential
and instability, especially in alkaline solution. difference across the membrane in proportion to
Several types of glasses are available for differ- the difference in oxygen partial pressure.
ent process environments (standard, highly alka-
line, highly acidic, high temperature). Problems
may arise with glass electrodes due to contam- 8.4. Amperometry, Voltammetry, and
ination of the surface by precipitation or film Coulometry
formation. Cleaning and maintenance of glass
electrodes on a regular basis are critical for suc- Amperometric, voltammetric, and coulometric
cessful on-line pH measurements. techniques are not so widely used as other
Glass electrodes with counterpressure are ap- electroanalytical methods for reaction monitor-
plicable for on-line monitoring of reactions up to ing. They are characterized by electrode reac-
temperatures of about 80 ◦ C and pressures up to tions at polarized electrodes that are detected
60 bar. Mechanical instability is a major draw- by current – voltage measurements. Because of
back of glass pH electrodes in high-pressure ap- the electrode reactions the electrodes have to be
plications. cleaned on a regular basis, and a certain fraction
Solid-state ion-sensitive field effect transistor of the mixture under investigation is consumed
(ISFET) sensors show faster response, lower al- during the measurement.
kaline errors, and improved mechanical stability Applications include the amperometric de-
than glass electrodes. However, they also suffer termination of chlorine, dissolved oxygen, hy-
from surface contamination. The applicability of drazine, and ozone in pulp-bleaching baths; tap,
ISFET pH sensors is limited to pressures well be- industrial, and wastewater, amperometric mon-
low 50 bar and temperatures up to 85 ◦ C [341]. itoring of hydrogen peroxide in textile bleach-
There is no solid-state sensor on the market ap- ing baths [346], the amperometric monitoring
plicable for pressures above 60 bar. An as-yet of gases and air at work places, the voltam-
not commercially available ZrO2 sensor for pH metric determination of heavy metals in waste
measurements under high pressure (83 bar) and streams, and the coulometric analysis of sulfur
high temperature (285 ◦ C) is described in [342]. compounds.
A number of different optical pH sensors have
been developed [343–345].
Redox Potential. The oxidizing or reducing

character of a solution can be measured with (in-
ert) precious metal electrodes (Pt, Au) relative to
9. Miscellaneous Methods MS can be used to monitor gaseous impurities

in high-purity gases, to study plasma etching
9.1. Mass Spectrometry processes [357], molecular beam epitaxy, and
chemical vapor deposition processes [358].
In the 1990s, mass spectrometry (MS) emerged
as technique for on-line analytical purposes. The
method is highly sensitive and fast with an ex-
traordinary molecular selectivity. The detection
principle of MS is based on an ionization of
chemical species followed by a sparation of the
fragments according to their mass-to-charge ra-
tio. Due to the wide variety of ionization tech-
niques, most types of sample can be analyzed
by MS. Ionization techniques for process appli-
cations include electron impact (EI), resonance-
enhanced multiphoton ionization (REMPI), mi-
crowave plasma ionization, thermal ionization,
and electrospray ionization (ES). Direct capil-
lary and membrane inlets are most commonly
used for sample introduction. MS process appli-
cations are reviewed in [347–350].
In an increasing number of process applica-
tions MS is interfaced to pre-separation tech-
niques such as GC or LC to improve resolu-
tion and selectivity in the analysis of complex
(reaction) mixtures. Reduced costs, size, and
complexity of the instruments have even made
portable MS devices possible. Efforts have been
undertaken within the last couple of years to
miniaturize MS instruments (“MS on a chip”).
The traditional on-line fields of use of MS
are process gas stream and environmental gas
analysis, environmental and wastewater mon-
itoring, and monitoring of fermentation pro-
cesses. Trace amounts of aromatics and chlo-
rinated compounds in flue gases of industrial
incinerators have been detected by REMPI-MS
[351].
MS has also been applied to monitoring
liquid-phase and gas-phase chemical reactions.
On-line MS is useful for monitoring alkanes and
alkenes in rubber production [352], monomers
and solvents in polyethylene production [353],
or electrochemical polymerization of aniline
Figure 21. U-shaped tube for density measurements (cour-
[354]. tesy of Anton Paar KG)
The modern semiconductor industry relys
heavily on MS process monitoring [355], [356].
9.2. Densimetry and Dilatometry 1

start
− 1
(t)
Xr (t) = (44)
1
start
− 1
end
The physical basis of densimetry and dilatom-
etry is the mass density difference (if any) bet- where start and end are the density of the mix-
ween initial reaction mixture and the final re- ture at the beginning and end of the reaction.
action product. As the reaction proceeds, this Most of the common principles to perform
density difference leads to an increase or de- density measurements (pyknometer, buoyancy)
crease in the density of the mixture (t) and to are unsuitable for reaction monitoring. Methods
an overall shrinkage or expansion, respectively, that have been applied to process monitoring
of the volume of the reaction mixture V . Den- include hydrostatic pressure measurement, the
sity changes can be measured continuously with maximum bubble pressure technique, oscilla-
responses on the order of one measurement per tions of U-shaped tubes, cylinders or plates, and
second, while the repetition time for measure- absorption of radioactive radiation or X-rays.
ments of volume changes is in the millisecond Table 6. Densities of monomers and polymers at 20 ◦ C
range. Therefore, the extent of reaction can be
calculated at any time if the amount of ingredi- Monomer Density, g/cm3
ents initially charged to the reactor and/or con- Monomer Polymer
tinuously fed to the reaction mixture is known.
Acrylic acid 1.051 1.37
The following factors must be considered in Acrylonitrile 0.806 1.17
applying these techniques: 1,3-Butadiene 0.621 0.97
Butyl acrylate 0.899 1.08
1) For a quantitative analysis of density n-Butyl methacrylate 0.886 1.06
changes, it has to be checked carefully Ethyl acrylate 0.924 1.12
2-Ethylhexyl acrylate 0.887 0.99
whether the reaction mixture behaves as an Ethyl methacrylate 0.914 1.13
ideal mixture or not; that is, does Equation 43 Methyl acrylate 0.954 1.22
Methyl methacrylate 0.944 1.19
o-Methylstyrene 0.916 1.01
Vtotal = Vi + Vexcess (43) Styrene 0.906 1.04
i Vinyl acetate 0.932 1.18
Vinyl chloride 0.911 1.39
with V excess = 0 hold, where V total , Vi , and Vinyl methyl ether 0.750 1.06
V excess are the volume of the reaction mix-
ture, volume of component i, and excess vol- A rather robust technique is the measurement
ume, respectively. of the resonance frequency of a U-shaped tube
2) Accurate densimetric and dilatometric mea- (Fig. 21). This resonance frequency is a very sen-
surements rely substantially on the accu- sitive function of the mass of fluid within the
racy of temperature control to be better than tube, and, hence, of its density. The densimeter
± 0.1 K (in some cases even better than has to be calibrated with a liquid of known den-
± 0.01 K). sity cal that gives a period T osc,cal of the U-tube
3) As with all other “integral” methods, a sin- oscillations. The density of the mixture (t) can
gle variable (density, volume, temperature, be derived from the change of the period of os-
pressure) is insufficient to describe multi- cillations T osc (t) provided the temperature T of
component reaction mixtures. the mixture is held constant (Eq. 45)

Density measurements are suitable for re- (t) − cal = const. Tosc
2
(t) − Tosc,cal
2
(45)
action monitoring of polymerizations (in bulk,
solution, emulsion, suspension) because of
To obtain noise-free results, gas bubbles
the considerable density differences between
should be avoided while circulating the reac-
monomers and polymers (Table 6). In a two-
tion mixture through the tube densimeter. In low-
component system, the extent of reaction (e.g.,
viscosity media, bubble traps can prevent bub-
conversion x r (t) in polymerizations) can simply
bles entering the densimeter tube. A prerequi-
be calculated according to Equation 44 by as-
site for the application of Equation (45) is that
suming ideal mixing behavior
the viscosity of the calibration liquid is roughly
equal to the viscosity of the mixture because For density measurements, two capillaries
of its influence on the tube attenuation. The ac- of equal diameter are inserted into the mix-
curacy of density measurements with commer- ture at different depths hi beneath the surface.
cially available oscillating tubes can reach the This leads to a difference of pressure readings
range 10−6 to 10−7 g/cm3 . Applications of U- ∆pbubble of the two capillaries, and
shaped tube density measurements to monitor-
∆pbubble
ing reactions can be found in [359–361]. = (47)
(h1 − h2 ) g
In addition to gas bubbles and temperature
uncertainties, film formation on the inner surface The internal bubble pressure due to surface ten-
of the tube, formation of sediments, and clog- sion is identical for the two capillaries.
ging of the pipe may cause problems with this In addition, the two-capillary principle can
method. These problems can be partially over- also be used to measure the surface tension of
come by the inverse arrangement: a tuning fork the liquid. In this case, two capillaries of dif-
inserted into the mixture. Again, the change of ferent diameters r 1 and r 2 are immersed into the
resonance frequency of the fork is related to the liquid at the same depth and experience the same
density of the surrounding liquid, and the am- hydrostatic pressure but different internal pres-
plitude with which the fork oscillates (i.e., the sures due to different bubble curvatures. Thus,
attenuation) is a function of the viscosity of the
∆p
medium. γ = bubble (48)
The maximum bubble pressure technique is 2 r
1
− r1
1 2
based on the pressure pbubble of a spherical gas
Corrections must be made to account for the in-
bubble of radius r at a capillary tip immersed
fluence of capillary forces and nonspherical bub-
in the reaction mixture at depth h (Fig. 22). This
ble shapes [362]. In stirred or turbulent media,
pressure is the sum of the hydrostatic pressure of
bubble shear-off may cause problems as well as
the liquid above the capillary tip, and the pres-
coagulum formation or clogging of capillaries
sure generated by the liquid – bubble interfacial
in film-forming media. The accuracy of bubble
tension γ
densimeters is on the order of 10−3 g/cm3 .
pbubble = gh +
2γ
(46)
The hydrostatic pressure ph of a liquid mea-
r sured at a depth h is
where g is the acceleration due to gravity [362],
[363]. Thus, pbubble depends on both the immer- ph = gh (49)
sion depth of the capillary tip into the liquid, and The hydrostatic pressure difference ∆ph bet-
the capillary and, therefore, bubble diameter. ween two pressure sensors at different depths of
distance ∆h = h1 - h2 is directly proportional to
the liquid density
∆ph
= (50)
∆hg
The physical basis of Equations (49) and (50) is
essentially identical. In stirred or flowing media,
the hydrodynamics may add considerable noise
to the pressure readings of the sensor.
The absorption of radioactive radiation
(including X-rays) depends on the molecu-
lar/atomic absorption coefficient, the density
(concentration) of the ingredients, and the thick-
ness of the material through which the radiation
passes (path length d). After calibration of the
absorption of both the source/cell/detector ar-
Figure 22. Schematic of maximum bubble pressure method rangement and the mixture, the density can be
calculated according to
Id ∞I0 exp (−d) (51)

critical molecular weight M w,crit [368]. Equa-
tion 52 holds also for branched polymers if M w
where I 0 and I d are the intensity of the radiation is replaced by gM w , where the contraction fac-
source and the detected radiation, respectively. tor g is defined as the ratio of the radius of gyra-
Radiometric density determination is advan- tion of the branched molecule to that of a linear
tageous in systems under very high pressure and molecule of the same weight average molecular
in corrosive media because neither the source mass.
nor the detector is in direct contact with the mix- In cross-linking reactions, the viscosity of the
ture. mixture increases dramatically while approach-
The application of dilatometry to reaction ing the gel point [369], [370]. After reaching the
monitoring is discussed in detail in [364]. In gel point, the cross-linked reaction mixture be-
general, dilatometry is a very useful tool for aca- haves like a soft solid. For temperatures above
demic research but only of limited value for re- the glass transition temperature T g the mechan-
action monitoring in (continuously stirred) in- ical properties of the material may be treated by
dustrial reactors. rubber elasticity theory.
The viscosity of disperse systems depends on
the volume fraction ϕ of disperse material, par-
9.3. Rheometry ticle shape and size distribution, interparticular
interaction, etc. For monodisperse spherical par-
The theory of rheology, instrumentation and ap- ticles at low ϕ, viscosity is proportional to the
plications are extensively described in [365– volume fraction of the disperse phase
367] (see also → Fluid Mechanics).
Various processes in the plastics industry are η = η0 (1 + 2.5 ϕ) (53)
accompanied by viscosity changes of the reac-
tion mixture: where η 0 is the viscosity of the dispersion
medium. For higher volume fractions and sys-
1) Most of plastics manufacturing processes tems with dominant interparticle interaction, nu-
lead to a substantial increase of viscosity merous theoretically based, semi-empirical, and
because of growing chains, branching, and empirical η – ϕ relations can be found in the
cross-linking. Rheological characterization literature [371], [372]. Thus, viscosity reflects
of plastics is essential for understanding and changes of particle number and size [373] in
influencing their processability. heterophase reactions (e.g. emulsion formation,
2) Curing reactions transform liquids into gels emulsion polymerization, suspension polymer-
and solids. Thus, the resistance of the mate- ization, dispersion polymerization).
rial to flow changes by orders of magnitude. Principles and methods for on-line rheome-
3) Melt flow index is an important parameter try include rotational and capillary process vis-
for monitoring and controlling reaction ex- cometers, as well as the application of ultrasound
trusion, reaction blending, and reaction in- (see Chap. 3), and tube or fork oscillations (see
jection molding [35], [36]. Section 9.2).
Widely used techniques for measuring melt
Increasing viscosity in noncross-linked sys- viscosity in extruders are capillary viscom-
tems can be related to the molecular mass etry and pressure drop analysis [35], [36],
and concentration of growing chains. For linear [374], [375]. The pressure drop ∆p of melt
polymers, the bulk viscosity η is a function of flow through a nozzle is directly propor-
the weight average molecular mass M w similar tional to the melt vicosity according to the
to the Kuhn – Mark – Houwink equation for the Hagen – Poiseuille law
intrinsic viscosity [η] of polymers in solution
8ηv̄l
a ∆p = − (54)
η = Kη Mwη (52) R2
where Kη is a parameter that depends on inter- where ῡ, l, and R are the average velocity in the
chain friction. The exponent aη is about 1 – 2 pipe, its length, and diameter, respectively.
for short chains, and increases to 3.4 above a
9.4. NMR Spectroscopy 3. A. Penlidis, T. A. Duever, Macromol. Symp.

111 (1996) 195.
Nuclear magnetic resonance (NMR) spec- 4. K. J. Clevett: Process Analyzer Technology,
troscopy is probably the most important spec- Wiley-Interscience, New York 1986.
troscopic technique for studying chemical struc- 5. D. E. Podkulski, Chem. Eng. Prog. (1997) no.
tures. Signals of molecules and sub-units of 10, 33.
molecules, and the signals of their various spatial 6. K. G. Carr-Brion, J. R. P. Clarke: Sampling
arrangements and configurations are much more Systems for Process Analyzers,
pronounced in NMR than in any other spec- Butterworth-Heinemann, London 1996.
troscopical method. Nevertheless, NMR is still 7. K. H. Koch: Industrielle Prozeßanalytik,
mainly an off-line technique because of elab- Springer-Verlag, Berlin – Heidelberg – New
orate sample preparation requirements, the in- York 1997.
struments sensibility to temperature variations, 8. G. Oesterle: Prozeßanalytik – Grundlagen und
the necessity of instrument tuning (magnet shim- Praxis, R. Oldenbourg Verlag,
ming, drift compensation), and the time required München – Wien 1995.
to run spectra. However, some recent develop- 9. L. Olsson, U. Schulze, J. Nielsen, Trends Anal.
Chem. 17 (1998) 88.
ments in instrumentation (magnets, radio fre-
10. H. U. Moritz in K. H. Reichert, W. Geiseler
quency source and detector circuitry), and the
(eds.): Polymer Reaction Engineering, VCH
adaption to flow cells have made NMR spec- Verlag, Weinheim 1989, p. 248.
troscopy applicable to on-line analysis. A major 11. R. Riesen in B. F. Mathot (ed.): Calorimetry
advantage of NMR spectroscopy is the noninva- and Thermal Analysis of Polymers, Hanser
sive character of the technique. Publ., München 1994, p. 319.
Most of the process measurements so far uti- 12. T. Stockhausen, VDI-Berichte No. 429,
lize pulsed NMR in which the free induction VDI-Verlag, Düsseldorf 1996.
decay (FID) signal of magnetic-field aligned 13. T. Basalik, Amer. Lab. 30 (1998) 33.
molecular spins after the application of a per- 14. W. Regenass, Thermochim. Acta 95 (1985)
pendicular radio frequency pulse is analyzed 351.
as a function of time. Network formation dur- 15. H. Schuler, C. U. Schmidt, Chem. Eng. Sci. 47
ing the radiation-induced polymerization of N- (1992) 899.
isopropylacrylamide has been monitored by T 2 16. R. S. H. Wu, Chem. Eng. Prog. 81 (1985) 57.
spin – spin relaxation time measurements [376]. 17. P. Hugo, Chem. Ing. Tech. 65 (1993) 1497.
The solids content of rubber latex can be deter- 18. L. Guldbaek, J. Villadsen, Chem. Eng. Sci. 42
mined without any special sample preparation (1987) 1153.
with a total measurement time of ca. 10 s by 19. F. Groenlund, Thermochim. Acta 175 (1991)
quasi-on-line application of pulsed NMR [377]. 63.
Other applications include determination of hy- 20. D. Dollimore, S. Lerdkanchanaporn, Anal.
Chem. 70 (1998) 27R.
drogen in various materials, and several solvents
21. L. Verala de la Rosa, E. D. Sudol, M. S.
in gasoline.
El-Aasser, A. Klein, J. Polym. Sci., A: Polym.
FT-NMR spectroscopy has been rarely ap- Chem. 34 (1996) 461.
plied to on-line analysis. Because of its natural 22. R. Carloff, A. Proß, K.-H. Reichert, Chem.
abundance, 1 H NMR is superior to all other nu- Eng. Tech. 17 (1994) 406.
clei for process measurements. Applications are 23. A. Tietze, A. Proß, K.-H. Reichert,
monitoring processes in refineries [378] and the DECHEMA Monogr. 131 (1995) 673.
emulsion polymerization of butyl acrylate [379]. 24. Philips Petroleum, US 3 275 809, 1963 (E. D.
Tolin, D. A. Fluegel).
25. ICI, UK 1 217 325, 1967 (B. N. Hendy).
10. References 26. ICI, UK 1 549 841, 1975 (B. F. Beckingham,
B. N. Hendy, J. V. Simons).
1. C. Hassell, E. M. Bowman, Appl. Spectrosc.
27. DOW, DE 2 834 569, 1977 (L. C. Walker).
52 (1998) 18A.
28. M. Mosebach, K.-H. Reichert, J. Appl. Polym.
2. D. C. H. Chien, A. Penlidis, J. Macromol.
Sci. 66 (1997) 673.
Sci. – Rev. Macromol. Chem. Phys. C30
(1990) 1.
29. A. Pross, K. Platkowski, K.-H. Reichert, 50. P. Sladky, L. Parma, I. Zdrazil, Polym. Bull. 7
Polym. Intl. 45 (1998) 22. (1982) 401.
30. A. Urretabizkaia, E. D. Sudol, M. S. El-Aasser, 51. H. G. Lüscher, Kunststoffe-Plastics 23 (1976)
J. M. Asua, J. Polym. Sci., A: Polym. Chem. 31 10, 16.
(1993) 2907. 52. E. P. Papadakis, J. Appl. Phys. 45 (1974) 1218.
31. J. R. Infante et al., J. Appl. Polym. Sci. 62 53. F. Dinger, P. Hauptmann, R. Säuberlich, S.
(1996) 2311. Wartewig, Acta Polym., 34 (1983) 303.
32. A. Urretabizkaia, J. R. Leiza, J. M. Asua, 54. P. Hauptmann, F. Dinger, R. Säuberlich,
AIChE J. 40 (1994) 1850. Polymer, 26 (1985) 1741.
33. I. S. de Buruaga et al., AIChE J. 43 (1997) 55. W.-D. Hergeth, P. Starre, K. Schmutzler, S.
1069. Wartewig, Polymer, 29 (1988) 1323.
34. F. Stoessel, Chem. Eng. Progr. 89 (1993) 68. 56. S. Canegallo, M. Apostolo, G. Storti, M.
35. A. Grefenstein: Reaktive Extrusion und Morbidelli, J. Appl. Polym. Sci. 57 (1995)
Aufbereitung, Carl Hanser Verlag, München, 1333.
Wien 1996. 57. A. Siani, M. Apostolo, M. Morbidelli,
36. C. W. Macosko: RIM – Fundamentals of DECHEMA Monogr. 131 (1995) 149.
Reaction Injection Molding, Hanser Publ., 58. I. Alig, M. Fedtke, K.-G. Häusler, W. Tänzer,
München – Wien – New York 1989. S. Wartewig, Progr. Colloid Polym. Sci. 78
37. K. S. Anseth, R. A. Scott, N. A. Peppas, (1988) 54.
Macromolecules 29 (1996) 8308. 59. I. Alig, K.-G. Häusler, W. Tänzer, S. Unger,
38. B. Sandner, N. Kotzian, J. Tübke, S. Wartewig, Acta Polym. 39 (1988) 269.
O. Lange, Macromol. Chem. Phys. 198 (1997) 60. I. Alig, K.-G. Häusler, K. Nancke, E.
2715. Domaratius, M. Fedtke, Acta Polym. 40
39. R. A. Scott, N. A. Peppas, AIChE J. 43 (1997) (1989) 590.
135. 61. I. Alig, D. Lellinger, K. Nancke, A. Rizos, G.
40. J. L. Han, Y. C. Chern, K. H. Hsieh, W. Y. Fytas, J. Appl. Polym. Sci. 44 (1992) 829.
Chiu, C. C. M. Ma, J. Appl. Polym. Sci. 68 62. M. Younes, S. Wartewig, D. Lellinger, B.
(1998) 121. Strehmel, V. Strehmel, Polymer 35 (1994)
41. P. Hauptmann, R. Lucklum, B. Henning in H. 5269.
Baltes, W. Göpel, J. Hesse (eds.): Sensors 63. I. Alig, K. Nancke, G. P. Johari, J. Polym. Sci.,
Update, vol. 3, Wiley-VCH Verlag GmbH, B: Polym. Phys. 32 (1994) 1465.
Weinheim 1998, p. 163. 64. J.-F. Zhou, G. P. Johari, Macromolecules 30
42. L. C. Lynnworth: Ultrasonic Measurement for (1997) 8085.
Process Control, Academic Press, New York 65. M. Petrick, Thesis, RWTH Aachen, 1975.
1989. 66. R. Gendron, J. Tatibouët, J. Guévremont,
43. J. W. Grate, G. C. Frye in H. Baltes, W. Göpel, M. M. Dumoulin, L. Piché, Polym. Eng. Sci.
J. Hesse (eds.): Sensors Update, vol. 2, 35 (1995) 79.
Wiley-VCH Verlag GmbH, Weinheim 1997, 67. I. Alig, D. Lellinger, R. Lamour, J. Ramthun,
p. 37. Kunststoffe-Plastics (in press).
44. K. S. Suslick (ed.): Ultrasound: Its Chemical
68. A. M. Howe, A. R. Mackie, M. M. Robins, J.
Physical and Biological Effects, VCH
Disp. Sci. Technol. 7 (1986) 231.
Publishers, New York 1988.
69. D. Hibberd et al., J. Colloid Interface Sci. 193
45. P. Hauptmann: Sensoren – Prinzipien und
(1997) 77.
Anwendungen, Hanser Verlag, München 1991.
70. S. Biggs, F. Grieser, Macromolecules 28
46. B. Hartmann in R. A. Fava (ed.): Methods of
(1995) 4877.
Experimental Physics, vol. 16c, Academic
71. G. Cooper, F. Grieser, S. Biggs, J. Colloid
Press, New York 1980, p. 59.
Interface Sci. 184 (1996) 52.
47. J. P. Lorimer, T. J. Mason: Sonochemistry:
72. M. Romdhane, A. Gadri, F. Contamine, C.
Theory, Applications and Uses of Ultrasound
Gourdon, G. Casamatta, Ultrasonics
in Chemistry, Ellis Horwood, Chichester 1988.
Sonochem. 4 (1997) 235.
48. T. J. Mason: Sonochemistry: The Uses of
73. D. J. McClements, Adv. Colloid Interface Sci.
Ultrasound in Chemistry, The Royal Society
37 (1991) 33.
of Chemistry, Cambridge 1990.
74. D. Roberts, International Laboratory News,
49. P. Sladky, I. Pelant, L. Parma, Ultrasonics 16
June 1996.
(1979) 32.
75. A. S. Dukhin, P. J. Goetz, Langmuir 21 (1996) 99. I. Alig, W. Jenninger, M. Junker, L. A. de

4336. Graaf, J. Macromol. Sci.-Phys. B35 (1996)
76. A. S. Dukhin, P. J. Goetz, Langmuir 12 (1996) 563.
4987. 100. M. Fedtke, F. Schramm, KGK Kautschuk
77. A. S. Dukhin, P. J. Goetz, C. W. Hamlet, Gummi Kunststoffe 51 (1998) 201.
Langmuir 12 (1996) 4998. 101. D. Schuele, R. Renner, D. Coleman, Mol.
78. R. W. O Brien, D. W. Cannon, W. N. Cryst. Liq. Cryst. 299 (1997) 343.
Rowlands, J. Colloid Interface Sci. 173 102. E. H. B. deLacey, L. R. White, J. Chem. Soc.
(1995) 406. Faraday Trans. 2 77 (1981) 2007.
79. Z. Lin, M. D. Ward, Anal. Chem. 68 (1996) 103. R. M. Fitch, L. S. Su, S. L. Tsaur in M. S.
1285. El-Aasser, R. M Fitch (eds.): Future Directions
80. A. Weerawardena, C. J. Drummond, F. Caruso, in Polymer Colloids, Martinus Nijhoff,
M. McCormick, Langmuir 14 (1998) 575. Dordrecht – Boston – Lancaster, 1987.
81. S. J. Martin, A. J. Ricco, Sensors Actuators 104. R. M. Fitch, L. S. Su, S. L. Tsaur in F. Candau,
A21 – A23 (1990) 712. R. H. Ottewil (eds.): Scientific Methods for the
82. A. J. Ricco, A. W. Staton, R. M. Crooks, T.
Study of Polymer Colloids and Their
Kim, Faraday Discuss. 107 (1997) 247.
Applications, Kluwer Academic, Dordrecht
83. J. Dorighi, S. Krishnaswamy, J. D. Achenbach,
1990.
Rev. Progr. Quant. Nondestruct. Eval. 15
105. L. S. Su, S. Jayasuriya, R. M. Fitch in J. W.
(1996) 657.
84. B. Mitra, D. J. Booth, Ultrasonics 35 (1998) Goodwin, R. Buscall (eds.): Colloid Polymer
569. Particles, Academic Press, London 1995.
85. S. Havriliak, S. J. Havriliak: Dielectric and 106. F. Carrique, A. V. Delgado, Colloid Polym. Sci.
Mechanical Relaxation in Materials, Hanser 274 (1996) 848.
Publishers, Munich – Vienna – New York 1997. 107. A. A. Garrouch, H. M. S. Lababidi, R. B.
86. J. R. Macdonald: Impedance Spectroscopy, Gharbi, J. Phys. Chem. 100 (1996) 16996.
John Wiley & Sons, New York 1987. 108. Y. Chonde, M. Shabrang, J. Colloid Interface
87. G. Williams, Adv. Polym. Sci. 33 (1979) 60. Sci. 186 (1997) 248.
88. A. K. Jonscher: Dielectric Relaxation in Solids, 109. B. B. Sauer, R. S. Stock, K.-H. Lim, W. H. Ray,
Chelsea Dielectrics Press, London 1983. J. Appl. Polym. Sci. 39 (1990) 2419.
89. J. Mijovic, F. Bellucci, TRiP 4 (1996) 74. 110. J. M. Harnly, R. E. Fields, Appl. Spectrosc. 51
90. K. Funke, C. Cramer, Curr. Opin. Solid State (1997) 334A.
Mat. Sci. 2 (1997) 483. 111. C. W. Brown in F. M. Mirabella: Modern
91. A. Rost: Messung dielektrischer Techniques in Applied Molecular
Stoffeigenschaften, Akademie-Verlag, Berlin Spectroscopy, John Wiley & Sons, New York
1978. 1998, p. 377.
92. F. Kremer, M. Arndt in J. P. Runt, J. J. 112. G. Rinke, U. Hoeppener-Kramar, GIT Fachz.
Fitzgerald (eds.): Dielectric Spectroscopy of Lab. 10/95, 939.
Polymeric Materials, American Chemical 113. G. Vishnoi, T. C. Goel, P. K. C. Pillai, Sensors
Society, Washington 1997, p. 67. Actuators B 45 (1997) 43.
93. D. A. Wasylyshyn, M. G. Parthun, G. P. Johari, 114. S. A. Merschman, D. C. Tilotta, Appl.
J. Mol. Liq. 69 (1996) 283. Spectrosc. 52 (1998) 106.
94. D. E. Kranbuehl in J. P. Runt, J. J. Fitzgerald 115. J. C. Phelan, C. S. P. Sung, Macromolecules
(eds.): Dielectric Spectroscopy of Polymeric 30 (1997) 6845.
Materials, American Chemical Society, 116. H. J. Paik, N. H. Sung, C. S. P. Sung, Polym.
Washington D.C. 1997, p. 303. Prep. 32 (1991) 669.
95. G. Williams, C. Duch, J. Fourier, J. R. Hayden 117. J. B. Reeves, J. Near Infrared Spectrosc. 2
in A. H. Fawkett (ed.): Polymer Spectroscopy, (1994) 199.
John Wiley & Sons, Chichester 1996, p. 275. 118. P. J. Gemperline, Chemotr. Intell. Lab. Syst. 39
96. S. Andjelic, J. Mijovic, F. Bellucci, J. Polym.
(1997) 29.
Sci., B: Polym. Phys. 36 (1998) 641.
119. E. Bouveresse, C. Hartmann, D. L. Massart,
97. S. Andjelic, J. Mijovic, Macromolecules 31
I. R. Last, K. A. Prebble, Anal. Chem. 68
(1998) 2872.
(1996) 982.
98. E. Tombardi, C. Ferrari, G. Salvetti, G. P.
120. J. Workmann, J. Near Infrared Spectrosc. 1
Johari, J. Polym. Sci., B: Polym. Phys. 36
(1993) 221.
(1998) 303.
121. W. F. McClure, Anal. Chem. 66 (1994) 43A. 147. A. Khettry, M. G. Hansen, Polym. Eng. Sci. 36
122. D. Noble, Anal. Chem. 67 (1995) 735A. (1996) 1232.
123. M. Xanthos, S. H. Patel, Adv. Polym. Tech. 14 148. M. G. Hansen, S. Vedula, J. Appl. Polym. Sci.
(1995) 151. 68 (199´8) 859.
124. D. E. Podkulski, Chem. Eng. Progr. (1997) 149. S. Vedula, M. G. Hansen, J. Appl. Polym. Sci.
Oct. 33. 68 (1998) 873.
125. N. Poisson, G. Lachenal, H. Sautereau, Vib. 150. A. Hirsch, B. E. Bridgland, Can. Spectrosc.
Spectrosc. 12 (1996) 237. May 1967, 101.
126. J. Mijovic, S. Andjelic, Polymer 36 (1995) 151. E. G. Chatzi, O. Kammona, C. Kiparissides, J.
3783. Appl. Polym. Sci. 63 (1997) 799.
127. J. Mijovic, S. Andjelic, J. M. Kenny, Polym. 152. C. Decker, K. Moussa, Macromolecules 22
Adv. Technol. 7 (1996) 1. (1989) 4455.
128. J. P. Dunkers, K. M. Flynn, M. T. Huang, W. G. 153. J. E. Dietz, B. J. Elliot, N. A. Peppas,
McDonough, Appl. Spectrosc. 52 (1998) 552. Macromolecules 28 (1995) 5163.
129. L. Xu, J. R. Schlup, Appl. Spectrosc. 50 154. J. E. Puskas, M. G. Lanzendörfer, W. E.
(1996) 109. Pattern, Polym. Bull. 40 (1998) 55.
130. H.-R. Bjørsvik, Appl. Spectrosc. 50 (1996) 155. R. F. Storey, A. B. Donnalley, T. L. Maggio,
1541. Macromolecules 31 (1998) 1523.
131. E. D. Yalvac, M. B. Seasholtz, M. A. Beach, 156. P. MacLaurin, N. C. Crabb, I. Wells, P. J.
S. R. Crouch, Appl. Spectrosc. 51 (1997) 1565. Worsfold, D. Coombs, Anal. Chem. 68 (1996)
132. C. Wu, J. D. S. Danielson, J. B. Callis, M. T. 1116.
Eaton, N. L. Ricker, Process Control Qual. 8 157. A. H. Ali, K. S. V. Srinivasan, J. Appl. Polym.
(1996) 25. Sci. 67 (1998) 441.
133. S. Schönkopf, Chem. Tech. 27 (1998) 10. 158. X. Fang, D. F. Rogers, D. A. Scola, M. P.
134. C. Coffey, A. Predoehl, D. S. Walker, Appl. Stevens, J. Polym. Sci., A: Polym. Chem. 36
Spectrosc. 52 (1998) 717. (1998) 461.
135. H. W. Ward II et al., Appl. Spectrosc. 52 159. A. M. Kaminski, M. W. Urban, J. Coat.
(1998) 17. Technol. 69 (1997) 113.
136. F. Cuesta Sanchez et al., Fresenius J. Anal. 160. S. J. Oh, J. L. Koenig, Anal. Chem. 70 (1998)
Chem. 352 (1995) 771. 1768.
137. S. S. Sekulic et al., Anal. Chem. 68 (1996) 161. T. Kimura, H. Ezure, S. Tanaka, E. Ito, J.
509. Polym. Sci., B: Polym. Phys. 36 (1998) 1227.
138. R. de Maesschalck, F. Cuesta Sanchez, D. L. 162. D. Qin, G. Cadet, Anal. Chem. 69 (1997)
Massart, P. Doherty, P. Hailey, Appl. Spectrosc. 1942.
52 (1998) 725. 163. A. Beenen, R. Niessner, Analyst 123 (1998)
139. R. M. Mosley, R. R. Williams, J. Near Infrared 543.
Spectrosc. 2 (1994) 119. 164. M. W. Urban, E. M. Salazar-Rojas, J. Polym.
140. W. H. A. M. van den Broek et al., Chemometr. Sci., A: Polym. Chem. 28 (1990) 1593.
Intell. Lab. Syst. 35 (1996) 187. 165. T. Heitz, B. Drevillon, J. E. Bouree, C. Godet,
141. W. H. A. M. van den Broek, D. Wienke, W. J. Appl. Phys. Letts. 72 (1998) 780.
Melssen, L. M. C. Buydens, Anal. Chim Acta 166. P. Marteau, F. Adar, N. Zanier-Szydlowski,
361 (1998) 161. Amer. Lab. 28 (1996) 21H.
142. W. H. A. M. van den Broek et al., Appl. 167. J. M. Chalmers, N. J. Everall, Trends Anal.
Spectrosc. 51 (1997) 856. Chem. 15 (1996) 18.
168. B. Chase, Appl. Spectrosc. 48 (1994) 14A.
143. D. Fischer, T. Bayer, K.-J. Eichhorn, M. Otto,
169. B. Schrader, A. Hoffmann, A. Simon, J.
Fresenius J. Anal. Chem. 359 (1997) 74.
Sawatzki, Vib. Spectrosc. 1 (1991) 239.
144. M. Stephan, O. Franzheim, D. Fischer in
170. S. M. Angel, M. Carrabba, T. F. Cooney,
Jahresbericht 1997, IPF Institut für
Spectrochim. Acta A51 (1995) 1779.
Polymerforschung Dresden e.V., Dresden
171. I. R. Lewis, P. R. Griffiths, Appl. Spectrosc. 50
1997.
(1996) 12A.
145. L. Jakisch, D. Fischer, M. Stephan, K.-J.
172. C. K. Chong et al., Vib. Spectrosc. 3 (1992) 35.
Eichhorn, Kunststoffe 85 (1995) 1338.
173. T. F. Cooney, H. T. Skinner, S. M. Angel, Appl.
146. M. G. Hansen, A. Khettry, Tappi J. 78 (1995)
Spectrosc. 50 (1996) 836, 849.
129.
174. B. Chase, Microchim. Acta 14 (1997) 1.
175. F. Adar, R. Geiger, J. Noonan, Appl. Spectrosc. 199. W. C. Bell, K. S. Booksh, M. L. Myrick, Anal.
Rev. 32 (1997) 45. Chem. 70 (1998) 332.
176. D. Ben-Amotz, F. LaPlant, Y. Jiang, T. 200. P. Jacob, B. Wehling, W. Hill, D. Klockow,
Biermann, Proceedings 35th Ann. Appl. Spectrosc. 51 (1997) 74.
Polyurethane Technical/Marketing Conference 201. M. Cakmak, F. T. Serhatkulu, M. Graves, J.
1994, 375. Galay, ANTEC 97, 1794.
177. C. Henry, Anal. Chem. News Feat. 1997, 309A. 202. G. J. Gervasio, M. J. Pelletier, AT-Proc. 1 – 2
178. M. Pelletier, K. Davis, Amer. Lab. 28 (1996) (1997) 7.
34C. 203. M. L. Myrick, S. M. Angel, M. Gallagher, 21st
179. M. B. Denton, D. A. Gilmore, Proc. SPIE – Int. Conf. Fed. Anal. Chem. Spectrosc. Soc., St.
Soc. Opt. Eng. 2388 (1995) 121. Louis 1994, no. 220.
180. K. Witke, W. Kimmer, Plaste & Kautschuk 23 204. E. D. Lipp, R. L. Grosse, Appl. Spectrosc. 52
(1976) 799. (1998) 42.
181. K. Witke, H.-G. Buge, K.-W. Brzezinka, W. 205. J. F. Lübben, B. Schrader, J. Mol. Struct.
Kimmer, Acta Polym. 34 (1983) 627. 410 – 411 (1997) 543.
206. C. L. Aardahl, J. F. Widmann, E. J. Davis,
182. B. Chu, G. Fytas, G. Zalczer, Macromolecules
Appl. Spectrosc. 52 (1998) 47.
14 (1981) 395.
207. E. J. Davis, C. L. Aardahl, J. F. Widmann, J.
183. W. M. Sears, J. L. Hunt, J. R. Stevens, J. Chem.
Dispersion Sci. Technol. 19 (1998) 293.
Phys. 75 (1981) 1589, 1599. 208. J. Musick, J. Popp, M. Trunk, W. Kiefer, Appl.
184. E. Gulari, K. McKeigue, K. Y. S. Ng, Spectrosc. 52 (1998) 692.
Macromolecules 17 (1984) 1822. 209. M. W. Urban: Vibrational Spectroscopy of
185. S. Damoun, R. Papin, G. Ripault, M. Molecules and Macromolecules on Surfaces,
Rousseau, J. C. Rabadeux, D. Durand, J. John Wiley & Sons, New York 1993.
Raman Spectrosc. 23 (1992) 385. 210. A. Ruperez, J. J. Laserna in J. J. Laserna (ed.):
186. M. Kamath et al., Macromolecules 26 (1993) Modern Techniques in Raman Spectroscopy,
5954. John Wiley & Sons, New York 1996, p. 227.
187. L. Feng, K. Y. S. Ng, Macromolecules 23 211. D. L. Stokes, J. P. Alarie, T. Vo-Dinh, Proc.
(1990) 1048. SPIE – Int. Soc. Opt. Eng. 2504 (1995) 552.
188. C. Wang, T. J. Vickers, J. B. Schlenoff, C. K. 212. W. Hill, B. Wehling, C. G. Gibbs, C. D.
Mann, Appl. Spectrosc. 46 (1992) 1729, and Gutsche, D. Klockow, Anal. Chem. 67 (1995)
47 (1993) 928. 3187.
189. T. J. Vickers, C. K. Mann, Proc. SPIE – Int. 213. W. Hill, B. Wehling, V. Fallourd, D. Klockow,
Soc. Opt. Eng. 2367 (1995) 219, and 2504 Spectrosc. Europe 7 (1995) 20.
(1995) 310. 214. R. Kellner, B. Mizaikoff, M. Jakusch, H. D.
190. T. Özpozan, B. Schrader, S. Keller, Wanzenböck, N. Weissenbacher, Appl.
Spectrochim. Acta A53 (1997) 1. Spectrosc. 51 (1997) 495.
191. A. Brookes, J. M. Dyke, P. J. Hendra, A. 215. E. P. C. Lai, H. S. Ghaziaskar, Appl. Spectrosc.
Strawn, Spectrochim. Acta A53 (1997) 2302. 48 (1994) 1011.
192. J. Haigh, A. Brookes, P. J. Hendra, A. Strawn, 216. P. Douša, C. Koňak, V. Fidler, K. Dušek,
C. Nicholas, M. Purbrick, Spectrochim. Acta Polym. Bull. 22 (1989) 585.
A53 (1997) 9. 217. J. C. Song, D. C. Neckers, Polym. Eng. Sci. 36
193. A. N. Shchegolikhin, O. L. Lazareva, (1996) 394.
Spectrochim. Acta A53 (1997) 67. 218. J. L. Jessop, A. B. Scranton, G. J. Blanchard,
194. J. B. Cooper, T. M. Vess, L. A. Campbell, B. J. Polym. Mat. Sci. Eng. 72 (1995) 58.
Jensen, J. Appl. Polym. Sci. 62 (1996) 135. 219. L. T. Pearson, P. E. J. Louis, R. G. Gilbert,
195. S. M. Angel, M. L. Myrick, Proc. Ann. Meet. D. H. Napper, J. Polym. Sci., A: Polym. Chem.
Adhes. Soc. 19 (1996) 379. 29 (1991) 515.
196. J. F. Aust, K. S. Booksh, C. M. Stellmann, R. S. 220. M. A. Winnik, H. Xu, R. Satguru, Macromol.
Parnas, M. L. Myrick, Appl. Spectrosc. 51 Chem., Macromol. Symp. 70/71 (1993) 107.
221. I. Lacik, J. Bartoň, G. G. Warr, Macromol.
(1997) 247.
Chem. Phys. 196 (1995) 2223.
197. M. Ghosh, S. Chakrabarti, T. N. Misra, J.
222. Z. J. Wang, J. C. Song, R. Bao, D. C. Neckers,
Raman Spectrosc. 29 (1998) 263.
J. Polym. Sci. B Polym. Phys. 34 (1996) 325.
198. W. Kessler, G. Luft, W. Zeiß, Ber. Bunsenges.
223. M.-A. Chung, J. Adams, J. Fuhrmann, Polym.
Phys. Chem. 101 (1997) 698.
Bull. 40 (1998) 195.
224. S. Rudschuk, J. Adams, J. Fuhrmann, 248. T. Kourti, A. Penlidis, A. E. Hamielec, J. F.

Macromol. Chem. Phys. 199 (1998) 771. MacGregor, Polym. Mat. Sci. Eng. 53 (1985)
225. D. R. Kim, D. H. Napper, Macromol. Rapid 147.
Commun. 17 (1996) 845. 249. T. Kourti, J. F. MacGregor, A. E. Hamielec,
226. M. A. Winnik, M. D. Croucher in M. S. Polym. Mat. Sci. Eng. 62 (1990) 301.
El-Aasser, R. M. Fitch (eds.): Future 250. J. A. Maroto, F. J. de las Nieves, Colloid
Directions in Polymer Colloids, Martinus Polym. Sci. 275 (1997) 1148.
Nijhoff, Dordrecht – Boston – Lancaster 1987. 251. J. A. Maroto, F. J. de las Nieves, Colloids
227. S. Sosnowski, J. Feng, M. A. Winnik, J. Polym. Surfaces A132 (1998) 153.
Sci., A: Polym. Chem. 32 (1994) 1497. 252. U. Apfel, R. Grunder, M. Ballauff, Colloid
228. A. Malliaris, Adv. Colloid Interface Sci. 27 Polym. Sci. 272 (1994) 820.
(1987) 153. 253. U. Apfel, K. D. Hörner, M. Ballauff, Langmuir
229. F. M. Winnik, S. T. A. Regismond, Colloids 11 (1995) 3401.
Surfaces A118 (1996) 1. 254. E. J. Röhm, K. D. Hörner, M. Ballauff, Colloid
230. G. Komaromy-Hiller, R. von Wandruszka, J. Polym. Sci. 274 (1996) 732.
Colloid Interface Sci. 177 (1996) 156. 255. A. O. Moser, O. Fromheim, F. Hermann, H.
231. E. Alami, M. Almgren, W. Brown, J. Francois, Versmold, J. Phys. Chem. 92 (1988) 6723.
Macromolecules 29 (1996) 2229. 256. E. Elbing, A. G. Parts, C. J. Lyons, B. A. W.
232. D. Dibbern-Brunelli, T. D. Z. Atvars, J. Appl. Coller, I. R. Wilson, Aust. J. Chem. 42 (1989)
Polym. Sci. 58 (1995) 779. 2085.
233. Ö. Pekcan, M. A. Winnik, M. D. Croucher, 257. T. Kourti, J. F. MacGregor, A. E. Hamielec,
Macromolecules 23 (1990) 2673. D. F. Nicoli, V. B. Elings in C. D. Craver, Th.
234. Ö. Pekcan, M. Canpolat, J. Appl. Polym. Sci. Provder (eds.): Polymer Characterization,
59 (1996) 277. Adv. Chem. Series. 227, American Chemical
235. M. Canpolat, Ö. Pekcan, J. Appl. Polym. Sci. Society, Washington D.C. 1990
59 (1996) 1699. 258. D. Horn, H. Auweter, W. Ditter, J. Eisenlauer,
236. M. Canpolat, Ö. Pekcan, J. Polym. Sci., B: Org. Coat. 1986, 251.
Polym. Phys. 34 (1996) 691. 259. D. Lilge, D. Horn, Colloid Polym. Sci. 269
237. J. W. Haas III, M. M. Carrabba, R. W. Forney, (1991) 704.
Field Screening Methods Hazard. Wastes 260. S. Sadasivan, D. H. Rasmussen, J. Colloid
Toxic, Chem Proc. Int. Symp. (1995) 443. Interface Sci. 193 (1997) 145.
238. R. Kotzick, R. Niessner, Fresenius J. Anal. 261. H. Wiese, D. Horn, Ber. Bunsenges. Phys.
Chem. 354 (1996) 72. Chem. 96 (1992) 1818.
239. J. Lou, T. A. Hatton, P. E. Laibinis, Anal. 262. P. C. Killgoar, R. A. Dickie, J. Appl. Polym.
Chem. 69 (1997) 1262. Sci. 21 (1977) 1813.
240. S. Sasaki, Y. Ando, M. Dejima, Y. Arikawa, I. 263. R. M. Fitch, R. C. Watson, J. Colloid Interface
Karube, Anal. Letts. 31 (1998) 555. Sci. 68 (1979) 14.
241. Y. Wang, W. Liu, K. Wang, G. Shen, R. Yu, 264. A. R. Goodall, K. J. Randle, M. C. Wilkinson,
Fresenius J. Anal. Chem. 360 (1998) 702. J. Colloid Interface Sci. 75 (1980) 493.
242. K. P. McNamara, X. Li, A. D. Stull, Z. 265. R. M. Fitch, T. H. Palmgren, T. Aoyagi, A.
Rosenzweig, Anal. Chim. Acta 361 (1998) 73. Zuikov, Angew. Makromol. Chem. 123/124
243. J. E. Parks II, J. S. Armfield, T. E. Barber, (1984) 261.
J. M. E. Storey, E. A. Wachter, Appl. Spectrosc. 266. F. B. Malihi, T. Provder, M. E. Koehler, J.
52 (1998) 112. Coat. Technol. 55 (1983) 41.
244. B. Chu: Laser Light Scattering, Academic 267. J. C. Thomas, V. Dimonie, Appl. Optics 29
Press, San Diego 1991. (1990) 5332.
245. W. Brown: Dynamic Light Scattering – The 268. J. C. Thomas, ACS Symp. Ser. 472 (1991) 98.
Method and Some Applications, Oxford 269. G. Maret, P. E. Wolf, Z. Phys. B – Condensed
Science Publications, Oxford 1993. Matter 65 (1987) 409.
246. W. Brown: Light Scattering – Principles and 270. S. Fraden, G. Maret, Phys. Rev. Letts. 65
Development, Oxford Science Publications, (1990) 512.
Oxford 1996. 271. D. Bicout, G. Maret, Physica A 210 (1994) 87.
247. C. Kiparissides, J. F. MacGregor, S. Singh,
272. E. Sevick-Muraca, J. Pierce, H. Jiang, J. Kao,
A. E. Hamielec, Can. J. Chem. Eng. 58 (1980)
AIChE J. 43 (1997) 655.
65.
273. M. Mohammadi, Adv. Colloid Interface Sci. 298. C. J. Venkatramani, J. B. Phillips, J.

62 (1995) 17. Microcolumn Sep. 6 (1994) 229.
274. F. J. Schorck in M. S. El-Aasser (ed.): 299. R. G. Mathews, J. Torres, R. D. Schwartz, J.
Advances in Emulsion Polymerization and High Resol. Chromatogr. Chromatogr.
Latex Technology, 23rd Annual Short Course, Commun. 1 (1978) 139.
Lehigh University, Bethlehem 1992. 300. M. G. Bloch, R. B. Callen, J. H. Stockinger, J.
275. J. Kim, S. Y. Jeong, K. U. Kim, Y. H. Ahn, Chromatogr. Sci. 15 (1977) 504.
R. P. Quirk, J. Polym. Sci., A: Polym. Chem. 301. J. Clemmons, Adv. Instrum. Control 50 (1995)
34 (1996) 3277. 97.
276. J. G. Dos Ramos, Thesis, Lehigh University, 302. J. Durand, J. Beboulene, A. Ducrozet,
Bethlehem 1998. Analusis 23 (1995) 481.
277. J. Venkatesan, Thesis, Lehigh University, 303. J. P. Durand, Y. Boscher, M. Dorbon, J.
Bethlehem 1992. Chromatogr. 509 (1990) 47.
278. C. M. Miller, E. D. Sudol, C. A. Silebi, M. S. 304. F.-Q. Ma, D.-S. Lu, Z.-Y. Guo, J. Chromatgr.
El-Aasser, J. Colloid Interface Sci. 172 (1995) A 740 (1996) 65.
249. 305. K. Snavely, B. Subramaniam, Ind. Eng. Chem.
279. J. C. Giddings, Science 260 (1993) 1456. Res. 36 (1997) 4413.
280. J. C. Giddings, Anal. Chem. 67 (1995) 592A. 306. E. Dorrestijn, P. Mulder, J. Anal. Appl.
281. P. Blau, R. L. Zollars, J. Colloid Interface Sci. Pyrolysis 44 (1998) 167.
183 (1996) 476. 307. V. Pacakova, V. Kozlik, Chromatographia 11
282. L. Dulog, T. Schauer, Progr. Coat. 28 (1996) (1978) 266.
25. 308. O. Kammona, E. G. Chatzi, C. Kiparissides, J.
283. P. J. Wyatt, J. Colloid Interface Sci. 197 Macromol. Sci. - Rev. Macromol. Chem. Phys.
(1998) 9. C39 (1999) 57.
284. S. K. Ratanathanawongs, P. M. Shiundu, J. C. 309. A. Guyot, J. Guillot, C. Pichot, L. Rios
Giddings, Colloids Surf. A 105 (1995) 243. Guerrero in D. R. Basset, A. E. Hamielec
285. D. Roessner, Thesis, University of Hamburg (eds.): Emulsion Polymers and Emulsion
1994. Polymerization, ACS Symp. Ser. 165 (1981)
286. P. J. Wyatt, Anal. Chim. Acta 272 (1993) 1. 415.
287. R. Annino, R. Villalobos: Process Gas 310. A. Urretabizkaia, J. R. Leiza, J. M. Asua,
Chromatography: Fundamentals and AIChE Journal 40 (1994) 1850.
Applications, Society of America, Research 311. M. Alonso, M. Recasens, L. Puigjaner, Chem.
Triangle Park, NC 1992. Eng. Sci. 41 (1986) 1039.
288. K. B. Beebe et al., Anal. Chem. 65 (1993) 312. M. Alonso, M. Alivers, L. Puigjaner, M.
199R. Recasens, Ind. Eng. Chem. Res. 26 (1987) 65.
289. W. W. Blaser et al., Anal. Chem. 67 (1995) 313. J. Janata, M. Josowicz, D. M. DeVaney, Anal.
47R. Chem. 66 (1994) 207R.
290. J. Workman et al., Anal. Chem. 71 (1999) 314. J. Janata, M. Josowicz, P. Vanysek, D. M.
121R. DeVaney, Anal. Chem. 70 (1998) 179R.
291. V. Lopez-Avila, H. H. Hill, Anal. Chem. 69 315. P. H. Müller, D. Werner, Chemie Technik 26
(1997) 289R. (1997) 48.
292. R. Villalobos, R. Annino, Adv. Instrum. 316. C. L. Guillemin, Process Control Qual. 3
Control 46 (1991) 707. (1992) 153.
293. R. G. Melcher, P. L. Morabito, Anal. Chem. 62 317. R. E. Cooley, C. E. Stevenson, Process Control
(1990) 2183. Qual. 2 (1992) 43.
294. W. R. Slater et al., Water Research 24 (1990) 318. N. C. van de Merbel, I. M. Kool, H. Lingeman,
121. U. A. T. Brinkman, A. Kolhorn, L. C. de Rijke,
295. E. R. Lindgren, D. W. Preshing, D. A. Chromatographia 33 (1992) 525.
Kirchgessner, D. C. Drehmel, J. Chromatogr. 319. F. J. Sauter, Am. Lab. 10 (1992) 33.
585 (1991) 353. 320. E. Verette, F. Qian, F. Mangani, J. Chromatogr.
296. R. E. Berkley, Process Control Qual. 5 (1993) A 705 (1995) 195.
159. 321. Z. Ge, R. Thompson, D. Detora, T. Maher, P.
297. P. A. David, R. E. Pauls, J. Chromatogr. Sci. Mckenzie, D. Ellison, J. Crutchfield, J. Proc.
36 (1998) 44. Anal. Chem. 3 (1997) 1.
322. M. G. Musolino, G. Neri, C. Milone, S. 348. S. Bohatka, Adv. Mass. Spectrom. 13 (1995)
Minico, S. Galvagno, J. Chromatogr. A 818 199.
(1998) 123. 349. M. A. DesJardin, S. J. Doherty, J. R. Gilbert,
323. J. C. Thompson, R. H. Smith, Proc. Control. M. A. LaPack, J. Shao, Proc. Control Qual. 6
Qual. 2 (1992) 55. (1995) 219.
324. L. Ebdon, H. W. Handley, P. Jones, N. W. 350. K. D. Cook, K. H. Bennet, M. L. Haddix, Ind.
Barnett, Microchim. Acta 2 (1991) 39. Eng. Chem. Res. 38 (1999) 1192.
325. M. A. Rey, J. M. Riviello, C. A. Pohl, J. 351. R. Zimmermann, H. J. Heger, A. Kettrup,
Chromatogr. A 789 (1997) 149. Fresenius J. Anal. Chem. 363 (1999) 720.
326. M. Nonomura, T. Hobo, J. Chromatogr. A 808 352. C. Didden, J. Duisings, Proc. Control Qual. 3
(1998) 151. (1993) 263.
327. G. J. Lynch, Proc. Control. Qual. 1 (1991) 353. A. M. Gregory, L. A. Kephart, Adv. Instrum.
249. Control 50 (1995) 933.
328. R. M. Montgomery, R. Saari-Nordhaus, L. M. 354. H. Deng, G. J. van Berkel, Anal. Chem. 71
Nair, J. M. Anderson, J. Chromatogr. A 804 (1999) 4284.
(1998) 55. 355. P. Fiorani, G. Margutti, G. Mariana, G.
329. H. B. Wan, J. Liu, K. C. Ang, S. F. Y. Li,
Moccia, Proc. SPIE-Int. Soc. Opt. Eng. 3509
Talanta 45 (1998) 663.
(1998) 221.
330. B. A. P. Buscher, U. R. Tjaden, J. van der
356. J. J. Chambers, K. Min, G. N. Parsons, J. Vac.
Greef, J. Chromatogr. A 788 (1997) 165.
Sci. Technol. B 16 (1998) 2996.
331. B. E. Richter, B. A. Jones, N. L. Porter, J.
357. V. M. Donelly, Mater. Res. Soc. Symp. Proc.
Chromatogr. Sci. 36 (1998) 444.
332. Y. Shen, M. L. Lee, J. Chromatogr. A 778 406 (1996) 3.
(1997) 31. 358. D. R. McKenzie, W. D. McFall, W. G. Sainty,
333. M. H. Wright, A. M. James, Kolloid-Z. Z. Y. Yin, A. Durandet, R. W. Boswell, Surf.
Polym. 251 (1973) 745. Coat. Technol. 82 (1996) 326.
334. S. Bisal, P. K. Bhattacharya, S. P. Moulik, J. 359. S. Canegallo, G. Storti, M. Morbidelli, S.
Phys. Chem. 94 (1990) 350. Carra, J. Appl. Polym. Sci. 47 (1993) 961.
335. L. F. J. Noël, R. Q. F. Janssen, W. J. M. van 360. F. Bleger, A. K. Murthy, F. Pla, E. W. Kaler,
Well, A. M. van Herk, A. L. German, J. Macromolecules 27 (1994) 2559.
Colloid Interface Sci. 175 (1995) 461. 361. A. Penlidis, J. F. MacGregor, A. E. Hamielec,
336. J. L. Reimers, F. J. Schork, J. Appl. Polym. Sci. J. Appl. Polym. Sci. 35 (1988) 2023.
60 (1996) 251. 362. F. J. Schork, W. H. Ray, J. Appl. Polym. Sci. 28
337. K. Voloudakis, P. Vrahliotis, E. G. Kastrinakis, (1983) 407.
S. G. Nychas, Meas. Sci. Technol. 10 (1999) 363. F. J. Schork, W. H. Ray, J. Appl. Polym. Sci. 34
100. (1987) 1259.
338. A. M. Santos, P. Vindevoghel, C. Graillat, A. 364. R. G. Gilbert: Emulsion Polymerization – A
Guyot, J. Guillot, J. Appl. Polym. Sci. 34 Mechanistic Approach, Academic Press, San
(1996) 1271. Diego 1995.
339. M. Patek, S. Bildstein, Z. Flegelova, 365. W. R. Schowalter: Mechanics of
Tetrahedron Lett. 39 (1998) 753. Non-Newtonian Fluids, Pergamon, Oxford
340. S. Zoll, Chemie Technik 27 (1998) 34. 1978.
341. N. Le Bris, D. Birot, Anal. Chim. Acta 356 366. H. A. Barnes, J. F. Hutton, K. Walters: An
(1997) 205. Introduction to Rheology, Elsevier,
342. L. W. Niedrach, Angew. Chem. 99 (1987) 183. Amsterdam 1989.
343. T. Werner et al., Fresenius J. Anal. Chem. 359 367. C. W. Macosko: Rheology: Principles,
(1997) 150. Measurements and Applications, VCH
344. E. Pringsheim, E. Terpetschnig, O. S. Publishers, New York 1994.
Wolfbeis, Anal. Chim. Acta 357 (1997) 247. 368. K.-F. Arndt, G. Müller:
345. U.-W. Grummt, A. Pron, M. Zagorska, S.
Polymercharakterisierung, Carl Hanser
Lefrant, Anal. Chim. Acta 357 (1997) 253.
Verlag, München – Wien 1996.
346. P. Westbroek, E. Temmerman, P. Kiens, Anal.
369. P. J. Halley, M. Mackay, Polym. Eng. Sci. 36
Comm. 355 (1998) 21.
(1996) 593.
347. R. G. Cooks, S. H. Hoke, K. L. Morand, S. A.
370. D. Hesekamp, H. C. Broecker, M. H. Pahl,
Lammert, Int. J. Mass Spectrom. Ion Processes
Chem. Ing. Tech. 70 (1998) 286.
118 (1992) 1.
371. R. M. Fitch: Polymer Colloids: A 375. D. J. Fleming, T. W. Dobbie, A. L. Kelly, P. D.

Comprehensive Introduction, Academic Press, Coates in Polymer Testing 97 Design and
San Diego 1997. Rheological Data in the Plastics Industry,
372. E. J. Schaller in P. A. Lovell, M. S. El-Aasser RAPRA, Paper 2, 1.
(eds.): Emulsion Polymerization and Emulsion 376. A. Safranj, M. Yoshida, H. Omichi, R.
Polymers, John Wiley & Sons, Chichester Katakai, Radiat. Phys. Chem. 46 (1995) 987.
1997. 377. S. A. Jones, H. J. Stronks, BRUKER minispec
373. R. Pal, AIChE J. 42 (1996) 3181. application note # 20.
374. R. Trim in Polymer Testing 97 Design and 378. T. W. Skloss, A. J. Kim, J. F. Haw, Anal. Chem.
Rheological Data in the Plastics Industry, 66 (1994) 536.
RAPRA, Paper 1, 1. 379. K. Landfester, S. Spiegel, R. Born, H. W.
Spiess, Colloid Polym. Sci. 276 (1998) 356.
Plant and Process Design
Process Development 873
Process Development
Herbert Vogel, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . 873 3.4.1.4. The Limitations of the Miniplant

1.1. The Objective of Industrial Technique . . . . . . . . . . . . . . . . 894
Research and Development . . . . 873 3.4.2. Pilot Plant . . . . . . . . . . . . . . . . 894
1.2. The Production Structure of the 4. Process Evaluation . . . . . . . . . . 895
Chemical Industry . . . . . . . . . . 874 4.1. Preparation of Study Reports . . 895
1.3. The Task of Process Development 876 4.1.1. The Summary . . . . . . . . . . . . . . 895
2. Process Data . . . . . . . . . . . . . . 876 4.1.2. Basic Flow Diagram . . . . . . . . . 895
2.1. Chemical Mechanism . . . . . . . . 876 4.1.3. Process Description and Flow
2.2. Physicochemical Data . . . . . . . . 877 Diagram . . . . . . . . . . . . . . . . . 895
2.3. Processing . . . . . . . . . . . . . . . 878 4.1.4. Waste-Disposal Flow Diagram . . . 896
2.4. Patenting and Licensing Situation 878 4.1.5. Estimation of Capital Expenditure . 896
2.5. Development Costs . . . . . . . . . . 879 4.1.5.1. Introduction . . . . . . . . . . . . . . . 896
2.6. Location . . . . . . . . . . . . . . . . . 879 4.1.5.2. ISBL Investment Costs . . . . . . . . 896
2.7. Market Situation . . . . . . . . . . . 879 4.1.5.3. OSBL Investment Costs . . . . . . . 898
2.8. Raw Materials . . . . . . . . . . . . . 880 4.1.5.4. Infrastructure Costs . . . . . . . . . . 898
2.9. Plant Capacity . . . . . . . . . . . . 880 4.1.6. Calculation of Production Costs . . 898
2.10. Waste-Disposal Situation . . . . . . 882 4.1.6.1. Feedstock Costs . . . . . . . . . . . . 899
2.11. End Product . . . . . . . . . . . . . . 882 4.1.6.2. Utilities . . . . . . . . . . . . . . . . . 899
3. The Standard Course of Process
4.1.6.3. Waste-Disposal Costs . . . . . . . . . 902
Development . . . . . . . . . . . . . . 883
4.1.6.4. Staff Costs . . . . . . . . . . . . . . . . 902
3.1. The Iterative Nature of Process
4.1.6.5. Maintenance Costs . . . . . . . . . . 903
Development . . . . . . . . . . . . . . 883
4.1.6.6. Overheads . . . . . . . . . . . . . . . . 903
3.2. Drawing up an Initial Version of
4.1.6.7. Capital-Dependent Costs
the Process . . . . . . . . . . . . . . . 885
(Depreciation) . . . . . . . . . . . . . 903
3.2.1. Tools used in Drawing up the Initial
Version of the Process . . . . . . . . 887 4.1.7. Technology Evaluation . . . . . . . . 903
3.2.1.1. Databases . . . . . . . . . . . . . . . . 887 4.1.8. Assessment of the Experimental
3.2.1.2. Simulation Programs . . . . . . . . . 887 Work . . . . . . . . . . . . . . . . . . . 907
3.2.1.3. Expert Systems . . . . . . . . . . . . . 888 4.2. Return on Investment . . . . . . . . 907
3.3. Checking the Individual Steps . . 889 4.2.1. Static Return on Investment . . . . . 908
3.4. Testing the Entire Process on a 4.2.2. Dynamic Return on Investment . . . 908
Small Scale . . . . . . . . . . . . . . . 890 4.3. Economic Risk . . . . . . . . . . . . 909
3.4.1. The Miniplant Technique . . . . . . 890 4.3.1. Sensitivity Analysis . . . . . . . . . . 909
3.4.1.1. Introduction . . . . . . . . . . . . . . . 890 4.3.2. Amortization Time . . . . . . . . . . 909
3.4.1.2. Construction . . . . . . . . . . . . . . 891 5. Trends in Process Development . 909
3.4.1.3. The Limits of Miniaturization . . . . 893 6. References . . . . . . . . . . . . . . . 910
1. Introduction 302], an amount which is often of the same order

of magnitude as the profit of the undertaking.
1.1. The Objective of Industrial It is the job of research management to
Research and Development use these resources to achieve competitive ad-
vantages. After all, for the chemical industry
In the chemical industry, ca. 6 % of turnover is the halcyon days of the sellers’ market (de-
spent on research and development [1, pp. 282, mand > supply) have receded into the distant
874 Process Development
past; it is now the customer who calls the tune

(buyers’ market).
Unlike consumer goods such as cars and
clothes, most commercial chemical products are
faceless (e.g., hydrochloric acid), and as a rule
the customer is therefore only interested in sales
incentives such as price, quality, and availability.
All the research activities of an industrial en-
terprise must therefore ultimately boil down to
two basic competitive advantages, namely those
of being “cheaper” and “better” than the com-
petitor.
At the same time, “better” now refers not only
to availability and product quality, but also envi-
ronmental compatibility of the process, and the
quality assurance approach of the supplier, etc.
1.2. The Production Structure of the

Chemical Industry
If the production structure of the chemical in-
dustry is examined, it is seen that there are only
a few hundred major basic products and inter-
mediates that are produced on a scale of at least
a few thousand to several million tonnes per an-
num worldwide.
This relatively small group of key products,
which are in turn produced from only about ten
raw materials, are the stable foundation on which
the many branches of refining chemistry (dyes,
pharmaceuticals, etc.), with their many thou-
Figure 1. Product family tree of the chemical industry:
sands of often only short-lived end products, are starting from raw materials and progressing through the ba-
based [2, p. 57 ff]. This has resulted in the well- sic products and intermediates, to the refined chemicals and
known family tree (see Fig. 1), which can also final consumer products [3], [4]
be regarded as being synonymous with an in-
tegrated production system, with synergies that
are often of critical importance for success.
A special characteristic of the major basic
products and intermediates is their longevity.
They are statistically so well protected by their
large number of secondary products and their
wide range of possible uses that they are hardly
affected by the continuous changes in the range
of products on sale. Unlike many end products,
which are replaced by better ones in the course
of time, they do not themselves have a so-called
life cycle. However, the processes for producing
them are subject to change. This is initiated by
new technical possibilities and advances opened
up by research but is also dictated by the current Figure 2. How the raw material base of the chemical in-
raw material situation (see Fig. 2). dustry has changed with time
Figure 3. Life cycles of the acrylic acid processes

a) Cyanohydrin,acrylonitrile,and propiolactone processes; b) Reppe process; c) Propylene oxidation; d) New process?[4]
Here it is not the individual chemical product, technology to a new trend-setting technology,
but the production process or technology which the productivity in the research and development
has a life cycle. Figure 3 shows the life cycles of sector increases appreciably, thus enabling sub-
the acrylic acid processes [4]. stantial competitive advantages to be achieved.
Enterprises which already have competitive It is precisely on this innovative activity that
advantages must take account of this technol- the prosperity of highly developed countries
ogy S curve [5] in their research and develop- with limited raw material sources such as Ger-
ment strategy (see Fig. 4). The curve shows that many and Japan is based.
as the research and development expenditure on
a particular technology increases, the produc-
tivity of such expenditure decreases with time
[6]. If enterprises are approaching the limit of
a particular technology, they must accept dis-
proportionately high research and development
expenditure, with the result that the contribution
made by these efforts to the research objectives
of “cheaper” and/or “better” becomes increas-
ingly small, thereby always giving the competi-
tor the opportunity of catching up on the techni-
cal advantage.
Once an enterprise has reached the upper re-
gion of the product or technology S curve, the
question arises whether it is necessary to switch
from the standard technology to a new trend-
setting technology in order to gain a new and suf- Figure 4. The technology S curve [8]: The productivity of
ficient competitive advantage [7]. Figure 4 de- the research and development expenditure increases con-
picts this switch to a new technology schemat- siderably by switching from the basic technology to a new
trend-setting technology
ically and shows that on switching from a basic
To assess whether a “better” and/or “cheaper” Thermodynamic Equilibrium. Many reac-

research and development strategy is still accept- tions, such as esterifications and dimerizations,
able in the long term for a given product or pro- proceed to chemical equilibrium. The thermody-
duction process, the R & D management must namic equilibrium provides information about
develop an “early warning system” that deter- the maximum possible conversion, and to assess
mines the optimum time for switching to a new the potential conversion it is essential to know
product or a new technology [9]. how far the intended reactions are from chemical
equilibrium.
Example 2.1. The formation of trioxane from
1.3. The Task of Process Development formaldehyde
The task of process development is to extrap-

olate a chemical reaction discovered and re-
searched in the laboratory to an industrial scale,
taking into consideration the economic, safety, in the gas phase is a typical equilibrium reaction.
and ecological boundary conditions. The equilibrium constant, which is given by
The starting point is the laboratory equipment
pT 4 p0F −p
and the outcome of development is the produc- Kp = = 3
(2.2)
p3F 3p−p0
F
tion plant; in between, process development is
required. The following account shows how this where
task is generally handled. Although the sequence p = total pressure at equilibrium
of steps in the development process described p0F = initial partial pressure of formaldehyde
are typical, they are by no means obligatory, and
pT , pF = equilibrium partial pressure of triox-
it is only possible to outline the basic framework.
ane or formaldehyde, respectively,
can be expressed according to [10] as:
7350
2. Process Data log Kp /bar −2 = −19.8 (2.3)
T /K
When the laboratory phase has been completed It follows that if the process conditions as-
and before the actual process development is sumed are T = 353 K and p0 F = 0.2 bar, a maxi-
started, further information must be obtained mum formaldehyde conversion of:
since the latter stage is normally associated with 3·pT
high costs. U= ·100 = 35% (2.4)
p0F
can be achieved in one throughput. The conver-
sion actually achieved will be < 35 % and de-
2.1. Chemical Mechanism pends on the catalyst and reactor systems.
The thermodynamic data (standard enthalpy
The core of a chemical plant is the reactor. Its
and entropy of formation, specific heat of the
input and output decide the structure of the en-
reactants) required to calculate the equilibrium
tire plant built up around it. Therefore, detailed
constant can be found in published tables or
knowledge of the chemical reaction must be
can be estimated by approximation methods (see
available at the earliest possible stage. In partic-
→ Estimation of Physical Properties ) [11].
ular, the following questions must be clarified:
1) Thermodynamic equilibria Kinetics. In order to specify the type of reac-
2) Kinetics of the main, secondary, and side re- tor to be used later, information must be available
actions on the potential reaction routes to the main and
3) Dependence of selectivity and conversion on secondary products and the byproducts. The rate
the process parameters of formation and its dependence on process pa-
4) Heats of reaction rameters such as temperature, pressure, and cat-
alyst concentration should, if possible, be known
quantitatively.
Example 2.2 [12, pp. 173 – 175]. The starting k1 ·c0A

cP =
material A reacts not only to form product P, but k1 −k2
also (1) to form an undesirable byproduct Y in · {exp (−k2 ·t) −exp (−k1 ·t)} (2.14)
a parallel reaction or (2) to form an undesirable
secondary product X in a sequential reaction:
(
k1
cX =c0A · 1+ ·exp (−k2 ·t) −
k2 −k1
)
k2
·exp (−k1 ·t) (2.15)
1) First-order parallel reaction k2 −k1
For the starting material A:
dcA
= − (k1 +k3 ) ·cA (2.6) 2.2. Physicochemical Data
dt
with cA = c0A at time t = 0, integration results A knowledge of exact physicochemical data has
in: become more important for a number of reasons:
1) The increasing use of simulation programs
cA =c0A ·exp {− (k1 +k3 ) ·t} (2.7)
has made the requirements for exact physi-
For the useful product P: cochemical data increasingly important. The
result of a simulation calculation can only be
dcP as good as the quality of the physicochemical
=k1 ·cA (2.8) data.
dt
2) To approve chemical plants, the authorities
with cP = c0P for t = 0, integration gives demand information on the toxicity, degrad-
ability, and safety of the materials involved
k1 ·c0p [13], [14].
cp = c0p +
(k1 +k3 ) 3) The public are demanding more information
· {1 − exp [− (k1 +k3 ) ·t]} (2.9) on the effect of the materials being handled
on the environment.
The same applies to cY .
2) First-order sequential reaction At the start of process development, mate-
This is covered by three simultaneous differ- rial data files for pure substances as well as bi-
ential equations: nary and ternary mixtures are started. As devel-
opment advances, these grow and must be con-
dcA tinually updated. They subsequently form a doc-
= −k1 ·cA (2.10)
dt ument which is passed to the planning and plant
construction departments.
The layout shown in Table 1 has proved
dcP useful as a model for the collection of pure-
=k1 ·cA −k2 ·cP (2.11)
dt substance data.
Only data which have been reliably evaluated
are kept in the files and these are the only values
dcX fed into the simulation programs.
=k2 ·cP (2.12)
dt At the start of process development, the first
If c 0P = c0X = 0, integration of these equations step is to collect all available literature data on
yields: a material (see→ Estimation of Physical Prop-
erties).
cA =c0A ·exp (−k1 ·t) (2.13)
Many companies now maintain their own ma- Table 1. Important pure-substance data frequently required in pro-
cess development using acrylic acid as an example [15]
terial databases. The data have been evaluated
and should have been found satisfactory when Product name acrylic acid
used in practice. The times when a single com- CAS no. [79-10-7]
Formula C3 H4 O2
pany had 10 different sets of Antoine parameters Molar mass, kg/kmol 72.06
for water between 0 and 100 ◦ C ought now to be
Melting point, ◦ C 13.5
over. Boiling point, ◦ C 141.0
If no material values can be found in the lit- Antoine parameters ∗
erature, which is often the case for binary and A 9.135
ternary data, they should initially be estimated B −3 245
C 216.4
by using empirical formulae or realistic val- Vapor pressure at 20◦ C, mbar 10
ues that have proved themselves for many sub- Heat of evaporation at bp, kJ/kg 633
stances (e.g., heat capacity≈2 kJ kg−1 K−1 for Heat capacity, kJ kg−1 K−1 1.93 (liquid)
Density, kg/m3 1 040 at 30◦ C
most organic liquids). However, experimental
Viscosity, mPa · s 1.149 at 25◦ C
determination or confirmation of the most im- Heat of formation, kJ/mol
portant values on which the plant design is based Gross calorific value, kJ/kg 19 095
is unavoidable. Heat of transformation, kJ/kg 1 075 (polymerization)
Heat of fusion, kJ/kg 154 at 13◦ C
It is sheer negligence to rely on physicochem- Solubility in H2 O miscible
ical data originating from a single literature ref- Solubility of H2 O in acrylic acid miscible
erence. MAK
Toxicity (LD50 , rat, oral) 340 mg/kg
Water hazard class 1 (“low water hazard”)
2.3. Processing Odor threshold pungent
Flash point, ◦ C 54
Processing is intimately linked to the chemical Ignition temperature, ◦ C 390
reaction. While the chemical aspects are still Lower explosion limit, vol % 2.4 (47.5◦ C)
Upper explosion limit, vol % 16 (88.5◦ C)
subject to extensive modification (for instance,
in the choice of catalyst, solvents, etc.), there ∗ ln (p/bar) = A + B/(C + T /◦ C).
is little point in paying a great deal of attention
to processing. It is only when the reaction mix-
ture is being produced in a representative man-
ner that an initial processing procedure can be 2.4. Patenting and Licensing Situation
devised (see Section 3.2). There is no generally
accepted way of going about this. It is more an If a new idea is to be used in developing a pro-
art than craft, and reliance must be placed on in- cess, a careful check should be made to deter-
spiration and experience. It has, however, always mine whether any third-party proprietary rights
been helpful to gather as many experienced spe- would be infringed.
cialists as possible and to discuss the problems The best situation is one in which the ideas are
regularly. Although tentative efforts are now be- completely new and the company can file its own
ing made to compile collective know-how in ex- patents to ensure it can use the ideas without re-
pert systems for processing strategies, these are striction. However, patent applications not only
still far from being universally applicable. provide protection but also represent a source of
The above deliberations culminate in a sep- information for competitors [16]. Careful con-
aration concept which can be broken down into sideration must therefore be given to the ques-
individual unit operations. Initially, these oper- tion of whether it is desirable to keep an idea
ations can be examined in the laboratory either secret or whether it should be patented.
on a batch basis, or in a continuous process to The risk involved in deciding against patent-
determine whether they are feasible in princi- ing in-house knowledge can be reduced by elimi-
ple (e.g., are azeotropes formed?, how difficult nating the patentable novelty of that information
is separation?, what is the dissolution rate?, can on a worldwide basis through publication in a
the phases be separated?, etc.). This gives the ini- suitable form, e.g., in an in-house journal or a
tial process concept, which can be used as a basis technical bulletin, etc.
for starting the actual process development.
If the idea is restricted by third-party propri- The development costs determined in this
etary rights, the following questions should be way do not contain any contributions arising
answered: from personnel not directly involved in devel-
opment, such as management or patent special-
1) When do those rights expire?
ists. Nor is account taken of unsuccessful de-
2) How can they be rendered void?
velopments. It nevertheless seems reasonable to
3) How can they be circumvented by modifica-
apportion the direct development costs to the
tions?
product and to allow for the other research and
If the idea is completely covered by third-party development costs in some other way, for exam-
proprietary rights, the only way out is to enter ple by means of a general cost provision (see
into licensing negotiations. Section 4.1.6.6). Although this method only ac-
Normally, a process should only be developed counts for the costs of successful development
after the legal situation has been clarified. projects, the financial burdens on the product
will be relatively high if it must bear all the de-
2.5. Development Costs velopment costs of the first plant.
Development costs often constitute a consider-

able proportion of the total cost of a project. If 2.6. Location
the process is completely new, these costs are
often around 50 % of the investment costs for The main competitive advantages such as price
the industrial plant, and perhaps more if a pilot and availability are nowadays often dependent
plant must be built. on the location of the production plant. Thus,
Development costs can be quoted with suf- there is now an increasing tendency to move
ficient accuracy if the following items are as- the production of major basic chemicals such as
sessed: methanol to the oil-producing countries. How-
ever, products whose production requires con-
Man years: This involves determining how siderable know-how are less location-dependent
many chemists and engineers will be employed and will continue to be produced in the indus-
on the project and for how long. Since the costs trialized countries, even in the future. Extreme
associated with each of the specialists working cases are those in which legal requirements de-
on the individual investigations are known, the cide the location, as is the case in the field of
man-year costs can then be calculated. gene technology.
In deciding on location, consideration should
Setting up costs: A rough estimate of the be given to the following aspects:
costs of setting up a small-scale plant is suffi-
cient since this item is normally the smallest in 1) Proximity to the sales market
the development costs. Once some notion of the 2) Proximity to the sources of raw materials or
process is available (a rough process flow dia- precursors
gram), these costs can be determined with rea- 3) Transport facilities (ship, rail, road)
sonable accuracy. 4) Quality of the available labor
5) Availability of cooling water
Operating costs: The operating costs can be 6) Waste-disposal management (sewage treat-
estimated from the assumed development time ment plant, incineration plant)
and the supervisory staff (shift personnel) re- 7) Political considerations (tax, investment aid,
quired. A rule of thumb is that the annual op- approval situation)
erating costs of an experimental plant will be at
least equal to those required to set it up.
More difficult to estimate are the amounts re-
quired annually for modifications and repairs to 2.7. Market Situation
the experimental plant. These depend very much
on whether new or already proven technologies The competitive advantages generated by pro-
are being used. cess development should ultimately benefit the
market and its customers. It is therefore impossi- Since the exact purchase prices (transfer
ble to target process development correctly with- prices) are an important source of information
out a precise knowledge of that market. The fol- in assessing manufacturing costs, they must al-
lowing information is required if the basic data ways be available and kept up to date in a chemi-
needed to plan production (plant size, maximum cal company. Figure 6 shows the variation in the
production costs) are to be obtained price of some basic chemicals.
It is not only the price of potential raw ma-
1) Market price (how it will develop and vary
terials which must be determined but also their
with time)
availability and quality (purity, state as deliv-
2) Demand, broken down into in-house and
ered).
third-party demand
It is never possible to reach a generally appli-
3) Market growth
cable decision on a particular raw material since
4) Utilization of capacity in existing plants,
much depends on its availability at a particular
with a breakdown in terms of location
location and variation with time.
(United States, Western Europe, Japan) and
production process
5) Competitive situation (who is the largest
competitor?) 2.9. Plant Capacity
6) Customer situation (are there many small
customers or a few large ones?) Optimum plant capacity, i.e., the size of plant
which yields the maximum return (see Sec-
The question of whether a process development tion 4.2), will be achieved if a degree of capacity
or improvement will be worthwhile can be ana- utilization of 100 % is reached 3 – 5 years after
lyzed by using a portfolio representation (Fig. 5). start-up. However, since the plant capacity must
Portfolio analysis is a strategic planning tool, be decided about 4 – 5 years before start-up for
used to concentrate research investment on prod- planning and legal approval reasons, and plants
ucts for which market prospects appear favor- which are not fully utilized over a period of time
able and competitive advantages can be ex- increase the specific production costs, it is essen-
ploited [17]. tial to be able to look 7 – 10 years into the future
in determining the optimum capacity. Therefore,
precise knowledge of the market potential and of
2.8. Raw Materials market growth trends is required.
The relationship between production price
Raw materials, their availability, and their price and degree of capacity utilization is as follows
structure have always been crucial factors re- [19]
sponsible for shaping the technological base
of the chemical industry and, consequently, its P 1+F/V
= (2.16)
growth and expansion (see Fig. 2). P0 1+F/V ·Keff /K0
The chemical industry produces a wide vari-
ety of products from only a few inorganic and where
organic raw materials. P = production price in monetary units per
Thus, raw materials such as natural gas, pe- kilogram,
troleum, air, and water are used to produce ba- P0 = production price at rated capacity,
sic chemicals such as synthesis gas (CO – H2 F = fixed costs,
mixture), acetylene, ethylene, propene, benzene, V = variable costs,
ammonia, etc. These are used in turn to manu- K eff = effective plant capacity, in tonnes per
facture intermediates such as methanol, styrene, annum,
urea, ethylene oxide, acetic acid, acrylic acid,
cyclohexane, etc. (see Fig. 1). K0
Any change in the price and availability of = rated capacity, in tonnes per annum.
raw materials will therefore have a substantial Thus, as the degree of capacity utilization
effect on the production processes for secondary drops, the production price increases hyperbol-
products. ically and this dependence is the greater, the
Figure 5. Portfolio matrix [17]

A) Sleeping dog products These are problem products whose competitive situation is weak because of their low market share.
In such cases process development would not be worthwhile.
B) Cash cow products These are products which, although their market growth is low, have a high market share. To exploit the
cost advantages to the full, there is little point in heavily investing in process improvements. Instead, these products should be
“milked” and the resulting cash flow used to support the star products.
C) Star products All the efforts should be concentrated on these products since they will safeguard the survival of the company
in the long term.
D) Question mark products In these cases the company must decide whether to increase the market share (turn them into star
products) or to abandon them if the prospects are slim.
Figure 6. Variation in the price of some basic chemicals with time [18]
higher the contribution made by the fixed costs be undecided and the process should therefore be
(see Fig. 7). designed to produce only waste products which
can be readily incinerated. Processes which pro-
duce salts or large amounts of dilute aqueous
solutions containing materials that are difficult
to degrade biologically are inherently location-
dependent.
2.11. End Product

It is essential to determine the demand for the
end product as well as its specification and
achievable price. A strongly competitive situa-
tion will mean particularly severe changes with
time, and in this case it is necessary to adopt a
particularly critical approach to forecasting. The
product specification is of particular significance
for process development. In the simplest case, it
Figure 7. Dependence of the relative production price
consists of a minimum purity, for example, that
on degree of capacity utilization for different fixed the end product should contain at least 99 % of a
cost/variable cost ratios F/V particular chemical compound. The permissible
impurity content may vary considerably from
The greater the uncertainty in the market
one product to another. Thus while it may be a
studies and the newer the technology used, the
few percent in the case of dyes, the limit is often
greater will be the preference for choosing a
only a few parts per million for monomers.
lower capacity. Many Japanese chemical com-
However, in most cases the end product can-
panies adopt this approach and prefer to set up
not be specified so simply since its subsequent
several plants with smaller capacities. However,
use may be affected in different ways by individ-
lower capacities result in higher specific plant
ual impurities. In such cases, it is not sufficient
costs and therefore in higher production costs.
to specify an upper limit for the sum of impuri-
This is represented by the following empirical
ties; instead, limits must be specified for impor-
relationship:
tant individual components. Often, the chemical
I2 =I1 · (K2 /K1 )χ (2.17) analysis is not sufficient or is not sufficient on
its own for specifying the end product, a case
where in point being, for example, polymers. In such
I = capital expenditure (investment), cases chemical analysis is supplemented by pro-
K = capacity, cess engineering properties which, in the sim-
χ = degression exponent. plest case, can be reduced to simple physical
properties.
For individual items of equipment, χ = 0.6, The process development engineer endeav-
and for plants containing the same number of ours to obtain as detailed a specification as pos-
items of equipment χ = 2/3 [20]. sible for the end product before he starts work,
but usually the specification will only be final-
ized during process development.
2.10. Waste-Disposal Situation Statements such as “as pure as possible” are
(see Section 4.1.6.3) inadequate since the removal of the final traces
of impurities is time consuming and expensive.
Waste-disposal facilities (incineration, sewage Individual specifications which are of no signif-
treatment plant, waste-disposal site) depend on icance in characterizing the end product should
the location. However, at the beginning of probe avoided. If possible, a composition which
cess development the location will generally still can be determined analytically is preferable to a
purely physical characterization since it is more the maximum capacity of the next larger plant
closely related to the process sequence. whose operating performance can be calculated.
It is here that the process development engineer
has an opportunity to save time and money. If
3. The Standard Course of Process reliable documents can be drawn up which en-
able the maximum scale-up of four powers of
Development ten (100 g/h×104 = 1 t/h) to be spanned in de-
signing a production plant, omitting the interme-
3.1. The Iterative Nature of Process diate stage also eliminates the costs of the pilot
Development plant and 3 – 4 years’ development time [23],
providing an important advantage in terms of
The development of chemical processes is a cost effectiveness and marketing. Consequently,
complex procedure. efforts are now made to extrapolate directly from
The first hurdle in establishing a new process the miniplant to the production scale.
is overcome when a promising synthetic route, The following list summarizes some of the
usually with associated catalysts, is discovered, important process steps and typical maximum
but many issues must be clarified and many prob- scale-up values above which reliable scale-up is
lems solved before industrial implementation is no longer possible [24]:
feasible and all the documents necessary to de-
sign and operate a chemical plant have been as- Reactors
sembled [21], [22]. How are these planning doc- Multitubular reactor,
uments arrived at? homogeneous tube,
homogeneous stirred tank >10 000
The conventional procedure is carried out in Bubble column < 1000
three stages (see Fig. 8): Fluidized-bed reactor
An initial process concept is developed on 50 – 100
the basis of an optimized laboratory synthesis.
This is not usually continuous (see Section 3.2),
and the individual process steps are examined Separation processes
Distillation and rectification 1000 – 50 000
independently of each other in the laboratory Absorption 1000 – 50 000
(see Section 3.3). A continuous laboratory plant Extraction 500 – 1 000
(the so-called miniplant) is then designed, set up, Drying 20 – 50
and operated (see Section 3.4.1). This is a small Crystallization 20 – 30
but complete plant handling production quanti-
ties of ca. 100 g/h and consisting of a synthesis
section, working-up, and all recycling streams. Larger scale-up factors are possible for gas-
Once the process concept has been confirmed phase reactors such as multitubular reactors.
in the miniplant, the next step is to design and An overview of the main types of reactor and
set up a trial plant with a much higher capacity, a discussion of the criteria for the choice of a par-
the scale of this pilot plant being between that ticular reactor and reactor scale-up during pro-
of the miniplant and that of the industrial plant. cess development can be found in Parts A and
The quantities produced are a few kilograms per B of this volume. The use of dimensional analy-
hour or tonnes per annum and enable, for ex- sis in scale-up is discussed in→ Scale-Up in the
ample, application tests to be carried out on the Chemical Industry.
product or large-scale deliveries to be made to The unit operations of distillation, rectifica-
customers. Operation of the pilot plant makes it tion, and absorption can be scaled up without
possible to complete and verify data and docu- an intermediate stage. This explains, for exam-
mentary information obtained at an earlier stage ple, why much effort is expended on obtaining
of process development (see Section 3.4.2). operating conditions that allow the reaction and
The scale-up factor from one stage to the processing of gases and liquids. The behavior
next is always limited by the “minimum princi- of gases and gas – liquid equilibria can be ex-
ple”, i.e., the process stage or piece of equipment plained well in physical terms and calculation is
with the lowest scale-up feasibility determines therefore straightforward.
Figure 8. The stages involved in developing a process

The time intervals specified for design, installation, and operation are only tentative and, in specific cases, the real values may
differ greatly from those given
Example 3.1. Vapor – liquid equilibria can The vapor pressure of the pure component i,
readily be measured experimentally and can be P0i (T ), is often represented by a three-parameter
described well in mathematical form. The gen- Antoine expression:
eral relationship for the equilibrium between a Bi
liquid phase and an ideal gas phase takes the Pi0 (T ) =Ai + (3.2)
Ci +T
form:
Several models are available for describing the
γi (xi ) ·Pi0 (T ) activity coefficient γ i . Examples are the Wilson
yi (xi ,T ) = ·xi (3.1) model, which can be applied to completely mis-
P
cible mixtures, and the NRTL model, which is
where suitable for systems with a miscibility gap [25],
yi = mole fraction of component i in the gas [26].
phase, For solids, scale-up factors are several or-
xi = mole fraction of component i in the liq- ders of magnitude lower because of complica-
uid phase, tions such as deposits, encrustations, and abra-
P0i (T ) = saturation pressure of pure component sion. This is true not only for synthesis (e.g., in
i at the system temperature T , fluidized-bed reactors), but also for processing
P = vapor pressure of the mixture, (e.g., drying and crystallization).
γi = activity coefficient of component i. Process development does not, however, take
place as a one-way street. Assumptions are made
for the individual development stages which are
only confirmed or refuted when the next stage is possible so that consideration of a larger num-
being worked on. It may be necessary therefore ber of possibilities is restricted to the labora-
to go through the individual stages several times tory. Prolonged investigation of two variants on
with modified assumptions, resulting in a cyclic a trial-plant scale should be avoided.
pattern (see Fig. 9). Most mistakes are made at the beginning of
the activity, but it is still relatively easy and cheap
to eliminate them at the miniplant stage. How-
ever, the further process development advances,
the more expensive it becomes to eliminate mis-
takes (see Fig. 10). In the final production plant,
corrections can only be made with an enormous
expenditure of time and money.
As shown in Figure 9, each development
stage is followed by an evaluation to de-
cide whether development should be continued,
stopped, or started again at an earlier develop-
ment level (see Section 4).
3.2. Drawing up an Initial Version of the

Process
Once all the information has been assembled, an
initial version of the process is drawn up [27].
In general, it has been found useful to adopt the
following procedure:
After the initial versions of the process, which
should be the most reasonable ones possible at
that stage, have been drawn up, they should be
discussed by the project team. This discussion
should take account of all the information gath-
ered hitherto and, after all the advantages and
disadvantages have been reviewed, only one ver-
sion of the process should remain.
There is at present no method which will re-
sult in the “best” version of the process being
Figure 9. The cyclic pattern of process development invariably chosen at the outset and there will
presumably not be one in the future either [28],
[29]. Finding the optimum version of a process
requires not only knowledge and experience but
The most important task is to find the weak also a considerable creativity, since the number
points and subject them to particularly close of possible ways of carrying out a given task is
scrutiny. The entire process will then be exam- almost infinite and many of the rules can still not
ined again with the improved data obtained in be quantified [30].
this way, and so on. The fact that many deci- Example 3.2 : The esterification of an im-
sions must be taken with incomplete knowledge pure organic acid with methanol yields a reac-
is a fundamental but inevitable difficulty. To de- tion mixture containing at least 5 components
lay development until all uncertainties have been (N = 5): unreacted acid, unreacted alcohol, es-
eliminated would be just as wrong as starting inter, volatiles such as H2 O, lower esters, di-
dustrial development on the basis of laboratory methyl ether, and high-boiling components such
discoveries alone. as higher esters.
A start should be made on choosing between According to Stephanopolous [31] the pos-
various processes or process variants as early as sible number of arrangements for the separation
Figure 10. The costs of eliminating mistakes and the investment costs increase by a factor of 10 from one development stage
to the next
operations can be calculated from the relation- variants, to compare them, and then select one is
ship: not feasible because of the large number. Many
of the variants can of course be eliminated at the
[2· (N −1)] ! (N −1)
Z= ·S (3.3) start for trivial reasons (industrial, economic, le-
N !· (N −1) !
gal reasons, etc.). However, even the number of
where potential variants left is still so large that it is im-
possible to calculate investment and production
Z = number of alternative arrangements, costs for all of them. Furthermore, at this point
N = number of components, the information available for doing this is often
S = number of separation processes. inadequate and there is consequently a risk of
eliminating promising variants.
If all components can be separated by distil-
Perhaps this example reveals why inventing
lation, (N − 1) = 4 separation columns are nec-
processes is still an art rather than a craft. How-
essary, which can be arranged in 14 differ-
ever, the tools available for performing this art
ent ways. If a second separation process – for
are being continuously improved [30], [32], [33]
example, an extraction, if the ester, alcohol,
(see Section 3.2.1).
and water form azeotropes – must be added,
On the basis of this initial version, an indus-
this already results in 224 possible arrange-
trial plant is designed. The individual unit op-
ments. If the number of possible reaction pro-
erations (reactor, absorber, distillation, etc.) are
cedures (e.g., batch/continuous; gas/liquid; ion
designed on the basis of the existing informa-
exchanger/mineral acid) is also taken into con-
tion (approximate size and diameter of columns,
sideration, there will be an almost infinite num-
etc.).
ber of ways of carrying out the process (a so-
By scaling down this hypothetical large-scale
called combinatorial explosion).
plant a trial plant is designed, which is nowadays
To find the best process among all these vari-
generally a miniplant (see Section 3.4.1). At the
ants is quite impossible simply because the ideal
same time, the industrial plant is simulated by
solution is unknown. To calculate all possible
using a computer program and an initial com- Databases differ as to whether they contain
plete mass and energy balance sheet is drawn the information itself (primary information or
up. factual data) or whether they refer to other infor-
mation sources (secondary information or liter-
ature data).
3.2.1. Tools used in Drawing up the Initial Some types of data which are important for
Version of the Process process development are [36]:
Requirements which must be met by modern 1) Material properties [37]

EDP tools are as follows: 2) Physicochemical data
3) Ecological and toxicological data
1) Fast access to the information 4) Costs of raw materials, intermediates, and
2) Information which can be conveniently han- end products
dled at the workplace 5) Energy and equipment costs
3) The information must be continuously up- 6) On-line literature searches
dated
Table 2. A selection of simulation programs for steady-state pro-

cesses
Program Supplier
ASPEN PLUS Aspen Technology Inc.,

251 Vassar Street
Cambridge, MA 02139
United States
CHEMASIM BASF AG,
Ludwigshafen,
Germany
CHEMCAD Chemstations Engineering
Software COADE
10375 Richmond Ave.,
Suite 1225
Houston, TX 77042
United States
DESIGN II Chemshare
FLOWPACK ICI
HYSIM Hydrotech. Ltd.
400, 119 14th Street N.W.
Calgary, Alberta T2N1Z6
Canada
PROCESS Simulation Science Inc.,
PRO/II 1 051 W Bastanchury Road,
Fullerton, CA 92633
United States
Figure 11. On-line service components [35] VTPLAN Bayer AG,
(CONTI) Leverkusen,
Germany
3.2.1.1. Databases [34]

3.2.1.2. Simulation Programs [38]
To carry out process development as efficiently
as possible, it is important to avoid duplicate Simulation using computer programs furnishes
activities. This includes taking account of ex- the process development engineer with a very
isting knowledge or exploiting it. For this rea- effective tool. The development of very fast,
son, chemical companies not only build up inter- large computers and effective physical models
nal databases but also utilize external databases. has now made it possible to simulate individual
Figure 11 provides an overview of the structure units (e.g., distillation), networks of units of the
of an on-line data bank.
same type (e.g., a stirred tank cascade, a heat ing conclusions and using experimental knowl-
exchanger network) and networks of dissimilar edge. In this case, however, the knowledge does
units (e.g., chemical plants). not only consist of facts which can be stored in
In practice, the simulation program used de- databases but is acquired by carrying out process
pends on the objective; there is, after all, little development, experiencing failures, being suc-
point in trying to solve detailed problems with cessful, repeating the same process, and learning
a simulation program which, although it is all- at the same time; in short, by acquiring a feel for
embracing, is slow if there are very much more a problem. Knowledge is gained as to when it is
efficient programs available which are designed necessary to stick to the rules and when they can
for the specific requirement. Programs for solv- be broken; a stock of practically proven, heuris-
ing specific problems are usually developed by tic knowledge is built up [30].
the user himself and are not generally available Some examples of heuristic rules in process
or are available only in rare cases. development are:
Numerous programs for dealing with flow
sheet problems are available from universities, 1) Carry out each reaction or separation only
industry, or the commercial market (see Tables 2 once (e.g., volatiles should only be removed
and 3) [33]. once)
2) Remove substances which can be readily iso-
lated immediately after they are produced
Table 3. A selection of simulation programs for dynamic systems and do not spread them over the entire
[39–42] working-up process
Program Supplier 3) Design recycling paths so that, if possible,
they only result in small feedbacks
CHEMADYN BASF AG,
Ludwigshafen, 4) If possible, use substances which are in any
Germany case present in the reaction output as aux-
DIVA Prof. Dr. Gilles, iliary solvents since this may reduce the
University of Stuttgart,
Germany
working-up costs considerably
SATU Höchst AG,
Frankfurt, Combinatorial problems such as drawing up
Germany an initial version of a process or developing a
SIMUSOLV The Dow Company complex catalyst system result in a combinato-
Midland, Mi 48674,
United States
rial explosion (see Section 3.2). Time does not
SPEEDUP Prosys Technology Ltd., allow all the possible solutions to be tested. The
Cambridge, human expert copes with such a combinatori-
England, al explosion by eliminating those possibilities
(since 15.10.1991 Aspen
Technology Inc.) which seem to him to be unfruitful, concentrat-
ing on those which seem to be feasible and using
heuristic knowledge which steers him towards
the optimum solution but does not guarantee it.
3.2.1.3. Expert Systems The main components of an expert system are
The difference between simulation programs as follows (see also Fig. 12):
and expert systems is that in the former the mod- 1) Knowledge base: heuristic knowledge is re-
eling is rigidly embodied by an algorithm, while presented in this case by a system of symbols
in the latter, knowledge of the model is stored in 2) Knowledge editor: a module which assists
the knowledge base independent of the deduc- in changing, adding, or removing rules and
tive mechanism [43–45]. formalizes their evaluation
An expert system is a computer program 3) The deductive mechanism, which combines
equipped with knowledge and ability which can knowledge and problem data by deriving fur-
carry out complex tasks by imitating human in- ther data from the rules stored in the knowl-
telligence. Such systems are therefore particu- edge base
larly suitable for use in process development 4) input – output systems
where complex problems are solved by draw-
gramming languages such as LISP (List Proces-

sor) were introduced. These are able to process
symbols and symbol structures using a computer
[48]. In addition a wide range of computer tools
became available. Although these have made
the development and handling of expert systems
easier, they have contributed almost nothing to
an understanding of the phenomena [49].
It is now beyond dispute that expert systems
Figure 12. Structure of an expert system [46] have justified themselves, although the eupho-
ria of the 1970s has given way to a more sober
This technique was first applied in 1969 for assessment. The belief that a lack of knowledge
describing and designing composite heat ex- and understanding can be overcome by an ex-
changer systems [47]. It was rule-oriented, i.e., pert system has been found to be completely er-
the expert system involved a series of rules roneous. On the contrary, an expert system can
whose combination led to different results. The only be used efficiently by experts.
system was controlled by weighting factors,
which were in turn dictated by success. The sys-
tem “learned” through this method of changing 3.3. Checking the Individual Steps
weights and was therefore capable of yielding
increasingly better results. Like the reaction step or steps, the cho-
sen preparatory and separation steps are first
checked individually and independently of one
another on a laboratory scale. Even at this stage,
new requirements may be imposed on the reac-
tion stage. For example, difficulty in removing
a byproduct may make it necessary to alter the
reaction conditions or modify the catalyst.
Along with the experimental work, e.g., test-
ing an absorber (see Fig. 13), thermodynamic
simulation calculations are carried out for the
unit concerned.
Laboratory experiments are generally carried
out with pure, well-defined materials. Thus, the
solvent selected for the absorption is used as re-
ceived from the chemical stores. This differs,
of course, from the subsequent situation, where
the solvent must be recycled for cost reasons
and inevitably becomes enriched with byprod-
ucts, some of which are unknown, however, at
this point in time.
The feedstock used is a synthetic mixture of
gases prepared from pure materials which also
does not contain byproducts. The experiment
shows whether it is physically possible to absorb
Figure 13. Checking the individual steps in the laboratory the useful product from the gas stream with rea-
using pure feedstock with the absorber stage as an example sonable amounts of solvent. If the absorber can
(see Fig. 14)
be simulated with the available material data in
a calculation run in parallel, work on this step
The first expert systems were laboriously will be complete. The unit is then another piece
written in FORTRAN, but the technique ac- which can be fitted into the jigsaw puzzle of the
quired a new impetus in the 1980s when pro-
entire process, which is the next item which must tion, the solvent circuit may become enriched in
be considered in an integrated trial plant. byproducts and this may lower product purity.
In principle, these problems can only be
solved by mathematical simulation, but since
many of the quantities that are required for a
mathematical description are unknown, an ex-
perimental approach must be adopted.
Example 3.3. When a plant which includes
recycling streams (see Fig. 15) is operated, the
solvent circuit becomes enriched in a high-
boiling substance whose existence was not pre-
viously known because it was below the analyt-
ical limit of detection in the reaction product.
This high-boiling substance also has the trou-
blesome property of depositing when it reaches
a certain concentration in the solvent and forms
a coating in the column.
Since the high-boiling substance was not
known before, it was not possible to include it
in the mathematical simulation. Now that it has
been discovered as a result of operating an inte-
grated plant, it can be characterized and incor-
porated in the simulation.
Figure 14. An initial version of a process for oxidizing a

starting material with air and then isolating the product by
3.4.1. The Miniplant Technique
absorption and distillation
3.4.1.1. Introduction
Once all the individual steps have been suc- Improvement in computer programs for mod-
cessfully tested, it is possible to draw up a reli- eling processes has resulted in the integrated
able flow sheet of the entire process (see Fig. 15). miniplant technology acquiring ever increasing
However, if any subsidiary step is found not to be importance because the synergism between the
feasible at this stage, the process concept must miniplant technique and mathematical simula-
be changed. tion means that the margin of safety in scaling
This preliminary flow sheet, which has not up is as good as that obtained by setting up a
as yet been fully tested as a whole, can be used pilot plant [50–52], [53, pp. 179 –182].
to draw up an initial rough cost estimate (see The miniplant technique has the following
Section 4). characteristics:
1) The trial plant includes all the recycling paths
3.4. Testing the Entire Process on a (it is a so-called integrated miniplant) and it
Small Scale can consequently be extrapolated with a high
degree of reliability.
As Figure 15 shows, when the individual steps 2) The components used (columns, pumps,
are put together, recycling streams are created condensers, pipelines) are often the same
(in this case one gas and one solvent recycling as those used in the laboratory. In addition,
path). These recycling streams or feedbacks are they are largely reusable standardized com-
an economic necessity, but they raise new pro- ponents which have been tried and tested in
cess engineering problems. Thus, material re- continuous operation. For these reasons, in-
cycled to the reactor may drastically affect the vestment costs are low and flexibility is high.
activity and service life of the catalyst. In addi-
Figure 15. Example of a simplified process flow chart produced after testing the individual steps
3) The plant is operated round the clock on a 3.4.1.2. Construction

shift basis for weeks and it therefore must
be as fully automated as possible to keep op- The following design documents are required as
erating costs low, but not, however, at the a minimum for constructing a miniplant:
expense of flexibility.
The measuring and control instruments used 1) A process flow sheet showing all the quan-
are standard components which are nowa- tity flows in the miniplant and the associated
days generally connected to a small process temperature and pressure conditions
control system [54, pp. 183 – 186], thus mak- 2) Engineering flow diagram
ing it possible to carry out modifications in Required information:
the measurement and control rapidly. a) All equipment and machines
4) The entire plant is normally set up in an b) Internal diameters and pressure ratings of
extracted chamber so that explosion-proof pipelines and construction material
operation is possible and safety-at-work re-
quirements can be met more easily.
Next Page
c) The objectives of the instrumentation efficiently (because of excessive temperature

d) Information on the insulation of the equip- differences, foaming, etc.).
ment and pipelines Example 3.4. A miniplant produces a high-
3) List of measuring points (measuring point boiling residue at a rate of 1 g/h. This residue
number, specification, parts list, point of in- is removed from the bottom of a distillation
stallation) column with a distillation boiler capacity of
4) Safety concept, i.e., how the sensors (e.g., for 200 mL, so that the mean residence time is 200 h.
temperature, pressure, flow) are linked to the The time required to reach the steady state is
actuators (e.g., valves, pumps) by the safety consequently about 25 d (about 3 times the mean
logic residence time). Only then will it be possible to
assess this bottom residue and draw conclusions
about its fouling behavior, composition, proper-
ties, etc.
Specification of Material Balance. In Sec-

tion 3.2 it was shown that a miniplant should be
designed by scaling down a hypothetical large-
scale plant. The scale-down factor is determined
by finding the points in the process where the
smallest and largest quantity flows occur. The
levels at which these flows can be handled de-
termine the scale-down factor.
Normally only flows of 1 g/h and 10 kg/h
can be handled in a miniplant. At the same time,
the minimum flow is primarily determined by
the time required to reach a steady state (see Ex-
ample 3.4), while the upper limit of the flow is
set by the maximum hydrodynamic load of the
laboratory column used.
Example 3.5. In a hypothetical large-scale
plant producing 5 t/h, the minimum flow is
50 kg/h of a high-boiling substance which must
be removed and incinerated, while the maximum
flow is 100 t/h of the reaction throughput, which
contains the useful product as a 5 % aqueous so-
lution.
Scale-down factor:
Figure 16. Example of a miniplant
for the minimum flow: 50 kg/h ÷ 1 g/h =
50 000,
for the maximum flow: 100 t/h ÷ 10 kg/h =
Specification of Equipment Size. In a 10 000.
miniplant, the hold-up for a given throughput is Thus the miniplant should be designed to pro-
almost always greater than in an industrial-scale duce not less than 100 g or not more than 500 g
plant. The size of the vessels and column bot- of useful product per hour.
toms should therefore be minimized, otherwise
it will take too long for the miniplant to reach Specification of Type of Equipment. Un-
a steady state because of long residence times. like normal laboratory experiments in which the
In the column bottoms, which are particularly equipment operates only during the daytime,
critical, a hold up of 100 – 200 mL is normally miniplants must run continuously over a period
the lower limit. Below this level, a laboratory of weeks to be able to fulfil their task. This is
evaporator can usually no longer be operated due to the fact that the time required to reach
Previous Page
a steady state is often long and because it is monitor liquid levels, deposits, foam formation,
only possible to draw reliable conclusions about etc., than in the large-scale plant. Schulz-Walz
long-term effects such as corrosion, fouling, has given examples of measuring and metering
catalyst deactivation after a long time (1 week techniques for miniplants [55]. In the last two
to 6 months). decades, important advances have been made
Unlike laboratory plants, the requirement imin sensor technology and, along with electron-
posed on the reliability of miniplant compo- ics and processor technology, this has consid-
nents are therefore very high and almost the erably simplified the miniaturization of sensors
same as for a large-scale plant. Occasionally this for miniplants (see Table 5).
sets very tight restraints on choosing equipment
and in some cases necessitates in-house devel-
opment if nothing suitable is available on the Table 5. Established miniaturization limits for instrumentation com-
market. ponents [51]
Measured quantity Principle of Established

measurement minimum
3.4.1.3. The Limits of Miniaturization measurement range
Gas flow thermal 0.02 – 0.6 L/h
Table 4 lists the minimum dimensions for which volumetric 2 – 200 L/h
it is possible to scale-up a process. Liquid flow thermal 2 – 30 g/h
Coriolis force 0.07 – 1.5 kg/h
magnetic inductance 0.6 – 6 L/h
volumetric 0.1 – 1 L/h for piston
Table 4. Examples of tried and tested miniaturization limits [51] meters
2 – 40 L/h for oval
Example Tried and tested limit disk meters
1 mL/h upwards for
Columns 30 mm diameter packed columns metering pumps
35 mm diameter columns with structured gravimetric 2 – 50 g/h (balance
packing, dual-flow plate columns range 0 – 5000 g)
50 mm diameter bubble-cap columns Temperature resistance change T min range 30◦ C
Pumps 1 mL/h injection pumps (maximum range
10 mL/h piston pumps −200 to 600◦ C)
100 L/h rotary pumps thermoelectric T min range 50◦ C
Belt filter 50 mm belt width voltage (maximum range
0 – 1000◦ C)
Centrifuges delivery 5 L/h
Level conductive >50 mm
Pipelines 1.5 mm diameter, metal or Teflon
capacitive >50 mm
hydrostatic >4 mbar
Differential pressure strain gauge 0 – 1.25 mbar
piezoresistive
Columns can still be operated effectively capacitive
down to 35 mm diameter when filled with an
ordered packing. For plate columns having one
bubble cap per plate, the limit is ca. 50 mm. At
still smaller dimensions, wall effects are difficult There are four stages in the automation of a
to suppress. miniplant:
Experimental equipment for handling solids Stage 1. At this stage, the electrical instru-
or dealing with extreme operating conditions is mentation of the miniplant consists of compact,
often not available. This often necessitates in- self-contained individual components, e.g., bal-
house developments and cooperation with spe- ances, metering controls, metering pumps, ther-
cialist firms, university institutes, and research mostats, temperature controllers, pH sensors,
companies. individual controllers, control valves, pressure
Expenditure on instrumentation is often very sensors, and plotters. Monitoring and operation
much lower for a miniplant than for the corre- is the responsibility of the shift personnel.
sponding large-scale plant. For this to be the Stage 2. At this stage the structure of the sen-
case, however, most of the miniplant compo- sors, actuators, and individual components is the
nents must be made of glass and therefore oper- same as in Stage 1, but the individual compo-
ate at low-pressure, thus making it much easier to nents may be connected to a data processing
computer via a data interface. Monitoring and 3.4.2. Pilot Plant

operation is again the responsibility of the shift
personnel. It may be necessary to construct a pilot plant if
Stage 3. Here the system for logging the mea- one of the following conditions applies:
sured data is the same as in Stage 2, but the 1) The scaling-up risk is too large to proceed
lower-ranking self-contained individual compo- directly from the miniplant to the industrial-
nents are controlled and provided with set points scale plant. The reasons for this may be:
by a higher-ranking automation software, so that a) The process involves several critical
shift personnel are able to concentrate on moni- stages (e.g., handling of solids) which can-
toring tasks. not be described by physical models
Stage 4. At this stage the miniplant is b) a difficult or completely novel technology
equipped with a compact process control sys- is being used
tem. While the actuator and sensor system is the
2) It is necessary to provide representative
same as at Stage 1, all the other functions such as
product quantities, e.g., for the market
controlling, measuring, regulating, calculating,
launch, and these cannot be produced by the
processing data, optimizing, keeping records,
miniplant in a reasonable time
alerting, logging, operating, and observing are
performed by the process control system. The operation of the pilot plant should clar-
The choice of automation stage is decided ify all the issues which have not been fully dealt
during the miniplant design phase on the basis with in the miniplant.
of the specific plant requirements and boundary These may include, for example [56], [57]:
conditions as well as on the results of trials. The 1) Checking design calculations
higher automation Stages 3 and 4 are only justi- 2) Solving scale-up problems
fied if a miniplant is to be operated over a long 3) Checking experimental results obtained with
period of time. the miniplant
4) Measuring the true temperature profiles in
the reactors and columns under adiabatic
3.4.1.4. The Limitations of the Miniplant conditions
Technique 5) Gaining process know-how (dynamic behav-
ior of the plant, start-up and shut-down pro-
A disadvantage of the miniplant approach cedures)
emerges if individual steps in the process are 6) Producing representative sample quantities
subject to an unduly large risk in extrapolat- in fairly large amounts
ing from the miniplant to the industrial-scale 7) Precisely assessing fairly small flows (e.g.,
plant. For example, scale-up factors of ca. 104 residues)
are still not feasible for extraction and crystal- 8) Training the personnel who are to run the
lization steps even today. This disadvantage can plant
often be circumvented by isolating critical sec- 9) Improving the estimate of the expected ser-
tions of the process and working on them in an vice life
intermediate stage (pilot stage). If enough of the 10) Carrying out material tests under realistic
unmodified product can then be collected from conditions
an integrated miniplant at an acceptable cost for
it to be possible to operate, e.g., an extraction A pilot plant should be designed as a scaled-
column or a crystallizing plant on a pilot scale down version of the industrial-scale plant and
with a representative feed for a sufficiently long not as a larger copy of the existing miniplant
time, the entire plant can again be extrapolated [58]. Nowadays it costs almost as much to de-
upwards with a calculable risk. This may obvi- sign, construct, and operate a pilot plant as an
ate the need for constructing a cost-intensive and industrial-scale plant.
time-consuming pilot plant for the entire process The decision to build a pilot plant results in
[56]. considerable costs. As a rule of thumb, the ini-
tial investment is at least 10 % of the invest-
ment costs of the subsequent industrial-scale
plant. Moreover, if they use particularly toxic 1) A summary

substances, pilot plants now often require ap- 2) A basic flow diagram
proval, and this may considerably lengthen the 3) A process flow diagram and a description of
time required to put them into operation. the process
Once process development on a pilot scale 4) A waste-disposal flow diagram
has been successfully concluded, the pilot plant 5) An estimate of the capital expenditure
must be kept on stand-by until the industrial- 6) A calculation of the production costs
scale plant is running satisfactorily. Normally, 7) A technology evaluation
when the larger plant is started up, the pilot plant 8) The level to which the experimental details
is operated simultaneously so that any problems have been worked out
which occur in the former can be dealt with
rapidly. 4.1.1. The Summary
The summary must start with a precise defini-

4. Process Evaluation tion of the objective. This is followed by a short
description of the process and of the most im-
After each development stage (see Section 3.1) portant process stages.
the existing knowledge should be documented The chemistry of the process should be re-
and the status of the process evaluated. This in- presented by overall reaction equations, with the
volves preparing study reports and is now stan- assumed conversion and selectivity being spec-
dard in many enterprises. ified.
At this stage it is necessary to answer the Details of the result of the study, the produc-
question posed in Section 1 as to whether the tion costs, the capital expenditure for a specified
process is “better” and “cheaper” than that of annual production output with an indication of
the competitors. the accuracy of the estimate and the planned lo-
cation of the plant, if known, are other important
points.
4.1. Preparation of Study Reports The summary concludes with information on
the state of knowledge and on the major risks.
The study report documents knowledge about
the status of the development of a process af- 4.1.2. Basic Flow Diagram
ter specified time intervals or specified develop-
ment stages to provide the basis for making a The basic flow diagram provides a quick
decision. The objective of the study report is to overview of the total process. It shows the in-
answer three important questions: put, output, and recycling streams and identifies
the individual process stages (see Fig. 14).
1) Can the production process be implemented
in this way in principle? 4.1.3. Process Description and Flow
2) What is the return on investment? Diagram
3) How big is the risk in economic and techno-
logical terms? All the individual steps of the process should be
At least three project study reports must be described as accurately as possible on the basis
completed in the course of the development of a of all the information available at the time, ref-
process: erence being made to the process flow diagram
(see Fig. 15).
1) One at the beginning of process development The latter should clearly show the process in
2) One in the course of working out the details detail and the composition of the flows.
of the process The following information should be in-
3) One at the end of process development cluded in the process flow diagram:
A study report should include the following 1) All equipment and machines (columns, ves-
items: sels, heat exchangers, reactors, etc.)
Table 6. Example of a material balance table
2) All product streams (with numbering) 2) Incineration in a power station or an inciner-

ation plant
Beneath the process flow diagram the material 3) Central hazardous waste incineration
balance should be presented in a clearly laid out 4) Waste-disposal site
table (see Table 6).
When development is at an advanced stage
or is complete, the process flow diagram should
4.1.5. Estimation of Capital Expenditure
show the following additional information:
1) Identification of the energy carriers (type of 4.1.5.1. Introduction
steam, cooling water, compressed air, elec- An important reason for preparing study reports
tric power, nitrogen, deionized water, heat- is to determine the capital expenditure (invest-
ing gas, refrigerants, etc.) ment) of a project [59], [60]. This is made up
2) Details on the construction materials, size of the independent location ISBL (inside bat-
and power of the equipment and machines tery limits) process plant costs such as invest-
3) Typical operating conditions (e.g., pressure ment in the production plant and the associated
and temperature in columns and pipelines) control rooms, laboratories, employee facilities,
4) Important fittings tank farms, and loading and unloading stations,
5) Purpose of instrumentation as well as the location-dependent OSBL (outside
battery limits) costs of all the service facilities,
such as investment in storage buildings, cooling
4.1.4. Waste-Disposal Flow Diagram towers, and waste-disposal facilities. Infrastruc-
ture costs are also to be included (see Fig. 17).
The waste-disposal flow diagram illustrates the The accuracy of the investment cost estimate
waste streams for which there is no further eco- depends critically on the level of maturity the
nomic use in the plant (see Section 1.3) and in- process has reached [62].
dicate their flow numbers from the process flow
diagram. Precise information should be given on 4.1.5.2. ISBL Investment Costs
the toxicity, degradability, water danger, flash
point, ignition temperature, MAK, odor thresh- Of the many methods for determining the cap-
old, etc. of the individual components, their mass ital required to set up a plant, a method of es-
flows, and the state of aggregation of the flow timation which derives the costs of a new plant
(viscosity, sediment content, etc.). This infor- from the known costs of existing plants with an
mation makes it possible to specify the type of accuracy of ± 30 % is now firmly established
waste disposal required, for example: (the additional-cost calculation method). Such
a method is only possible because the structure
1) Sewage treatment plant
of chemical plants is always very similar, i.e.,
Figure 17. Subdivision of a project into ISBL, OSBL, and infrastructure activities [61]
they are made up of interlinked pieces of equip- mined from the average value of the machines
ment of similar construction whose number does and equipment (see Fig. 18).
not vary widely. For this reason, the overall in- This results in the following simple relation-
vestment cost of the entire plant when installed ship:
exceeds the average value of the machines and
equipment (= total machine and equipment costs directplantcosts = overallfactor×
divided by the number of machines and pieces Σ (valuesof machinesanditemsof equipment) . (4.1)
of equipment) by a factor which depends on the
capacity. Since direct plant costs are always estimated
The total machine and equipment costs are for some date in the future, it is necessary to de-
determined from the parts list, while the costs of termine the effect of increases in price. Use is
individual units can be obtained from in-house therefore made of price indexes which are pub-
databases or directly from the manufacturers. lished for chemical plants in the individual coun-
Example 4.1 [59]. The overall factor for the tries (see Table 7). The price index i determined
chemical plant construction projects handled by by extrapolation is divided by the index i0 at
BASF in 1984 was on average 3.9; i.e., the direct the date of the cost determination. The ratio i/i0
plant costs of an average chemical plant is 3.9 is then a measure of the increase in investment
times the machine and equipment costs. costs to be expected.
The overall factor is essentially determined The direct plant costs make no allowance for
by the following items: the cost of engineers (usually 10 – 20 %) or for
contingencies (ca. 5 – 10 %).
1) Operating conditions (pressure, tempera- This method of estimation has the disadvan-
ture) tage that while the machine and equipment costs
2) Type of construction materials used (steel, can be determined fairly precisely, the average
stainless steel, special materials) value of these items is multiplied by a compara-
3) Size of machines and pieces of equipment tively inexact overall factor. The accuracy can be
considerably increased by breaking the overall
According to Miller [63], the effect these factor down into individual factors.
items have on the overall factor can be deter-
Figure 18. Overall factor for the direct plant costs as a function of the average value of the machines and pieces of equipment
in 1984 [59]:
a) Best-fit curve; b) Confidence limits for a statistical confidence interval of 95 %
Table 7. Price indexes i for chemical plants in Germany , p. 280[64] while for larger plants it is likely to be close to
Year i
the lower limit.
If the location is known, the OSBL costs can
1976 100
be estimated very accurately.
1980 125.3
1981 132.9
1982 140.5
1983 144.4 4.1.5.4. Infrastructure Costs
1984 147.2
1985 150.4
1986 154.0 The infrastructure costs depend on the location
1987 159.6 of the plant. They are not, however, related ex-
1988 164.7 clusively to the project since the infrastructure,
1989 170.9
such as workshops, the central store, and the
canal system, is also used by other production
facilities. Obviously, this type of cost can only
4.1.5.3. OSBL Investment Costs be specified if the precise position of the plant
at a location is known.
The OSBL investment depends on the loca-
tion of the plant. It includes, for example, the
cost of storage buildings, cooling towers, waste- 4.1.6. Calculation of Production Costs
disposal facilities, linking the OSBL facilities to
the location in question (e.g., water and electric- The cost effectiveness of a new process depends
ity supply), etc. Since the question of location is on the production costs of a product (unit of
generally still unresolved at an early stage in de- currency divided by unit of quantity) (see Sec-
velopment, it is not possible to specify the OSBL tion 4.2). The following information is required
costs explicitly but they can be tentatively taken to determine these costs:
as 20 – 30 % of the ISBL costs. For small plants
the percentage tends to lie near the upper limit, 1) Material balance
2) Waste-disposal flow diagram this does not overcome the problem of the im-
3) Utilities pact of the proposed plant on the market – it only
4) Investment shifts it. The significance of raw material costs in
cost estimation varies widely. Thus, in processes
The production costs can be calculated by involving a high level of material refinement (as
adding up the following items: is the case for some pharmaceuticals) or in those
1) Feedstock costs (raw materials and auxil- with high specific energy costs (e.g., chlorine
iaries) production), precise determination is not as im-
2) Manufacturing costs, which can be subdi- portant as in the case of cheap, mass-produced
vided into: products, such as petrochemicals, manufactured
in large plants.
a) Utility costs
Credits for byproducts can be set against the
b) Waste-disposal costs
raw material costs from the outset.
c) Staff costs (wages and salaries)
d) Maintainance
e) Miscellaneous costs (concern overheads) 4.1.6.2. Utilities
3) Capital-dependent costs (depreciation, inter-
est, insurance taxes) For large-scale processes, the cost effectiveness
depends appreciably on the cost of the utilities.
The combination of utilities required in the plant
therefore acquires considerable importance and
consideration must be given to the ideal thermal
coupling even at an early stage in the process de-
velopment since it can have a considerable im-
pact on the configuration of the process [66]. For
example, whether the energy derived from con-
densing vapors can be utilized depends on the
behavior of the materials. Clean and stable con-
densates usually present no problem in using the
heat of condensation to raise the temperature of
cold streams, but in the case of products which
tend to form deposits (by decomposition, poly-
merization, etc.) optimum thermal utilization of
Figure 19. Temperature – enthalpy diagram this type of energy is not possible since the va-
pors must be quenched to prevent deposits and
this results in loss of energy. This type of ques-
4.1.6.1. Feedstock Costs tion should be resolved in the miniplant phase.
A suitable aid for systematizing such con-
The raw material requirements are given by the siderations is Linhoff analysis [67], [68]. The
material balance for the chosen capacity, but to Linhoff analysis determines the process config-
determine the feedstock costs the prices of the uration for which the energy supplied from or
raw materials are required. The change in raw lost to the surroundings is a minimum. The prob-
material prices while the process is being devel- lem which must be solved is how to couple the
oped can be estimated, but it is more difficult to heat sinks and heat sources within the plant such
allow for the fact that the erection of the plant that minimum energy consumption is achieved.
will have an impact on the raw material mar- The initial step in the calculation is to determine
ket and consequently alter the price structure. the so-called composite curves and pinch tem-
Therefore, in some cases it is necessary to enter perature, which is the temperature above which
into negotiations with the raw material suppliers heat can be lost and below which heat can be
at an early stage. If the raw materials originate absorbed (see Fig. 19).
from another plant in the same concern, market For a given interconnection system, the Lin-
prices are replaced by transfer prices [65], but hoff analysis shows how far the heat utilization
is from being ideal. However, there are often rea- An initial estimate of the steam requirement
sons for not choosing an ideal interconnection: of a column is given by:
1) Start-up operations often require start-up
t/hsteam = 1/5 (reflux + headproduction) t/h (4.2)
heat exchangers, and this means higher in-
vestment costs This is based on the assumption that:
2) Energy utilization only becomes possible as
a result of increasing the column pressure, 1) The thermal combination is optimum (e.g.,
and this means higher investment costs and the hot discharge from the bottom is used to
may result in material problems (decompo- heat the feed)
sition, side reactions, etc.) 2) Normal organic liquids are involved (heats
3) Problems associated with the formation of of evaporation ca. 110 kWh/t)
deposits during heat transfer, which necessi-
tates direct heat removal (quenching) Electrical energy is more than twice as ex-
Generally, as the plant capacity increases, re- pensive as steam, and because of the explosion
ducing the operating utilities (i.e., optimizing the hazard it is normally not suitable for heating
thermal combination) rather than increasing the columns. Its most important applications are in
investment will have a more beneficial effect on feeding material (pumps, impellers, compres-
production costs. sors) and in carrying out operations such as size
The energy analysis is used to find the reduction, mixing, and separation.
amounts of energy required or released and to The pump delivery N required can be esti-
calculate the energy per unit quantity. The deter- mated using the following formula [70]:
mination of energy costs requires information on V̇ ·H ··g
the prices of the different types of energy, which N /kW = (4.3)
3600·103 ·ηtot
depend on the quantities required and the loca-
tion. where
Steam is the energy carrier most widely used V̇ = the useful feed flow in m3 /h,
for heat columns because it offers the following H = delivery head in m,
advantages: = density in kg/m3 ,
g = acceleration due to gravity (10 m/s2 ),
1) It is inexpensive since it can often be gener- η tot = overall efficiency.
ated directly in the synthesis section of the
plant The overall efficiency is made up of the
2) There are no explosion hazards provided the mechanical and the electrical efficiencies:
hot pipe surfaces are properly insulated
3) The temperature range covered is large (see ηtot =ηmech ·ηelectr. (4.4)
Table 8) For rotary pumps, the overall efficiency is
ca. 0.7 – 0.8 while for piston pumps it is
Table 8. Enthalpy and temperature of some frequently used steam
pressures [69] 0.8 – 0.9. For small pumps (< 5 m3 /h), the over-
all efficiency may, however, be much lower.
Gauge pressure, p, Temperature, ◦ C Heat of
bar vaporization ∗, Another application for electrical energy in
kWh/t chemical plants is in auxiliary electrical heating
0 100 627 systems (e.g., frost protection).
1.5 127 605
4 153 585
16 204 534
Fuels are only used in chemical plants if
25 226 508 streams must be heated to such high tempera-
40 252 477 tures that steam is no longer economical (the
100 312 361 limit is ca. 100 bar of steam, i.e., 310◦ C). How-
∗ With indirect heating, only the difference between the ever, the use of fuels in chemical plants always
incoming stream and the discharged condensate can be utilized. entails a risk from the ignition source.
Only the net calorific value of the fuel can be The cooling water required to remove a given
used since the steam formed can generally not quantity of heat depends on the temperature of
be condensed. the water and its quality. If more detailed infor-
A few typical values of the standard enthalpy mation is not available, it is sufficient as a first
of combustion are given in Table 9. approximation to determine the amount of cool-
ing water required by assuming its temperature
Table 9. Standard enthalpy of combustion at 25◦ C [71]
rises by 20◦ C.
Substance kWh/t For high product temperatures, an alterna-
tive to water cooling is to use air coolers. Al-
Acetaldehyde 7 360
Acetic acid 4 040 though these require a higher investment than
Carbon 9 110 water-cooled condensers, they are often cheaper
Carbon monoxide 2 810 to operate and are less prone to fouling.
Ethane 14 440
Ethanol 8 250
However, unless there is a shortage of cooling
Formaldehyde 5 190 water at a known location, it is generally suffi-
Formic acid 1 590 cient to assume water cooling in an initial cost
Hydrogen 39 740 effectiveness calculation.
Methane 15 460
Methanol 6 310
Refrigeration Energy. If temperatures be-
low approximately 25 – 30◦ C must be achieved
in a process, energy must be expended on refrig-
Cooling water can be drawn from a body eration. Refrigeration is generally achieved by
of surface water or from the groundwater [72]. compressing, cooling, and adiabatically expand-
Compared with surface water, brackish water or ing coolants in the plant itself; i.e., the refriger-
seawater has the advantage of a more constant ation requirement can be expressed as a require-
temperature and a lower infestation with algae, ment for electrical energy and cooling water. To
but requires special measures to be taken against remove a given quantity of heat, about 20 – 50 %
corrosion. A recirculating procedure (Fig. 20) is of that quantity, depending on the temperature
preferred to a once-through system, with only level required, must additionally be expended in
sufficient cold river water being used for top- the form of electrical energy, thereby increasing
ping up as is required to maintain the speci- the amount of heat which must be removed to
fied temperature (the advantages of this are that about 120 – 150 %.
economies in river water are possible in the cold
season, the minimum temperature can be kept Compressed Air. Small quantities of com-
constant, and high flow rates in the circuit pre- pressed air are drawn from pipelines. An ex-
vent corrosion and fouling). ample is the control air required by closed-loop
control instruments (the rule of thumb is 1 m3 /h
(STP) of control air per instrument).
Larger amounts are produced by an air com-
pressor in the plant and the requirement can then
be expressed in electrical energy [73]. The power
N expended on compressing gases is given by:
n−1
n P2 n
Ntheo =P1 ·V̇1 · · −1 (4.5)
n−1 P1
where
n = cp /cv ,
P1 or P2 = initial or final pressure, respectively,
cp or cv = heat capacity of the gas at constant
Figure 20. Example of a recirculation system for cooling
a chemical plant with river water pressure or constant volume,
V̇ 1 = initial volumetric flow.
For air compression (n = 1.4, overall effi- should have a sufficiently high biological degra-
ciency η ≈ 0.7): dation rate, regardless of its total content in the

stream. This requirement prevents individual un-
N/kW = 0.14·V̇1 / m3 /h · degradable substances being lost in an otherwise
6 7 readily degradable mixture. To assess whether
(P2 /bar)0.286 −1 (4.6) disposal of a stream via a sewage treatment plant
is possible, the following information must be
collected for each substances it contains:
4.1.6.3. Waste-Disposal Costs 1) BOD5 and COD value [79]
2) Zahn – Wellens test [80]
The waste-disposal situation has become much 3) Bacteria and fish toxicity [81–84]
more difficult for chemical plants, a trend which 4) Water hazard class [85]
is continuing. The delivery of effluent and wastes
to central sewage plants, waste incineration Incineration Plants [86, pp. 213 – 217].
plants, or waste-disposal sites is restricted by of- Waste streams which consist only of compounds
ficial regulations, and as a result waste-disposal containing carbon, hydrogen, and oxygen as
costs have risen dramatically in Germany in re- aqueous solutions with a concentration >10 %
cent years (see Fig. 21). are ideally suitable for disposal in an incinera-
tion plant or a power station (if the content is
>10 %, the heat of incineration is roughly equal
to the heat of evaporation of the water).
Disposing of waste by incineration is more
difficult if other elements such as nitrogen, chlo-
rine, sulfur, and metals are present. Such wastes
can only be disposed of economically in a cen-
tral waste incineration plant equipped with suit-
able absorption systems for NOx , HCl, SO2 , etc.
[87], [88].
Waste-Disposal Site. The restrictions im-

posed on wastes which can be dumped are con-
tinuously increasing, and new dumping space is
no longer available. Consequently, this waste-
disposal option is virtually no longer available
Figure 21. Expenditure on environmental protection infor new processes.
vestment in the chemical industry in Germany [74, p. 303]
This poses a challenge to process develop- 4.1.6.4. Staff Costs

ment. The slogan “built-in rather than add-on
environmental protection” expresses the current Operating staff costs in chemical plants can vary
demand for environmental pollution to be re- widely. For large automated plants, they may
duced in the manufacturing process itself and for be less than 3 % but for small batch processes
efforts to be made to put even the byproducts of they may amount to 25 % of the manufacturing
a chemical process to good use if possible [75– costs. Often they are 5 – 10 % of the manufac-
78]. turing costs.
In new plants, whether batch-operated or of
Sewage Treatment Plant. Effluents dis- the single-train type, the trend is towards the
charged into a sewage treatment plant must fullest possible automation. The introduction of
be readily capable of biological degradation and process control engineering has made it possible
must not be toxic to the bacteria in the plant. In to operate and monitor virtually every aspect of a
addition, each substance in an effluent stream plant using pictorial displays [89, pp. 158 –162].
Almost regardless of the size of the plant, a well- 4.1.6.6. Overheads

planned and automated single-train installation
requires the following minimum staff: The overheads of the company consist of the
total costs of the central facilities (research, per-
1) One shift foreman or his deputy sonnel, energy-supply department), works man-
2) Two shift employees for the control room agement, staff facilities, internal plant traffic,
3) One shift employee for outside operations etc. These costs are very dependent on the struc-
4) One shift employee as a reserve ture of the company. As a rule they are ca. 5 –
20 % of the combined energy, staff, and depre-
This minimum staff of five should be multi-
ciation costs.
plied by a factor, specific to the company, which
reflects the type of shift model, the sickness
statistics, and vacations to give the total num-
4.1.6.7. Capital-Dependent Costs
ber of employees required. Special operating re-
(Depreciation)
quirements such as frequent changes in produc-
tion schedule, periodic start-up and shut-down
The plant capital can be depreciated by various
of the plant, loading and unloading of tankers
methods [92]. For a cost efficiency calculation
may make additional staff necessary.
it is generally sufficient to assume linear depre-
ciation over a ten-year utilization period. The
annual depreciation is then 10 % of the plant
4.1.6.5. Maintenance Costs
capital:
Annual repair and maintenance costs generally I
Depreciation = (4.7)
amount to 3 – 6 % of the invested capital [90]. 10·N
About half of this amount is material costs and
where
the rest wages. Their long-term increase can
therefore be assumed to be between that of the I = total investment in currency units
investment costs (see Table 7) and that of the N = nominal capacity in kg/a
wage rates (see Table 10). Experience shows that
high repair costs are incurred shortly after a plant
is put into operation, in eliminating start-up diffi-
4.1.7. Technology Evaluation
culties, and after a prolonged operation because
of the need to carry out major repairs. Depending Technology evaluation should provide informa-
on how new a process is, annual costs of 5 – 10 % tion on the technical risk associated with a pro-
of the estimated total investment should be al- cess. This risk is equivalent to the economic
lowed for in an initial estimate. damage which would occur in the extreme case
if the process did not work at all or could only be
rendered operational by carrying out subsequent
Table 10. Gross hourly earnings of an average worker in the chem- improvements.
ical industry in Germany , p. 286[91] Technology evaluation should also reveal
Year Earnings, ¤/h
whether the individual unit operations or the
equipment and machines used are of techni-
1980 7.22
1981 7.68
cally established types and whether particular
1982 8.10 risks are incurred by breaking new ground (size,
1983 8.47 construction, material, scale-up factor, etc.). It
1984 8.72 is also necessary to include a statement as to
1985 8.99
1986 9.30
whether the process is based on a technol-
1987 9.69 ogy with which the company is familiar (e.g.,
1988 10.06 high pressure, gas-phase oxidation, phosgena-
1989 10.42
tion technology, etc.) or whether fundamental
1990 11.11
innovations are involved. If limits are exceeded
(e.g., if the dimensions of the largest extraction
column previously operated by the company are train plant increases as the number of process
considerably exceeded in the new project), the steps and the probability of failure of individ-
limits which have been tested should be speci- ual steps increase: a single-train plant can only
fied. function if each step is operational.
This information should be elaborated in de- If partial streams are fed back to earlier
tail as early as possible in order to recognize, stages, the coupling between them is particu-
consider, and evaluate potential risks and causes larly strong. This is also true of the energy cross-
of failure. During operation of the miniplant, links within a process (see Section 4.1.6.2). The
close attention should be paid to deposits, fre- increase in risk as the number of process steps
quently occurring malfunctions, etc., since such increases is independent of whether the process
problems often subsequently lead to insupera- is continuous or batch.
ble difficulties in the industrial-scale plant (e.g., In practice, various options are now adopted
foaming, emulsion formation, aerosol forma- in resolving this dilemma (see Figs. 22 and 23):
tion, etc.).
The technology evaluation gives a list of 1) Decoupling by inserting tanks for intermedi-
weak points arranged in order of technical risk ates (the greater the buffer tank, the greater
(e.g., catalyst service life, corrosion, etc.). This the independence). For larger quantities of
list can then be used to take steps which reduce product or gaseous intermediates, this ap-
such risks. In principle, two steps are possible: proach is virtually impracticable.
2) Decoupling by installing parallel arrange-
1) Expenditure on R & D can be increased at the ments of equipment which is particularly
weak point (e.g., the unit concerned may be susceptible. For example, filters and fittings
checked on a pilot scale or a well-established that are susceptible to failure should be pro-
solution may be sought). This option should vided with a by-pass if safety considerations
always be chosen if, in an extreme case, fail- permit (e.g., heat exchangers in the main flow
ure of the unit concerned would be accom- in which severe fouling is to be expected).
panied by a total investment loss.
2) Failure scenarios can be developed, i.e., what
can be done later if problems occur or if a unit
fails completely?
Normally, these two options have to be
weighed against each other, i.e., it is necessary to
clarify whether it is more economic to minimize
the risk by increasing R & D expenditure (e.g.,
by building a pilot plant), or to reduce or elimi-
nate it at a later date by technical measures (e.g.,
additional instrumentation or backup units).
Some general aspects, which may be useful
in assessing the technical reliability, are summa-
rized below.
From the estimate of the risk and the mea-
sures it suggests, the economic effect can be
quantified very exactly (surcharges on the de-
velopment costs or on the investment and repair
costs). This transforms technical reliability into
cost effectiveness considerations and results in
the possibility of expressing the risk of a devel-
opment project in monetary units.
Improving Technical Reliability Figure 22. Example of decoupling a single-train plant:

Decoupling Process Steps. The susceptibil- a) Intermediate tank to smooth out variations in feed flow;
ity to failure of a process carried out in a single- b) Recycling to smooth out variations in feed flow
If solids are processed, the process must be

assessed with particular care. The scaling-up of
equipment for separating solids should be sub-
jected to particularly careful scrutiny. Even the
bunkering and transportation of solids present
difficulties which are often specific to the mate-
rials.
If new technology is employed, the opera-
tional safety can be expected to be lower than
that of well-established processes. It can be in-
creased if similar types of equipment are used in
the experimental plant as in the industrial-scale
plant. This allows scaling-up to be possible but
in the case of reaction equipment, it is not always
the case.
Materials to be Processed. If toxic, inflam-
mable, caustic, or otherwise hazardous sub-
stances are to be handled, a higher degree of op-
erational safety is required from the outset than
in the case of harmless substances.
Corrosion is an ever-present risk and neces-
sitates the use of special materials. In making an
initial selection, use may be made of published
tables (see → Corrosion), but in most cases it
Figure 23. Decoupling of a single-train plant by including is necessary to carry out corrosion tests. Trace
redundant equipment impurities can lead to considerable difficulties if
A) Filter station with single by-pass; B) Pumping station they accumulate at particular points in the equip-
with A and B pump; C) Preheater with flushing facilitya)
Auxiliary preheater; b) Double block and bleed; c) Preheater ment. The most reliable information in this con-
nection is provided by operating an integrated
Each measure which is aimed at increasing miniplant.
the uptime of a single-train plant results in an If the flow rate of mixed phases is high, ero-
increase in investment costs. In practice it is of- sion of the wall material can be expected. The
ten the case that such steps are only taken after extent of erosion can often be lowered by the
the plant is put into operation for the first time. choice of material and by effective design. In-
Choice of Process Steps which can be Safely creases in wall thickness are generally of no help
Scaled-Up. An example of the dependence of because the erosion usually takes the form of
technical reliability on the operational method pits. Miniplant experiments are of no assistance
employed is mass transfer. While simple stan- in this connection since they are usually not re-
dard equipment can be used for rectification, a presentative in hydrodynamic terms.
wide variety of equipment in which phases are In the case of moving solids, not only the
mixed in several stages and then separated has walls of the equipment but also the solids them-
been developed for extractions. Such equipment selves are subject to abrasion. If a process is in-
generally requires more expenditure for safe op- tended to give a particular size, the abrasion loss
eration than distillation columns. may have a considerable effect and, moreover,
The complexity of an operation increases as an increase in this abrasion is always expected
the number of substances and phases it involves on scaling up a process.
increases and as the operating conditions be- Solids often deposit inside equipment and re-
come more extreme. Thus, the presence of two sult in fouling. Valuable information about this is
liquid phases requires special precautions to be provided by miniplant results. In heat exchang-
taken. The same applies if particularly high or ers, allowance is made for fouling by increasing
low temperatures or pressures are involved. the heat transfer resistance by empirically deter-
mined amounts (fouling factors) (see Fig. 24).
der to regenerate the contaminated catalyst, but

fluidized-bed catalysts can usually be regener-
ated in the reactor. Often it is also possible to
remove, regenerate, and replace the catalyst in
a sidestream while the plant is operating. Foul-
ing that arises both from the material being pro-
cessed and from the material of which the equip-
ment is made is more troublesome. For example,
in many polymerization reactors, wall deposits
can be suppressed by suitable choice of the wall
material and processing method. In such cases,
steps should be taken to ensure that the same
wall material is used in the trial plant and in the
industrial-scale plant.
Figure 24. Effect of the fouling factor Fi on the heat trans-
fer coefficient k If wall erosion or deposit growth occurs
F 1 = 7×10−4 m2 K W−1 (typical value for river water); at a constant rate, the difficulties can be ex-
k 0 = 1000 W m−2 K; pected to decrease in bulk-storage equipment
Q̇ = k A ∆T ; and pipelines with increasing scale-up but to re-
1/k = 1/k 0 + Fi ;
Fi = Si /λs main unchanged in columns and heat exchangers
where Si = thickness of fouling layer; λs = thermal conduc- (equipment with large surface areas).
tivity of fouling layer; Q̇ = heat flux; A = surface area of heat Machines. Since machines have moving
exchanger parts, they are always a potential source of mal-
If the expected operating time is inadequate, function and the reliability of a process de-
a back-up heat exchanger must be installed in creases as the proportion of machines it em-
parallel. In larger plants, heat exchangers are ploys increases. In general, machines having re-
usually subdivided into several units for design ciprocating parts are regarded as less reliable
reasons. Thus, if suitable fittings (double block than those employing only rotating parts. For
and bleed) are provided to ensure that each heat this reason it is particularly important to pro-
exchanger can be cleaned while the plant is op- vide a reasonable level of back-up. Because of
erating, the effect on the availability of the en- their relatively low cost, duplicate full-capacity
tire installation is small (see Fig. 23). However, pumps are usually installed, but occasionally
this is only true provided the cleaning frequency two pumps having different functions can be
is technically feasible. The design of heat ex- provided with a common backup. In the case
changers and the cleaning operations should be of reciprocating machines, in addition to a com-
carefully matched to the type of fouling, and ex- plete backup (2×100 % capacity), 2×66 % ca-
tensive automation is always worthwhile in the pacity, or in exceptional cases 3×50 % capacity,
case of large pieces of equipment. may also be considered.
If fouling is expected in columns, larger Turbo machines are usually installed at
columns should be designed for whole-body ac- 1×100 % capacity, but provision is made for
cess to each plate, while in small columns a rapid replaceability of parts which are subject
manual-access hole should be provided for each to wear. Alternatively, two machines with 50 %
plate to allow cleaning. Furthermore, designs capacity are often installed.
should be used whose operation is relatively in- Instrumentation. The narrower the limits in
sensitive to fouling and which can readily be which quantity flows and operating conditions
cleaned. have to be kept for reliable operation, the higher
The choice of reaction equipment can be will be the requirements imposed on the instru-
considerably influenced by fouling. As foul- mentation.
ing increases, the pressure drop in fixed-bed To increase plant availability, provision is
reactors increases, whereas fluidized-bed reac- made for n measurements instead of one mea-
tors are virtually unaffected. Moreover, fixed- surement in the case of critical circuits and con-
bed reactors must be opened and emptied in or- trol loops. The complete unit will operate as
specified provided m of the n measurements
(m<n) are in the “good” range (m of n circuits). grated miniplant) should be specified and the du-
The greater m is, the higher will be the safety ration and conditions of the experiments given.
margin and the lower the plant availability. In The aim is to arrive at an as objective assess-
the case of chemical plants, “two out of three” ment as possible of the quality of the data ob-
circuits have been found to be satisfactory, thus tained since this is of major importance for the
providing a compromise between safety margin accuracy of the project cost estimate.
and availability.
Multiple-Train Design. According to Equa-
tion (2.17), the increase in investment costs 4.2. Return on Investment
on scaling up the plant is approximately
proportional to the capacity to the power After the individual cost factors have been esti-
2/3. Consequently, the specific investment costs mated, a rough cost effectiveness calculation is
for a single-train plant are approximately 20 % possible. This should provide information on the
lower than for a twin-train plant of the same to- return on investment (= ratio of profit to capital
tal capacity. In addition, the personnel costs are employed) for the planned project. Investment
lower for a single-train plant than for several in- in the process under consideration will be prof-
dividual plants of the same total capacity. How- itable if the sum of the revenues exceeds the total
ever, certain plant components can often not be outlay and the profit (revenue – outlay) makes it
scaled up to the required total capacity with an possible to amortize and pay reasonable interest
adequate safety margin. Thus, the maximum ca- on the capital invested.
pacity of polymerization vessels may be limited The return on investment provided by a pro-
because a breakdown of the cooling system must cess can be increased by minimizing the pro-
be insufficient to bring about dangerous operat- duction costs. Exposing the main cost factors
ing conditions, or it may be impossible to in- (raw material, energy, waste disposal, personnel
crease the size of an oxidation reactor for cost costs, depreciation) will therefore indicate the
reasons. In such cases, the total capacity is pro- direction the development should take in order
vided by using the requisite number of individual to improve the process (see Table 11).
pieces of equipment.
A significant advantage of multiple-train de- Table 11. Examples of measures which may result in the reduction
of the main cost factors
sign is that it is easier to cope with a temporary
reduction in load, which would normally mean Main cost factor Measures
shutting down and then starting up again. If the Raw materials a) Increase selectivity of catalyst
plant is underloaded, the specific consumption b) Minimize processing losses
c) Use raw materials of lower quality
figures of multiple-train plants are lower. Fur- Energy a) Optimize the thermal integration
thermore, the capacity of such plants can more b) Use multistage evaporation
easily be increased at a later date, particularly if c) Extraction instead of distillation
this has been planned from the outset. The ad- d) Air condenser instead of water
condenser
vantages of multiple-train design can, of course, Waste disposal a) Integrated waste utilization
only be exploited if it is possible to link any line b) Choice of location
in a process stage with any of the lines of the sub- Depreciation a) Simplify the reaction control and
work-up
sequent stage. For this purpose manifolds will be b) Reexamine choice of materials
needed. c) Reexamine dimensioning of pipeline
system
d) Exploit synergies of the location
4.1.8. Assessment of the Experimental Work

Minimizing the production costs does not,
This part of the project study should contain in- however, maximize the return on investment if
formation on whether the existing experimental the full capacity of the plant is not reached.
results have been obtained in-house or are de- In such cases, a plant with lower capacity and
rived from third parties. If in-house knowledge higher production costs might provide a larger
is available, the test units in which the exper- return on investment despite being less econom-
iments were carried out (e.g., laboratory, inte- ical.
Some of the indicators frequently used in case, the sales are, of course, unchanged but the
practice to assess return on investment are de- production and investment costs are:
scribed below.
P C2 =P C1 −∆P C
I2 =I1 −∆I (4.10)
4.2.1. Static Return on Investment
In its simplest form, the return on investment cal- where

culation widely adopted in practice relates the PC 1 , I 1 are the production and investment costs before the
change,
expected annual profit to the capital invested: PC2 , I 2 are the production and investment costs after the
change.
(E −P C)
R= ·100 (4.8)
I
The return offered by a particular approach is
then given by the ratio of the changes:
where
∆P C
R is the percentage return in %/a R12 = (4.11)
E is the annual sales proceeds (= amount sold ∆I
multiplied by production or transfer price) in
monetary units per year
The change in the overall return resulting from
PC is the annual production costs in monetary units per adopting this particular approach is then:
year
I is the capital expenditure in monetary units R1 ·I1 +∆P C
R2 = (4.12)
E − PC is the annual profit in monetary units per year I1 +∆I
The weakness of static return-on-investment in-
The method can be made more informative by dicators is that they take a short-term view and,
taking the sales into consideration separately: since they do not allow for future changes, they
favor short-lived investments. Their advantage
(E −P C) E
R= · ·100 (4.9) is that they can easily be determined.
E I
The first factor indicates the sales success and
the second the capital turnover. 4.2.2. Dynamic Return on Investment
Instead of R, use may also be made of the
reciprocal value, i.e., the payback time 100/R. The dynamic return on investment method is su-
This indicates the time required to recover the perior to the static method because allowance
invested capital so that the plant begins to make is made for the timing of the cash movements.
a profit. Since only contemporaneous monies are com-
The return on capital from the process being parable, the investment outlay and the earnings
studied should be compared with that of known from the profit must be discounted to a fixed
processes. Above a threshold value, which varies point in time, usually the start of production. If
from case to case, the process will provide a re- a certain rate of interest p is assumed, all the cap-
turn on investment. A minimum return R of 20 % ital movements can be referred to that point to
is often employed, but because of the consider- obtain the so-called net value of a capital move-
able vulnerability to technical risk and market ment:
certainty, this is only a guideline. While the value
(E −A)t=0 = (E −A)t · (1+p)−t (4.13)
may be lower if the risk is low, it is prudent to
impose a minimum value up to a factor of two where
higher in the case of new high-risk products.
Generally the process development engineer E = expected earnings, e.g., from product
is not faced with the question of how profitable sales in monetary units per year
a project is but of whether a particular process A = expected outlay, e.g., investment costs,
engineering approach is more profitable than an production costs, in monetary units per
other, alternative solution within the framework year
of the process being studied or not [61]. In this p = interest rate
t = number of years (negative before start- 4.3.1. Sensitivity Analysis

up and positive after start-up)
For example, when started up, a plant has Sensitivity analysis yields information about the
to bear double the cost of an outlay incurred sensitivity of the process to variations in individ-
five years before start-up if the rate of interest ual influencing variables and therefore about the
is 15 %. Conversely, a revenue five years after reliability of the result of the return on capital
start-up will only carry half the weight and one analysis. It also provides pointers to the direc-
ten years after start-up will be virtually insignifi- tion in which the process should be developed
cant. The capital value K of a project is therefore further. The development is particularly worth-
the sum of the net values: while if it alters influencing variables to which
the return on capital is highly sensitive. The pro-

t=+n
cedure is to vary the different influencing vari-
K= (E − A)t · (+1p)−t (4.14)
t=−m
ables in Equation (4.15) one after the other in the
where unfavorable direction (while keeping all the oth-
ers constant) by a certain fraction (for example,
m = duration of process development in 10 %) and then determine how much the internal
years rate of return p0 differs from the original value
n = useful life of project in years (usually (see Table 12).
10 years)
Table 12. Relative change in the internal rate of return on varying
To compare different projects, a useful life of the influencing variable x ∗
ten years is usually assumed for chemical plants. Parameter x ∆x/x
An investment is only beneficial if its capital
value is equal to zero or is positive. Development costs +10 %
Investment costs +10 %
The internal rate of return method ( dis- Product price −10 %
counted cash flow, DCF) tries to find the rate Capacity utilization −10 %
of interest which will result in a capital value Net raw material costs +10 %
Operating resources costs +10 %
of zero, i.e., the rate at which the net values of
Staffing costs +10 %
the incoming and outgoing payments are equally
large (the internal rate of return). The internal ∗ By successively changing the parameters x in the unfavorable
direction, the change in the internal rate of return can be
rate of return p0 is determined by setting the calculated from Equation (4.15).
above capital value function equal to zero:

t=+n
(E − A)t · (1+p0 )−t = 0 (4.15) 4.3.2. Amortization Time
t=−m
Projects are compared by comparing their cal- The risk as a function of time can be quantified
culated internal rates of return, the project with by means of the payback time t w . This indicates
the highest internal rate of return being the most the time which will be necessary for the cost
profitable. of the capital employed to be recovered. As an
initial estimate, t w is the ratio of the investment
costs I to the annual surplus income (E − A):
4.3. Economic Risk
I
The return on capital calculation indicates tw ≈ (4.16)
(E −A)
whether or not a project is economically worth-
while. To calculate the return, assumptions must
be made about the most probable product prices, 5. Trends in Process Development
the production outlay, the plant loading (actual
production/nominal capacity), investment costs, The pattern of process development should be
etc. Time will see whether these assumptions are such that it produces competitive advantages,
correct. The impact of these uncertainties on the i.e., a process should be developed rapidly and
cost effectiveness of the project can be quanti- cheaply. Some trends which promote this objec-
fied by using the following variables. tive are highlighted below [93]:
1) Nowadays only a team made up of members have a noticeable effect on the cost effective-
from all the scientific disciplines is capable ness of a new process.
of coping with the complex task of develop- 4) Another trend is the development and use of
ing a process. For this reason, a project team, expert systems. These are already available
usually consisting of a chemical process en- for simple, limited systems such as the op-
gineer, a chemist specializing in preparation, timization of individual unit operations. For
an engineer, and possibly the future works much more complex systems such as cata-
manager should be brought together at the lyst development or the optimization of en-
beginning [94]. tire plants, expert systems are at present still
If necessary, this group may recruit or con- a long way from general practical applica-
sult other specialists. Team work and team tion.
spirit are essential to the success of the ac-
Future tasks in process development will be
tivity, the synergies resulting from this type
in the following fields [95]:
of activity being exploited to the full.
When process development is complete, it 1) Improvement of plants and processes with a
is advantageous for at least one member of view to an integrated environmental protec-
the project team to continue working on the tion [96–98]
project during planning, construction, com- a)
missioning, and start-up, since otherwise a Residue reduction: Reduction in the
great deal of detailed knowledge would be amounts of byproducts by improving the
lost. catalysts and the reaction control
2) In the case of short-lived consumer-related b)
products (dyes, active substances, disper- Integrated residue utilization: Integrated
sions, etc.), which are preferably produced work-up of unavoidable waste streams
in batch processes, the trend is towards within the main plant, i.e., exploitation
equipment which is as flexible as possible of on-site synergies (thermal and material
(multipurpose production plants, multipur- coupling) and effective reuse of worked-
pose small-scale plants). Innovations in such up wastes
products are usually due to changes in for- 2) Development of new processes for the basic
mulation, and much less a result of modifi- products and intermediates on the basis of:
cations to the equipment. The ideal is to pro-
a) natural gas (C1 chemistry)
duce a wide variety of products in a batch
b) renewable raw materials
plant over a long period of time.
c) waste streams as raw material
3) In the case of basic products and interme-
diates produced in continuous plants, pro- 3) Development of processes that result in
cess development can make a contribution smaller, more economical, and cheaper
to competitiveness by reducing the time and plants.
the cost required to develop improved man-
ufacturing processes. This objective can be
achieved by increasing the scale-up factors 6. References
(see Section 3.1). In order to limit the re-
1. Jahrbuch der Chemiewirtschaft, VCH
sulting increase in technical risk, use is now
Verlagsgesellschaft, Weinheim 1991.
made of the synergy between an integrated 2. H.-B. Amecke: Chemiewirtschaft im
miniplant and a mathematical simulation. Überblick, VCH Verlagsgesellschaft,
This makes it possible to dispense with the Weinheim 1987.
pilot plant stage, i.e., the synergism bet- 3. H.-J. Quadbeck-Seeger: “Chemie für die
ween an integrated miniplant technique and Zukunft,” Angew. Chem. 102 (1990)
a mathematical simulation results in scale- 1213 – 1224.
up safety margins of similar quality to those 4. W. Jentzsch: “Was erwartet die Chemische
obtained by using a pilot plant. As a result Industrie von der Physikalischen und
it is possible to shorten the time required for Technischen Chemie?” Angew. Chem. 102
process development by ca. 30 %, which can (1990) 1267 – 1273.
5. C. Marchetti: “Die magische 26. J. M. Praussnitz: Molecular Thermodynamic of

Entwicklungskurve,” Bild Wiss. 10 (1982) Fluid-Phase-Equilibria, Prentice Hall,
115 – 128. Englewood Cliffs, N.Y. 1969.
6. E. G. Krubasik: “Angreifer im Vorteil,” 27. I. Hacker, K. Hartmann: “Heuristische Regeln
Wirtschaftswoche (1984) no. 23, 48 – 56. zum Entwurf verfahrenstechnischer Systeme,”
7. M. Perlitz, H. Löbler: “Brauchen Unternehmen in Probleme der modernen chemischen
zum Innovieren Krisen? ”, Zeitschrift für Technologie, Akademie-Verlag, Berlin 1980,
Betriebswirtschaft 55 (1985) 424 – 450. pp. 194 – 244.
8. G. Specht, K. Michel: “Integrierte 28. E. Blaß: “Methodische Entwicklung
Technologie- und Marktplanung im verfahrenstechnischer Prozesse,”
Innovationsportfolio,” ZfB 58 (1988) Chem.-Ing.-Tech. 57 (1985) 201 –210.
502 – 520. 29. G. Kaibel, E. Blaß, J. Köhler: “Gestaltung
9. M. E. Porter: “Technology and Competitive destillativer Trennungen unter Einbeziehung
Advantage,” Journal of Business Strategy thermodynamischer Gesichtspunkte,”
(1985) 60 – 78. Chem.-Ing.-Tech. 61 (1987) 16 – 25.
10. W. Busfield, D. Merigold, J. Chem. Soc. (A) 30. H. H. Erdmann, J. Kussi, K. H. Simmrock:
1969 2975 – 2977. “Möglichkeiten und Probleme der
11. H. Knapp: “Methoden zur Beschaffung von Prozeß-Synthese,” Chem.-Ing.-Tech. 56
Information über Stoffeigenschaften,” (1984) 32 – 41.
Chem.-Ing.-Tech. 59 (1987) 367 – 376. 31. G. Stephanopoulos, A. W. Westerberg:
12. E. Fitzer, W. Fritz: “Technische Chemie,” “Studies in Process Synthesis-II,” Chem. Eng.
Springer-Verlag, Berlin 1975. Sci. 31 (1976) 195 –204.
13. B. Streit: Lexikon Ökotoxikologie, VCH, 32. E. Blaß: Entwicklung verfahrenstechnischer
Weinheim 1991. Prozesse – Methode, Zielsuche, Lösungssuche,
14. L. Roth, G. Rupp: Sicherheitsdatenblätter, Lösungsauswahl, 1st ed., Verlag Salle und
VCH, Weinheim 1991. Sauerländer, Frankfurt 1989.
15. BASF, Acrylsäure rein, technical information, 33. K. Hartmann, L. Dietzsch: “Modellierung und
TI/ED 1330 d, Ludwigshafen 1987. Simulation verfahrenstechnischer Systeme,” in
16. F. Dolder: “Geheimhalten oder patentieren?” Probleme der modernen Technologie,
Management Zeitschrift 60 (1991) 64 – 68. Akademie-Verlag, Berlin 1980, pp. 43 – 77.
17. E. D. Dichtl, O. Issing: Vahlens Großes 34. E. Blaß: “Aufgabengerechte
Wirtschaftslexikon, Verlag C. H. Beck, Verlag Informationssammlung für die
Franz Vahlen, München 1987. Verfahrensentwicklung,” Chem.-Ing.-Tech. 56
18. Chemical Week, International ICIS/Chemical (1984) 272 – 278.
Week Price Report, Europe spot prices, $/m.t. 35. M. Buder, W. Rehfeld, T. Seeger: Grundlagen
19. Ullmann, 4th ed., 4, 24. der praktischen Information und
20. K. W. Schneider: “Großanlagen in der Dokumentation, vol. 1, K. G. Saur, München
Mineralölindustrie und Petrochemie,” 1990, pp. 366 ff.
36. “Dechema-Informationssysteme für die
Chem.-Ing.-Tech. 37 (1965) 875 – 877.
Chemische Technik und Biotechnologie,”
21. G. Lück: “Verfahrensentwicklung,” Fortschr.
Achema-Jahrbuch 1991, vol. 1, Frankfurt
Verfahrenstech. 21 (1983) 473 – 486.
1990, p. A60.
22. H. Harnich, R. Steiner, K. Winnacker:
37. R. Berenz: “Das Rad nicht zweimal erfinden,”
Chemische Technologie, Carl Hauser Verlag,
Jahrbuch der Chemiewirtschaft, VCH
München 1984.
Verlagsgesellschaft, Weinheim 1991,
23. W. Hofen, M. Körfer, K. Zetzmann:
pp. 172 – 174.
“Scale-up-Probleme bei der experimentellen
38. M. Zeitz: “Simulationstechnik,”
Verfahrensentwicklung,” Chem.-Ing.-Tech. 62
Chem.-Ing.-Tech. 59 (1987) 464 – 469.
(1990) 805 – 812.
39. G. Wozny: “Software macht den Fortschritt,”
24. J. Krekel, G. Siekmann: “Die Rolle des
Jahrbuch der Chemiewirtschaft, VCH
Experiments in der Verfahrensentwicklung,”
Verlagsgesellschaft, Weinheim 1991,
Chem.-Ing.-Tech. 57 (1985) 511 – 519.
pp. 153 – 158.
25. J. Gmehling, U. Onken, W. Aret: 40. D. Gilles, P. Holl, W. Marquardt: “Dynamische
Vapor – Liquid Equilibrium Data Collection, Simulation komplexer chemischer Prozesse,”
DECHEMA, Frankfurt 1977. Chem.-Ing.-Tech. 58 (1986) 268 – 278.
41. W. Scheiding, H. Hartmann, P. Tönnishoff: 58. R. P. Palluzi: “Understand Your Pilot-Plant

“SATU 86 – Simulationsrahmen zur Options,” Chem. Eng. Prog. 87 (1991) no. 1,
dynamischen Prozeßsimulation für den 21 – 26.
industriellen Einsatz,” Chem.-Ing.-Tech. 61 59. P. Prinzing, R. Rödl, D. Aichert:
(1989) 292 – 299. “Investitionskosten-Schätzung für
42. W. Marquardt: “Rechnergestützte Erstellung Chemieanlagen,” Chem.-Ing.-Tech. 57 (1985)
verfahrenstechnischer Prozeßmodelle,” 8 – 14.
Chem.-Ing.-Tech. 64 (1992) 25 – 40. 60. E. Muthmann: “Ermittlung der
43. W. Klar: “Expertensysteme,” Elektronik 8 Investitionskosten von Chemieanlagen in
(1991) 108 – 123. verschiedenen Projektphasen,”
44. J. J. Ferrada, J. M. Holmes: “Developing Chem.-Ing.-Tech. 56 (1984) 940 – 941.
Expert Systems,” Chem. Eng. Prog. 86 (1990) 61. W. Frey, F. Heimann, S. Maier:
34 – 41. “Wirtschaftliche und technologische
45. A. Lieberam: “Expertensysteme für die Bewertung von Verfahren,” Chem.-Ing.-Tech.
Verfahrenstechnik,” Chem.-Ing.-Tech. 58 62 (1990) 1 – 8.
(1986) 9 – 14. 62. J. Jung: “Aspekte der Vorausberechnung von
46. P. Trum, N. R. Judica: Anlagenkosten bei der Projektierung
“Expertensysteme – Aufbau und verfahrenstechnischer Anlagen,” Chem. Tech.
Anwendungsgebiete,” Chem.-Ing.-Tech. 58 (Heidelberg) 12 (1983) 9 – 18.
(1986) 6 – 9. 63. C. A. Miller: “New Cost Factors Give Quick,
47. A. H. Masso, D. F. Rudd: “The Synthesis of Accurate Estimates,” Chem. Eng. 13 (1965)
System Designs,” AICHE 15 (1969) no. 1, 226.
10 – 17. 64. Jahrbuch der Chemiewirtschaft, VCH
48. G. L. Steele: Common LISP, Digital Press, Verlagsgesellschaft, Weinheim 1991, p. 64.
1984. 65. K. E. Lunde: “Transfer Pricing,” Chem. Eng. 4
49. L. Puigjaner, A. Espuña: Computer-Oriented (1985) 85 – 87.
Process Engineering, Elsevier Science 66. H. Körner: “Optimaler Energieeinsatz in der
Publishers, Amsterdam 1991. Chemischen Industrie,” Chem.-Ing.-Tech. 60
50. D. Greß, H. Hartmann, G. Kaibel, B. Seid: (1988) 511 –518.
“Einsatz von mathematischer Simulation und 67. B. Linnhoff, J. A. Turner: “Heat Recovery
Miniplant-Technik in der Networks: New Insights Yield Big Savings,”
Verfahrensentwicklung,” Chem.-Ing.-Tech. 51 Chem. Eng. 88 (1981) no. 22, 56 – 70.
(1979) 601 – 611. 68. B. Linnhoff: “New Concepts in
51. S. Maier, G. Kaibel: “Verkleinerung Thermodynamics for Better Chemical Process
verfahrenstechnischer Versuchsanlagen – was Design,” Chem. Eng. Res. Des. 61 (1983)
ist erreichbar?” Chem.-Ing.-Tech. 62 (1990) 207 – 223.
169 – 174. 69. D’Ans Lax: “Taschenbuch für Chemiker und
52. L. A. Robbins: “The Miniplant Concept,” Physiker,” 3rd ed., vol. 1, Springer Verlag,
Chem. Eng. Prog. 75 (1979) no. 9, 45 – 48. Berlin 1967.
53. W. Brust, F. Heimann, G. Kaibel, S. Maier:
70. F. A. Henglein: Grundriss der chemischen
“Klein, aber fein,” Jahrbuch der
Technik, Verlag Chemie GmbH, Weinheim
Chemiewirtschaft 1991, VCH, Weinheim
1963.
1991, pp. 179 – 182.
71. Chemiker Kalender, 3rd ed., Springer Verlag,
54. U. Wörsdörfer, U. Müller-Nehler: “Ein
Berlin 1984.
Gewinn für die Forschung,” Jahrbuch der
72. W. Hellmund, R. Auelmann, J. Wasel-Nielen,
Chemiewirtschaft 91, VCH, Weinheim 1991,
A. Rothert: Chem. Ind. (Düsseldorf) 114
pp. 182 – 186.
(1991) no. 9, 12 – 13; 114 (1991)
55. A. Schulz-Walz: “Meß- und Dosiertechnik
no. 10,10 – 12; 114 (1991) no. 11, 10 – 12.
beim Betrieb von Miniplants,”
73. J. M. Coulson, J. F. Richardson: Chemical
Chem.-Ing.-Tech. 62 (1990) 453 – 457.
Engineering, 4th ed., Pergamon Press, Oxford
56. J. M. Berty: “The Changing Role of the Pilot
1990.
Plant,” Chem. Eng. Prog. 75 (1979) no. 9,
74. Jahrbuch der Chemiewirtschaft 1991, VCH
48 – 51.
57. J. G. Lowenstein: “The pilot plant,” Chem. Verlagsgesellschaft, Weinheim 1991, p. 303.
Eng. 9 (1985) no. 23, 69 – 76.
75. W. Swodenk: “Umweltfreundlichere 86. P. Reher: “Produktion mit umweltgerechter

Produktionsverfahren in der chemischen Entsorgung,” Jahrbuch der Chemiewirtschaft,
Industrie,” Chem.-Ing.-Tech. 56 (1984) 1 – 8. VCH Verlagsgesellschaft, Weinheim 1991,
76. G. Lipphardt: “Produktionsintegrierter pp. 213 – 217.
Umweltschutz, Verpflichtung der Chemischen 87. W. Hüning, H. Nentwig, C. Gockel: “Die
Industrie,” Chem.-Ing.-Tech. 61 (1989) verbrennungstechnische Entsorgung eines
855 – 860. Chemiebetriebes,” Chem.-Ing.-Tech. 56
77. T. Bakay, K. Domnick: (1984) 521 – 526.
“Produktionsintegrierter 88. W. Hüning, P. Reher: “Verbrennungstechnik
Umweltschutz – Verminderung von für den Umweltschutz,” Chem.-Ing.-Tech. 61
Reststoffen, gezeigt anhand ausgeführter (1989) 26 –36.
Beispiele,” Chem.-Ing.-Tech. 61 (1989) 89. G. Färber: “Standardtechnik löst Probleme,”
867 – 870. Jahrbuch der Chemiewirtschaft 1991, VCH
78. H. Lenz, M. Molzahn, D. W. Schmitt: Verlagsgesellschaft, Weinheim 1991,
“Produktionsintegrierter pp. 158 – 162.
Umweltschutz – Verwertung von Reststoffen,” 90. D. Wagener: “Kostenermittlung am
Chem.-Ing.-Tech. 61 (1989) 860 – 866. Anlagenbau für die chemische Industrie,”
79. DIN 38 409,Bestimmung des Biochemischen Tech. Mitt. 65 (1972) 542 –547.
Sauerstoffbedarfs (BSB), DIN 38 409 part 51; 91. “Bruttostundenverdienst,” Jahrbuch der
DIN 38 409, Bestimmung des Chemischen Chemiewirtschaft 1991, VCH
Sauerstoffbedarfs (CSB); DIN 38 409 part 41. Verlagsgesellschaft, Weinheim 1991, p. 286.
80. “Modifizierter Zahn-Wellens-Test,” OECD
92. H. Kölbel, J. Schulze: “Neuentwicklungen zur
Guidelines for Testing of Chemicals, Paris
Berechnung von Preisindices für chem.
1981, p. 302 B.
Anlagen,” Chem. Ind. (Düsseldorf) 19 (1967)
81. I. Juhnke, D. Lüdemann: “Ergebnisse der
340 – 343, 701 – 706.
Untersuchung von 200 chemischen
93. G. Bogenstätter, H. Gerrens: “Die chemische
Verbindungen auf akute Fischtoxizität mit dem
Fabrik der Zukunft,” Chem. Ind. 37 (1985)
Goldorfentest,” Z. Wasser Abwasser Forsch.
275 – 277.
11 (1978) 161 – 164.
82. G. Bringmann, R. Kühn: “Grenzwerte der 94. J. Platz, H. J. Schmelzer: Projektmanagement
Schadwirkung wassergefährdender Stoffe in der industriellen Forschung und
gegen Bakterien (Pseudomonas putida) und Entwicklung, Springer, Berlin 1986.
Grünalgen (Scenedesmus quadricauda) im 95. R. Shinnar: “The Future of the Chemical
Zellvermehrungshemmtest,” Z. Wasser Industries,” CHEMTECH 1991, 58 – 64.
Abwasser Forsch. 10 (1977) 87 – 98. 96. M. Zlokarnik: “Umweltschutz – eine ständige
83. DIN 38 412,Testverfahren mit Herausforderung,” Chem. Ing. Tech. 61 (1989)
Wasserorganismen, 1991, part 8. 378 –385.
84. DFG Deutsche Forschungsgemeinschaft: 97. G. Scharfe, B. Sevekow: “Das Beispiel Bayer,”
Toxikologische Untersuchungen an Fischen, Chem. Ind. (1991) 17 – 20.
Verlag Chemie, Weinheim 1983. 98. J. Wiesner: Produktionsintegrierter
85. Kühn Birett Merkblätter Gefährliche Umweltschutz in der chemischen Industrie,
Arbeitsstoffe, 25th suppl., Nov. 1984, “VI-4 DECHEMA, Frankfurt, 1990.
Wassergefährdende Stoffe.”
Separation Processes, Introduction 915
Separation Processes, Introduction

C. Judson King, University of California, Berkeley CA 94 720, United States
1. Introduction . . . . . . . . . . . . . . . . . . 915 6. Selection of a Separation Process . . . . 919

2. Definitions . . . . . . . . . . . . . . . . . . . 915 7. Factors Influencing Phase Equilibria . . 920
3. Process Configurations . . . . . . . . . . . 916 8. Sources of Equilibrium Data . . . . . . . 920
4. Separation Principles . . . . . . . . . . . . 918 9. References . . . . . . . . . . . . . . . . . . . 921
5. Advantages and Disadvantages
of Different Separation Methods . . . . . 918
1. Introduction Separation processes constitute more than

half of the total equipment investment for the
Separation processes are used to convert feed chemical and fuel industries. They are also
mixtures into two or more products differing widely used in pharmaceutical and food indus-
in composition. Unit operations with diffusional tries, in beneficiation of mineral ores and recov-
separation processes suitable for feeds that are ery of metals, in processing effluents, and in a
homogeneous mixtures: diverse array of other industries. Separation pro-
cesses may have a number of purposes, which
Evaporation can be loosely categorized as follows:
Distillation and Rectification
Sublimation 1) Purification: Removal of impurities, thereby
Liquid – Liquid Extraction enabling a desirable substance to be obtained
Absorption at a higher level of purity; e.g., refining of
Adsorption sugar and treatment of drinking water.
Process-Scale Chromatography 2) Concentration or Recovery: Increasing the
Biochemical Separations (mainly diffusional concentration of a desired substance in so-
processes) lution, usually by removal of a substantial
fraction of solvent; e.g., production of fruit
These contrast with mechanical separation juice concentrates and recovery of metal val-
of heterogeneous mixtures, in which the prod- ues from effluents.
uct phases are already present on a microscale. 3) Fractionation: Separation of desired sub-
These are discussed in the following articles: stances from one another; e.g., primary distil-
lation of crude oil and chromatographic sep-
Filtration
arations.
Centrifugation, Filtering
Centrifugation, Sedimenting The first two categories imply separation of a
Hydrocyclones small amount of one substance from a large
Sedimentation amount of another. The desired products are the
Dust Separation major and minor constituents, respectively, in
Screening the first and second processes.
Elutriation
Air Classification
Mineral Sorting 2. Definitions
Magnetic Separation
Electrostatic Separation Most separation processes are based on the prin-
Gravity Concentration ciple that different phases of matter have dif-
Dense-Media Separation ferent compositions at equilibrium. Examples
Flotation are vapor and liquid phases in distillation, and
916 Separation Processes, Introduction
immiscible liquid phases in liquid – liquid ex- 3. Process Configurations

traction. These processes achieve separation by
allowing the phases to proceed toward equilib- Often, the species being separated is separated to
rium, hence the name equilibration processes. an insufficient degree by a simple equilibration
Another category, known as rate-governed or by a single passage through a barrier. In these
processes, achieves separation by means of dif- cases, the degree of separation between species
ferences in rates of transport of different species can be improved by staging or countercurrency.
through a medium or barrier. Here the prod- Examples of each are shown in Figure 1. By
ucts are probably fully miscible with the feed; sending the product from one contacting or stage
the separation would be destroyed by remixing to another and appropriately recycling interme-
them. Examples are ultrafiltration and gaseous diate products to previous stages (Fig. 1 A), the
diffusion. degree of separation between species in the ul-
A separating agent is added to achieve sep- timate products can be improved considerably.
aration. In equilibration processes, this agent For a distillation operated at total reflux (in-
serves to create the second phase. The separat- finitesimal feed and product flow), the separa-
ing agent takes the form of energy or matter. tion factor for products from a single equilibrium
Examples of energy separating agents are re- stage is αij , as already noted, whereas that from
boiler heat, which forms the vapor in distillation, N equilibrium stages joined countercurrently is
N
and chilling or refrigeration, which causes ice to αij (the Fenske equation).
form in freeze concentration processes. Exam- Continuous countercurrent contacting can be
ples of mass separating agents are an absorbent used to accomplish the same effect, as shown in
used to separate gases and an ion-exchange resin Figure 1 B. Here, two phases flow countercur-
used to desalt water. Typically, most of the util- rent to each other through an open material such
ities costs for a separation process are associ- as a structured packing, which serves to create
ated with the separating agent, e.g., the cost of interface for mass transfer between phases. The
steam to drive the reboiler of a distillation col- action is analogous to that of a countercurrent
umn or the cost of regenerating a mass separating heat exchanger, where the exit temperature of
agent for reuse. Economics and environmental the hot stream can be lower than the exit tem-
restrictions usually dictate that a mass separat- perature of the cold stream. Sometimes contac-
ing agent should be regenerated and reused. A tors are built with elements of both discretely
separation process based upon a mass separat- staged and continuous countercurrent contact-
ing agent thereby requires a second, subsequent ing, for example, rotating disk contactors used
separation process. for liquid – liquid extraction.
The degree of separation achieved between Another way of improving the degree of sep-
two substances in different products relates to aration achievable in a simple contacting is the
the separation factor between them. For equi- chromatographic mode. Here a mobile phase
libration processes, the separation factor αij is flows along a thin, stationary phase.
usually defined as the ratio of the partition coef- The thinness of the stationary phase provides
ficients (Ki and Kj ) of the two species between rapid rates of mass transfer, giving the effect of
the two phases at equilibrium (αij = Ki /Kj ). The many stages or “transfer units” per unit length of
constants Ki and Kj are the partition coefficients the stationary phase. In elution chromatography,
of species i and j, which are defined as the con- components of a mixture injected as a pulse at
centration of a particular species in phase 2 di- the inlet end of the contactor proceed along the
vided by that in phase 1. Any concentration units stationary phase at different rates, determined by
may be used for Ki and Kj in either phase, pro- the different equilibrium distributions between
vided the same units are used for both species in phases, and emanate as a succession of isolated
a given phase. Phases 1 and 2 are usually chosen peaks (Fig. 2). Field-flow fractionations are rate-
so that αij is greater than unity. governed processes operated in an analogous,
elution-chromatographic mode.
Figure 1. Staging and countercurrency

A) Staged mixer – settler system for solvent extraction; B) Continuous countercurrent extractor.
A continuous staged or countercurrent con-

tactor provides high feed capacity but generates
only two products of high purity. (Intermediate
products, or sidestreams, of lesser purity can also
be present.) The elution-chromatography mode
can separate a complex mixture into many pure
peaks or products, but its inherent capacity is
low because the feed is injected intermittently
as pulses.
When a solid feed is used (e.g., leaching of
roast and ground coffee to form coffee extract or
a solid mass separating agent is employed (e.g.,
an adsorbent), movement of the solids should
generally be avoided because attrition and unde-
sirable mixing may result. Fixed-bed processes
are commonly used (e.g., the home water soft-
ener filled with ion-exchange resin or a bed of
activated alumina for drying air) when a solid
Figure 2. Typical output from a gas or liquid chromatograph
(peak height, as sensed by any of various detection methods, feed or mass separating agent is used. A regen-
vs. elution time). erated fixed-bed separation can handle a sub-
stantial feed rate but in its simplest form proof the need for circulating and regenerating the
vides only one highly purified product, the ini- mass separating agent or else disposing of and
tial effluent, before a second component leaves replacing it. Similarly, when staging or counter-
the bed. Among the more notable innovations in currency is needed, equilibration processes tend
industrial separation during the past few decades to be more attractive economically than rate-
have been effective ways of simulating counter- governed processes that give an equivalent sepa-
currency with fixed beds. ration factor, because equipment and energy can
Yet another fundamentally different ap- be utilized more efficiently in the former.
proach to separation involves migration of dif- Separation processes involving a solid phase
ferent species to equilibrium positions within a can suffer drawbacks associated with low or van-
gradient field. One example is isoelectric focus- ishingly small transport rates in the solid phase
ing. These processes are inherently slow but can and with the desirability of keeping the solid
give separations that are not possible by other phase stationary.
means. Certain methods of separation are better
suited for certain ranges of feed concentration. In
particular, fixed-bed operations are most effec-
4. Separation Principles tive for removing relatively dilute solutes, since
the diluteness necessitates less bed volume and
For a feed of any particlular phase condition, less frequent regeneration. Thus, adsorption and
an equilibration separation process can be based ion-exchange processes tend to be used to re-
upon formation of, or contact with, any immisci- cover solutes from relatively dilute feeds or to
ble second phase of matter. For a liquid feed, the remove impurities. Along this spectrum of feed
second phase may be a gas (stripping), an im- concentration, extraction (with liquids) and ab-
miscible liquid (extraction), or a solid (crystal- sorption (with gases) are usually considered for
lization, adsorption). Equilibration may be with a middle range of concentration, because the sol-
the bulk of the second phase or with a surface. vent flow rate required tends to be relatively in-
Surface-based separation processes include ad- dependent of the feed solute concentration. Op-
sorption, as well as foam, bubble, and emulsion erational upper limits on feed solute concen-
fractionation. tration can come from the need to keep liquid
For rate-governed processes, differences in phases immiscible in extraction or to avoid too
any form of transport can be exploited. These in- large a percentage decrease of the flow rate of
clude rates of permeation through a solid mem- the feed phase. Distillation works well over a
brane, Knudsen diffusion in a porous medium wide range of feed concentrations but can expe-
(as used for separation of uranium isotopes rience low stage efficiencies at very low solute
in UF6 ), thermal diffusion, electrophoresis, or concentrations.
pressure diffusion. Membrane separation can provide high se-
Often, two separation principles used in con- lectivity for removing or concentrating (ultra-
cert can operate synergistically. Examples are filtration) high molecular mass or macromolec-
the use of cross fields for rate-governed separa- ular solutes, for removing salts from water or
tion and the enhancement of relative volatility concentrating them (reverse osmosis, electro-
in a distillation by adding a substance that mod- dialysis), and for fractionating solutes of high
ifies the equilibrium between phases, as done in and low molecular mass (dialysis). Economi-
azeotropic and extractive distillation. cal, high-capacity membranes that effectively
remove polar organic solutes of lower molec-
ular mass have yet to be developed, but are an
5. Advantages and Disadvantages of area of research. The solute throughput capac-
Different Separation Methods ity and selectivity provided by membranes can
be enhanced by impregnation of the membrane
When the same separation factors can be at- with an appropriate extractant (solid-supported
tained, equilibration processes using energy liquid membranes, facilitated transport). Mem-
separating agents tend to be less costly than brane processes are best suited for low molar so-
those using a mass separating agent, because lute concentrations, because providing the driv-
ing force for transport across the membrane is acceptor, chelation, clathration, etc.) are much
otherwise difficult and expensive. more readily reversible and can be used advanta-
Cost and Scaleup. Different methods of sep- geously in separations to increase the selectivity
aration have inherently different costs. An in- among solutes or the capacity for a desired so-
verse relationship tends to exist between the lute. Reversible chemical interactions can be im-
value of the product and the scale of production. plemented in extraction; sorption; ion exchange;
For high-value substances produced on a small azeotropic and extractive distillation; impreg-
scale, a much wider range of separation tech- nated membranes; and foam, bubble, and emul-
niques can be considered than for substances of sion fractionation. Finally, the common pro-
lower value. Often the cost or value of a sub- cesses for concentrating a solute in solution by
stance is influenced strongly by the difficulty of removal of solvent (evaporation, reverse osmo-
separation; therefore, for a high-value substance, sis, ultrafiltration, freeze concentration) incur
utilization of a newer or less common means of expense in proportion to the amount of solvent
separation may be necessary in order to perform that must be removed. Extraction or sorption of
the desired separation at all. Furthermore, cer- the solute(s) of interest can lead to concentra-
tain separation processes (e.g., distillation, ex- tion as well, because only a limited amount of
traction) can be scaled up more readily than oth- the solvent will accompany the solute into or
ers. Those methods that rely on very thin phases onto the extractant or sorbent. Reversible chem-
or thin flow channels (chromatography), laminar ical interactions can be used effectively here as
flow (field-flow processes), or ready dissipation well.
of heat (electrophoresis) are particularly difficult
to scale up to large capacities. 6. Selection of a Separation Process
Thermosensitive Product. In many cases, the
feed or products are sensitive to thermal degra- In seeking one or more appropriate methods of
dation, contamination, or changes due to a separating a particular mixture, the first consid-
change in the chemical environment, such as eration is the size of the separation factor likely
denaturation of proteins. These constraints are to be attained by different methods of separation.
particularly common in the food and pharma- Differences in volatility (distillation, evapora-
ceutical industries. Here, methods of separation tion, stripping), solubility (crystallization, ex-
that avoid these problems will have an advan- traction, absorption), charge-to-mass ratio (ion
tage. To avoid thermal degradation, low temper- exchange, electrophoresis), molecular size and
atures and short residence times should be used. shape (adsorption with molecular sieves, crys-
Processes that avoid heating the feed (extraction, tallization, gel permeation, clathration, dialysis),
sorption, crystallization, etc.) are advantageous; and chemical reactivity can all be used for sep-
if vaporization must be used, operation under arations.
vacuum is helpful. Concerns about contamina- Next, whether ordinary or extreme conditions
tion and chemical environment limit the types (very high or low pressure, very high or low
of mass separating agents that can be used. For temperature, etc.) are needed to obtain attractive
instance, in bioprocessing, many solvents have separation factors must be determined. Methods
toxic effects, so precipitation and the use of solid that require excessive temperature – time com-
sorbents are relatively advantageous. Similarly, binations or result in contamination or chemical
proteins may denature if they are taken into a change may be ruled out by the nature of the feed
nonaqueous phase. or product. Also, as already noted, the value of
Processes Involving Reversible Chemical Re- the substance and the desired scale of operation
actions. Most industrial separations are carried can determine the number and types of alterna-
out by processes that do not involve chemical re- tives to be considered, because of the varying
actions, because of the consumption of reagents cost of different separation methods and their
required to accomplish the reaction, the cost of suitability for scaleup. Finally, a very practical
reagents needed to regenerate the original de- consideration is the amount of previous experi-
sired substance, and the need to dispose of un- ence with a particular process.
wanted reaction products. However, chemical Among near equals, distillation has an advan-
complexation or association reactions (donor – tage because it avoids solids, it is easy to stage
and scale up, and a vast backlog of experience many organic compounds based upon a single
exists. Rate-governed processes are usually con- set of chemical parameters related to dispersion
sidered seriously only when the desired separa- forces, polarity and polarizability, and acidity
tion can be achieved in a single stage. Separa- and basicity, serve to correlate such seemingly
tion of uranium isotopes by gaseous diffusion is diverse partitioning properties as solubility in
a notable exception to this generalization, how- water [2], adsorption from water onto activated
ever. With processes utilizing a mass separat- carbon [3], and extraction from water into 1-
ing agent, ease of regeneration becomes a dom- octanol [4]. All of these situations are dominated
inant factor. Finally, as already noted, fixed-bed by aqueous-phase nonidealities.
processes gain a compensating advantage when Dimerization or polymerization of the solute,
substances at relatively low concentration are to or formation of solute molecules into micelles in
be removed. one of the phases, serves to increase the distribu-
tion (i.e., increase Ki ) of the solute in that phase
at higher solute concentrations.
7. Factors Influencing Phase Another common equilibrium feature is the
Equilibria saturation of a phase. In adsorption processes,
the finite amount of solid surface area present
Several general factors influence phase equilib- provides an upper limit on the amount of solute
ria and can be utilized in the logic of selecting that can be taken up within the capacity of the
processes and choosing mass separating agents. selective layer adjacent to the surface. The same
A generalized equilibration separation process is true of gas – liquid surface capacity in foam or
may be regarded as having a source (feed) phase bubble fractionation. In these cases, the partition
and a second, receiving phase. For the solute(s) coefficient toward the surface phase decreases
of interest to move in the desired direction, the as saturation is approached. This is another rea-
chemical potential of the solute in the receiving son why surface-based separation processes are
phase must be less than that in the source phase. more useful when the solute to be removed is
The partition coefficient Ki for a solute bet- present in low concentration.
ween two bulk phases is independent of solute A similar situation exists where chemical re-
concentration when ideal solutions exist in both actions are involved (e.g., ion exchange, re-
phases or, in most instances, when the solute is versible chemical complexation). The reactant
very dilute in both phases. The partition coeffi- in the receiving phase has a limited capacity,
cient is simply the ratio of the activity coefficient in that the stoichiometry of the underlying re-
in the source phase to that in the receiving phase, action(s) cannot be exceeded. Thus, a solvent
if the activity coefficients and the partition co- phase containing a reactive organic extractant
efficient are based upon the same concentration of molecular mass 400 at 40 wt % in an organic
units (moles or mass per volume, weight frac- diluent can at most take up 5 wt % of a solute
tion, etc.). If preferential interactions occur bet- of molecular mass 50, with which the extrac-
ween solute and solvent [defined as the major tant forms a 1:1 complex. Complexation of addi-
component(s)] in either phase, the distribution tional solute molecules with a reactant molecule
of the component toward that phase will be en- engenders additional uptake.
hanced. Similarly, if less affinity exists between
solute and solvent molecules than between sol-
vent molecules themselves, the solute will be 8. Sources of Equilibrium Data
driven toward the other phase.
The values of Ki for many phase-distribution Many measurements of phase-equilibrium
processes are dominated by the nonidealities in properties exist, but they are widely scattered in
one of the two phases. This is particularly true for the literature. For a particular system, a search
processes that remove nonpolar or low-polarity of Chemical Abstracts may be the most useful
solutes from aqueous solution in which the aque- approach. Complications of data are given in [5–
ous phase is highly nonideal (very large activ- 8] for vapor – liquid equilibria; [9] for liquid–
ity coefficients) and the receiving phase is much liquid equilibria; [10] and [11] for solubilities
more nearly ideal. Thus relationships among of gases and solids in liquids; [12] and [13] for
bulk solid – liquid equilibria; and [14] for phase 7. J. Gmehling, U. Onken, et. al.: Vapor-Liquid
diagrams in general. Equilibrium Data Collection, vol. 1, 1 a,
Methods for prediction, correlation, and in- 2abcd, 3, 4, 5, 6abc,7, 8, Dechema, Frankfurt
terpretation of vapor–liquid and liquid – liquid 1977 ff.
phase equilibria are treated in [15] and sum- 8. H. Knapp, R. Döring, L. Oellrich, U. Plöckner,
marized in [16]. Prominent among these is the J. M. Prausnitz: Vapor-Liquid Equilibria for
UNIFAC method, described for vapor – liquid Mixtures of Low-Boiling Substances,
equilibria in [17] and for liquid – liquid equilib- Chemistry Data Ser., vol. 6, Dechema,
ria, in a more general context, in [18] and [19]. Frankfurt 1982.
9. J. Wisniak, A. Tamir: Liquid-Liquid
This method is suitable for mixtures with mod-
Equilibrium and Extraction, 2 vols., Elsevier,
erate degrees of nonideality but cannot yet be
Amsterdam 1980 – 1981 Suppl. 1, 1985.
extended to situations involving simultaneous 10. J. Wisniak, M. Herskowitz: Solubility of Gases
strong, specific chemical interactions. and Solids, 2 vols., Elsevier, Amsterdam 1984.
11. A. Seidell, W. F. Linke: Solubilities of
Inorganic and Metal-Organic Compounds,
9. References Van Nostrand, New York 1958.
General References 12. J. Timmermanns: The Physico-chemical
1. C. J. King: Separation Processes, 2nd ed., Constants of Binary Systems, Interscience,
McGraw-Hill, New York 1980. R. W. New York 1959 – 1960.
Rousseau (ed.): Handbook of Separation 13. H. Stephen, T. Stephen (eds.): Solubilities of
Process Technology, Wiley, New York 1987. Inorganic and Organic Compounds,
P. A. Schweitzer (ed.): Handbook of Pergamon, New York 1964.
Separation Techniques for Chemical 14. J. Wisniak: Phase Diagrams, 2 vols., Elsevier,
Engineers, McGraw-Hill, New York 1979. Amsterdam 1981.
15. J. M. Prausnitz, R. N. Lichtenthaler, E. Gomes
Specific References de Azevedo: Molecular Thermodynamics of
2. R. W. Taft, M. H. Abraham, R. M. Doherty, Fluid-Phase Equilibria, 2nd ed.,
M. J. Kamlet, Nature (London) 313 (1985) Prentice-Hall, Englewood Cliffs NJ 1986.
384. 16. R. C. Reid, J. M. Prausnitz, T. K. Sherwood:
3. M. J. Kamlet, R. M. Doherty, M. H. Abraham, Properties of Gases and Liquids, 3rd ed.,
R. W. Taft, Carbon 23 (1985) 549. McGraw-Hill, New York 1977.
4. R. W. Taft, M. H. Abraham, G. R. Famini, 17. A. Fredenslund, J. Gmehling, P. Rasmussen:
R. M. Doherty, et al., J. Pharm. Sci. 74 (1985) Vapor-Liquid Equilibria Using UNIFAC,
807. Elsevier, Amsterdam 1977.
5. I. Wichterle, J. Linek, E. Hala (eds.): 18. J. M. Sørensen, T. Magnussen, P. Rasmussen,
Vapor-Liquid Equilibrium Data Bibliography, A. Fredenslund, Fluid Phase Equilib. 2 (1979)
Elsevier, Amsterdam 1973 Suppl. 1, 1976. 297; 3 (1979) 47; 4 (1980) 151.
Suppl. 2, 1979. Suppl. 3, 1982. Suppl. 4, 1985. 19. T. Magnussen, P. Rasmussen, A. Fredenslund,
6. M. Hirata, S. Ohe, K. Nagahama: Computer Ind. Eng. Chem. Process Des. Dev. 20 (1981)
Aided Book of Vapor-Liquid Equilibria, 331.
Elsevier, Amsterdam 1975.
Solid – Liquid Separation, Introduction 923
Solid – Liquid Separation, Introduction

Christian Alt, München, Federal Republic of Germany
1. General Considerations . . . . . . . . . 923 2.2. Filtration . . . . . . . . . . . . . . . . . . . 927

2. Separation Processes . . . . . . . . . . . 926
2.1. Sedimentation . . . . . . . . . . . . . . . . 926 3. References . . . . . . . . . . . . . . . . . . 929
1. General Considerations Separators are used for coarsely dispersed

solid – liquid mixture systems with particle sizes
A wide variety of equipment and machinery is of several millimeters down to finely dispersed
available for the separation of solids and liq- systems of molecular dimensions. In addition,
uids. Counting the many possible optional vari- highly concentrated slurries are separated as
ations, a potential user can choose from among well as dilute suspensions. For the evaluation of
more than 100 separation devices. Since some separation equipment such inherent parameters
of the equipment was developed to solve spe- as different geometries of the particles, inter-
cific problems, its use is confined mainly to those facial effects, and electrostatic interactions are
or to other closely related tasks. However, most considered first; they can be influenced by pre-
equipment is universally applicable and lends treatment. Therefore, a number of important fac-
itself to comparisons. tors must be observed.
The equipment considered in this article is A systematic collection of factors to be con-
used principally in the following separation pro- sidered may be helpful for selecting separation
cesses: equipment and avoiding basic mistakes. Some
criteria for the use of liquid separation processes
1) screening (wet screening or screen filtration) are listed below; see also [1]:
2) sedimentation
3) filtration 1) Material Factors
4) expression, and 1.1) Feed
5) electrokinetic or magnetic separation. Solids:
concentration
In this classification, equipment for elutria- density
tion occupies a special place. Although it in- particle size
cludes separation of the two phases of a sol- particle size distribution
id – liquid mixture, its major task is selective particle shape
separation within the solid phase. particle structure (aggregates,
Each of the listed separation processes can be flocs and crystals)
further categorized by additional characteristics. stability and hardness
Figure 1 shows a classification according to the solubility
forces that are necessarily active in every separa- corrosiveness
tion process. Accordingly, separation processes chemical composition
are basically differentiated by the motion of the
Liquids:
phases to be separated, and the equipment can
chemical composition
be classified into sedimentation apparatus and
density
filters. Nevertheless, this classification is not al-
viscosity
ways unambiguous, since a large number of de-
pH value
vices comprise both mechanisms.
volatility, vapor pressure
924 Solid – Liquid Separation, Introduction
Figure 1. Classification of equipment for solid – liquid separation
Impurities Feed variation (concentration and a-

Foaming tendency mount)
Temperature Residual moisture
Toxicity Solids breakage
1.2) Wash Liquor Washing (separate collection of effluents)
Foaming tendency
Material properties; see “liquids”
Temperature range
1.3) Equipment Auxiliary processes:
Corrosion protection flocculation
Abrasion protection precoating
Load capacity filtration aids
2) Performance Requirements foam suppression
Preceding and subsequent process steps
Amount of feed
Residual moisture 4) Equipment Conditions
Effluent clarity Energy requirement
Wash liquor concentration Auxiliaries’ requirement
Residual mother liquor Space requirement
Solids transportability Pollution (e.g., gases or noise)
3) Operating Conditions Corrosion tendency
Abrasion tendency
Continuous versus discontinuous
Personnel requirements
Throughput
Automatic control purchase price of each piece of equipment and of

Durability the necessary auxiliaries, one must consider the
Spare parts costs of installation, erection, and connections
Accessories as well as safety, both of the operating person-
Special adaptation nel and of the environment. The investment cost
Apparatus combination divided by the throughput always decreases as
Availability the capacity of the equipment increases. As an
example, the net purchase price of filters is
This list does not claim to be complete for
IA =k1 A−k2 (1)
extreme cases. However, very often only a frac-
tion of the factors mentioned above must be ob- where IA is the purchase price per square meter
served. of filter area, k 1 and k 2 are constants that de-
The properties of materials to be separated pend on the type of equipment and the material
sometimes vary widely in similar processes and of construction, and A is the filter area.
fluctuate frequently in the course of produc- Only an expert is able to compare easily and
tion, which further complicates comparisons and effectively separation processes and associated
evaluations made for the purpose of selecting the equipment, considering all nuances of the fac-
optimal separation equipment. tors and criteria mentioned above. If, in addition,
Nevertheless, some generally valid relations economic factors are to be taken into account, it
narrow the comparison of different separation is almost impossible to select the optimum sepa-
processes. A separation process utilizing gravity ration equipment without expert knowledge and
usually requires less energy than most other pro- years of experience. Therefore, it is, frequently
cesses. Thus, for example, a sedimentation tank impossible to avoid the type of laboratory stud-
can be operated with only a few joules per cubic ies that until recently were practiced routinely.
meter of liquid to be separated, while filters and Certain types of testing equipment are useful,
centrifuges rarely require less than 10 000 J per in such cases, e.g., long-tube apparatus, hand
cubic meter of liquid to be separated. Both ma- filter plates or compression filter cells, and bot-
chines require less than half the energy needed tle centrifuges. Frequently, pilot-plant or small-
to operate a drier, although the latter is capable scale production testing cannot be avoided. The
of achieving a lower residual moisture content. corresponding production technique can then be
Thus, energy consumption and residual mois- simulated, if necessary.
ture content determine to some extent the type Even the relatively favorable energy con-
of separation process to be used. Another fac- sumption in the solid-liquid separation, men-
tor to be considered is the intensity of operation tioned at the outset, should be compared in re-
of the separation equipment; thus, the energy relation to the subsequent process steps. Initially,
quirement for the same apparatus can be reduced the energy consumption of the equipment un-
considerably if, for example, a higher residual der consideration certainly forms the basis of
moisture content of the solids can be tolerated. planning studies, especially for new plants and
The particle size of the dispersed solids also within the context of cost saving measures. How-
shows a relationship between material param- ever, it should be kept in mind that the situation
eters and the equipment that can be used. Fig- can be altered by overriding factors. For exam-
ure 2 surveys proven application ranges of typ- ple, dilutions should be avoided in a produc-
ical separators. The plot along the ordinate is tion process wherever possible, since the solids-
roughly proportional to the optimum feed con- related separation costs are increased by reduc-
centration for the various separator devices; in tions in feed concentration. Nevertheless, dilu-
Figure 2 the ordinate extends to a solids concen- tion of a suspension prior to separation may be
tration of about 40 wt %. However, in individual useful; it can, for example, advance flocculation.
cases a lower or even a higher feed concentration In certain filtration processes a more compact fil-
may be preferable. ter cake can result from a dilute suspension than
A comparison of separation processes should from a concentrated one.
also include investment costs. In addition to the
Figure 2. Ranges of application of solid – liquid separation equipment as a function of particle size and slurry concentration
2. Separation Processes may be as high as 90 to 100 %. The degree of

liquids separation, on the other hand, is lower.
Each separation process exhibits its own spe- At throughputs of up to 1 m3 m−2 d−1 the
cific behavior based on physical and structural specific performances are relatively modest and
situations which characterize the ranges of ap- require suitably large units at higher through-
plication from the outset [2]. puts. Concrete basins are cheap, but require a
lot of space. Because of their low operating
costs, simplicity of automation devices, and the
2.1. Sedimentation small number of operators required, thickeners
are used widely in the separation and wastewater
Gravity Sedimentation. Sedimentation in treatment plants.
the gravitational field should be considered in
principle only for highly dilute dispersions with Centrifugal Sedimentation. Sedimentation
relatively finely divided solids particles. It is, in a centrifugal force field clearly requires more
indeed, the simplest separation process and en- complicated equipment and more careful assess-
tails the lowest cost. Even broadly dispersed and ment than gravity sedimentation. For example,
extremely structured, flaky solids particles can with solid bowl centrifuges and disk-type cen-
be separated at relatively high throughputs with trifuges operating at an acceleration of 1000 g
very few problems, if suitably long sedimenta- (g: acceleration due to gravity), high sedimen-
tion times are provided. tation rates can be achieved, even with fine-
Thickeners and clarifiers are, as a rule, not op- grained particles, which permit high through-
erated in a free-standing, single-step mode, but puts per machine unit. With scroll discharge
often as preliminary stages if both of the phases of solids, in continuous decanter centrifuges,
to be separated are to be obtained with high effi- about 200 m3 /h of wastewater slurry can be
ciency. The liquid contents (residual moistures) dewatered in large modern units. With the aid
of the sludges are comparatively high. Neverthe- of flocculation, the sedimentation rate can be
less, the degree of solids separation is good and increased further by about a factor of 10. The
flocculating agent, which in this case remains Commensurate with their importance, filters
in the separated solids, may be undesirable at are also available for extremely high perfor-
times; for that reason, separation processes free mance. Filtration areas can be up to 1000 m2 in
of flocculating agents, for example, in disk-type size and permit throughputs of several hundred
centrifuges, are then preferred. Also suitable, al- cubic meters per hour.
though at reduced throughput, are special mod-
ifications of solid bowl scroll discharge cen- Particle Size and Solids Concentration.
trifuges. Ternary systems – two liquid phases Coarse-grained suspensions are reserved for
and one solid phase – can be successfully and vacuum filters or occasionally for hydrostatic fil-
completely separated both in differently modi- ters. Both devices are energetically more favor-
fied solid bowl scroll discharge centrifuges and able and simpler than pressure filters. For slur-
in disk-type separators with peripheral solids ries containing fine particles deep-bed filters and
discharge through jets or annular slots. dynamic (cross flow) filters are available in ad-
A comparison of sedimentation equipment dition to prevalent pressure filters. The feed con-
should usually also include the wear that is centration largely determines the preferred type
expected. Centrifuges are considerably more of filter. Pressure filters generally require higher
subject to wear than gravity basins; therefore, solids concentrations than the others which are
a number of devices are available to protect selected more on the basis of what is expected
against wear, especially for the highly stressed subsequently of the separated phases. For ex-
conveyors in continuous decanter centrifuges. ample, it is difficult to further concentrate solids
retained in deep-bed filters; in dynamic filters
Hydrocyclones. Hydrocyclones are simple such concentration is routine.
devices and require very little expenditure. To When highly concentrated slurries contain
be sure, they do not provide sharp phase sepa- solids that are finely divided or otherwise diffi-
rations; for this reason, they are used more as cult to separate, such as slimy particles, they can
pre-stages for concentrating dilute suspensions also be separated by precoat filtration, prefer-
ahead of a filter and for similar purposes. ably on drum filters, centrifugal discharge plate
A key disadvantage of most sedimentation or candle filters; this involves the use of filter
equipment is that sludges cannot be washed. If aids. However, relatively dry solids obtained in
the washing of solids is strictly required, solid this way contain the filter aids, except for those
bowl scroll discharge centrifuges and disk-type shaved off the drum filter.
centrifuges are applicable, though only to a lim- Coarse-grained and simultaneously fast set-
ited extent. tling solids are less suitable for drum and disk fil-
ters since the solids form a sediment in the tanks.
Likewise, slurries with relatively large fractions
2.2. Filtration of fine particles are more difficult to handle in
these filters since the finest particles, which build
A very large number of different filters are up the filter cake first, may frequently blind the
available on the market. They can be used for filter medium.
coarse-particle suspensions of up to a several
millimeters particle size and even with a broad Residual Moisture. Filters in comparison to
particle size distribution on the one hand, and thickeners clearly yield lower residual moisture.
for colloidal suspensions on the other hand. However, minor differences in individual filters
The very fine-particle suspensions have be- should be noted. Thus, lower residual moisture
come amenable to mechanical separation be- is obtained in pressure filters, filter presses, and
cause membranes of various configurations have especially in press filters. In this connection, dy-
become available. In addition, filters can be used namic filters give above-average residual mois-
for almost any solids concentration. ture. Deep-bed filters generally are not intended
In contrast to sedimentation equipment, fil- for the production of dry solids with low residual
ters are independent of phase density. Even slur- moisture, but are preferred to clarify liquids.
ries with only minute differences in density can Particularly low residual moisture is obtained
be filtered without problems. in centrifugal filters, since centrifugal forces act
on the retained liquid more efficiently than do is true for centrifuges. However, by combining
the other liquid displacement mechanisms usu- clarifiers and filters, as in solid bowl centrifuges
ally employed in filters. in which the lip ring is perforated for filtration,
compression can become almost insignificant.
Bleeding. If everything else is equal, bleed-
ing of solids to the filtrate is higher in cen- Durability. Some filters are distinguished by
trifuges than in filters. Therefore, slurries con- long durability. This includes particularly filter
taining a relatively wide particle size distribution presses. However, drum and disk filters also have
are preferably conveyed to filters. a relatively long durability. The reason for this
lies in the design of these filters which mini-
Solids Discharge. Typical cake filters occa- mizes component parts exposed to abrasion and
sionally have problems with removing the filter wear. Centrifuges, in contrast, are more sub-
cake from the filter medium. For example, if the ject to wear, especially in those component parts
filter cake clings strongly to the filter medium, which come into contact with solids at high ve-
whether because the solids have adhesive sur- locities.
face properties or because some of the solids are
entrapped at higher rate within the interstices of Economy. Some filters have relatively favor-
the filter medium, the filter cake no longer drops able economics such as nutsche filters and can-
off the filter medium. Only drum and disk filters dle filters. Centrifugal-discharge filters and fil-
with scrapers and the like permit safe removal; ter centrifuges are considerably more expensive.
with pan, table, leaf, and candle filters, as well Considering their specific throughputs, however,
as with filter presses, cake removal can present it is largely found that they also increase with
difficulties. construction cost. Many cost advantages are bal-
anced in this way. However, minimizing costs
Washing of the Filter Cake and Filter is always an important development objective;
Medium. Some separations also require com- it results in improved and novel filters. An ex-
plete removal of the liquid that remains in the ample is seen in the electrokinetic filter, much
filter cake after dewatering, for example, when discussed recently.
a corrosive mother liquor or solvent is involved.
For this purpose, filter cakes can be washed. Throughput. The throughputs attainable per
Good possibilities for washing exist in belt, filter surface area for equivalent products are
plate, and table filters, because the washing liq- generally greater in centrifuges than in the con-
uid does not remove the filter cake from the filter ventional filters. For the same reason, slurries
medium. Newer spraying devices make it possi- which are difficult to filter, can be more effi-
ble to wash the filter medium in pressure leaf fil- ciently treated in centrifuges (Fig. 3) [3]. Ac-
ters and filter presses as well; for the latter, high cordingly, filter cakes with small cake formation
pressure spraying devices with up to 10 MPa wa- times also require shorter cycles in centrifuges.
ter pressure are on the market.
Energy Consumption. The energy con-
Accessibility of Filter Area. It is often de- sumption per mass rate of liquid or solid sepa-
sirable that the filter area be accessible to oper- rated is only slightly higher in centrifuges than
ating personnel for instant intervention in case of in filters, given the same conditions. Only ex-
a breakdown. Vacuum filters offer the best con- tremely simple designs such as nutsche filters
ditions for access. In line with the general trend behave differently.
toward process automation, however, this need Occasionally, however, filters consume more
may recede more and more into the background. energy, for example, if greater demands are
made with respect to the degree of washing
Cake Compression. Compressible filter rate or residual moisture, which frequently re-
cakes are less suited to pressure filtration than quires additional equipment. As a rule, filters
to vacuum filtration, since the relatively high and filter centrifuges, including the necessary
pressure drops which exist in pressure filters auxiliary equipment, consume between 1 and
favor consolidation of the filter cake. The same
10 kW h per ton of dry solids. The lower val- between a filter press and a centrifugal discharge
ues apply to coarse-grain and crystalline prod- plate filter. Higher residual moistures resulted in
ucts. The higher values must be expected for the latter, especially in opposite membrane filter
fine-grain and especially for pasty materials. The presses. Of course, to achieve equal elutriation
observed behavior of filters often varies widely the centrifugal discharge plate filter requires two
with a corresponding broad scatter in the sepa- to three times the amount of wash water. The
ration efficiencies. availability was equal in both cases. Cleanup of
the centrifugal discharge plate filter following
possible product changes is disproportionately
more expensive.
Another comparison between a pusher cen-
trifuge and a belt filter, using a crystalline prod-
uct, indicated a better durability for the filter.
Bleeding of solids is also lower in the filter than
in the centrifuge which is provided with rela-
tively large wide slots for economic reasons. To-
tal energy consumption, however, was greater
for the filter. Total operating costs of the filter
are lower because of the high wear of the cen-
trifuge.
Figure 3. Typical ranges of application of cake filtration
equipment
The cake formation time is the time required for the buildup 3. References
of the first centimeter of filter cake.
1. D. A. Dahlstrom: “Selection of Solid-Liquid
Separation Equipment”, in H. S. Muralidhara
Quantitative Comparison. Because the ef- (ed.): Advances in Solid-Liquid Separation,
fectiveness of a separation is strongly related Battelle Press, Columbus, OH, 1986.
to the product, it is difficult to find quantitative 2. H. F. Trawinski: “Current Liquid-Solid
comparisons of different separators. A causative Separation Technology”, Filtr. Sep. 17 (1980)
factor is the impossibility of making precise no. 4, 326 – 335.
studies on identical products in industrial-scale 3. W. Gösele: “Filterapparate–eine Übersicht”,
Aufbereit. Techn.18 (1977) no. 5, 210 – 214.
operations.
4. W. Gösele: “Vergleich von ausgeführten
Some examples, however, have recently been
Anlagen zur Fest-Flüssig-Trennung”,
published [4]. In the separation of a pigment that Preprints GVC-Dezember-Tagung 1987,
was difficult to filter, one comparison was made Verein Deutscher Ingenieure, Düsseldorf 1987.
Solid – Solid Separation, Introduction 931
Solid – Solid Separation, Introduction

Henry E. Cohen, Imperial College of Science and Technology, Royal School of Mines, London, United
Kingdom
1. Introduction . . . . . . . . . . . . . . . 931 3.2. Gravity Separation . . . . . . . . . . . 935

2. Preparatory Processes . . . . . . . . . 932 3.3. Magnetic Separation . . . . . . . . . . 935
2.1. Comminution . . . . . . . . . . . . . . . 932 3.4. Electrostatic Separation . . . . . . . . 935
2.2. Size Separation . . . . . . . . . . . . . 933
3.5. Separation Based on Surface
2.2.1. Screening . . . . . . . . . . . . . . . . . . 933
Phenomena . . . . . . . . . . . . . . . . 936
2.2.2. Classification . . . . . . . . . . . . . . . 934
3. Physical Separation Processes . . . . 934 4. Process Design Economics . . . . . . 937
3.1. Radiation Sorting . . . . . . . . . . . . 934 5. References . . . . . . . . . . . . . . . . . 937
1. Introduction Hence it is prudent to restrict the number of unit

processes in a treatment scheme so as to achieve
The need to separate solids occurs in many dif- an optimized balance between costs of process-
ferent industrial activities and for a variety of ing, recovery of values, grade of the product,
materials. Examples include the separation of transport charges and attainable product price.
food grains such as nuts, beans, peas, or rice from In most cases, a trade-off is necessary between
contaminants or waste such as shells, husks, product grade and percentage recovery of val-
stones, or vermin. Other examples are the re- ues, because an increase in one generally entails
moval of print from recycled paper, the sepa- a decline in the other. Total literation may be pos-
ration of granulated plastics and copper in recy- sible, but that would result in losses of values due
cling electric cables, or the recovery of precious- to excessive comminution. Similarly, 100 % re-
metal contacts from scrapped electronic equip- covery of values may be possible with less com-
ment. minution, but the grade of the product would be
By far the largest application of solid – solid low due to the presence of unliberated particles.
separation, in both tonnage of throughput and Thus, the choice of processes of preparation and
value of product is in the utilization of mineral separation is necessarily a compromise condi-
resources. Physical methods of separation are tioned by financial constraints.
essential for the successful recovery of metals, For attaining best separation, the differences
industrial minerals, and fuels (the values) from in physical and chemical properties of values
their ores. “Ores” are defined as any kind of rock and tailings need to be displayed and enhanced
or mineral deposit from which marketable prod- as much as possible by appropriate preparatory
ucts can be extracted profitably. To meet subse- treatment. Physical liberation from each other
quent processing and user requirements, the de- is essential for effective separation of the con-
sired values need to be separated from unwanted stituents of an ore. The product quality (grade)
or harmful ore constituents (waste or tailings) by and the proportion of the values extracted from
methods collectively known as mineral process- an ore (recovery) depend on the degree of liber-
ing. ation and the enhancement of differential prop-
Solid – solid separation relies on differences erties achieved during preparation.
in physical and chemical properties of the con- Broadly, all ores can be divided into two cat-
stituents of an ore to devise engineering solu- egories:
tions for separating wanted values from the rest
of the ore. In industrial practice, no separation 1) Ores that contain high-priced values (e.g.,
process can attain 100 % recovery of the val- gold or other precious metals, nickel, tin,
ues in a feed within acceptable processing costs. diamonds, emeralds, etc.) in low concentra-
932 Solid – Solid Separation, Introduction
tions. A typical gold ore contains a few grams liberated cassiterite. Further comminution of the
of gold per tonne of rock. remaining ore, followed by separation of a prod-
2) Ores that contain low-priced values (e.g., uct (or of a waste reject) can be repeated several
iron, manganese, chromium, gypsum, china times at progressively smaller size ranges.
clay, etc.) in relatively high concentrations. This is practiced with ores where locked mid-
A typical iron ore contains 60 % iron, or dlings persist over wide size ranges. Repetition
nearly two-thirds of a tonne of iron per tonne ends when the remaining values are insufficient
of rock. to justify the costs of further treatment. Complex
These two categories influence selection, ap- sequences of preparation and separation may
plication, and performance of methods of solid– also be necessary for ores that contain several
solid separation. The highest possible percent- different value minerals. For example, ores con-
age recovery (better than 90 %) of a small containing sulfides of copper, lead, and zinc require
tent of high-priced values is essential (e.g., with repeated and different surface conditioning for
gold ores) to cover the cost of treatment. By selective recovery of these minerals into sepa-
contrast, modest recoveries (60 – 70 %) can be rate concentrates.
tolerated with low-priced values, but the prod-
uct grade must be high enough to qualify for
good market prices. For china clay, practically 2.1. Comminution
100 % purity (i.e., 100 % grade) is necessary for
its acceptance as a paper-coating material and Comminution serves two related, but separate
relatively low recovery has to be accepted. purposes: to liberate minerals from each other
and to render the resulting particles within de-
fined size ranges suitable for subsequent separa-
2. Preparatory Processes tion, or to meet user requirements. For both pur-
poses, comminution usually needs to be closely
Essential preparatory processes include com- linked with size separation. In industrial prac-
minution for solid rocks (or other heterogeneous tice, comminution–also called size reduction–
solids), dry or wet scrubbing for unconsolidated is usually divided into crushing and grinding.
materials such as sand or clay deposits, and size Crushing employs processes of compression or
separation processes for mixed populations of impact shattering and is applied to coarse par-
particles. ticles, from meters down to centimeters in size.
Although preparation processes necessarily Power consumption is relatively low, up to ca.
precede solid–solid separation, complex alter- 3 kW · h per tonne of throughput. Grinding em-
nating sequences of preparation and separa- ploys processes of abrasion, with or without im-
tion are commonly employed. Such sequences, pact, and is applied to fine particles, from cen-
termed stage processing, are advantageous if the timeters down to submicrometers in size. Power
values show some inhomogeneous liberation be- consumption is relatively high, commonly in the
havior or if different values in the ore require range of 10 – 20 kW · h and up to 200 kW · h per
separate recovery after dissimilar preparation. tonne for very fine products. Grinding is usu-
For example, the tin mineral cassiterite ally the most energy-intensive process in any
(SnO2 ) may occur in granite in natural crys- sequence of treatment and can account for more
tal sizes from 10 mm down to 0.05 mm. Dur- than 70 % of the total energy consumed (hence
ing comminution to liberate the cassiterite from of the total costs incurred).
waste minerals such as silicates, iron oxides, This presents one of the reasons for stage pro-
etc., breakage to < 5 mm may produce substan- cessing. If substantial proportions of waste ma-
tial proportions of coarse, liberated cassiterite terial can be liberated from values at relatively
particles. Having to break such particles further coarse particle sizes, separating and discarding
during comminution to liberate smaller crystals such waste ahead of the expensive grinding stage
of cassiterite would be wasteful in terms of pro- may be economically advantageous.
cessing cost and possible loss of values. Hence it For example, in the treatment of iron ores in
is good industrial practice to interrupt comminu- Minnesota, some 40 % of the feed tonnage was
tion and first separating a coarse concentrate of
removed as coarse waste before grinding. Mag- cles coarser than 0.1 mm are oversize and require
netic separators were used to produce a clean further grinding. In contrast, when jigs are used
nonmagnetic waste and a magnetic “middling” for gravity concentration of tin ores, particles
which passed to the grinding stage. About 10 % smaller than around 0.2 mm are undersize. The
of the total iron in the feed was lost with the jig would be inefficient in treating − 0.2 mm par-
coarse waste, but this loss was far outweighed ticles (i.e., particles < 0.2 mm), therefore these
by the savings in grinding costs. are treated separately by other means.
The use of repeated comminution combined The two dominant industrial processes for
with size separation is common, because many performing size separation are screening and
separation processes work best within specific classification. They can be used for wet parti-
ranges of particle sizes. For example, recovery cles carried in water (or other fluids) or for dry
in froth flotation usually declines sharply for par- particle populations that are free-flowing.
ticles coarser than 0.2 mm or finer than 0.02 mm.
Hence preparation needs to be arranged so as to
achieve liberation of the greatest possible pro- 2.2.1. Screening
portion of the values in a flotation feed within
these size limits. In screening (or sieving), each individual in a
particulate material is presented to apertures
which may be circular, square, or rectangular
2.2. Size Separation and which act as two-dimensional gauges. Abil-
ity to pass through depends on size but is also
Size separation is necessary for various aspects affected by particle shape which may be platy,
of preparation. For efficient handling, for good nearly equidimensional, needle-like, or irregu-
separation, and subsequent use or disposal of lar. Thus, with increasing aspect ratios, the ori-
products, ores are generally divided into three entation of a particle relative to the aperture be-
size groups: oversize, product size (one or sev- comes an important factor which blurs the def-
eral), and undersize. Oversize material is too inition of particle size. For example, consider a
coarse for an intended process of separation. square screen aperture of 10×10 mm. With fa-
It may contain values that need further com- vorable presentation, this aperture would per-
minution because they are insufficiently liber- mit passage of a 9-mm square disk, a 9-mm
ated. There may be coarse free values that should cube, or a rectangular block 9 mm square and
be extracted by some other suitable method, or 90 mm (or more) in length. Screening assigns
coarse gangue low enough in value content not particles roughly into size groups, each group
to merit costs of further treatment. User require- having passed through a larger aperture and hav-
ments may also limit oversize contents. For ex- ing failed to pass through the next smaller aper-
ample, china clay for coating paper needs to be ture used in a given process.
at least 80 % finer than 2 µm. Product sizes are The difficulty of passage increases as parti-
those most suitable for a separation process; they cle dimensions approach aperture size, and this
may also be defined according to size specifica- can lead to blockage. Therefore, good industrial
tions imposed by users. For example, commer- practice is to avoid aperture sizes that are near
cial specifications for iron ores usually include the dominant particle size in a given product.
upper and lower size limits. The term under- Screening is used generally for coarse parti-
size refers to particles that are too small for a cles, from meters down to about 1 mm and even
given process of separation or for commercial smaller sizes occasionally (e.g., 0.02 mm for
acceptance of a product. Particle-size analysis is china clay). Under laboratory conditions, wo-
treated elsewhere in this volume. ven wire sievescan be used down to 0.015 mm
All three terms–oversize, product size, and for some minerals. Fragile electroformed per-
undersize–are relative and can cover widely dif- forated sheets and molecular sieves can be em-
ferent size ranges for different materials and pur- ployed down to submicrometer sizes, but then
poses. For example, in treating gold ores, an up- throughput is very slow.
per product size limit of about 0.1 mm is usually
necessary to ensure adequate liberation. Parti-
2.2.2. Classification have retained their natural characteristics and

crystal structures.
Classification is commonly employed in indus- Another important group of processes is
try for size separation of particles below about based on chemical reactivity, e.g., acid leach-
1 mm. The process relies on different terminal ing, solvent extraction, or other methods of se-
velocities (different settling rates) for particles lective dissolution that entail the partial or total
of different sizes moving through fluids (usu- destruction of ore constituents. These processes
ally water) or through gases (usually air). Parti- are termed chemical separation or hydrometal-
cles accelerating under the influence of gravity lurgy.
(or some other force) encounter increasing re-
sistance from the enveloping medium. Terminal
velocities are reached when the forces of accel- 3.1. Radiation Sorting
eration and resistance are equal. Larger particles
then move away from smaller ones, and separate Radiation sorting depends on differential re-
size groups can be collected. sponses to externally applied radiations. Some
However, differences in specific gravity must processes utilize differential radiation emis-
yield different terminal velocities. Hence, each sions, with or without externally applied stim-
classified size group in heterogeneous popula- uli. Many types of radiation can be used for
tions of particles includes larger particles of solid–solid separation, including visible, ultravi-
lower specific gravity and smaller particles of olet, and infrared light; X-rays, gamma-rays, and
higher specific gravity. This distinguishes a clas- electron beams; ultrasound; and a range of radio
sified size fraction from a screened product, frequencies. The methods of separation rely on
which contains the same size range for all parti- differential effects of transmission, absorption,
cles, irrespective of specific gravities. Classified reflection,modulation, or emission For example,
feed is preferred for some separation processes, reflection of visible light can be used to sepa-
e.g., gravity separation on shaking tables. rate particles by color. Similarly, transmission of
Classification used for the recirculation of light can be used to separate opaque from trans-
oversize material in grinding circuits can cause parent species. Some particles in mixed popula-
undesirable overgrinding of value minerals. If tions emit radiation selectively under ultraviolet
the latter have higher specific gravities than the illumination, e.g., the tungsten mineral scheel-
associated gangue minerals, they may undergo ite fluoresces bright blue and the mineral calcite
selective recirculation, with further grinding, fluoresces bright pink under ultraviolet illumi-
even though they are fine enough for process- nation. The selective emissions from radioactive
ing. substances are another example.
The necessary process mechanisms include a
sequence of presentation, inspection, and sort-
3. Physical Separation Processes ing. Each particle, in free flight or traveling on
a conveyor, must be presented individually to
Physical processes of solid – solid separation one or several radiation sources. The particle is
utilize differences in the physical properties of inspected, and the resultant information is ana-
mixed solids and may be grouped broadly as lyzed to trigger an accept – reject signal which
operates a sorting mechanism (e.g., a moving
1) Radiation sorting,
splitter, an air or water jet, or a trap). The size
2) Gravity separation,
range of particles suitable for such sorting ex-
3) Magnetic separation,
tends from about 150 mm down to about 2 mm,
4) Electrostatic separation,
but individual feeds must be sized relatively
5) Separation based on surface phenomena.
closely. Throughput rates are proportional to
particle size, and separation is most efficient if
Physical separation methods normally pro- the ejected material is a minority constituent.
duce concentrates of unaltered minerals that
3.2. Gravity Separation The flow velocities and amplitudes of oscil-

lation must match the dynamic characteristics
Processes of gravity separation utilize differ- of the particles; hence, size-classified feeds are
ences in specific gravity and are divided into two usually necessary. Throughput capacities range
groups: from hundreds of tonnes per hour (e.g., jigs for
coarse feed) to less than 0.5 t/h (e.g., shaking
1) Sink – float separation and tables for very fine feeds).
2) Differential acceleration.
Sink – float separation, also called dense 3.3. Magnetic Separation

medium separation or heavy medium sepa-
ration, employs heavy liquids or suspensions, Most natural minerals are more or less feebly
which have effective densities intermediate bet- paramagnetic and a few are very weakly diamag-
ween the specific gravities of species in a mixed netic. Magnetic separation processes can sepa-
population. For example, quartz (d 2.65) can be rate species of relatively higher magnetic sus-
separated from hematite (d 5.1) by using a heavy ceptibility from others of lower susceptibility.
liquid such as tetrabromoethane which has a spe- The strength of the available magnetic force lim-
cific gravity of 2.95. If a mixture of quartz and its the applicability of a separator, and the dif-
hematite is immersed in tetrabromoethane, the ference in susceptibility determines the possi-
quartz floats on the liquid and the hematite sinks ble efficiency of separating a given mixed feed.
to the bottom. Similarly, the heavy liquid may Magnetic separators employ various methods of
be replaced by a suspension of finely pulver- presenting feed to convergent magnetic fields
ized heavy minerals in water. Suspensions with which provide directional tractive forces. Coun-
effective relative densities up to about 3.5 are terforces, such as fluid drag, gravitational accel-
achievable with suspensions of barites, galena, eration, and others, are arranged singly or jointly
magnetite, or ferrosilicon. For the separation of to act in a divergent direction from the magnetic
coal from shale, quartz sand suspensions with forces. The balance of forces is arranged so that
effective densities in the range of 1.4 – 1.6 are the more susceptible particles (the “magnetics”)
used. Heavy suspensions are much more eco- follow the magnetic force and the less suscep-
nomical for industrial use than organic heavy tible particles (the “non-magnetics”) follow the
liquids, such as tetrabromoethane, which are em- counterforces.
ployed mainly in laboratory work. In industrial Magnetic separation can be carried out dry
use, the heavy suspensions are usually reco- or in fluid suspension. The magnetic force ex-
vered, cleaned, and recycled to the separation perienced by a particle is mass related; hence,
process. no theoretical upper or lower size limit exists.
The second major group of gravity separa- However, problems of physical handling usu-
tion processes relies on gravitational accelera- ally impose an upper limit of about 150 mm.
tion to exploit differences in specific gravity; a Electrostatic charges in dry feed and fluid drag
difference of not less than 1 is normally required in wet feed generally impose lower size lim-
for efficient separation. Gravitational accelera- its around 0.01 – 0.05 mm. Throughput rates de-
tion causes particles of higher specific gravity to pend on particle size, but for different types
advance faster from rest than particles of lower of separators they can range from hundreds of
specific gravity, irrespective of their sizes. Path tonnes to a few kilograms per hour.
lengths must be short so that the particles can-
not reach terminal velocities (i.e., zero acceler-
ation). Thus, gravity separation, which employs 3.4. Electrostatic Separation
differential acceleration over short path lengths,
differs from size classification, which depends Electrostatic separation is based on differences
on differential terminal velocities. in surface electrical properties, particularly sur-
Various separator designs employ films of face conductivity, and the associated ability to
flowing water or oscillatory motion to produce acquire, retain, or lose charges. Dry particles
repeated acceleration over short path lengths. can acquire charges by induction, convection,
or conduction. If different species in a mixture be made to coagulate and to settle from a sus-
are charged selectively, they can be separated by pension. This is known as selective flocculation.
application of external electrical forces. More important, hydrophobic particles can
For example, conduction charging can arise be attached to air bubbles which are made to
through spontaneous migration of electrons in stream through a pulp suspension. The air bub-
a heterogeneous population of pulverized parti- bles transport the hydrophobic particles to the
cles. Electrons will pass from a poorer to a better surface of the pulp, forming a scum or froth
conductor; thus, the latter acquires a negative which can be collected as a concentrate. This
charge and the former is left with a net posi- process, known as froth flotation, is one of
tive charge. If this population passes between a the most important and widespread methods of
pair of electrode plates, one positively and one solid–solid separation in the mineral industry.
negatively charged, each particle will experience A variety of reagents have been developed for
repulsion from the plate of like charge and at- specifically enhancing the selectivity of flota-
traction from the plate of opposite charge. The tion. The use of reagents usually necessitates
geometry, level of charge, and speed of passage stringent control of pH and of dissolved ions in
can be arranged so that the particles separate into the water.
two streams. With different reagent regimes, froth flota-
In another example, a mixed particle popu- tion has such diverse applications as the re-
lation of conductors and nonconductors can be covery of sulfides of copper, lead, zinc, nickel,
charged by means of a corona discharge from molybdenum, antimony, and other nonferrous
a wire electrode. The nonconductors retain the metals; oxides of iron, titanium, tungsten, tin,
charge, but the conductors lose their charge dur- etc.; calcium fluoride, phosphates, various car-
ing passage over a rotating drum. A second bonates, silicates, and many other mineral com-
charged electrode can then “pin” the charged pounds. Flotation is an extremely versatile pro-
particles to the drum and “lift” the discharged cess, limited only by the development of selec-
particles. A typical application is the separation tive reagents for specific applications. It oper-
of zircon (a nonconductor) from rutile (a con- ates most efficiently on particles in the range of
ductor) in the treatment of beach sand. 0.2 – 0.02 mm, but coarser and finer sizes can be
Various separator designs utilize different treated successfully under favorable conditions.
combinations of charging and discharging to The throughput capacity of individual flota-
achieve discrete products. Full liberation, total tion machines varies, according to unit size, from
absence of surface moisture and a restricted size kilograms to tonnes per hour. Multiple units in
range of feed are usually important for attaining very large flotation plants, achieve throughputs
good separation. Several repeated treatments are in the range of 30 000 – 50 000 t/d. The process
normally needed to attain acceptable clean prod- route is usually arranged so that a first flotation,
ucts. Throughput rates range up to several tonnes the rougher stage, is followed by one or more
per hour. cleaner stages for the float product. The clean-
ers reject misplaced sink material. Similarly, one
or more scavenger stages for the sink residue can
3.5. Separation Based on Surface rescue misplaced float material. These stages
Phenomena may be interspersed with regrinding of some
products, so as to achieve higher product grades
Surface chemical properties of solids can be ma- through improved liberation. Reagent additions
nipulated selectively in various ways to generate can be made at various stages, so as to improve
differential behavior of the different constituents selectivity.
in a mixed population of particles. For example, Another application of surface chemistry, oil
traces of reagents can be selectively adsorbed agglomeration, employs various reagents for
on species, rendering them either hydrophobic specific conditioning of mineral species so that
or hydrophilic. The hydrophobic particles can they are selectively taken into an organic fluid
that is immiscible with water.
4. Process Design Economics gangue and retention of values for further pro-
cessing to attain the desired grade. Thus, waste
Under normal economic conditions, the cost of is removed in stages until the product reaches
processing must be less than the resultant added market specification.
value of the product. Processing costs are mini- Detailed factors influencing the selection of
mized when the simplest possible process route appropriate processes of solid – solid separation
is used to attain the best possible recovery, at the are discussed in the other articles to which ref-
lowest product grade acceptable to the customer. erence is made here.
Variations in the three basic cost components–
capital, energy, and labor–can influence process
choices in relation to specific local conditions. 5. References
The resultant costs for any separation route con-
sist of only two elements: 1. N. L. Weiss (ed.): SME Mineral Processing
Handbook, Society of Mining Engineers,
1) processing costs, which are definable as cap- AIMMPF, New York 1985, pp. 7 – 5 to 7 – 29.
ital and operating charges, and 2. B. A. Wills: Mineral Processing Handbook,
2) loss of values due to inevitable process inef- 3rd ed., Pergamon Press, Oxford 1985,
ficiencies. The recoverable values are always pp. 522 – 530.
lower than 100 % of the values contained in 3. G. Tarjan: Mineral Processing, Akademiai
the feed. Klado, Budapest 1981, pp. 419 – 423.
4. P. Somasundranan (ed.): Advances in Mineral
Both cost elements are related to the balance Processing, Society of Mining Engineers,
between grade and recovery, as well as to the Boulder, Col., 1986.
complexity of the processing route. 5. L. White (ed.): E & MJ Second Operating
For high-priced values which are minority Handbook of Mineral Processing,
constituents of the feed, high recovery is more McGraw-Hill, New York 1980.
important than grade; hence, the process design 6. E. G. Kelly, D. J. Spottiswood: Introduction to
should aim at the earliest possible removal of Mineral Processing, Australian Mineral
concentrates. This points to treatment in stages Foundation, Auckland 1995.
so that values can be extracted as soon as they are 7. D. Bradley: The Hydrocyclone, Pergamon
liberated in any significant quantity. Repeated Press, London 1965.
further preparation of the remaining bulk of the 8. H. E. Cohen: “Energy Usage in Mineral
material and separation of values should con- Processing,” Trans. Inst. Min. Metall. Sect. C
tinue until the residual values cannot justify the 92(1983) C160-164.
9. J. C. Guillaneau, J. Villeneuve, P. Blot:
cost of further processing. Thus, values are re-
“Advances in the Design and Optimisation of
moved in stages, until the remaining waste is of
Mineral Processing Plants,” Proc., APCOM
sufficiently low grade for disposal.
92, 23rd International Symposium on the
Low-priced values which are major con- Application of Computers and Operations
stituents of a feed must be worked up to high- Research in the Mineral Industry, Tucson,
grade specifications, but high recovery can be 1992.
sacrificed. To keep processing costs as low as 10. T. Yalcin (ed.): Innovations in Mineral
possible, the process design should aim at early Processing, ACME, Sudbury 1994.
gangue removal, especially to avoid fine grind- 11. A. F. Taggart: Handbook of Mineral Dressing,
ing. This requires stage separation of liberated Wiley, New York 1945.
Mixing, Introduction 939
Mixing, Introduction
Marko Zlokarnik, Bayer AG, Leverkusen, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . . . . . 939 3. Mixing in Heterogeneous Systems . . . . 940

2. Mixing of Homogeneous Miscible 4. Mixing of Pastes and Granular
Substances . . . . . . . . . . . . . . . . . . . 939 Materials . . . . . . . . . . . . . . . . . . . . 940
1. Introduction ment than viscous, pastelike substances. Bearing

these considerations in mind, mixing operations
Mixing, stirring, and kneading have been used can be divided into the groups listed in Table 1.
by man since time immemorial in the prepara-
tion of food and drink, and belong to the clas-
sical unit operations used in the most diverse
branches of industry–production of building ma-
2. Mixing of Homogeneous Miscible
terials, glass, chemicals, food processing, etc. In Substances
the chemical industry, this technology is of spe-
cial importance: to carry out a chemical reaction, A mixture that is homogeneous at the molecular
the solutions and mixtures must be prepared in level results only when mixing gases or misci-
such a way that the reagents have a suitable form ble liquids. Here the mixing operation can be di-
for reaction. During the reaction itself, the mix- vided into two steps: (1) pre-mixing taking place
ing operation must ensure that the reagents stay through the large-scale convective transport of
in close contact with each other; this is particu- eddies and (2) elimination of concentration dif-
larly important when the reagents have a differ- ferences through purely diffusive transport. The
ent aggregate state. former is governed by the physical properties as
well as by the type of mixing device and the mix-
ing energy expenditure; it is scale-dependent.
Table 1. Classification of mixing operations according to the
aggregate state of the predominant component
The better the pre-mixing, i.e., the smaller the
eddies produced, the faster the following mix-
Aggregate state Operation Most common ing process can proceed. The latter is governed
mixing equipment
by those material properties of the system that
Gaseous ∗ mixing mixing chamber,
nozzle influence diffusion (viscosity, diffusion coeffi-
Liquid stirring stirrer cient) and is only rate-limiting if the premixing
Paste kneading kneader, screw was not intensive enough. Good mixing devices
extruder
Solid (granular) mixing mixer
(nozzles, stirrers causing a pronounced bulk cir-
culation) usually function so well that the pro-
∗ The mixing of gases is treated under → Continuous Mixing
of Fluids.
cess of diffusion has no effect on the homoge-
nization time (no effect of the Schmidt number
Sc on the homogenization characteristic).
The operations used for mixing must first be In the last few years, micromixing has re-
classified according to the state of aggregation of ceived special attention; this refers to the pro-
the predominant component; as a rule, the result- duction of extremely small eddies with the pur-
ing mixture has this state, too. From the process pose of mixing the reaction components as fast
engineering point of view, stirring a gas into a as possible. For example, micromixing plays a
liquid is not the same as mixing a liquid into a gas key role in competitive reactions of the type
stream. Even the term liquid state must be made
A + B −→ C (1)
more specific, since low-viscosity liquids place
drastically different demands on mixing equip- A + 2 B −→ D (2)
940 Mixing, Introduction
In this case, the selectivity of the desired Re- must be based on experiments in several dif-
action (1) can be increased through a fast reduc- ferent scales. The exact physical properties that
tion of the reagent concentrations. If the reac- determine coalescence are still not known: some
tion, however, is of the competitive-consecutive substances suppress coalescence strongly, even
type, in extremely small concentrations (a few ppm),
while others increase the coalescence tendency.
A + B −→ C (3)
Especially in the dispersion of gases in liquids,
A + C −→ D (4) the coalescence behavior of the system must be
then it is also important to avoid backmix- determined through appropriate experiments in
ing of the reagents with the product C. In such the laboratory.
cases a plug-flow reactor is used, and mixing is
performed with a nozzle or an in-line mixer.
4. Mixing of Pastes and Granular
Materials
3. Mixing in Heterogeneous Systems
The main objective of the mixing operation in Pastes and powders or granular materials are
the spraying of liquids in a gas and in the dis- usually mixed to achieve the best possible blend-
persion of immiscible liquids or gases in a liq- ing. Here, however, only a stochastically homo-
uid is to create as large an interfacial area as geneous mixture is possible, a mixture that de-
possible. In these operations, however, fine pri- pends strongly on the physical properties of the
mary droplets or gas bubbles often have the ten- substances to be mixed (viscosity and rheologi-
dency to coalesce; i.e., a part of the work done in cal behavior for pastes, size and morphology for
forming the interfacial area is wasted. During the granular solids). In the mixing of granular ma-
production of fine bubbles or droplets in stirred terials, mixture separation, determined by the
vessels, the size distribution of the bubbles or state of flow in the device and therefore scale-
droplets is the result of a continuous process of dependent often presents a problem. Since the
dispersion and coalescence. sampling, analysis, and the statistical evaluation
Thecoalescence process depends to a great of experimental data are problematic, there are
extent on the state of flow in the mixing de- comparatively few reliable design and scale-up
vice, thus requiring care in equipment scale- guidelines for these mixing devices. In the fu-
up. To allow reliable conclusions, design guide- ture, significantly more intensive research activ-
lines for mixing devices for these operations ity in this field is necessary.
Solids Technology, Introduction 941
Solids Technology, Introduction

Klaus Borho, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany
Friedrich Richard Faulhaber, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany
Reinhard Polke, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany
Peter Thoma, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany
1. Objectives of Solids Technology . . . 941 3.1. Measurement of Product Properties 949

2. Stages of Implementation . . . . . . . 942 3.1.1. Application-Related Product
2.1. First Stage: Formulation of Working Properties . . . . . . . . . . . . . . . . . . 949
Hypotheses . . . . . . . . . . . . . . . . 943 3.1.2. Production-Related Product Properties 950
2.2. Second Stage: Testing of Working 3.1.3. Measurement of the Dispersity
Hypotheses . . . . . . . . . . . . . . . . 945 Variables . . . . . . . . . . . . . . . . . . 950
2.3. Third Stage: Development of 3.2. Measurement of Product-Specific
Processing Strategy . . . . . . . . . . . 946 Characteristics . . . . . . . . . . . . . . 950
2.4. Fourth Stage: Verification of 3.3. Measurement of Process Parameters 951
Processing Strategy . . . . . . . . . . . 949 4. Research and Development . . . . . 951
3. Measurement Methods . . . . . . . . 949 5. References . . . . . . . . . . . . . . . . . 951
1. Objectives of Solids Technology a disperse state in the course of their production.

The situation for the European chemical indus-
Solids technology is concerned with the pro- try is estimated to be similar.
duction of disperse solid products. Characteris- This introduction to particle technology is in-
tically, the properties of solid products depend tended to demonstrate an approach, based on the
not only on chemical composition but also on the underlying principles of unit operations, to the
state of dispersion. The significance attached to design of a solids process. This involves opti-
the objective of systematically adjusting product mization of the interaction of the various unit
characteristics, often referred to as product en- operations with a view to the goal of solids tech-
gineering or formulation, is indicated by the fact nology, namely, the economical preparation of
that almost all studies in recent years describe products having specific characteristics in terms
this as an important task for the future [1], [2]. of production and application.
Production processes are composed of individ- The principles of particle technology were
ual process steps (unit operations) which include only developed in the 1900s by the pioneers of
all necessary activities from forming the solid up process engineering and their students in various
to packaging the product for sale. Other articles countries. Rumpf [4] introduced the concept of
of this encyclopedia deal with the scientific prin- the “property function” which identified the re-
ciples, the various options in terms of equipment, lationship between the state of dispersion of a
and the scale-up methods for individual unit product (particle size, crystal modification, etc.)
operations. The significance of particle technol- and its properties (quality: color strength, activ-
ogy becomes clear from a survey by Davies [3]: ity, etc.).
about 60 % of all of DuPont’s chemical products The production of disperse solid products is
are disperse substances, that is, powders, gran- characterized by the generation and repeated
ular materials, dispersions, slurries and pastes. modification of disperse states. In the follow-
About half of the remaining 40 % pass through ing, the term “disperse state” or “dispersity vari-
942 Solids Technology, Introduction
able” refers not only to particle size, but also These are complemented by additional
includes all the variables which characterize the application-related properties required by cus-
product state, such as the morphology of the par- tomers who further process the products:
ticles, interfacial characteristics, and agglomer-
Resistance to attrition
ation strength.
Dusting
A typical example of a solids processing
Flowability
chain consists of the unit operations crystalliza-
tion, filtration, drying, and size conversion. Each The ultimate objective of modifying the state
unit operation modifies the physical state of the of dispersion throughout the production process
product within the processing chain (Fig. 1 A). is to develop specific application-related product
Crystallization changes the state from solution properties. Therefore, the production process af-
to suspension; filtration changes it from suspen- fects the application properties both in intended,
sion into filter cake; drying converts the filter and quite often unintended, ways. Many appli-
cake into a powder or lumpy product; and size cation properties become apparent only in the
conversion converts powders into granular ma- end product, although they originate at various
terials or lumpy product into powder. stages throughout the production process.
At the same time the state of dispersion of Just to illustrate the concepts of these prop-
the solid changes (Fig. 1 B). The original suspen- erties, which initially may seem rather abstract,
sion contains individual particles or loose floc- consider the following examples:
cules. On filtration, these are compacted signifi- • A tablet which fails to dissolve or cannot be
cantly and form moist, loose agglomerates. The digested and therefore does not release its
drying process produces considerably stronger active ingredient
agglomerates, which can be formed into larger • A paint whose pigment settles to the bottom
secondary agglomerates or reduced in size in the of the can as a solid layer
size conversion stage. • Powdered instant coffee which clumps to-
The state of dispersion affects the production gether on the spoon
properties of a product (Fig. 1 C). It constitutes • Crystals which cannot be filtered
a crucial factor that determines whether specific • A powder which cakes in bins
processing operations are possible or defines the
cost of carrying out these operations. Production Products with these properties clearly do not
properties can be characterized by the following meet the ultimate objective of the process. A pro-
terms: cess engineer must realize that choice of equip-
ment and process conditions will affect the phys-
Crystallizability ical states of the products, which in turn are re-
Filterability sponsible for the application properties.
Washability
Dryability
Pumpability 2. Stages of Implementation
Storability in bins
The various stages in the development of a pro-
The user of solid chemicals requires the end cess are shown in Figure 2. In the first stage the
products to have well-defined properties which, property profile is defined. A concept covering
as has already been shown, depend on the state of the interrelationships of product properties and
dispersion of the material. Application-related dispersity variables is formulated and this con-
properties such as color strength of dyes or accept is then used to derive working hypotheses.
tivity of pharmaceuticals are deployed only if In the second stage the working hypotheses are
further characteristics are present: subjected to experimental tests on a laboratory
scale. In the third stage the process steps (unit
Wettability operations) must be selected and worked out in
Dispersibility detail so as to achieve an overall optimal pro-
Rate of dissolution cessing chain. In a final stage, the process is val-
idated, if necessary, on a pilot scale.
Figure 1. A) A typical solids technology processing chain; B) Change of product states during the processing chain; C)
Development of production properties during the processing chain
Figure 2. Four stages in process development and scale of experimental work
2.1. First Stage: Formulation of a final specification of the characteristic profile

Working Hypotheses at the start of process development. This is due
to the fact that the desired product properties, in
The formulation of working hypotheses involves almost every case, represent a compromise bet-
a number of steps (Figure 3). In developing a ween what is possible in terms of process tech-
process, the first step is to specify the objective, nology and what is acceptable in terms of manu-
that is, the characteristic profile of the end prod- facturing costs. Final specifications are therefore
uct. This observation may seem trivial at first, arrived at only during the development process.
but in practice it often proves difficult to define
Figure 3. Four steps in the formulation of working hypotheses
Once the characteristic profile is available, This procedure may seem over complicated
Step 2 requires a conceptual model to be devel- and laborious. Fortunately, the route described
oped to define in what state the end product must can be truncated in practice. In the most fa-
be if it is to give the desired final properties. In vorable case the relationships between product
many cases the desired properties can be reduced properties and physical variables are known. An-
to simple physical principles. Thus a description other frequently effective approach is to make
of the required product condition which at least use of extensive knowledge acquired in the aca-
points in the right direction is possible [4], [5]. demic sector by resorting to existing conceptual
This state must be achieved by means of process models.
engineering. This frequently results in a number The following example is presented to clarify
of conceptual models and numerous parameters these ideas. For the sake of simplicity, it involves
that act by means of physical mechanisms. a single product property as the target variable.
Given the high costs involved, empirical Initial laboratory samples of a new product show
testing by measuring all the parameters of all that the product has the required activity but that
the concepts produced is not feasible. There- its flowability is very poor. The aim is therefore
fore, this only leaves the option of select- to improve the flow properties. Step 1 in Figure 3
ing those physical variables, on the basis of a is thus defined.
chosen concept, which are likely to have the The qualitative relationships between flow
most significant effect on the desired product properties and physical variables have been ad-
properties. Thus, various working hypotheses dressed in fundamental research which shows
are formulated and then tested experimentally. how flow properties depend on the structure of
The iterative cycle – model concept – working the bulk material and the adhesion mechanisms
hypothesis – verification – may have to be reacting between particles [6]. Therefore, a con-
peated several times before a working hypoth- ceptual model for the first processing stage (Step
esis can be accepted. The point of the proce- 2 in Figure 3) already exists in the present ex-
dure described is not to confirm models, but to ample. Only the adhesion mechanisms can be
use models to enable physical parameters to be affected by the process to a significant extent.
found rapidly and thus to obtain a solution to These can be classified into various groups:
the overall problem. To select the right model is 1) Adhesion mechanisms without material
therefore of key importance. The process engi- bridges
neer must have been trained in drawing up mod-
a) Van der Waals forces
els and must be fully conversant with the avail-
b) Electrostatic forces
able concepts.
c) Mechanical interlocking
Figure 4. Melt conditioning: cold plate test
2) Adhesion mechanisms with solid bridges 2) The poor flow behavior is due to solid bridges
a) Crystallization of dissolved substances formed by crystallization of dissolved sub-
b) Recrystallisation of dissolved substances stances. The flow behavior can be improved
c) Sintering processes by reducing the impurity content.
d) Chemical reactions
The severe restriction to a few adhesion
3) Adhesion mechanisms with liquid bridges
mechanisms and hence in turn to a few physical
In the following discussion, two specific ad- variables highlights the hypothetical nature of
hesion mechanisms which influence the flowa- this procedure. What is determined in this stage
bility have been selected (Step 3, Fig. 3): Van is therefore not the complete property function
der Waals forces (1a) and crystallization of dis- as defined by Rumpf, but merely the essential
solved substances (2a). Physically relevant vari- parameters.
ables for these two mechanisms are listed in the The next stage requires experimental tests to
following: decide which hypotheses should be rejected and
which can be retained for further process devel-
1 a) Van der Waals forces opment.
• Particle-size distribution
• Particle shape
• Interparticle distance
• Interaction constant 2.2. Second Stage: Testing of Working
• Hardness Hypotheses
2 a) Crystallization of dissolved substances
Samples have to be prepared which will ensure
• Particle-size distribution
that the postulated main parameters are varied
• Solubility of product and impurities
over a wide enough range. It is necessary for
• Moisture transport
the required product property to be quantified
This leaves the further task, in Step 4, of se- as far as possible as a function of the physical
lecting those variables which have a suitably variables. On the one hand this assumes experi-
strong effect on the property in question. In the mental techniques which permit straightforward
present case the following working hypotheses preparation of such samples, and on the other
are formulated: hand it assumes effective measurement methods
which are capable of quantifying the relation-
1) The poor flow behavior is caused by Van der ships.
Waals forces. Possible remedies: The large number of samples required means
a) Larger particles that this procedure can only be carried out on a
b) Different crystal modifications (hardness laboratory scale. Only at this level is it possible
or shape) for sufficiently varied samples to be produced
rapidly at reasonable cost in amounts which, as empirical testing. This test procedure must pro-
experience has shown, should not exceed 1 kg. vide all the necessary or supplementary data re-
At the same time, the laboratory apparatus must quired to ensure that the process goal of achiev-
be able to set or to modify the physically rel- ing specific product properties can be attained
evant variables of the product. The laboratory economically. Initially the main effort will be
apparatus should not, in this context, be seen as directed at those unit operations which have a
a scaled-down version of production equipment. dominant effect on the desired properties.
This stage can be clarified further, again tak-
ing the example of flow properties. To test the
working hypothesis 1 (Van der Waals forces,
particle size, crystal modification), samples con-
taining different particle sizes and different crys-
tal modifications must be prepared. This can be
achieved by classifying or by controlling parti-
cle size during crystallization. Different crystal
modifications are obtained by maintaining spe-
cial crystallization or drying conditions. In this
way, the relationship between flowability, parti-
cle size and crystal modification is established.
Working hypothesis 2 (solid bridges, impurities)
can be tested by more thorough washing of the
filter cake or by reducing the concentration of
impurities in the mother liquor.
This stage may be concluded with the result
that working hypothesis 1 is accepted and work-
ing hypothesis 2 should be rejected. The stud-
ies of hypothesis 1 provide information on the
minimum particle size and crystal modification
required to achieve the desired flowability.
Figure 5. Laboratory cold plate (melt conditioning)
In some cases a product can be defined so

2.3. Third Stage: Development of effectively by means of material-specific char-
Processing Strategy acteristics, that possible solutions in terms of
equipment can be represented in the form of de-
The result reached in the previous stage is that cision trees. Figure 4 illustrates this, in a sim-
the relationship between the properties and the plified manner, for the example of melt condi-
state of dispersion of the end product has been tioning. The implementation options, in terms of
determined. At this stage it is then necessary to equipment, depend to a great extent on the solid-
establish which process steps and process pa- ification behavior of the melt. This behavior can
rameters will lead to the desired state of dis- be described physically by the crystallization of
persion. The experimental testing of the work- the melt, involving the individual processes of
ing hypotheses will have provided some rele- nucleation and growth, which depend on a num-
vant partial data, since some initial experience ber of parameters. The effort involved in de-
and experimental values for production prop- scribing these individual processes would be ex-
erties will have been gathered in the process cessive for the purpose of equipment selection.
of preparing the laboratory samples. Additional A simple laboratory apparatus for obtaining the
measurements of material-specific characteris- necessary data is shown in Figure 5. Varying the
tics, within the relevant boundary conditions, parameters melt temperature, cold plate temper-
allow the range of feasible technologies to be ature, layer thickness and seed conditions pro-
considerably reduced. Consequently, only a few vides information on the cooling times with the
variants remain which require more thorough corresponding layer thicknesses, whether nucle-
Figure 6. Product from solution
ation is inhibited (i.e., seeding is required), and • Temperature/time stability

on the adhesion behavior of the layer. The deci- • Sorption isotherm
sions required on the tree in Figure 4 can there- Safety
fore be made. • Flash point
The selection of dryers is based on the re- • Dust explosiveness
quired end product properties as shown, for ex- • Minimum ignition energy
ample, in Figure 6 for a solution as the starting • Electrostatic chargeability
material. In this case the required end product
properties have a very significant impact on the
choice of process and equipment. If the stud-
ies of the dependence of end product proper-
ties on the various parameters show that only a
porous morphology and a particle size of less
than 500 µm allow the required dissolution rate
to be achieved, then an FSD (see Fig. 6) process
might be the appropriate solution.
To specify process parameters and to aid in
deciding which equipment to use if a number
of alternatives are available, one requires a large
number of material-specific characteristics:
Moist product
• Consistency
• Moisture
• Meterability
• Formability
• Sprayability
Product during drying
• Sticking behavior
• Encrustation behavior
• Reaction with drying gas
• Crystal modification conversion Figure 7. Measurement of sticking behavior
One example worth discussing is that of stick-

ing behavior. The flow properties of products
change as a result of changes in the adhesive
forces acting between them, as discussed in Sec-
tion 2.1. Particularly important for drying is the
behavior of the products as a function of mois-
ture content and temperature. This behavior can
be determined very simply with the laboratory
equipment shown in Figure 7. A sample whose
moisture content has been adjusted beforehand
is slowly heated in a test tube. Its temperature is
monitored by means of a thermometer, and the
product is agitated. Visual inspection reveals at
what point the flow behavior and the adhesion
behavior on the wall change. This information
is important for specifying temperatures [7].
Note that the overall optimum is not neces-
sarily represented by the sum of individually op-
timized process steps. This means that the entire
process chain has to be economically optimized.
This point may again seem trivial, but it can re-
quire possible procedural variations to be stud-
ied in parallel or the same process chain to be
iterated repeatedly. In extreme cases, new work-
ing hypotheses will have to be introduced even
at this stage or objectives may have to be mod-
ified, i.e., the stages described above must be
repeated.
The data obtained should contain information
on how sensitive the process is to any deviations
in the individual unit operations, with a view to Figure 8. Measurement of solubility (crystallization)
possible scale-up. The development stage is fi-
nally complete with a preliminary process flow
diagram including a measuring and control plan. The result of applying this stage to our ex-
At this stage, too, rapid and cost-effective example of improving the flow properties could
perimental techniques are required, and these be that the most promising process chain is
must be sufficiently sophisticated that the prod- crystallization – filtration – drying. The process
ucts have the same properties as industrially pro- objective of flowability should be attained if the
duced products and that the parameters mea- desired crystal modification and/or a previously
sured allow sufficiently accurate scale-up. This required particle size can be achieved during
is too costly on the pilot scale, given the long crystallization and retained during subsequent
timescale required for setting up the equipment processing. The detailed design of the crys-
and the handling of relatively large quantities of tallization operation involves choices between
product. These objectives must therefore like- batch or continuous cooling, and vacuum or
wise be addressed on a laboratory scale. The evaporation crystallization. Figure 8 shows the
fundamental research carried out over the last corresponding laboratory equipment. The cen-
decades will, on the whole, allow these objec- terpiece of the equipment is a 1-L stirred vessel
tives to be met. made of glass, which can be heated and cooled
via a double jacket. At the bottom of the ves-
sel there is a valve through which representative
product samples can be drawn off during and af-
ter a crystallization experiment. More recently,
fast in-line sensors have become available for times, heat and mass transfer, temperature, and
this purpose (see QI in Fig. 8). The particle size shear gradients. It is precisely in disperse sys-
distribution is determined by the processes oc- tems that these aspects can be particularly sig-
curring during nucleation and growth, which in nificant. If the process includes such features,
turn are effected by supersaturation and mechan- they are studied on a pilot plant scale and the
ical stresses to which the crystals are subjected. processing strategy is verified. This then means
The sensitivity of these parameters in terms of that all the information required for definitive
the result can be studied in the laboratory equip- process development will have been provided.
ment shown.
The other unit operations involved are stud-
ied in a similar manner. In the present example 3. Measurement Methods
it is very important to consider the movement
of product in and between the process steps, The procedure as described for developing
as attrition or size reduction is possible at ev- solids technology requires informative measur-
ery point, thereby potentially compromising the ing techniques. If a process is to be characterized
process objective. it is necessary to measure both product proper-
Optimization involves selecting the technol- ties and process conditions.
ogy and the process conditions of each unit so as
to ensure that the process objective of flowabil- • The product is characterized by the product
ity is likewise achieved reliably and most cost- properties and/or those dispersity variables
effectively. To do this, a sensitivity analysis is which effect them.
carried out to establish what tolerance limits • Selection and design require product-
must be observed for the operational states to specific parameters which characterize the
ensure that the set objective is indeed achieved. product behavior within the unit. These in-
A commercial assessment of various options can clude safety characteristics and toxicological
be based on the costs for energy, ancillary ma- properties.
terials, repairs, and personnel, which can be de- • To ensure that the eventual plant will operate
rived from the analysis of the process, and on reproducibly and reliably, the process condi-
methods for estimating the capital expenditure. tions must be specified, i.e., the essential pro-
Some of the costs of the process design stage cess parameters, their nominal values and
in the laboratory may be saved if the overall pro- tolerance limits have to be determined (sen-
cess or individual steps of the process can be sitivity analysis).
simulated, as is the case at present for processes
involving fluids. Simulation would then allow The development of novel processes and the
relatively complex process structures to be re- causal analysis in the event of product properties
presented by means of simple laboratory experi- deviating from the target values is more likely
ments, and the product condition to be predicted. to require and justify the comparatively costly
This would permit experiments and optimiza- measuring methods for the physical variables
tions to be carried out on a computer and conse- than would be the case for production monitor-
quently provide for more effective process de- ing, where measurements of auxiliary variables
velopment. This is one of the reasons why many or production-related properties are often suffi-
research groups are active in this field. cient.
2.4. Fourth Stage: Verification of 3.1. Measurement of Product Properties

Processing Strategy
3.1.1. Application-Related Product
The process development steps so far will not, as Properties
a rule, have addressed every aspect, e.g. the ef-
fects of impurity enrichment and the effect of re- The desired characteristics of intermediates or
cycle streams over extended production runs, the final products of a process are ultimately ob-
effects of different mixing kinetics and residence tained by measurements of the product proper-
ties. Properties summarize the effect of a num- 3.1.3. Measurement of the Dispersity
ber of variables; this applies both to application- Variables
related and production-related properties. Ex-
amples include the Jenike shear test to assess
flowability, or measurement activity to assess the The most important variables, albeit often not
efficacy of a catalyst. sufficient, for describing the disperse state are
Most of the application-related properties the particle size and the particle size distribu-
are evaluated by means of product-specific test tion. The particles in question must be assessed
methods, such as the mechanical strength of con- as they occur in the industrial process or the ap-
crete, the color strength of pigments, and the plication, i.e., the particle size distribution must
gloss resulting from matting agents. Other prop- not be altered either by sampling, preparation, or
erties cannot be represented on metric scales, measurement. For example, particles whose de-
e.g. taste or smell. In these situations, statistical position from gases is to be considered should be
methods of subjective assessment are resorted measured on an aerosol; once they are deposited,
to. agglomerates may form. Additionally prepara-
Frequently, the same quality characteristics tion or handling might well destroy agglomer-
are assessed by different test procedures, involv- ates and change the condition for deposition.
ing application-specific measuring equipment. The development of particle measurement
The dispersibility of tablets is not evaluated in techniques is characterized by progress in the
the same way as the dispersion ability of pes- fields of optics, acoustics, and electronics. For
ticides or of pigments. Such measurements are example, the principle of light scattering, known
often not particularly informative, owing to the since 1855, is utilized for measuring particle size
great variety of test equipment used or because distributions, by making full use of laser technol-
ogy, microelectronics, and fast calculations. The
they are single-point measurements, and take
familiar subjective assessment of particles and
virtually no account of actual functional rela-
collections of particles under a microscope is
tionships. In this situation test methods would be
now complemented by quantitative image anal-
desirable - especially for product development
ysis. Depending on the problem, other physi-
- which allow for more generally valid physi-
cal variables may be required for characterizing
cal insights into the mechanisms producing the
the condition of the product, for example the
product properties.
shape of the particles, the specific surface area,
the porosity or, in the case of nanoparticles, the
interfacial properties.
3.1.2. Production-Related Product Quantitative characterization of product
Properties properties and dispersity variables is an indis-
pensable tool in testing working hypotheses, in
establishing the property functions or in sensi-
Properties which are less important to the end
tivity analyses [8]. This requires not only a crit-
users but do matter to the manufacturer could
ical assessment of the measurement techniques,
lend themselves to being determined by gener-
but also of the measurement-related procedures,
ally valid measuring methods. The flowability
i.e., sampling and preparation prior to a mea-
of products, for example, can be assessed in the
surement, which at present are still essential for
Jenike shear cell, irrespective of whether it is the
most measurement methods.
feeding of pharmaceutical products to a tablet-
ting press or the storage and discharge of fertil-
izers from a silo which is being assessed.
Cross-exchanges of measuring methods 3.2. Measurement of Product-Specific
among individual sectors are most helpful and Characteristics
are among the aims set by professional bodies.
One particular advantage of measuring methods
which can be used in wider contexts is the physi- For process steps and equipment to be selected
cally meaningful information they provide. This it is necessary to characterize, for each unit, a
is an aspect worth striving for. material in terms of the most important material
properties or process-related parameters. For ex- this field. On the one hand, being a young sci-
ample, in crystallization studies, the solubility ence, it is in a state of rapid development; on
and the width of the metastable region are mea- the other hand, it can already pride itself on a
sured; for drying applications, a large number of rich fund of basic and applied research. More-
characteristics are discussed in Section 2.3. over, research and development in this field are
characterized by a lively exchange of ideas bet-
ween academic and industrial research institu-
3.3. Measurement of Process tions. Academic research is primarily devoted to
Parameters elucidating fundamental relationships, whereas
industrial research is concerned mainly with
The design and verification of a process requires gathering more information on the applicabil-
the process parameters to be measured and main- ity of the models produced in the academic sec-
tained (sensitivity analysis). With a view to re- tor. Fruitful collaboration in this manner clearly
taining them into production, the measurements is the only possible way to progress further in
at the design stage should establish what infor- solids technology. Numerous examples could be
mation must be available or should be available, presented to demonstrate the advances such col-
and how accurately, rapidly and frequently it is laboration has already achieved. However, this
measured to safeguard the process. The sensi- was considered inappropriate at this point for
tivity analyses form the basis of the measuring two reasons: firstly, given the many researchers
and control plan. While even simple pressure involved, there is the insoluble problem of mak-
or temperature measurements may present dif- ing a representative selection; secondly, the fol-
ficulties because of encrustation, the difficulty lowing specialized articles present the opportu-
with solids-loaded systems is that, as yet, few nity of applying the ideas outlined in this intro-
sensors exist which can be used to measure vis- duction to the individual areas and to the field of
cosity, throughput, or concentrations of different solids technology as a whole.
components, let alone catalytic activity.
More recently, optical sensors in particular
have provided new options for in-line process
monitoring by characterizing the state of dis- 5. References
persion and the concentrations or composition
(spectroscopy) [9]. Increasing insight into a pro- Specific References
cess additionally provides the opportunity to em- 1. Frontiers in Chemical Engineering, Research
ploy model-based measurement techniques in- Needs and Opportunities, National Research
volving easily measured auxiliary variables so Council, Washington, 1988.
as to control the process. 2. Technologien des 21. Jahrhunderts, press
Measurement technology developments in release 25/92, Bundesministerium für
the field of ultrasonic absorption and ultrasonic Forschung und Technologie, 1992.
spectrometry are likely, in the near future, to 3. B. J. Enmie, J. Green, R. Davies, Chem. Eng.
yield even deeper insights into what happens Prog. 90 (1994) 31 – 43.
in the course of a process. The advantage of 4. H. Rumpf, Staub-Reinheit-Luft 27 (1967)
both optical sensors and ultrasonic sensors is 3 – 13.
that even disperse systems can be character- 5. K. Borho, R. Polke, K. Wintermantel, H.
ized in the original state, several variables being Schubert, K. Sommer Chem.-Ing.-Tech. 62
recorded simultaneously, some of which may in- (1991) 907 – 915; 4th World Congr. of Chem.
teract with one another. Eng. Karlsruhe, Germany (1991) 93 – 98.
6. H. Rumpf: Mechanische Verfahrenstechnik,
Carl Hanser Verlag, München 1975.
4. Research and Development 7. W. Bühler, W. Liedy, Chem. Eng. Process 26
(1989) 27 – 34.
Solids technology is a relatively new industrial 8. J. Krekel, R. Polke, Chem.-Ing.-Tech. 64
science. This is demonstrated by the fact that (1992) no. 6, 27 – 34.
most of the solids process engineers active to- 9. R. Polke, 5th World Congr. of Chem. Eng. San
day are disciples of the “founding fathers“ in Diego USA (1996) VI, 551 – 556.
Reactor Types and Their Industrial Applications 953
Reactor Types and Their Industrial Applications

Klaus-Dieter Henkel, Buna AG, Schkopau, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . . 953 3.5.1. Reactors for Noncatalytic Gas – Solid

2. Basic Types of Reactors . . . . . . . . 954 Reactions . . . . . . . . . . . . . . . . . . 971
3. Survey of Real Reactors and Their 3.5.2. Reactors for Noncatalytic Liquid –
Uses . . . . . . . . . . . . . . . . . . . . . 955 Solid Reactions . . . . . . . . . . . . . . 973
3.1. Reactors for Gas-Phase Reactions . 956 3.5.3. Reactors for Noncatalytic Solid-Phase
3.2. Reactors for Liquid-Phase Reactions . . . . . . . . . . . . . . . . . . 973
Reactions . . . . . . . . . . . . . . . . . 956 3.6. Electrothermal Reactors . . . . . . . 973
3.3. Reactors for Gas – Liquid Reactions 962 3.7. Reactors for Electrochemical
3.4. Reactors for Solid-Catalyzed Processes . . . . . . . . . . . . . . . . . . 976
Reactions . . . . . . . . . . . . . . . . . 965
3.8. Reactors for Biochemical Processes 979
3.4.1. Reactors for Heterogeneous Gas
Catalysis . . . . . . . . . . . . . . . . . . 965 3.9. Reactors for Photochemical and
3.4.2. Reactors for Liquid-Phase and Gas – Radiochemical Processes . . . . . . . 980
Liquid Reactions over Solid Catalysts 965 3.9.1. Photochemical Reactors . . . . . . . . . 980
3.5. Reactors for Noncatalytic Reactions 3.9.2. Radiochemical Reactors . . . . . . . . 984
Involving Solids . . . . . . . . . . . . . 971 4. References . . . . . . . . . . . . . . . . . 985
1. Introduction 1) Activation by addition of heat

2) Catalytic activation
The reactor in which the chemical reaction takes 3) Activation by decomposition of an initiator
place occupies a central position in the chemi- 4) Electrochemical activation
cal process. Grouped around the reactor are the 5) Biochemical activation
process steps involving physical treatment of the
Less important options for activation are visible
material streams, such as conveyance, heat trans-
or ultraviolet light and radioactive radiation.
fer, and separation and mixing operations. The
With regard to phase relationships in the re-
reactor provides the volume necessary for the re-
action space, a number of combinations are pos-
action and holds the amount of catalyst required
sible. The reactants and reaction products can
for the reaction. The energy required to over-
be present, or be produced, in various states of
come the activation threshold of each partial re-
aggregation. Furthermore, inert diluents or heat-
action is also supplied in the reactor, and the
transfer media can be present in different phases.
proper temperature and concentration are main-
Finally, the catalyst, which is generally in the
tained.
solid or liquid phase, often has to be taken into
The most important reaction-related factors
consideration.
for the design of a reactor are
The (negative or positive) heat of the reac-
1) The activation principle selected, together tions taking place in a reactor influences the ex-
with the states of aggregation of the reactants tent and nature of provisions for heat transfer.
and the resulting number and types of phases Exothermic or endothermic reactions frequently
involved require supply or removal of large quantities of
2) The concentration and temperature depen- heat. Thermally neutral reactions involve con-
dence of the chemical reactions siderably less technical sophistication.
3) The heat of the reactions taking place The concentration and temperature depen-
dences of a chemical reaction are described by
The most important activation principles for a the reaction rate. In practice most reaction sys-
reaction mixture include tems are complex and include parallel, sequen-
954 Reactor Types and Their Industrial Applications
tial, and equilibrium reactions. To obtain the The thermally ideal operating states are the
highest possible yield of desired product under isothermal and adiabatic states, i. e., either very
these conditions, the temperature and pressure intensive heat exchange with the surroundings
must be held within certain ranges, the tempera- or no exchange at all is assumed.
ture must be controlled along the reaction path, In practical operation, the ideal states are
and a definite residence-time distribution in the achieved only approximately. Examples of typ-
reactor must be achieved. If, in addition, sub- ical nonidealities include
stances or energy have to be transferred from
one phase to another, appropriate transport con- 1) The formation of real flow patterns, such as
ditions have to be implemented. When catalysts dead zones, short-circuit flows, and channel-
are used, catalyst loss due to aging and poisoning
ing must be considered. These factors impose 2) Transport processes in the individual phases,
a complex of requirements that must be kept in such as axial backmixing
mind when designing a reactor. 3) The formation of concentration and temper-
Against the requirements established by the ature profiles as a result of transport resis-
process, the designer must balance costs of fab- tances in and between phases
rication, consumption of materials, and opera- 4) Segregation processes
tional reliability. In practice, many possibilities 5) Incomplete mixing of reactants
are often available for realizing a chemical pro-
cess, and in such cases the decision must depend
on an assessment of the overall process as well The essential advantages and disadvantages of
as commercial constraints on the plant. the three basic reactor types are discussed in
what follows.
2. Basic Types of Reactors Batch Stirred Tank

Principal Applications:
A variety of reactor designs are used in industry, 1) Liquid-phase reactions
but all of them can be assigned to certain basic 2) Liquid – solid reactions
types or combinations of these. The basic types
are as follows: Advantages:
1) Batch stirred-tank reactor 1) Quick production changeover possible; use

2) Continuous stirred-tank reactor for substances produced on a small scale
3) Tubular reactor 2) Process steps upstream or downstream of the
reaction can also be performed in the reactor
Given certain flow and thermal conditions, these 3) Better process control than in continuous op-
types are also referred to as “ideal” reactors. eration when solid or highly viscous phases
With respect to flow conditions the ideal stirred- form or are present
tank batch reactor is characterized by complete 4) Well-defined residence time
mixing on microscopic and macroscopic scales.
In the ideal tubular reactor, plug flow is assumed, Disadvantages:
i. e., no mixing occurs in axial (flow) direction,
but ideal mixing takes place in the ra-dial direc- 1) Relatively high operating costs due to long
tion. Thus, as in the batch stirred-tank reactor, downtimes and high manpower requirements
all particles experience a well-defined residence 2) Quality differences between charges because
time. In contrast, the continuous stirred-tank re- reaction conditions are only partly repro-
actor has a very broad residence-time distribu- ducible
tion. The ideal analysis is based on the assump- 3) Limited temperature control capabilities, es-
tion of a reaction system that is homogeneous pecially with highly endothermic or exother-
as regards the phase. Thus transport resistance mic reactions
between phases does not occur.
Continuous Stirred Tank Types of interconnections are series, parallel,

Principal Applications: and recycle.
1) Liquid-phase reactions
Series Connection:
2) Gas – liquid reactions
3) Gas – liquid reactions over suspended cata- 1) Multibed reactors
lysts 2) Tower reactors, reaction columns
Advantages: 3) Cascades of stirred tanks
4) Multiple-hearth reactors
1) Low operating costs, especially at high 5) Different reactor types connected in series
throughputs (e.g., stirred tank and tubular reactor)
2) Consistent product quality due to repro-
ducible process control
3) Wide range of throughput Parallel Connection: Multitubular reactors
Disadvantages: Recycle Connection: Loop reactors
1) Final conversions lower than in other basic Complicated reactor designs result, espe-
reactor types because of complete mixing cially when different reactor types are combined
(i.e., unreacted starting materials can get into in a single apparatus. At the same time, such a
the product stream) combination offers maximum adaptability to the
2) High investment costs to implement contin- requirements of a given reaction process. The
uous operation designer must, of course, examine every case
3) Changeover to other products generally individually to ensure that the results justify the
complex and time-consuming because of very high development and investment costs for
reaction-specific design such special reactors. The following survey of
real reactors includes these special types of re-
Tubular Reactor actor designs only when their utility extends be-
Principal Applications: yond a single case.
1) Homogeneous gas-phase reactions
2) Liquid-phase reactions
3) Gas- and liquid-phase reactions over solid
catalysts 3. Survey of Real Reactors and Their
4) Gas – liquid reactions Uses
Advantages:
The phase relationships in the reaction space are
1) Favorable conditions for temperature control crucial in the design of reactors for catalytic,
by heat supply or removal thermal, and polymerization processes and ac-
2) No moving mechanical parts, hence espe- cordingly form the top-level classification fea-
cially suitable for high-pressure service ture for such reactors. Since many different com-
Disadvantages: binations of phases are possible, the survey is
based only on the state of the reactants at the in-
1) Very high degree of specialization, often
let to the reactor or the beginning of the reaction
with complicated design and high investment
and the phase of the reaction site (catalyst phase,
costs
liquid phase with dissolved reactant). Reaction
2) Relatively large pressure drops
products that form additional phases and inert
Reactors are interconnected to make up for the substances of all types (except for solvents, as
drawbacks of a single reactor, especially to adapt just noted) are ignored.
reaction conditions during scale-up capacity, as Reactors used in electrothermal, electro-
well as to optimize conversion and yield. Partial chemical, biochemical, photochemical, and ra-
reactors can be combined in a single apparatus or diochemical processes are treated separately.
connected in a system of reactors; these partial Reactor types for which no industrial applica-
reactors may differ in shape and size. tion is currently known are not listed.
3.1. Reactors for Gas-Phase Reactions
Homogeneous gas-phase reactions utilized in

industry are generally characterized by large
positive or negative enthalpies of reaction and
high reaction temperatures. To obtain the desired
product spectrum, residence times must usually
be very short. The high reaction temperature can
be maintained or the requisite heat supplied by
burning part of the feed.
Tables 1 and 2 and Figures 1 and 2 summa-
rize the reactors used for such reactions as well
as their applications.
Figure 2. Reactors for endothermic gas-phase reactions

A) Burner; B) Reformer; C) Fluidized-bed reactor; D)
Moving-bed reactor; E) Reactor with fixed bed of inerts;
F) Regenerative furnaces
a) Oxygen or air; b) Hydrocarbon; c) Fuel gas; d) Prod-
uct; e) Heat-transfer medium; f) Steam; g) Flue gas; h) Air;
i) Quench; j) Reaction section; k) Regeneration section;
l) Catalyst; m) Convection zone
3.2. Reactors for Liquid-Phase

Reactions
Figure 1. Reactors for exothermic gas-phase reactions
A) Burner; B) Tubular reactor; C) Reactor with recycle; D) In general, liquid-phase reactions are exother-
Fluidized-bed reactor
a) Gaseous reaction mixture; a1 , a2 ) Gaseous feed compo-
mic. In the case of multiphase systems, inten-
nents; b) Gaseous product; c) Coolant; d) Partial stream of sive mass and heat transfer must be provided for;
product; e) Catalyst this is possible only in reactors with compulsory
mixing, such as stirred tanks. Along with a num-
Figure 3. Reactors for liquid-phase reactions

A) Tubular reactor; B) Reformer; C) Sulzer mixer – reactor; D) Reactor with external recirculation; E) Reactor with internal
recirculation (draft tube); F) Stirred tank; G) Cascade of stirred tanks; H) Column reactor; I) Multichamber tank; J) Fluidized-
bed reactor; K) Spray reactor; L) Falling-film reactor
a) Liquid reaction mixture; a1 , a2 ) Liquid feed components; b) Liquid product; c) Coolant; d) Heating agent; e) Water; f) Or-
ganic phase and water; g) Baffle; h) Organic phase; i) Partial stream of product; j) Catalyst; k) Reaction mixture from preceding
reaction stage; l) Water from preceding stage; m) Packing; n) Off-gas; o) Fuel gas for burners; p) Quench; q) Convection zone;
r) Mixing element consisting of tubes carrying heat-transfer medium; s) Mixing elements rotated 90◦
Figure 4. Special reactor designs for polymerization reactions

A) Multitubular reactor; B) Multistage multitubular reactor with interstage stirring; C) Reactor with external recycle (multi-
tubular or screw-conveyor type); D) Reactor with external recycle (annular); E) Reactor with internal recirculation; F) Sulzer
loop reactor (see Fig. 3C for detail of a single reactor); G) Loop reactor; H) Tower reactor; I) Ring-and-disk reactor; J) Extruder
reactor; K) Powder-bed reactor; L) Mixing head; M) Belt reactor with mixing head; N) Spinning jet with coagulating bath
a) Polymerization mixture; a1 , a2 ) Feed components; b) Polymerization product; c) Coolant; d) Static mixer; e) Pump; f) Screw-
conveyor design for viscous media; g) Sulzer mixer – reactor; h) Sulzer mixer – reactors in plug-flow configuration; i) Air;
j) Plunger; k) Nozzle; l) Mixing head; m) Belt reactor; n) Spinning bath; o) Packed bed of polymer granules
Table 1. Reactors for exothermic gas-phase reactions
Reactor type Features Examples of applications
Burner for high reaction rates combustion of H2 S to SO2 (Claus vessel)

very high reaction temperatures carbon black production (furnace, gas, thermal carbon
black processes)
explosion limits must be taken into consideration chlorine – hydrogen reaction
chlorination of methane
nitration of propane
Tubular reactor well-defined residence time (tubes up to 1000 m long) chlorination
of methane
intermediate injection possible of propene to allyl chloride
pressure drops of butadiene to dichlorobutane
good temperature control capability chlorolysis of chlorinated hydrocarbons
Reactor with recycle suitable for low reaction rates chlorination of methane
good mixing
cooling inside or outside reactor
Fluidized-bed reactor nearly isothermal conditions because heat transport is chlorination
very efficient
of methane
intensive mixing of 1,2-dichloroethane to tri- and perchloroethylene
chlorolysis of chlorinated hydrocarbons
Table 2. Reactors for endothermic gas-phase reactions
Burner very high reaction temperatures attainable by partial Sachsse – Bartholomé process for acetylene production
combustion of reactants
short residence times high-pressure gasification for synthesis gas production
(Texaco, Shell)
Reformer high reaction temperatures attainable mainly by steam cracking of naphtha and other hydrocarbons to
radiation ethylene
well-defined residence times vinyl chloride production by cleavage of dichloroethane
pyrolysis
of acetic acid to ketene
of 2-methyl-2-pentene
to isoprene (in presence of HBr)
of chlorodifluoromethane
to tetrafluoroethylene
Fluidized-bed reactor heat supplied along with solids Lurgi Sandcracker
Moving-bed reactor heat supplied along with solids Langer – Mond process for production of ultrapure
nickel
continuous removal of solid products
Reactor with fixed bed of fixed bed ensures heat storage and intensive mixing Kureha process for acetylene and ethylene production
inerts
production of CS2 from CH4 and sulfur vapor
Regenerative furnaces battery operation gas generation from heavy crudes
no dilution by heat-transfer medium
ber of other reaction types, nearly all industrially ethylene, linear low-density polyethylene, and
important polymerization reactions take place polypropylene).
in the liquid phase. For the sake of complete- The essential feature of polymerization re-
ness,a few important exceptions among poly- actions is that, in contrast to other liquid-phase
merization reactions are included in this sec- reactions, the viscosity increases rapidly during
tion, even though they do not fall under liquid- the course of reaction and causes difficulties in
phase reactions according to the classification heat and mass transport. In industry, this prob-
principle stated above. These are, in particular, lem is countered by (1) the use of special stirring
“gas-phase polymerization” reactions, some of and kneading devices; (2) running the process in
which take place over solid complex catalysts several stages; (3) raising the temperature as the
of the Ziegler – Natta type (high-density poly- conversion increases; and (4) carrying out poly-
merization in thin films.
Table 3. Reactors for liquid-phase reactions (one or more phases present)
Tubular reactor well-defined residence time polymerization reactions

good temperature control capabilities bulk polymerization to LDPE ∗
polycondensation to PA 66 ∗ (2nd stage)
hydrolysis reactions
of ethylene oxide and propylene oxide to glycols
of chlorobenzene to phenol and chlorotoluene to
cresol
of allyl chloride
production of ethyl acetate from acetaldehyde
production of isopropanolamine
dehydrochlorination of 1,1,2-trichloroethane to
vinylidene chloride
Reformer high reaction temperature visbreaking
well-defined residence time delayed coking
pyrolytic dehydrochlorination of tetrachloroethane to
trichloroethylene
high-pressure gasification of heavy crudes
Multitubular reactor large heat-transfer area bulk polymerization to PS ∗, HIPS ∗, and SAN ∗
multistage design with stirring elements between
stages is possible
Sulzer mixer – reactor mixing elements consist of tubes carrying bulk polymerization to PS ∗ and polyacrylates
(plug-flow configuration) heat-transfer medium
large heat-transfer area temperature-controlled starch conversion
suitable for processes in which viscosity increases
intensive radial mixing with little axial backmixing
very narrow residence-time distribution
Reactor with external good mixing and heat-removal conditions cleavage of cumene hydroperoxide to phenol and
recirculation acetone (2nd stage of Hock process)
no moving parts Beckmann rearrangement of cyclohexanone oxime to
caprolactam
suitable for low reaction rates production of hydroxylamine sulfate (Raschig process)
heat exchanger can be placed outside reactor production of phosphoric acid (wet process)
saponification of allyl chloride
bulk polymerization to PS ∗, HIPS ∗, SAN ∗, and
PMMA ∗
Reactor with internal very intensive mixing production of melamine from molten urea
recirculation (high-pressure process)
production of aromatic nitro compounds
production of adipic acid from cyclohexanol and nitric
acid
Bulk polymerization to PS ∗, HIPS ∗, and SAN ∗
Loop reactor for slurry polymerization polymerization reactions
suspension is circulated at high velocity to prevent slurry polymerization to PP ∗
buildup
production of HDPE ∗ and LLDPE ∗
Powder-bed reactor liquid monomers supported on already polymerization reactions
polymerized granules
polymerization to HDPE ∗ and PP ∗
block copolymerization to PE – PP ∗
for high conversion
evaporating and condensing monomer acts as
heat-transfer agent (boiling, cooling)
vertical and horizontal designs
precipitation polymerization to PAN ∗, IIR ∗, PE ∗,
PP ∗
Table 3. Continued

Stirred tank, batch or limited heat-transport capability polymerization reactions
semicontinuous
mechanical stirring means bulk polymerization to PS ∗, PMMA ∗,
suitable for slow reactions HIPS ∗, ABS ∗ (1st stage of each process)
polycondensation to PA 66 ∗
solution polymerization to PVAC ∗, PAN ∗, PE ∗,
PP ∗, EPM ∗, EPDM ∗, SB ∗, SB – S ∗, EO – PO ∗
polycondensation to UF ∗, MF ∗, PF ∗ resins
precipitation polymerization to PVC ∗, PAN ∗, PE ∗,
PP ∗, EPM ∗, EPDM ∗ suspension polymerization to
PVC ∗, EPS ∗, PMMA ∗, PVAC ∗, and ion-exchange
resins based on PS ∗, HIPS ∗, ABS ∗ (2nd stage)
emulsion polymerization to numerous polymer
dispersions
production of aromatic nitro compounds
sulfonation of benzene
esterification of PA ∗ and alcohol to diphthalates
many other syntheses of dyes and pharmaceuticals
Stirred tank, continuous suitable for fast reactions with large negative or polymerization reactions bulk and solution
positive heat of reaction approximately complete polymerization to PS ∗, PMMA ∗, HIPS ∗, and ABS ∗
mixing conversion generally not complete (1st stage in each case); copolymers with nonazeotropic
mechanical stirring means monomer ratios
precipitation polymerization to PAN ∗, IIR ∗, PE ∗,
PP ∗
emulsion polymerization to PVC ∗ and SAN ∗
esterification
of acrylic acid with alcohol
of acetic acid with ethanol
dehydration
of 1,4-butanediol to tetrahydrofuran
of ethanol to diethyl ether
saponification
of benzyl chloride
of fatty acids
dehydrochlorination
of 3,4-dichloro-1-butene to chloroprene
of 1,1,2-trichloroethane to vinylidene chloride
cyclization of glycols to 1,4-dioxane
nitration of aliphatic hydrocarbons
alkylation of isobutane with n-butenes
production of melamine from molten urea (Montecatini)
oxidation
of cyclohexanone/ol with HNO3 to adipic acid
of mono- to dicarboxylic acids
of allyl alcohol with H2 O2 to glycerol
Cascade of stirred tanks suitable for slow reactions adaptable to needed polymerization reactions transesterification of DMT ∗ to
reaction conditions stage by stage residence-time DGT ∗ polycondensation to PETP ∗ and PBT ∗ solution
distribution close to that of tubular reactor polymerization to BR ∗, IR ∗, UP ∗, UF ∗, MF ∗, PF ∗
resins
solution or precipitation polymerization to PE ∗, PP ∗,
EPM ∗, EPDM ∗
emulsion polymerization to SBR ∗, CR ∗, NBR ∗
production of hydroxylamine sulfate (Raschig process)
production of cyclohexanone oxime from cyclohexanol
and hydroxylammonium sulfate
nitration of aromatic hydrocarbons
decomposition of ammonium carbamate to urea
production of plasticizers from phthalic anhydride and
alcohol
production of MDA ∗ in conjunction with downstream
tubular reactor
production of methacrylamide from acetocyanohydrin
production of MDI ∗ from MDA ∗ and TDI ∗ from
TDA ∗

Reaction column reaction and separation in a single apparatus aldol condensation of n-butyraldehyde to 2-ethylhexenal
equilibrium can be modified by removing one or saponification
more components from reaction space
of chloropropanol with milk of lime
of fatty acids
esterification
of acetic acid with butanol
of phthalic anhydride with alcohols
decomposition
of amalgam
of ammonium carbamate to urea and water
Multichamber tank virtually identical to cascade of stirred tanks polymerization to LDPE ∗ (ICI)
requires little space
chamber-by-chamber feed injection possible alkylation of isoparaffins with olefins (Kellogg)
Tower reactor for continuous processes bulk and solution polymerization of PS ∗, HIPS ∗,
ABS ∗, SAN ∗, PA 6 ∗
section-by-section temperature control possible
little backmixing at high viscosity
also in cascade or with upstream stirred tank
Ring-and-disk reactor narrow residence-time distribution final stage in production of PETP ∗ and PBT ∗
Extruder for highly viscous media polymerization reactions
production of POM ∗ from trioxane
final stage in production of PA 66 ∗
Fluidized-bed reactor very good heat- and mass-transport conditions polymerization to HDPE ∗, LLDPE ∗, PP ∗
fluid coking of heavy residual oils (Exxon)
melamine production from molten urea
Mixing head with injection special design for bringing several liquid reactants production of PUR ∗
mold together
Belt reactor with mixing head for fabrication of sheets and films production of PIB ∗, PMMA ∗, PUR ∗, PVAL ∗
Spinning jet (with coagulating for production of strands viscose spinning
bath)
Spray reactor direct heating in hot stream of gas thermal H2 SO4 cleavage
production of MgO from MgCl2 (spray calci-
nation)
Falling-film reactor gentle temperature control due to large sulfation of fatty alcohols
heat-transfer area
diazotization of aromatic amines
diazo coupling
∗ The following abbreviations are used: ABS = acrylonitrile – butadiene – styrene copolymer; BR = butadiene rubber; CR = chloroprene
rubber; DGT = diglycyl terephthalate; DMT = dimethyl terephthalate; EO – PO = ethylene oxide –propylene oxide block copolymer;
EPDM = ethylene – (propene – diene) copolymer; EPM = ethylene – propene copolymer; EPS = expandable polystyrene;
HDPE = high-density polyethylene; HIPS = high-impact polystyrene; IIR = isobutylene – isoprene rubber (butyl rubber); IR = isoprene
rubber (synthetic); LDPE = low-density polyethylene; LLDPE = linear low-density polyethylene; MA = maleic anhydride;
MDA = 4,4 -diaminodiphenyl methane; MDI = methylene diphenylene isocyanate; MF = melamine – formaldehyde;
NBR = butadiene – acrylonitrile copolymer (nitrile rubber); PA = polyamide; PAN = polyacrylonitrile; PBT = poly(butylene terephthalate);
PE = polyethylene; PE – PP = polyethylene – polypropylene copolymer; PETP = poly(ethylene terephthalate);
PF = phenol – formaldehyde; PIB = polyisobutylene; PMMA = poly(methyl methacrylate); PO = poly(propylene oxide);
POM = polyoxymethylene; PP = polypropylene; PS = polystyrene; PUR = polyurethane; PVAC = poly(vinyl acetate); PVAL = poly(vinyl
alcohol); PVC = poly(vinyl chloride); SAN = styrene – acrylonitrile copolymer; SBR = styrene – butadiene rubber;
SB = styrene –butadiene block copolymer; SB – S = styrene – butadiene – styrene block copolymer; TDA = toluene diamine; TDI = toluene
diisocyanate; UF = urea – formaldehyde; UP = unsaturated polyester.
Table 3, Figures 3 and 4 summarize the types prerequisite for an efficient reaction is rapid
of reactors used in industry for liquid-phase re- mass transport between gas and liquid. Impor-
actions. Figure 4 shows special reactor designs tant criteria for assessment include
for polymerization reactions.
1) The interfacial area
2) The mass or volume ratio of gas to liquid
3.3. Reactors for Gas – Liquid Reactions 3) The energy required to mix the phases
Gas – liquid reactions include many industrially Other important factors are temperature control,
important processes, such as oxidation, alkyl- heat removal, and residence time (especially that
ation, chlorination, and flue-gas scrubbing. The of the liquid phase).
Reactor design is dictated largely by the way 3) Reactors with continuous gas phase and liq-
in which the interface is generated. The follow- uid dispersing devices (spray reactors, liq-
ing methods are possible: uid-ring pumps)
4) Thin-film reactors
1) Reactors with continuous liquid-phase and Figure 5 illustrates reactor types for gas – liquid
fixed gas distribution devices [bubble reactions. Important applications are listed in Ta-
columns, packed and tray reactors] ble 4.
2) Reactors with mechanical gas dispersion
(sparged stirred tanks)
Table 4. Reactors for gas – liquid reactions

Table 4. Continued
3.4. Reactors for Solid-Catalyzed and Figure 7 present reactor systems of this type
Reactions along with applications.
If the reaction process imposes special re-
Heterogeneous catalytic processes play a major quirements on temperature control, heat-trans-
role in chemical technology, because many key fer surfaces must be located throughout the re-
products and intermediates can be manufactured actor volume. The best-known design for such
in this way. Fluid reactants react in the presence a reactor is the multitubular reactor, which is
of a solid catalyst, the mechanism as a whole frequently used in the chemical industry. The
consisting of the reaction proper and a series of drawbacks relative to other fixed-bed reactors
upstream and downstream transport steps. include the much more complicated design and
the limitation on throughput due to the smaller
cross-sectional area available for flow.
3.4.1. Reactors for Heterogeneous Gas Temperature control is achieved by the use
Catalysis of gaseous and liquid heat-transfer media. One
highly effective approach is the use of boil-
Reactors with a fixed catalyst bed are distin- ing liquids (e.g., pressurized-water and evapo-
guished from those with moving catalyst. ratively cooled reactors). A special case is the
autothermal process regime, in which the reac-
tion mixture itself is used as a temperature con-
Fixed-Bed Reactors. The characteristic fea-
trol medium before it flows through the catalyst
tures of a reactor with fixed catalyst are the
bed. Fixed-bed reactors with continuous heat ex-
pressure drop of the flowing gas in the cata-
change are described in Table 7 and Figure 8,
lyst bed and the danger of unstable operation
along with applications.
points, especially with strongly exothermic re-
actions, when flow through the catalyst bed be-
Moving-Bed and Fluidized-Bed Reactors.
comes nonuniform. Fixed-bed reactors must be
In moving-bed reactors, transport of the cata-
shut down after a certain time onstream to re-
lyst is influenced by gravity and the drag force
generate or replace the catalyst.
exerted by the flowing reaction fluid on the cata-
Fixed-bed reactors can be classified by the
lyst particles. The regime in the reactor can vary
type of temperature control:
widely, depending on the ratio of these forces.
1) Reactors with no special temperature control The fol-lowing features must be taken into con-
features (adiabatic operation) sideration when using reactors of this type:
2) Reactor systems with stagewise temperature 1) The possibility of continuous catalyst regen-
control (chiefly for equilibrium reactions) eration
3) Reactors with continuous heat exchange 2) Increased mechanical loads on the catalyst
along the flow path (polytropic operation) and reactor materials
Fixed-bed reactors without equipment for tem- 3) The favorable conditions for heat and mass
perature control are marked by a particularly transport, resulting from rapid movement of
simple construction and low flow resistance, solids and small catalyst grain size
which makes them suitable for high gas through- Table 8 and Figure 9 list reactor types and appli-
puts. A summary of these reactors appears in cations.
Table 5 and Figure 6.
Reactor systems with stagewise temperature
control are used primarily for equilibrium reac- 3.4.2. Reactors for Liquid-Phase and
tions. Such a reactor consists of simple adiabatic Gas – Liquid Reactions over Solid Catalysts
reactor elements connected in series and takes
the form of several units or a system housed in Fixed-bed reactors (trickle-flow reactors and
a common reactor shell. Temperature control is packed bubble columns) are used for liquid-
accomplished by heat transfer between reactor phase reactions, as well as gas – liquid reactions
stages or by the injection of tempered gas or va- over solid catalysts. The presence of a liquid
por streams at points along the flow path. Table 6 phase, however, leads to much greater drag and
Figure 5. Reactors for gas – liquid reactions

A) Tubular reactor with injector; B) Bubble column; C) Liquid-ring pump; D) Sparged stirred tank; E) Buss loop reactor; F)
Sulzer mixer – reactor in loop configuration; G) Reaction column; H) Spray reactor; I) Falling-film reactor; J) Rotary kiln; K)
Cascade of stirred tanks
a) Liquid feed component; b) Gaseous feed component; c) Liquid product; d) Off-gas; e) Packing; f) Heating agent or coolant;
g) Drive unit; h) Catalyst; i) Reaction mixer with mixing nozzle; j) Pump; k) Heat exchanger; l) Gas separator; m) Sulzer
mixer – reactor (see Fig. 3C for detail of a single reactor); n) Static mixer
Figure 7. Fixed-bed catalytic reactors for gas-phase reac-

Figure 6. Fixed-bed catalytic reactors for gas-phase reactions with stagewise temperature control
tions with no special provisions for temperature control A) Cascade of simple fixed-bed reactors; B) Multibed re-
A) Simple fixed-bed reactor; B) Fixed-bed reactor with com- actor with cold-gas or steam injection; C) Multibed reactor
bustion zone; C) Radial-flow reactor; D) Shallow-bed reac- with intercooling (internal); D) Multibed reactor with inter-
tor; E) Regenerative furnace cooling (external)
a) Gaseous reaction mixture; b) Gaseous product; c) Cata- a) Gaseous reaction mixture; b) Gaseous product; c) Cata-
lyst; d) Air; e) Hydrocarbon; f) Flue gas; g) Reaction section; lyst; d) Heating agent; e) Cold gas; f) Coolant
h) Regeneration section; i) Condensate; j) Steam; k) Steam
generator; l) Burner; m) Inert guard bed
Table 5. Fixed-bed catalytic reactors for gas-phase reactions with no special provisions for temperature control
Simple fixed-bed very simple design reforming (Platforming, Rheniforming, etc.)

reactor not suitable for reactions with large hydrotreating
(axial flow) positive or negative heat of reaction CO converting
and high temperature sensitivity amination of methanol to methylamines
desulfurization and methanation in synthesis-gas
path upstream of primary reformer
hydrogenation of nitrobenzene to aniline (Allied, Bayer)
production of vinyl propionates from acetylene and
propionic acid
isomerization of n-alkanes
dehydrogenation of ethylbenzene to styrene
disproportionation of toluene to benzene and xylene
Fixed-bed reactor with direct heating by combustion methane cleavage in secondary reformer
combustion zone of part of hydrocarbon feed
Radial-flow reactor much lower pressure drop than ammonia synthesis (Topsoe, Kellogg)
axial-flow reactor dehydrogenation of ethylbenzene to styrene
multistage configuration possible (Dow)
enhanced backmixing due to small reforming
thickness of bed
uniformity of flow requires exact sizing
of distributing and collecting ducts
Shallow-bed reactor used for high reaction rates and unstable oxidation of ammonia to NOx
products oxidative dehydrogenation of methanol to formaldehyde
very short residence time
catalyst can also be in gauze form production of hydrocyanic acid from ammonia, methane,
and air (Andrussow process)
suitable for autothermal operation
Regenerative furnace suitable when catalyst ages rapidly and can be dehydrogenation of butane to butadiene (Houdry
regenerated process)
by burning off
reaction heat can be supplied by catalyst SO2 reduction with methane (Andrussow process)
regeneration
battery operation
Table 6. Fixed-bed catalytic reactors for gas-phase reactions with stagewise temperature control
Cascade of fixed-bed reactors large pressure and temperature differences are reforming of heavy gasoline
possible
hydrocracking
conversion of H2 S and SO2 to elemental sulfur (Claus
process)
isomerization of five-to-six-ring naphthenes
Multibed reactor with used for exothermic equilibrium reactions ammonia synthesis
cold-gas injection
injection of reaction mixture leads to lower methanol synthesis
conversion and thus increased number hydrocracking
of stages hydrogenation of benzene
injection of water lowers concentration at constant desulfurization of vacuum gas oil
conversion
adaptation of bed depth to progress of reaction
Multibed reactor with used for exothermic equilibrium reactions ammonia synthesis (ÖSW, Fauser, Montecatini)
interstage cooling
internal or external heat exchangers SO2 oxidation (with interstage adsorption)
no dilution effects hydrodealkylation of alkyl aromatics
adaptation of bed depth to progress of reaction
Multibed reactor with heat used for endothermic equilibrium reactions dehydrogenation of ethylbenzene to styrene (Dow)
supply
interstage heating or interstage injection of
superheated steam
Table 7. Fixed-bed catalytic reactors for gas-phase reactions with continuous temperature control
friction forces on the catalyst. If the reaction in- a danger, especially with exothermic reactions.
volves both gas and liquid phases, maintenance Fixed-bed reactors are well suited to high-pres-
of uniform flow conditions through the catalyst sure processes by virtue of their simple design.
bed and intensive mixing of the phases can be A second important group includes suspen-
difficult. The crucial factor for the efficiency of sion reactors, in which very fine catalyst par-
catalytic processes is the wetting of the catalyst ticles are distributed throughout the volume of
by the liquid. Since reactors of this type are usu- the liquid (stirred tanks and bubble columns
ally operated adiabatically, local overheating is with suspended catalyst). Because transport re-
Next Page
Figure 8. Fixed-bed catalytic reactors for gas-phase reac- Figure 9. Moving-bed catalytic reactors for gas-phase reac-
tions with continuous temperature control tions
A) Multitubular reactor; B) Tubular reformer; C) Fixed-bed A) Moving-bed reactor; B) Fluidized-bed reactor; C)
reactor with heating or cooling elements Entrained-flow reactor
a) Gaseous reaction mixture; b) Gaseous product; c) Heating a) Reaction mixture; b) Gaseous product; c) Catalyst; d) Air;
agent or coolant; d) Catalyst; e) Cooling tubes; f) Circulat- e) Flue gas; f) Blocking steam; g) Reaction section; h) Re-
ing water; g) Steam; h) Tube sheet; i) Fuel gas for burners; generation section
j) Off-gas
sistances are reduced, these reactors offer a close of the liquid phase, which affects product distri-
approach to isothermal operating conditions and bution.
a favorable utilization of the catalyst volume. The fluidized-bed reactor differs from the
Sophisticated techniques are required to sep- suspension reactor in the use of coarser catalyst
arate the finely divided catalyst from the liquid. particles and the formation of a well-defined ag-
Equipment for this purpose can be installed in- itated catalyst bed below the liquid level.
side or outside the reactor. At the same time, Industrially important reactors for liquid-
this arrangement permits continuous catalyst re- phase and gas – liquid reactions over solid cata-
placement. All suspension reactors have the dis- lysts are listed, together with their applications,
advantage of increased backmixing, especially in Tables 9 and 10 and Figures 10 and 11.
Previous Page

Table 8. Moving-bed catalytic reactors for gas-phase reactions
Moving-bed reactor gravity transport of catalyst cracking (TCC, Houdry flow process)
reaction conditions largely similar to those in dehydrogenation of butane
fixed-bed reactor
advantageous when catalyst can be
regenerated by burning off residues
Fluidized-bed reactor catalyst agitated by gravity and resistance cracking (Kellogg, FFC, Flexicracking)
force of gas flow
almost isothermal conditions can be achieved hydrocracking
in fluidized bed
pressure drop independent of gas throughput reforming
over a wide range
form of fluidized bed can be varied as a ammoxidation
function of geometric and hydraulic
conditions
strong backmixing internals to improve mass of propene to acrylonitrile (Sohio process)
transport and heat transfer are common
catalysts must have high abrasion resistance of o-xylene to o-phthalodinitrile
production of adiponitrile from adipic acid
and ammonia
oxychlorination of ethylene to
1,2-dichloroethane (Goodrich)
production of melamine from urea (BASF)
hydrogenation
of nitrobenzene to aniline (BASF,
Cyanamid)
of ethylene
oxidation
of o-xylene or naphthalene to phthalic
anhyride
of butane to MA∗ (Du Pont)
of SO2 to SO3
of ethylene to ethylene oxide
of NH3 to NO
of HCl to chlorine
dehyrogenation
of isopropanol
of n-butane to n-butene
production of chloromethylsilanes from
chloromethane (catalytic gas – solid reaction)
production of vinyl chloride (Cloe process)
chlorination of methane and ethylene
production of butadiene from ethanol
isomerization of n-butane
production of isoprene
postchlorination of PVC∗
combustion
Entrained-flow reactor uses very fine-grained catalyst Fischer – Tropsch process (Synthol process)
whole quantity of catalyst circulates
continuously between reaction section and
tempering or regeneration unit
∗ For abbreviations, see footnote to Table 3
3.5. Reactors for Noncatalytic Reactions 3.5.1. Reactors for Noncatalytic Gas – Solid
Involving Solids Reactions
A variety of specialized reactors are available

for noncatalytic reactions involving solids. The
discussion that follows deals only with the in- In general, noncatalytic gas – solid reactions are
dustrially important types. characterized by low overall reaction rates and
Table 9. Fixed-bed catalytic reactors for liquid-phase and gas – liquid reactions
Trickle-flow reactor can operate in cocurrent or countercurrent desulfurization and refining of petroleum products
temperature control by intermediate injection or hydrocracking
recirculation
danger of uneven liquid distribution and incomplete production of butynediol from acetylene and
wetting of catalyst formaldehyde
narrow residence-time distribution direct hydration of propene to 2-propanol (Texaco)
hydrogenation
of organic intermediates (butynediol, adiponitrile,
ethylhexenal)
of aldehydes, esters, and carboxylic acids to
alcohols
of natural fats to fatty acids
of residues (low-temperature hydrogenation of tars)
posthydrogenation
Packed bubble column danger of flooding limit throughput capacity amination of alcohols
catalyst subject to greater mechanical stress (retention cobaltizer and decobaltizer in oxo synthesis
necessary)
high liquid proportion promotes heat removal disproportionation of toluene to benzene and xylene
large amount of backmixing in liquid phase
Table 10. Suspended-bed and fluidized-bed reactors for liquid-phase and gas – liquid reactions over solid catalysts
Bubble column with simple design hydrogenation

suspended catalyst small pressure drop of CO (Fischer – Tropsch synthesis)
danger of undesired liquid-phase reactions of tars and coals (bottom phase)
inhomogeneous catalyst distribution must of benzene to cyclohexane
be prevented hydrodesulfurization
suitable if product drops out as solid
Reactor with external heat-exchange and mixing devices in external loop hydrogenation of organic intermediates (nitrobenzenes,
recirculation nitriles, nitronaphthalenes, etc.)
for continuous and batch operation
catalyst separation outside reactor
Sparged stirred tank with can also be operated in semicontinuous and batch hydrogenation of organic intermediates (nitro
suspended catalyst modes compounds, aromatics, butynediol)
ensures intensive mixing of all phases fat hydrogenation
increased cost for sealing and maintaining stirrer catalytic refining
drive
Cascade of sparged stirred higher final conversions than in single stirred tank hydrogenation of NO to hydroxylamine
tanks with suspended catalyst
suitable for slow reaction rates continuous hydrogenation of fats
adaptable to intermediate injection and other hydrolysis of fats to fatty acids and glycerol production
interconnections of toluenediamine from dinitrotoluene
Fluidized-bed reactor small pressure drop catalyst must have very high hydrocracking and desulfurization of heavy petroleum
mechanical strength fractions and still residues (H-Oil process; three-phase
fluidized bed)
high process temperatures; in addition, the struc- 1) Reactors with gravity transport of solids
ture and geometry of the solid can change during 2) Reactors with mechanical transport of solids
the reaction. 3) Reactors with pneumatic transport of solids
Reactors for this service can essentially be
These three groups differ widely with respect
grouped into those for semicontinuous opera-
to residence time, conditions of mass and heat
tion, that is, with no solids transport (vertical
transport between gas and solid phases, and
shaft kilns and rotary drums), and those for con-
heat-input capabilities. The first group includes
tinuous operation, that is, with continuous solids
moving-bed reactors. Since the gas has to flow
transport. The second type, in turn, can be di-
through the bed of solids, mass and heat trans-
vided into
port between the phases is relatively good. Tem-
perature control can be effected by simultane- Solids transport by the gas stream is possible
ously carrying out exothermic and endothermic only with small particle sizes and the narrow-
reactions in the same reactor. est possible grain-size distribution. This group
Reactors with mechanical transport of solids includes fluidized-bed and entrained-flow reac-
include rotary kilns and multiple-hearth fur- tors, dust roasters, and suspension furnaces. Be-
naces. Transport of gas and solid phases through cause of the favorable conditions for heat and
the reactor largely occurs separately. Intensive mass transport, these reactors offer shorter res-
heat and mass transfer occurs only at the surface idence times and thus higher throughputs than
of the bed of solids. Complete involvement of the other types. The installation of heat-transfer sur-
solid phase in the reaction process depends on faces, supplementary solid heat-transfer media,
continuous, intensive mixing of the solids. Heat and direct heating is possible.
is often supplied directly by burners. More than Industrially important reactor types for non-
one unit can be in operation in a single appara- catalytic gas – solid reactions are listed in Ta-
tus (e.g., drying, heating, cooling, and various ble 11 and Figure 12 along with applications.
reaction steps).
3.5.2. Reactors for Noncatalytic

Liquid – Solid Reactions
Reactors used for noncatalytic liquid – solid re-

actions must be designed for the transport and
mixing of phases, sometimes at high solids con-
tents. Batch and semicontinuous designs are
therefore dominant. Table 12 and Figure 13
present a survey of important reactor types for
noncatalytic liquid – solid reactions and sample
applications.
3.5.3. Reactors for Noncatalytic Solid-Phase

Reactions
Reactors used for noncatalytic solid-phase reac-

tions are similar to those used for noncatalytic
gas – solid reactions. Long residence times and
high reaction temperatures are necessary, espe-
cially for reactions between different solids, be-
cause of the low transport rates therein. Heat
can be supplied by indirect or direct heating or
by burning solid fuels.
Inert gases are employed for heat transport
and agitation of the solids. Important applica-
tions are listed in Table 13.
Figure 10. Fixed-bed catalytic reactors for liquid-phase and

gas – liquid reactions
3.6. Electrothermal Reactors
A) Trickle-flow reactor (countercurrent); B) Trickle-flow re-
actor (cocurrent); C) Packed bubble column A variety of electrical heating schemes are used
a) Liquid reactants; b) Gaseous reactants; c) Liquid product; for some important noncatalytic reactions bet-
d) Off-gas; e) Catalyst; f) Rupture disk
ween gases and solids when very high reaction
Table 11. Reactors for noncatalytic gas – solid reactions
temperatures and large quantities of heat are re- electric heating. Options here include arc, resis-
quired. In the simplest case, heating elements tance, and induction heating.
(rods, strips, etc.) are used for this purpose. A The very high temperatures produced by the
much more efficient method, however, is direct, arc cause ionization in gases and thus activate
Table 12. Reactors for noncatalytic liquid – solid reactions
Stirred tank batch or semicontinuous operation predominant production of alkali cellulose and nitrocellulose
solids content limited by power of stirring apparatus reduction of nitrobenzene with metals to aniline or
hydrazobenzene
bauxite digestion
production of salicylic acid from dry sodium phenolate
(Kolbe – Schmitt process)
hydrolysis of calcium cyanamide to cyanamide
production of BF3 from B2 O3 , CaF2 , and H2 SO4
production of alkylaluminums from aluminum, olefin,
and hydrogen
production of tetraethyllead
Cascade of stirred tanks for low reaction rates and high final conversions apatite digestion
Tank with liquid recirculation semicontinuous operation with solids fixed in tank cellulose digestion
and liquid recirculating
production of ammonium sulfate from ammonium
carbonate and gypsum
Rotary drum for batch operation, high solids content production of cellulose acetate and cellulose ethers
production of AlF3 by wet process
Fluidized-bed reactor Semicontinuous operation water treatment
intensive liquid circulation
Steeping press combination of reaction and liquid separation production of cellulose ether
batch operation
Kneader used for highly viscous media production of nitrocellulose, cellulose ether, and
cellulose acetate
for batch operation production of celluloid from nitrocellulose
production of superphosphate
Screw-conveyor reactor used for highly viscous media digestion of rutile or ilmenite with H2 SO4
batch operation
Multiple-hearth reactor continuous operation production of acetylene from carbide (dry gas generator)
long solids residence time
Rotary kiln direct heating for high reaction temperatures digestion of fluorspar or phosphate with H2 SO4 reducing
decomposition of H2 SO4 in presence of carbon
Table 13. Reactors for noncatalytic solid-phase reactions
Shaft reactor see Table 11 metallurgical processes, e.g.,

powder boriding of iron-based materials
direct reduction of iron ores with carbon (Kinglor – Metor
process)
Multiple-hearth reactor see Table 11 calcination
Rotary kiln see Table 11 cement production
burning of lime, dolomite, gypsum, and magnesite
calcination
thermal decomposition of FeSO4 and BaCO3
reduction of barite with carbon to BaS
reduction of ores with carbon (e.g., to ZnO)
Fluidized-bed reactor see Table 11 burning of lime (multistage)
the reactants; this feature is utilized in plasma no melting of the solid charge occurs. All elec-
processes for high-temperature pyrolysis. trothermal processes are characterized by very
Equipment used for solid reactions includes high equipment cost and high electric power
arc and resistance-heated reduction furnaces and consumption. The prerequisite for their econom-
the Acheson furnace. The Acheson furnace is ical operation is a low unit price for energy.
a resistance-heated device for pure solid – solid This group of reactors and their applications
reactions; that is, in contrast to other processes, are summarized in Table 14 and Figure 14.
Figure 11. Suspended-bed and fluidized-bed reactors for liquid-phase and gas – liquid reactions over solid catalysts
A) Bubble column with suspended catalyst; B) Fluidized-bed reactor; C) Buss loop reactor; D) Sparged stirred tank with
suspended catalyst; E) Cascade of sparged stirred tanks with suspended catalyst
a) Liquid feed components; b) Gaseous feed components; c) Liquid product; d) Catalyst; e) Off-gas; f) Heating agent or
coolant; g) Heat exchanger; h) Pump; i) Reaction mixer with mixing nozzle
3.7. Reactors for Electrochemical 2) Low reaction temperature (except for fused-
Processes salt electrolysis)
3) Easy control of reaction rate through varia-
In electrochemical reactions, electrons are sup- tion of electrode voltage
plied to a reactant in the electrolyte or re-moved They have the following disadvantages:
from it with the aid of an electric current. A min- 1) High energy losses in the system
imum voltage called the decomposition voltage 2) Large space requirements
must be applied to the electrodes for this pur- 3) High investment costs
pose. In addition to the electrochemical reac-
tions occurring on the electrode surface, trans- For these reasons, electrochemical processes are
port processes and chemical reactions in the used only when no available thermal or catalytic
electrolyte bath are important. process can accomplish the same purpose, which
Electrochemical processes have the follow- is especially true in the production of chlorine,
ing advantages: aluminum, and copper. A survey of important
applications for electrolytic processes is given
1) High product purity (no secondary reactions) in the following:
Figure 12. Reactors for noncatalytic gas – solid reactions

A) Shaft kiln; B) Moving-bed reactor; C) Multiple-hearth reactor; D) Rotary kiln; E) Fluidized-bed reactor; F) Spray reactor;
G) Entrained-flow reactor
a) Solid feed components; b) Gaseous feed components; c) Solid product; d) Off-gas; e) Air; f) Cyclone; g) Drive unit
Figure 13. Reactors for noncatalytic liquid – solid reactions

A) Stirred tank; B) Cascade of stirred tanks; C) Tank with liquid recirculation; D) Rotary drum; E) Fluidized-bed reactor; F)
Steeping press; G) Kneader; H) Screw-conveyor reactor; I) Multiple-hearth reactor; J) Rotary kiln
a) Liquid feed components; b) Solid feed components; c) Liquid product; d) Solid product; e) Drive unit
Table 14. Electrothermal reactors
Chlorine production by chlor – alkali elec- – Production of perfluorocaprylic acid

trolysis – Production of dihydrostreptomycin
– Mercury amalgam process
– Diaphragm-cell process The design of the reaction system (i.e., cell ge-
– Membrane process ometry and flow configuration), the electrode ar-
rangement and material, and control of phases
Metal winning by fused-salt electrolysis
and concentrations are highly process specific.
– Aluminum
Typical designs are illustrated in Figure 15.
– Magnesium
– Sodium
Metal refining
– Copper
3.8. Reactors for Biochemical Processes
– Nickel (→ Biochemical Engineering)
Electrolysis of inorganic materials

– Electrolysis of water Some important biochemical processes, such as
– Fluorine production by electrolysis of hydro- those used in making beer, wine, alcohol, and
gen fluoride baker’s yeast, have been known for centuries.
– Production of sodium chlorate by electroly- Typical of these reactions is their use of enzymes
sis of sodium chloride as biocatalysts. The enzymes can be present as
– Electrochemical oxidation of sodium chlo- cell constituents of living microorganisms, or
rate to perchlorate they can be isolated in dissolved form or bound
– Recovery of persulfuric acid to inert supports. The prerequisite for the use of
– Production of ozone live microorganisms is the provision of favor-
able living conditions. Such conditions include
Electrolysis of organic materials the presence of optimal amounts of nutrients and
– Production of adiponitrile from acrylonitrile oxygen (in aerobic processes); maintenance of
– Production of dimethyl sebacate the temperature, pressure, maintenance of pH in
– Reduction of nitrobenzene to aniline certain ranges, and sterile conditions.
Reactors for these processes can be classified

as follows:
1) Reactors with dissolved or suspended biocat-
alysts (submerged processes) for aerobic or
anaerobic conditions
2) Reactors with immobilized biocatalysts for
aerobic or anaerobic conditions
Reactors for use in submerged aerobic pro-
cesses have provisions for efficient aeration and
intensive liquid circulation. Aeration is accom-
plished with fixed or moving distributors, noz-
zles, or submerged or rotating jets. Liquid circu-
lation is ensured by various stirring systems or
by forced or natural convection.
A summary of the most important reactor
types and their applications is given in Table 15
and Figure 16.
Reactors for anaerobic conditions do not
have aeration equipment. Usually, sealed vessels
with or without stirrers are used (fermenters).
Applications of these reactor types include fer-
mentation processes (e.g., lactic acid fermenta-
tion, alcohol production, mash fermentation).
The immobilization of enzymes on suitable
supports enables the use of reactor designs sim-
ilar to those for heterogeneous catalytic process-
es. If the enzymes are supported on semiperme-
able membranes, separation and reaction can be
combined in membrane reactors.
Reactors with immobilized biocatalysts, to-
gether with their applications, are listed in Ta-
ble 16 and Figure 17.
3.9. Reactors for Photochemical and

Figure 14. Reactors for electrothermal processes Radiochemical Processes
A) Plasma torch; B) Fluohm reactor; C) Arc-heated reduc-
tion furnace; D) Resistance-heated reduction furnace; E)
Acheson furnace; F) Reactor with indirect electric heating
The photochemical and radiochemical princi-
a) Solids; b) Molten product; c) Gaseous reaction mixture; ples are used to a very limited extent in indus-
d) Gaseous product; e) Catalyst; f) Carrier gas; g) Electrodes; try because conditions for economical operation
h) Plasma; i) Slag; j) Resistive charge; k) Off-gas (e.g., high quantum efficiency) are seldom met.
In addition to these factors, metabolism is im-
portant for reactor design. Aerobic processes re- 3.9.1. Photochemical Reactors
quire an adequate supply of oxygen. In anaero-
bic processes, the admission of gas from outside
The rate of a photochemical reaction is deter-
must be prevented; gases and solvent vapors re-
mined by the concentration of reactants and by
sulting from the reaction must also be removed
the intensity, quantity, and wavelength of light
from the reactor.
supplied. Light in the wavelength range that is
absorbed by the reaction mixture can be formally
Figure 15. Reactors for electrochemical processes

A) Metal winning by fused-salt electrolysis; B) Electrolytic metal refining; C) Electrolysis of inorganic material; D) Electrol-
ysis of organic material; E) Mercury amalgam process; F) Diaphragm-cell process; G) Membrane process
a) Water; b) Chlorine; c) Sodium chloride; d) Hydrogen; e) Sodium; f) Sodium hydroxide; g) Anode; h) Cathode; i) Membrane;
j) Product; k) Amalgam; l) Recycle brine + chlorine; m) Mercury; n) Graphite; o) Diaphragm; p) Electrolytic salt solution of
metal to be refined; q) Anode slime; r) Electrolyte removal; s) Organic feed solution; t) Oxygen
treated as a reactant. As a consequence, pho- source. The feasible thickness of the reaction
tochemical reactions exhibit a position depen- space, and thus the type and size of reactor that
dence of the reaction rate, even with complete can be used, depend not only on the power of
mixing, because the flux density of light quanta the emitter, but also on the optical properties of
decreases with increasing distance from the light the reactor material and the reaction medium. In-
Figure 16. Reactors for submerged aerobic processes

A) Sparged stirred tank; B) Bubble column with forced circulation; C) Jet reactor with forced circulation; D) Submerged-jet
reactor with forced circulation; E) Bubble column with natural circulation; F) Loop reactor; G) Sieve-tray tower; H) Trickle-
bed reactor; I) Reactor with rotating internals
a) Gas; b) Fermentation medium; c) Product; d) Off-gas; e) Recycle stream
Table 15. Reactors for submerged aerobic processes
Sparged stirred tank various stirring and circulation apparatus suitable for higher production of antibiotics amino acids yeast
viscosities
Reactors with forced circulation
Bubble column very broad residence-time distribution production of yeast
good dispersion properties aerobic wastewater treatment
Jet reactor free jet, jet nozzle, or central tube designs possible
for low viscosities
high gas velocities, good mass transfer
Submerged-jet reactor very broad residence-time distribution processing of spent sulfite liquor
good mass transfer fermentation of waste substrates
danger of slime settling out
Reactors with natural
circulation
Bubble column much backmixing, broad residence-time distribution production of biomass citric acid
for low viscosities
simple construction
Loop reactor for low viscosities
little dispersive action
Sieve-tray tower good mass transfer due to fine bubble structures
Surface reactors
Trickle-bed reactor low mass-transfer coefficients and negligible dispersive action production of acetic acid aerobic
wastewater treatment
Reactor with rotating internals use of paddles, cylinders, etc. suitable for viscous media aerobic wastewater treatment
Table 16. Reactors for biochemical processes over immobilized biocatalysts (for aerobic and anaerobic conditions)
tensive mixing must be ensured, especially for a large amount of heat is evolved and supplemen-
thick beds. Light can be supplied from outside tal cooling devices must be employed.
(through the reactor wall) or by submerged light A survey of reactor types and their industrial
sources. When high-power light sources are used applications appears in Table 17 and Figure 18.
Figure 17. Reactors for biochemical processes over immo-

bilized biocatalysts (for aerobic and anaerobic conditions)
A) Stirred tank with suspended catalyst; B) Fixed-bed reac-
tor; C) Fluidized-bed reactor; D) Membrane reactor
Figure 18. Reactors for photochemical processes
a) Biocatalyst; b) Fermentation medium; c) Product; d) Off-
A) Tubular reactor; B) Bubble column; C) Stirred tank; D)
gas; e) Permeate; f) Membrane tube; g) Retentate
Falling-film reactor; E) Belt reactor
a) Gaseous feed components; b) Liquid feed components;
c) Product; d) Emitter; e) Coolant; f) Off-gas; g) External
reflector; h) Falling film; i) Belt
3.9.2. Radiochemical Reactors
Radiochemical reactions are induced by the ac- 2) Radiative cross-linking of poly(vinyl chlo-
tion of ionizing radiation. In addition to high ride) and polyethylene
energy consumption, the extremely complex de- 3) Production of alkyltin compounds
sign of radiation sources and shielding works 4) Degradation of polymers
against the wider use of this reaction principle.
The following are known applications:
1) Production of ethyl bromide (Dow process,

Fig. 19) Some reactions, such as chlorinations, can be
implemented in either photochemical or radio-
chemical form.
Table 17. Reactors for photochemical processes
Tubular reactor for homogeneous gas- and liquid-phase reactions chlorination of benzene to hexachlorocyclohexane
sulfochlorination
chlorination of methane to dichloromethane
Bubble column requires favorable optical conditions and low viscosity sulfochlorination of paraffins (cascade)
also used in cascades and with central tube side-chain chlorination of aromatics
production of dodecanethiol from 1-dodecene and
H2 S
Stirred tank optically induced differences in reaction rate equalized oximation of cyclohexane with nitrosyl chloride
by intensive stirring
production of provitamin D3
Falling-film reactor suitable for poor optical conditions because film is very production of vitamin D2
thin
Belt reactor especially for highly viscous media polymerization to PAN, PAC, PVC, PVAC ∗
∗ PAN = polyacrylonitrile; PAC = polyacrylate; PVC = poly(vinyl chloride); PVAC = poly(vinyl acetate).
4. References
1. “Chemische Reaktoren-Ausrüstungen und ihre

Berechnung,” Verfahrenstechnische
Berechnungsmethoden, part 5, VEB
Deutscher Verlag für Grundstoffindustrie,
Leipzig 1981.
2. H. Gerrens: “Über die Auswahl von
Polymerisationsreaktoren,” Chem. Ing. Tech.
52 (1980) 477 – 488.
3. K. H. Reichert, W. Geiseler (eds.): Polymer
Reaction Engineering, VCH
Verlagsgesellschaft, Weinheim 1989.
4. W.-D. Deckwer: “Bioreaktoren,” Chem. Ing.
Tech. 60 (1988) 583 – 590.
5. K. Schügerl: “Characteristic Features of
Bioreactors,” Bioreaction Engineering, vol. 2,
John Wiley and Sons, New York 1990.
Figure 19. A reactor for a radiochemical process (produc-
tion of ethyl bromide by the Dow process) 6. A. Heger: Technologie der Strahlenchemie von
a) Gaseous reaction mixture; b) Liquid product; c) Shielding Polymeren, Carl Hanser Verlag, München
1990.
Chemical Plant Design and Construction 987
Chemical Plant Design and Construction

Erich Mosberger, Lurgi AG, Frankfurt, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . 988 4.1.1. Patent Licenses . . . . . . . . . . . . . 1024

2. Feasibility Study . . . . . . . . . . . 988 4.1.2. Process Licenses . . . . . . . . . . . . 1024
2.1. Initial Work . . . . . . . . . . . . . . 989 4.1.3. Process Licenses via Engineering
2.2. Cost Estimation . . . . . . . . . . . . 990 Contractors . . . . . . . . . . . . . . . 1025
2.2.1. Investment Costs . . . . . . . . . . . . 990 4.1.4. Know-How Contracts via
2.2.1.1. Global Methods of Investment Cost Engineering Contractors . . . . . . . 1026
Estimation . . . . . . . . . . . . . . . . 991 4.2. Design and Supply Contracts with
2.2.1.2. Detailed Methods of Investment Engineering Contractors . . . . . . 1026
Cost Estimation . . . . . . . . . . . . 992 4.2.1. Selection of Engineering
2.2.1.3. Item-by-Item Calculation . . . . . . 994 Contractors . . . . . . . . . . . . . . . 1026
2.2.1.4. Cost Indexes . . . . . . . . . . . . . . 994 4.2.1.1. Importance of Risk in the Plant
2.2.2. Operating Costs . . . . . . . . . . . . 995 Business . . . . . . . . . . . . . . . . . 1026
2.2.3. EDP Support . . . . . . . . . . . . . . 995 4.2.1.2. Selection and Award Criteria . . . . 1027
2.3. Profitability Analysis . . . . . . . . 996 4.2.2. Form and Content of Contracts . . . 1028
2.3.1. Profitability Analysis 4.2.2.1. Basic Concerns in Contract Writing 1028
as an Engineering Task . . . . . . . . 996 4.2.2.2. Contract Types and Provisions . . . 1029
2.3.2. Methods of Profitability Analysis . 996 4.2.2.3. Essential Elements of a Contract . . 1030
2.4. Site Selection . . . . . . . . . . . . . . 997 5. Execution of the Project . . . . . . 1031
2.5. Decision between Alternative 5.1. Scope of Work . . . . . . . . . . . . . 1031
Investments . . . . . . . . . . . . . . 998 5.2. Project Organization and
3. Preliminary Design . . . . . . . . . 998 Management . . . . . . . . . . . . . . 1032
3.1. Preliminary Design Costs . . . . . 999 5.2.1. Matrix Project Management . . . . . 1033
3.2. Final Selection of Site Locations . 999 5.2.2. The Project Manager . . . . . . . . . 1033
3.3. Process Design . . . . . . . . . . . . 1001 5.2.3. The Project Team . . . . . . . . . . . 1034
3.3.1. Optimization . . . . . . . . . . . . . . 1004 5.2.4. The Start Phase of a Project . . . . . 1034
3.3.2. Safety Aspects and Environmental 5.3. Project Control
Control . . . . . . . . . . . . . . . . . . 1007 (Schedules, Progress, Costs) . . . . 1035
3.3.2.1. Protection Against Emissions . . . . 1008 5.3.1. Time Scheduling . . . . . . . . . . . . 1035
3.3.2.2. Noise Control . . . . . . . . . . . . . . 1008 5.3.2. Progress Planning and Control . . . 1038
3.3.2.3. Occupational Safety and Health . . 1010 5.3.3. Cost Planning and Control . . . . . . 1038
3.3.2.4. Plant Availability . . . . . . . . . . . 1011 5.3.4. Project Report . . . . . . . . . . . . . 1041
3.3.2.5. Authority Engineering . . . . . . . . 1011 5.4. Detail Engineering . . . . . . . . . . 1041
3.4. Basic Engineering . . . . . . . . . . 1013 5.4.1. Process Engineering . . . . . . . . . . 1041
3.4.1. Equipment Specification from the 5.4.2. Plant Layout . . . . . . . . . . . . . . 1041
Process Engineering Standpoint . . 1013 5.4.3. Apparatus and Machinery . . . . . . 1043
3.4.2. Materials of Construction . . . . . . 1014 5.4.4. Piping . . . . . . . . . . . . . . . . . . 1045
3.4.3. Plant Layout . . . . . . . . . . . . . . 1017 5.4.5. Control Systems . . . . . . . . . . . . 1051
3.4.4. Preliminary Piping and 5.4.6. Electrical Design . . . . . . . . . . . . 1053
Instrumentation Diagram . . . . . . . 1019 5.5. Procurement . . . . . . . . . . . . . . 1054
3.5. Calculation of Plant Costs . . . . . 1019 5.5.1. Purchase of Equipment and Services 1055
3.5.1. Equipment . . . . . . . . . . . . . . . . 1020 5.5.2. Expediting . . . . . . . . . . . . . . . . 1056
3.5.2. Bulk Materials . . . . . . . . . . . . . 1021 5.5.3. Shipping . . . . . . . . . . . . . . . . . 1056
3.5.3. Other Costs . . . . . . . . . . . . . . . 1022 5.6. Planning and Execution of Civil
3.6. Conclusion of Preliminary Design Work and Erection . . . . . . . . . . 1056
Phase . . . . . . . . . . . . . . . . . . . 1024 5.6.1. Planning of Civil Work and Erection 1056
4. Contract Writing and Forms of 5.6.1.1. Planning of Civil Work
Contracts . . . . . . . . . . . . . . . . 1024 (Including Structural Steel Work) . 1056
4.1. Licensing Agreements . . . . . . . . 1024 5.6.1.2. Erection Planning . . . . . . . . . . . 1057
988 Chemical Plant Design and Construction
5.6.2. Execution of Construction . . . . . . 1058 5.7.4. Preparation for Commissioning . . . 1064

5.6.2.1. Construction-Site Organization and 5.7.5. Plant Startup . . . . . . . . . . . . . . 1064
Management . . . . . . . . . . . . . . 1058 6. Computer Support . . . . . . . . . . 1064
5.6.2.2. Time Scheduling and Progress 6.1. Role of Computers in Project
Control . . . . . . . . . . . . . . . . . . 1059 Execution . . . . . . . . . . . . . . . . 1065
5.6.2.3. Construction Work . . . . . . . . . . 1060 6.2. EDP Infrastructure and Systems 1066
5.7. Commissioning . . . . . . . . . . . . 1061 6.3. Coordination and Interfaces . . . 1066
5.7.1. Plant Design and Commissioning . 1061 7. Quality Assurance . . . . . . . . . . 1067
5.7.2. Operating Manual . . . . . . . . . . . 1061 8. Training of Plant Personnel . . . . 1068
5.7.3. Responsibility and Organization . . 1063 9. References . . . . . . . . . . . . . . . 1069
1. Introduction project ends when an appropriate engineering

firm is chosen and the contract signed.
Since the 1930s, the design and construction The implementation phase consists of the en-
of chemical plants have become increasingly gineering of the chemical plant, procurement of
specialized. Chemists and engineers collabo- plant equipment and material, construction, and
rate to develop process and engineering con- commissioning. The engineering contractor ei-
cepts, which engineers and designers then trans- ther performs all of these tasks or brings in sub-
form into detailed plans and specifications for all contractors or personnel employed by the owner
the components of a chemical plant. Purchasing to carry out a portion of the work.
agents procure equipment from specialist manu- Plant equipment is fabricated by specialized
facturers. Construction and installation firms are manufacturers. Only in rare cases does the engi-
put under contract to build the plant. neering contractor or the plant owner have pro-
Plant design and construction starts as an duction facilities.
idea of the potential owner. Increasingly com- After a successful test run, the plant is handed
plex markets and the interrelations of the world over to the owner. (Fig. 1 shows a schematic di-
economic and political systems require critical agram of the development of a chemical plant
examination of every project for feasibility, eco- project.)
nomic relevance, and environmental impact. As This article does not discuss the design and
a rule, this is done with the aid of a feasibil- construction of small, simple plants that special-
ity study that includes preliminary design work. ized firms can supply “off the rack.” It deals with
Market analyses are carried out to determine po- larger, more complicated projects in the field of
tential sales, future demand dynamics, availabil- chemical plant construction. The term chemical
ity of raw materials, and the competitive situa- plant design and construction is used in a very
tion. The plant capacity and location are spec- broad sense. It also relates to allied technolo-
ified. Particular attention must be paid to envi- gies, such as metallurgy, environmental protec-
ronmental protection. Studies are supplemented tion, fiber and food production, and petroleum
by sufficiently accurate estimates of capital re- and natural gas processing. Some of these ba-
quirements and profitability. sic project development and execution princi-
Once the decision has been made to go ahead ples can also be applied to general industrial
with the construction project, whereby the owner plant construction.
may have opted not to carry it out himself,
the owner will prepare an accurate, comprehen- 2. Feasibility Study
sive definition of the plant which is used as
the basis for inviting bids from competent en- At the start of a project, the bases used for
gineering contractors. This approach is increas- planning are still very inexact. No major costs
ingly employed, especially for large projects. (If should be incurred until it is known whether the
the owner has an adequate pool of experienced project is feasible or not. Nevertheless, all al-
design engineers, construction specialists, and ternatives must be considered. A great deal of
procurement staff, he may plan and construct experience is needed if uneconomic variants are
the plant himself.) The conceptual phase of the to be discarded without generating high design
Figure 1. Development of a project
costs. The first steps toward accurate definition 2.1. Initial Work
of the project are carried out by the company that
wishes to erect the plant. A small working group Market Analysis and Production Capac-
is formed, consisting of process engineers, sales ity. Before the economically optimum plant ca-
engineers, and other engineering personnel. It pacity is set, a careful market analysis must be
is useful to appoint a project leader to coordi- carried out. This analysis must be performed by
nate the team. Normally, the same person will experienced market analysts, even if the prod-
later become responsible for implementing the uct has a comprehensive international sales his-
project if the decision is taken to proceed. tory. These specialists evaluate literature on the
development of similar products, determine the
Preliminary studies aimed at defining the ob-
capacity of existing production facilities, carry
jective partly depend on initial economic esti-
out representative surveys, obtain suitable con-
mates and generally include:
ditions from downstream processors in the case
1) Market analysis and trend analysis of intermediate products, and forecast the future
2) Fixing of production capacity market for the product. They must also provide
3) Examination of competing processes and of a realistic evaluation of the competition and the
the patent and license situation world economic situation. Forecasts of costs for
4) Legal aspects raw materials and working capital play an im-
5) Estimation of investment costs portant role in the economic analysis.
6) Estimation of production costs A new chemical product usually experiences
7) Estimation of profitability slow early growth with a relatively high price
8) Selection of an appropriate plant location and low output. The market then expands; pro-
duction climbs faster and prices drop. Finally,
prices stabilize at a low level, and older, smaller Simply calculating and analyzing the invest-
plants are shut down (see Fig. 2). If market anal- ment costs is not sufficient because, over the
ysis shows that world output of the product is service life of a plant, operating costs make up
still increasing rapidly, expansion of capacity a much greater proportion of lifecycle costs
through erection of a new plant may have a good than investment costs do. The goal of cost es-
outlook if other conditions are favorable. The fu- timation in the conceptual phase is to optimize
ture price decline must, however, be allowed for the lifecycle costs of a chemical plant. This of-
in the calculations. ten means increasing investment costs so as to
In the upper part of the trend curve, invest- lower operating costs. Operating costs are favor-
ment only makes sense if a clear demand is per- ably influenced by long component and equip-
ceptible in the market. The production curve for ment lifetimes, improvements in maintenance
the old process may fall off if a new, more eco- and consumption, and other factors. Cost predic-
nomical production process appears. (Example: tion as the basis for profitability analysis should
low-pressure process for methanol production therefore include the determination of invest-
forces shutdown of older high-pressure process.) ment costs as well as subsequent production and
The new process may open up new markets and operating costs.
lend new impetus to development [1–4]. The following sections discuss methods of
determining investment and operating costs.
2.2.1. Investment Costs
A proven technique in investment cost estima-

tion is to subdivide the project into onsite and
offsite items.
Onsite Items. The term onsites denotes all

facilities required to make the desired product.
Offsite Items. Offsites are all facilities that

Figure 2. Development of a new product are normally not located within the process
plant. They include facilities for the delivery
Competing Processes, Patent and License of steam, electric power, gas, solid or fluid
Situation. The patent and license situation must fuels, water, compressed air, and instrument
be investigated at the beginning of the study. For- air. Furthermore, this group includes stockpiles
eign patents may block the construction project and warehouses for raw materials and semifin-
if the owner of the patent is not prepared to grant ished and finished products; service facilities
a license (see also Chap. 4). (administrative buildings, canteens, workshops,
stores, laboratories, parking, fire protection,
Legal Aspects. Extensive, far-reaching en- roads, tracks, and harbor facilities); and, fi-
vironmental regulations mean that it is essential nally, power plants; loading docks; facilities for
to make an early approach to authorities that will treating raw materials, off-gas, wastewater; and
later have to approve the operation of the plant waste disposal facilities.
(see Section 3.3.2.5). In the United States, offsites are usually di-
vided into storage and handling (stocks of raw
materials and finished products), utilities (gen-
2.2. Cost Estimation
eration or delivery of energy as steam, electric-
ity, and water), and service facilities (e.g., of-
If initial planning work has shown that invest-
fices, recreation rooms, laboratories, workshops,
ment is desirable and the market analysis has led
warehouses).
to a tentative capacity figure, a first estimate of
On grounds of cost, an attempt must be made
investment costs and subsequent operating costs
to carry out an “order-of-magnitude” estimate
is performed.
at minimal cost. This estimate is of course inex- annual return on sales by the investment costs.
act, but later it makes it easier to decide whether A statistically determined turnover ratio and an
to bear the costs for an accurate analysis. The expected annual return on sales are then used
approximate determination of investment costs to estimate the investment costs of new plants.
is subdivided into simple “global” methods and Turnover ratios in the chemical industry lie bet-
“detailed” methods. Methods for estimating in- ween 1.2 and 1.5.
vestment costs are now well-established; those Statistical turnover ratios can be found for the
now in use are described in publications mainly analysis of individual plants, companies (based
dating from 1960 – 1984. on balance sheets and profit-and-loss statements
of typical firms), or a whole industrial sector.
2.2.1.1. Global Methods of Investment Cost Degression Exponents. The use of degres-
Estimation sion exponents (cost-versus- capacity expo-
nents) per-mits relatively accurate cost estima-
Global methods permit investment costs to be tion. The technique is based on costs for plants
estimated relatively easily and with an accuracy already on-stream. The exponents are used to es-
between ± 30 % and ± 50 %. Several methods timate investment costs for the planned facility
are outlined below [5]. as a function of plant capacity.
Investment costs for proces plants are pub-
lished from time to time and can be used for ini-
Single Complexity Factor. In the single-
tial cost estimation. The costs of identical or sim-
complexity-factor method [6] processes are clas-
ilar plants within the same company can be used
sified as having a low, medium, or high complex-
in a similar way. In 1967, J. E. Hasselbarth
ity factor.
[8] published the costs of process plants for 60
Low Complexity Factor.
chemical products, including investment costs
This class includes all batch processing plants
per tonne of annual capacity. His figures referred
and all processes involving simple syntheses
to costs within battery limits (i.e., within the
(e.g., production of sulfuric acid).
plant boundary), exclusive of land and offsite
Medium Complexity Factor.
facilities. In 1970, K. M. Guthrie [9] compiled
This class comprises processes with gas and
the investment and operating costs for 54 chem-
fluid phases that run at ordinary pressures and
ical and refinery processes covering a wider ca-
temperatures.
pacity range. The degression exponents cited in
High Complexity Factor.
both publications allow the calculation to be ap-
This class covers processes with high pres-
plied to other capacities. (Example: Given a de-
sures and/or temperatures, as well as polymer-
gression coefficient of 0.7, doubling the capacity
ization processes.
leads to an increase in investment costs by a fac-
Investment costs depend on the complexity
tor of 20.7 = 1.65.)
factor and the required plant capacity, and are de-
When specific degression exponents are used
termined from empirical data obtained in other
it should be noted that the error range grows with
processing plants. Auxiliary and utility units are
the capacity scaling factor. This type of calcula-
taken into account by adding 45 %.
tion generally gives acceptable results only for
This method has the advantage that it permits
scaling factors of up to 1: 3. Furthermore, the
estimation of investment costs in the orientation
use of the method depends on the state of the
phase when little information about the process
art because changes in processes, apparatus, and
is available.
mechanical technique can change the exponents.
Turnover Ratios. The turnover-ratio method Comparative Methods. When adequate

allows costs to be estimated without process in- data are available from an existing plant simi-
formation by using market information such as lar to that being planned, the investment costs of
product sale price and sales volume [7]. the old plant can obviously be used to calculate
On the basis of plants already on-stream, a the costs of the new one.
capital turnover ratio is obtained by dividing the The following information is needed [5]:
1) Production capacity If the costs for the main plant items are
2) Construction time taken as 100, total processing-plant costs are
3) Investment costs (inside and outside battery found by multiplying by 3.10 (solid-processing
limits) plant), 3.63 (solid – fluid-processing plant), or
4) Location 4.74 (fluid-processing plant).
Costs inside and outside battery limits are Chilton [13] and Hand [14] have improved
both determined with degression exponents. these approximate Lang factors by introducing
Cost estimation outside battery limits must, supplements to the costs of main equipment
however, be preceded by a critical analysis of items. Estimates of the total costs of a “grass-
the auxiliary and utility units needed. The fig- roots” plant can then be made. Figure 3 outlines
ures are adapted to the location by the use of the procedure for preliminary calculations by the
indexes to adjust for the following [5]: Lang – Chilton method.
Other authors have extended and refined the
1) Construction location Lang method. For example, Burgert in 1979
2) Economic situation of the industry published an analysis of investment- cost struc-
3) Taxes tures for more than 100 projects [15].
4) Labor market In 1965, Miller [16] devised another sys-
5) Qualifications of available labor tem based on modified Lang factors. Miller
assumed that the factors are influenced by three
2.2.1.2. Detailed Methods of Investment other parameters besides those used by Lang
Cost Estimation (solid, solid – fluid, fluid):
If the preliminary planning as embodied in tech- 1) Size of main equipment items

nical documents has reached an advanced stage, 2) Material from which the plant is constructed
it can form the basis for investment cost esti- 3) Pressure for which the plant is built
mation that takes into account specific details
Increasing size, more refined materials, and
of the project. Methods used for this are mainly
higher operating pressure increase the relative
based on analogies with plants that are already
costs of the main equipment items in relation
on-stream. Detailed methods of plant matching
to storage, utilities, and service facilities, thus
[10] and multiplication-factor techniques of cost
diminishing the factors. According to Miller,
determination are employed.
all factors can be referred to the mean per-piece
Lang Factor Method. If the process is well costs of plant parts and depend on these.
characterized, the required capacities of fur-
naces, apparatus, and machinery can be specified
in preliminary flow sheets [11]. These specifica-
tions cover main plant items such as furnaces, Guthrie’s Modular Technique. The modu-
columns, filters, reactors, heat exchangers, ves- lar technique published by Guthrie [17] in
sels, and machinery. The estimator can deter- 1968 is also based on Lang’s method and is
mine the costs “free-on-site” for such items or the best of the multiplication-factor approaches.
obtain the costs from suppliers. The project is first broken down into six modules
Lang used cost analyses of existing plants [10]:
to derive multiplication factors that allow de- Five direct modules
termination of the investment costs for process Chemical processes
units within battery limits if the costs of the main Solids handling
equipment items are known [12]. The factors de- Site development
pend on the type of plant. Lang distinguishes Industrial structures (civil work)
three types according to the state of aggregation Auxiliary and service facilities outside
of the raw material and product: “solid” (e.g., ore battery limits (offsites)
sintering), “solid – fluid” (e.g., oil – shale retort- One indirect module
ing with shale – tar recovery), and “fluid” (e.g., Indirect project costs
petroleum refineries, petrochemical plants).
Figure 3. Preliminary cost estimate using factors (Lang – Chilton method)
The key costs of the direct modules are deter- module costs” gives the investment costs for on-
mined first. For the “chemical process” module, and off-battery facilities.
these might be costs for machinery and equip- Guthrie proposes a variety of methods for
ment. As shown in Figure 4, the key costs of calculating the equipment costs of a module. The
the direct modules are multiplied by the gross multiplication factors required for this include
module factors. The sum of the individual “gross not only size of the component (magnitude fac-
Figure 4. Simplified modular concept for estimating investment costs

F = net module factor; F2 = gross module factor
tor) and the alloy factor, but also indirect effects. 2.2.1.3. Item-by-Item Calculation
This relatively accurate modular technique has
not found wide acceptance, however, because it When detailed methods of investment- cost esti-
is relatively difficult to perform the calculation mation do not give sufficient accuracy, the only
and maintain the statistical data base. alternative is to calculate investment costs item
by item. The plant equipment and the engineer-
ing work must be specified. The procedure and
amount of work required for such a cost estima-
tion are the same as those described for calcu-
lating plant costs (see Section 3.5). Close coop-
eration between the subsequent operator of the
plant and an engineering firm has proved advan-
tageous for this approach.
2.2.1.4. Cost Indexes
The methods of investment-cost estimation dis-

cussed above are generally based on historical
statistics derived from existing plants. The cost
figures obtained by these methods are therefore
referred to given periods, such as 1985. If in-
vestment costs are to be estimated for the year
1990, the estimates must be adjusted to current
prices. Every industrial country publishes one
or more indexes for this purpose. Some widely
used indexes for the United States and Germany
follow:
Figure 5. Development of cost indexes
a) CE Plant cost index, 1959 = 100, successively published
1) Bureau of Labor Statistics cost index for
in [18] (1982 revision of productivity factor from 2.50 to equipment, machinery, and materials in the
1.75); b) Kölbel – Schulze index, 1976 = 100, successively U.S. market
published in [19] 2) Chemical Engineering Plant cost index [18–
20]
3) Kölbel – Schulze index for chemical plants panies that manufacture the product in question
(Kölbel – Schulze Index für Chemieanlagen) as their main commodity may also be helpful.
[21]
4) Producer price index for commercial prod- Energy-Based Methods. Chemical produc-
ucts (Index der Erzeugerpreise gewerblicher tion processes involve large amounts of energy.
Produkte) compiled by the German Federal The chemical reactions themselves often con-
Statistical Service (Statistische Bundesamt) tribute very little to energy requirements but up-
stream and downstream operations do. This fact
These indexes are based both on chemical-
provides the basis for several methods used to
plant cost structures and on national primary
estimate operating costs [13], [23–25].
price indexes. Figure 5 compares important cost
indexes over time.
Key Cost Categories. If it is assumed
that chemical plants show relatively constant
2.2.2. Operating Costs operating- cost structures for a given product,
operating costs can be calculated with multipli-
Along with the investment costs, the operat- cation factors if a single cost category is known
ing costs incurred in the production of a given accurately [22].
product also play an important part in deciding
whether to erect a plant. The technical and eco- Scaleup Methods. When operating costs for
nomic literature, however, contains little infor- similar plants are known,specific data can be
mation on the preliminary calculation of oper- used to derive scaling coefficients for propor-
ating costs. Possible reasons are the complexity tional, personnel-dependent, and investment-
of the problem and the company’s possible loss dependent costs. The operating costs can then
of maneuvering room if internal operating data be estimated.
were published [22].
The methods of estimating operating costs
discussed below are based on data from com- 2.2.3. EDP Support
parable plants or empirical data from plants be-
longing to the same company [22]. A number of manufacturers and operators have
They are related, but differ as regards start- established electronic data processing (EDP)
ing information: published data, empirical data, programs for estimating investment and oper-
business information, physical data, correla- ating costs. Examples are Factest (ICI) [26] and
tions, and information from comparable plants. the ASPEN package [27]. The ASPEN PLUS
In order to check the reliability of the results, software, a flow sheet simulation program, is
operating costs should be estimated by several supplemented with a costing module.
methods so that the calculations can be verified The program sizes the most important equip-
and error ranges given. ment and machinery from the process simula-
tion. Investment costs are estimated by the use
Graphical Method. The graphical method of multiplication factors and cost indexes to ad-
is based on statistical evaluation of operating just to current price levels. ASPEN PLUS allows
costs in existing plants. Operating costs per unit the calculation not only of fixed costs for an in-
of product are plotted versus plant capacity. It is vestment, but also operating costs.
important to be aware of the scope of the plot- To determine operating costs, the program
ted costs. The graph usually includes only the calculates fixed and variable components sep-
manufacturing costs of a product: raw materi- arately. Variable costs include raw materials, fu-
als, power, catalysts, chemicals, wages, depreci- els, catalysts, disposal, and “running royalties”.
ation, and maintenance. Plant overheads, fixed Fixed costs comprise personnel costs for mainte-
costs, and indirect production costs should also nance and operation, overheads, insurance, and
be taken care of by multiplication factors. taxes. The program generates summaries and de-
tails of annual operating costs. Finally, the soft-
Business Analysis. The analysis of balance ware can evaluate a variety of profitability mea-
sheets and profit-and-loss statements from com- sures (Section 2.3).
2.3. Profitability Analysis (break-even point). Only then does the return
flow of capital begin.
2.3.1. Profitability Analysis as an The history of an investment is illustrated
Engineering Task schematically in Figure 6.
In profitability calculations, it is necessary to

keep in mind that a plant erected without re-
serves (standby units) for unavoidable shut-
downs and repairs will produce for only 330
days (or 8000 h) a year; that is, it will attain
only ca. 90 % of rated capacity on a long-term
basis. Manufacturers generally rate their equip-
ment for operation at 10 % over capacity. How-
ever, this figure only applies to intermittent over-
loads and is not guaranteed.
If full-load operation is required all year, the
plant must not be designed as a single-train (sin-
gle processing line) facility, unless it is set up for Figure 6. Schematic showing the course of capital invest-
110 % capacity and adequate storage is provided ment
for the finished product. Large storage areas are a) Accumulated profits; b) Return on investment; c) Total
needed if sales are seasonal (e.g., fertilizers). production costs (fixed and variable); d) Fixed costs; e) Ac-
cumulated cash flow
Because the feasibility study includes com-
parisons between alternative processes, two pro-
cesses with equal profitability need not be 2.3.2. Methods of Profitability Analysis
ranked equally. For example, both may have
equal production costs but different fixed costs. Methods for assessing the profitability of a
Fixed costs usually comprise interest pay- project [1, pp. 285 – 401], [28–33] differ in the
ments and operator wages. Nearly all other costs way investment, revenue, and risk are associ-
depend on output and are therefore variable ated. The three most important techniques are
(e. g., costs of raw materials, power, and fuel). described briefly below.
If market conditions make it necessary to re- These profitability calculations are combined
duce the output to, say, 80 % of rated capac- and linked with operations research techniques
ity, the plant with high fixed costs will become [34], [35], so that alternative proposals can be
unprofitable more quickly. Thus, in the case of obtained with a justifiable amount of effort.
two equally profitable plants, the plant with the
lower fixed-cost contribution will be preferred. Payout (Payback) Period. If alternatives
High fixed costs often have to be accepted, if the are only to be compared, it may be adequate
need for reliable operation dictates that critical to divide invested capital by gross excess rev-
parts of the plant must be designed with 100 % enues (proceeds from sales minus operating
standby capacity or the plant must be subdivided costs). This method gives a quick indication as
into parallel trains. to whether the investment is attractive. If, for ex-
The profitability calculations must take into ample, a value of 3 (payout period 3 years) or less
account that 2 – 2.5 years usually elapse between is obtained, the investment should be profitable.
the start of planning and the commissioning of This does not mean, however, that the plant will
the plant. Interest therefore has to be paid on be completely written off after three years on
design and construction costs. Working capi- stream.
tal is also needed for storage of raw materials A more realistic figure can be obtained by in-
and product. Finally, for technical or market- cluding taxes and interest under expenses and
related reasons, a period of 6 – 12 months gener- listing revenues by year after commissioning
ally elapses after commissioning before the uti- (higher operating costs in the first year when full
lization of the plant is sufficient to cover the costs capacity has not been reached, future decline in
earnings).
Return on Investment (ROI). In large che- the most important Japanese steel mills are lo-
mical companies, investments depend not so cated on the coast and import coal and ore from
much on the payout period but on whether the overseas. Petroleum refineries used to be sited at
investment will increase total profits, i.e., div- petroleum sources. Now that giant tankers and
idends to the stockholders. Thus a large com- pipelines have come into wide use, refineries are
pany will only invest if a certain return on in- often located in consumption centers.
vested capital is ensured. The ROI method is Many large chemical companies are now in-
employed in such cases. The annual profit be- vesting in coastal and foreign property. Good
fore taxes and interest, but after depreciation, is surveys of publications important in site selec-
divided by the invested capital. In contrast to the tion can be found in [1, p. 439], [36–38]. Sto-
preceding method, startup losses are neglected bough has devised a selection system, based on
and data for design- capacity operation are used a point ranking, which allows unsuitable sites to
in the calculation. The result is a pretax rate of be eliminated quickly. The short list of remain-
return on invested capital. ing sites should then be examined as described
below.
Dynamic calculations are based on the dis-
counted cash flow (DCF) method. The DCF Site Quality, Topography, Soil Conditions,
method is an advance over ROI. It allows for Climate, Flood Risk. The short list should in-
the fact that investment costs precede revenues. clude only locations that appear suitable for the
Since only funds existing at the same time can plant and possible subsequent expansions from
be compared, all revenues and expenses that are the standpoint of size, price, transportation fa-
directly or indirectly related to the project from cilities, and buildability.
the start of planning onwards are discounted to a If the terrain is not flat, it should be estab-
fixed time, usually the start of production. A rate lished whether grading or filling is necessary and
of return is then sought that makes the sum of whether piles must be driven for foundations. If
the discounted annual excess revenues equal to transportation facilities (roads, railroad tracks,
the cash value of the total investment at the start water routes) are lacking, the expense of devel-
of production. Since excess revenues are spread oping them must be ascertained. Only costs for
throughout the entire year, they are all recalcu- developed sites can be compared.
lated to the middle of the year and discounted
from then on. The calculation runs over the eco- Raw-Material Availability Including
nomic life of the project, but usually only 10 Power, Fuels, and Water. Raw materials of
years, since the longer-term market position can good quality must be available at a favorable
scarcely be foreseen. Furthermore, the equiva- price throughout the service life of the plant.
lent value of revenues after more than 10 years Other prerequisites are availability of sufficient
is so small that it has little effect on the result fresh water, electric power, and fuels. Obtaining
(internal rate of return). power and steam on a grass-roots site can be
expensive.
2.4. Site Selection
Environmental Conditions, Environmen-
The selection of an optimal site is a high-priority tal Legislation, and Infrastructure of the Con-
item in the feasibility study. Every economic re- struction Site. Improved roads, rail connec-
gion has its advantages and disadvantages. The tions, and location on harbors or year-round nav-
present and future importance of correct site se- igable rivers are important criteria.
lection can scarcely be overstated. Wrong site
choices cannot be corrected later and have led Long-Term Availability of Qualified
to the downfall of many companies. Labor. In developing countries, leading per-
The development of world trade and the de- sonnel – from foremen to management – must
cline of tariffs have changed the environment of meet very stringent requirements. Only after
many existing plants for the worse. Formerly, years of schooling will local personnel have the
for example, the steel mill was located near the required standard of education.
coke plant and iron ore transported to it. Today,
Raw-material costs, wages, and maintenance to be optimized in several steps. This approach
costs are also crucial in site selection. Finally, is called “design to cost.” Investment costs are
it must be taken into account that the phase of often minimized in this approach by designing
startup losses will be longer if an industrial site low- cost plants (usually open-air plants with
has to be developed from scratch. simple equipment and no storage capacity for
intermediate products).
2.5. Decision between Alternative Several iterations are usually required to
reach an optimum between investment costs and
Investments operating costs.
Preparation for Decisionmaking. Large Decisionmaking. Profitability, sensitivity,
investment projects involve exploration of and risk analyses may lead to the conclusion
widely varying options. In addition to straight that execution of the project is not desirable.
profitability analysis, qualitative factors should Recent publications may have already shown
also be considered (e.g., special site problems, that similar projects undertaken by third par-
political environment, market development). ties will oversaturate the market. Other compa-
These qualitative factors involve risks, which nies may have access to such good raw-material
must also be assessed. The preparation phase sources that the company considering the project
for decisionmaking therefore includes not only cannot compete. It may be that environmental
calculation of investment and operating costs, regulations have a prohibitive effect on costs.
but also risk and sensitivity analysis [39]. The planning work should then be stopped until
Risk Analysis. In risk analysis, all constraints new information or analyses suggest a different
that can have an adverse effect on lifecycle conclusion. The avoidance of huge losses on a
costs and earnings must be identified, docu- badly planned facility far outweighs the costs
mented, and assessed. These include: incurred up to this point. If, however, the feasi-
1) Estimation of sales market bility study reveals a positive situation, the next
2) Energy cost development step is to incorporate the capital requirement into
3) Availability of raw materials the company’s investment program and give the
4) Plant construction risks go-ahead to start preliminary design.
5) Management-related risks (e.g., site-
dependent problems, reliability of vendors 3. Preliminary Design
and subcontractors)
6) Organizational risks The following results from the feasibility study
provide the basis for deciding to proceed to the
The financial effects of the identified risks are preliminary design phase:
quantified by experts in risk-assessment proce-
dures and the results then evaluated in a Monte 1) Plant capacity has been set on the basis of
Carlo simulation [39]. market research
Sensitivity Analysis. Sensitivity analysis 2) The choice between expansion of an exist-
should be carried out to find out how the prof- ing facility and construction of a new one
itability and risk situation changes when certain has been made
assumptions and constraints are varied. For ex- 3) The list of potential sites has been shortened
ample, it might be asked how much the invest- to two or three alternatives
ment costs would have to be reduced to allow the 4) The projected capital outlay has been deter-
desired profit and an acceptable amortization. mined
A calculation of annual revenues based on 5) The projected production costs for the prod-
the quantity of product that can be sold in the uct have been determined
market and its price allows a variational calcu- 6) The payout time and profitability have been
lation of this type to be made. The expected profit estimated
is deducted from the sum over the project life. The main task in preliminary design is to ob-
The remainder represents the maximum avail- tain a more exact calculation that takes into con-
able investment and operating costs that have sideration all costs up until commissioning. The
first step toward this objective is to work out the The need to hold down design costs and main-
engineering details. tain the performance level of in-house engineer-
A qualified project leader directs the pre- ing staff on their specific tasks, forces even large
liminary design. Specialist engineering teams chemical firms to collaborate closely with exter-
(e.g., for process calculations, equipment de- nal engineering contractors who will later be in
sign, plant layout, and estimations) provide ad- charge of executing the project. External engi-
visory support [40]. neering firms usually offer cost advantages be-
cause they have so much experience in their rou-
tine fields that they can quickly estimate reliable
cost figures for projects based on well-known
3.1. Preliminary Design Costs processes.
The funds and time spent on preliminary de- The client’s role is limited – at least as far as
sign can be considerable, depending on how pre- established processes are concerned – to mak-
cise planning and budget are to be. Although ing process knowhow available, purchasing li-
highly accurate results are always sought, tech- censes, and cooperating with the engineering
nical documentation and calculations should contractor in customizing the plant to relevant
be refined only to the degree necessary for requirements.
subsequently deciding whether to implement Contract forms have been developed for the
the project. Events during the preliminary de- collaboration between the customer and the en-
sign period may force the abandonment of the gineering firm in the basic-design and/or de-
project. tailengineering phases, as well as for procure-
If the feasibility study predicts very favorable ment, supply, construction, construction super-
profitability, less accurate calculations (say ± vision, and commissioning (Section 4.2.2).
20 %) may be acceptable; if the project is ex- Another option for cutting design costs is for
pected to be marginally profitable, better ac- the chemical firm to obtain a process license,
curacy (e.g., ± 10 %) is needed. Figure 7 [41] with the licenser providing the complete “basic
shows the basic information required for given design.”
accuracy levels. Even if the upper and lower lim-
its of the percentage ranges in Figure 7 are made
equal, the probability of exceeding the projected 3.2. Final Selection of Site Locations
costs is greater than that of falling short of them.
This is primarily due to subsequent additions After the feasibility study two or three suitable
that are not known at the time when the calcu- sites are often available for the new plant. A final
lation is performed. A “contingencies” item is decision can be made only after detailed study.
therefore commonly included in the calculation. If the potential sites are close to the client’s
Design costs for preliminary calculations at parent plant, similar fringe conditions can be as-
various accuracy levels, according to the Ameri- sumed to apply for the purpose of site compari-
can Association of Cost Engineers [42], are pre- son. If, however, a branch plant is to be erected
sented in Table 1. Specific empirical figures are in a foreign country, conditions are usually dif-
given in [43]. ferent which means that each of the alternatives
has to be carefully analyzed.
Preliminary design requires a special project Important constraints besides those already
team consisting of persons with the necessary listed in Section 2.4 include:
expertise. A chemical company whose engineer-
ing staff is oriented mainly toward maintenance 1) Medium- and long-term capacity of the local
and the occasional addition of new pieces of (national) market to absorb the product
equipment should not attempt to perform the 2) Export to nearby countries
preliminary design of a large plant or a branch 3) Availability, quality, and price of raw mate-
plant in-house. Such a department lacks appro- rials
priate experience and is also short of capacity. 4) Political situation and risks (e.g., risk of na-
tionalization)
Figure 7. Accuracy of cost assessment based on available information [41]

Table 1. Design costs for cost estimates [43]
Type of estimate Synonymous terms Accuracy, % Costs as percentage of

project value
Order of magnitude estimate ratio estimate ± 30 – ± 50 0 – 0.1

seat of the pants estimate
ballpark estimate
guesstimate
Study estimate evaluation estimate ± 20 – ± 30 0.1 – 0.2
predesign estimate
factored estimate
Preliminary estimate sanction estimate ± 10 – ± 25 0.4 – 0.8
funding estimate
authorization estimate
budget estimate
Definitive estimate project control estimate ± 5 – ± 15 1–3
Detailed estimate tender estimate ±2–±5 5 – 10
contractor’s final cost estimate
5) Tax laws, tariffs, possibility of repatriating in which each block represents a unit operation
profits or, in complex plants, a plant section containing
several unit operations. The blocks are joined
If, for example, one country has cheap raw
by lines representing the principal material and
materials but a limited capacity to absorb the
energy streams.
product, partial upgrading of the raw material
The first step in process design is to establish
and fabrication of intermediate products should
the operating parameters for the major stages in
be considered. Manufacture of the end product
the process:
would then take place where there is adequate
long-term demand and a suitable distribution 1) In the case of chemical reactions, the pres-
network. sures, temperatures, concentrations, reactor
A team of the client’s experts should perform type, and reactor size are defined or esti-
a thorough on-site examination of each alterna- mated on the basis of the reaction kinetics
tive before the final decision is made; close con- and experience gathered in existing plants
tact with national and local government agencies 2) In the case of mixing (stirring, gas dispersion,
is important. The recommendations of this team suspension) or separation (distillation, dry-
should weigh heavily in the choice of site. ing, precipitation, filtration) of substances,
Partnership with qualified domestic enter- the pressures, temperatures, concentrations,
prises is becoming increasingly popular (e.g., and type and size of apparatus are defined or
joint ventures). estimated on the basis of established rules.
If information needed for setting the operat-
ing parameters or designing reactors/apparatus
3.3. Process Design (See also → Process is not known, it must be obtained in bench or
Development) pilot-plant tests or calculated approximately on
the basis of similar reactions or unit operations.
The feasibility study defines the process objec- The unit operations used in process engineer-
tive, i.e., it specifies products (type and quan- ing are described in [44–49].
tity), feedstocks and auxiliaries (type and quan-
tity), and local conditions (environmental situa- Process Flow Diagram. The next step is to
tion, elevation, climate, energy situation). This prepare a process flow diagram from the block
objective, together with the overall state of the flow diagram. Standard symbols (e.g., defined in
art and the experience of the operater, licenser, DIN 28 004) are used to represent reactors and
or plant design and construction contractor, pro- other apparatus, including equipment for con-
vide the basis for process selection. veyance and control of important streams.
Process selection can be done most simply In complex plants, it may be necessary first
in the form of a block flow diagram (Fig. 8), to prepare a synoptic flow diagram (Fig. 9) and
Figure 8. Block flow diagram (olefin plant)
then to draw up individual flow diagrams, giving balance is attained as simply as possible. The
the needed detail for plant sections and auxiliary following must always be ensured:
operations. 1) Compliance with emission limits.
2) Plant safety (i.e., adequate margins of safety
Determination of Final Process Data. relative to critical operating conditions).
When the desired effective operating time per 3) Maintenance of product quality.
year has been set (e.g., 8000 h, corresponding 4) Control of startup operations and of planned
to 91 % availability), the design capacity of the and unplanned shutdowns. This includes
plant (i.e., the mass throughput per unit time) is specification of components and media re-
defined. The next step is to compile the spec- quired (e.g., heatup burners, cooling and
ifications for all feedstocks, auxiliaries, cata- purge gases, and pressure-reducing valves).
lysts, utilities, and end products, and to esti- These calculations must also take account of
mate what intermediate products are to be ex- long-term effects, such as increasing contami-
pected. These specifications include relevant nation (resulting in a higher pressure drop and
physical and chemical properties as well as the less efficient heat transfer) or aging of catalysts
battery-limit states of all substances received (lower conversion, changes in temperature and
and shipped. concentration profiles).
On the basis of the process flow diagram, the The calculations give mass and energy values
preliminary process parameters, and the above- for all important points of the plant, preferably
mentioned specifications are used to prepare ma- downstream of each unit operation. The mass
terial and energy balances for the process steps and energy flow rates and the final process pa-
and finally for the entire process. This objec- rameters are tabulated at the foot of each process
tive is not generally achieved in a single set flow diagram and keyed to points in the plant
of computations. The experienced process en- (Fig. 10).
gineer must use an iterative procedure to mod- The preliminary sizes of the reactors and ap-
ify the process flow diagram and/or the process paratus are now checked and, if necessary, mod-
parameters so that a closed material and energy ified in the light of the final process parameters.
1003
Chemical Plant Design and Construction
Figure 9. Overall process flow diagram (olefin plant)

If a plant is to be operated at reduced capac- important function of such programs is to sim-

ity for short or long intervals, appropriate calcu- ulate the equipment when connected into sys-
lations must be performed. If unacceptable op- tems and to identify and remedy bottlenecks (de-
erating conditions or bottlenecks are found in bottlenecking).
certain plant sections, additional measures must Process simulators have integrated substance
be taken (e.g., supplementary heating, gas recy- data bases that meet the needs of most applica-
cle, or the partial shutdown of some unit oper- tions. Further data can be obtained from data
ations). A similar treatment applies when occa- bases [53] and compilations of physical and
sional overloading of the plant is expected. chemical data [54–56]. Proprietary data and em-
Other factors are then determined, namely the pirical factors (interactions, long-term effects)
quantities of substances that have to be avail- can also be input.
able for the initial charges and the storage ca-
pacities (including those outside the battery lim-
its) needed for feedstocks, auxiliaries, interme- 3.3.1. Optimization
diates, and end products.
Finally, a detailed process description is writ- The object of plant optimization is to obtain
ten. Assessments of known processes are avail- an optimal economic result. This is a continual
able on a subscription basis from Chem Sys- problem during the operation of a plant, espe-
tems Inc. and SRI International. A survey of cially if its capacity is diminished by aging or
production processes for initial and intermedi- increased by expansion, or if product earnings,
ate organic products is given in [50]. costs, or expected profits change during its life-
time. The parameters necessary for subsequent
Process Simulation. Process design calcu- optimization must, if possible, be established in
lations for multistage, interconnected processes the design stage. They relate to process design,
with material and energy recycle soon become the plant concept, the selection of equipment,
very complex. Computer tools enable designers and the process control system.
to develop key concepts in a reasonable time and The operating result is primarily determined
thus to optimize the process according to certain by product earnings, expected profit, and costs.
criteria (investment cost, yield, energy economy, Obviously, costs decrease with longer plant ser-
production costs). “Flow sheeting” programs are vice life and higher availability. The feasibility
complicated computer programs that model unit study should provide data about both of these
operations mathematically and allow them to be factors.
interconnected. A plant can thus be represented Most chemical production facilities are op-
as a network of unit operations with material and erated around the clock. Since fixed costs rep-
energy streams and thus simulated [51], [52]. resent a significant proportion of the operating
The material and energy balances can be calcu- costs (interest payments, personnel, energy sup-
lated as functions of the process parameters. An ply, overheads), high availability is essential for
iterative procedure can be carried out to bring an optimal result and is often more important
the balances to equilibrium for individual and than maximal process optimization.
interconnected unit operations. Single-train plants with many unit operations
Simulation programs are available for in series are more susceptible to breakdowns
steady-state operation and dynamic conditions than plants in which the critical sections are
(e.g., ASPEN PLUS, DESIGN II, PROCESS, multitrained or have standby equipment. The
HYSIM, and SPEED UP). drawback of a larger capital investment must be
Design calculations for reactors and other weighed against the advantage of a higher ex-
equipment (e.g., heat exchangers) can be per- pected availability.
formed with special-purpose design programs In established methods of risk analysis, the
and process simulation packages. The program plant concept is systematically analyzed on the
for a fired tubular furnace (e.g., steam reformer) basis of process flow diagrams, process descrip-
allows calculation of process conditions as a tion, equipment lists, and operating experience
function of the configuration and geometry of (e.g., reliability and maintainability, RAM). An
the tubes, burners, and combustion chamber. An initially higher expenditure on equipment not
Figure 10. Individual process flow diagram for a plant section

a) Heat exchanger; b) Purification tower; c) Control valve; d) Block valve; e) Steam trap; f) Blind; g) Control loop (temperature,
pressure, flow)
only results in better availability but also low- tal costs and variable production costs (feed-
ers repair and maintenance costs. stocks, auxiliaries, utilities, energy consump-
Optimization of process engineering must tion, disposal) as the following simplified ex-
then be investigated. The process design ob- amples show:
jective of a unit operation or a plant can be 1) In plants with high gas throughputs, the
achieved with various combinations of capi- cross-sectional areas of piping, fittings, and
reactors/apparatus determine the pressure cannot be completely optimized during the de-
drop in the plant and thus the energy that sign phase. The dimensions of such a program
must be expended to transport the gaseous exceed any reasonable and justifiable computer
media. Large cross sections, with corre- effort.
spondingly higher capital costs, lead to lower It is useful to begin by performing an
energy costs and vice versa. economic – technical analysis of the process
2) In heat exchangers, such as those used for based on the “standard design” (not yet opti-
waste-heat recovery, the quantity of trans- mized). This analysis reveals the process stages
ferred heat increases with increasing ex- in which significant fractions of the costs are
change area (= higher capital costs) and in- incurred, consumed, or transformed, and ex-
creasing flow velocities (= higher pressure presses them as a proportion of the total costs.
drop = higher energy consumption) and vice As a rule, a few key points dominate the eco-
versa. nomics of the entire plant. Optimization work
can thus be facilitated right from the start.
In each case, there is an optimum for given If individual cost items in subsequent operat-
economic parameters. The second example is ing periods are expected to deviate significantly
more complicated, because not only must the from the values chosen initially, new calcula-
cost optimum for a given quantity of heat be de- tions can be made for the few key points, tak-
termined but also the optimal quantity of heat to ing maximum and minimum values (sensitivity
be exchanged. It must further be taken into con- analysis).
sideration that the cost of waste-heat transfer to A practical application of this method is the
the environment decreases when more heat is comparison of designs “on an evaluated basis.”
recovered. The costs for the necessary capital (often with
Similar examples could be cited for the opti- allowance for the expected return on investment
mization of conversions, the optimization of the and tax considerations) and for capital goods are
product mix when products are coupled, and the represented in a formula. The actual require-
simultaneous minimization of byproducts and ments for capital and capital goods are sub-
residues and of their reprocessing or disposal. stituted into the formula. The lowest resultant
The examples lead to the following conclu- value identifies the best concept for the selected
sions: identical plants do not have a unique opti- premises. Details of cost structure and financing
mum; instead, they have a variety of optima that need not be known.
depend on the crucial technical and economic
constraints of a given site location. Optimal de- Optimization of Individual Tasks. For
sign of the plant is based on economic parame- the calculation of various reactor types,
ters employed in the design phase. Subsequent see → Mathematical Modeling and → Model
deviations may partly offset one another or may Reactors and their Design Equations.
accumulate in the result. Enthalpy – temperature (H/T ) diagrams and
The objective is thus to assign cost factors to exergy analysis (formerly also availability anal-
the functional dependences of the process design ysis) are being increasingly used in conjunction
or, in mathematical terms, to express the depen- with simulation programs to optimize the en-
dence of the costs on the engineering variables in ergy economy of the plant [57]. This is espe-
the form of a cost function. Limiting parameters cially worthwhile for processes with high heat
always have to be introduced, e. g., emissions, turnover or high compression ratios. Apparatus
plant reliability, product quality, and safety fac- costs must be determined separately.
tors for equipment and material (to ensure max- The design of heat-exchanger networks is
imum lifetime and on-line time). Optimization based on analysis of the heat fluxes in the net-
can be solved by a suitable method (linear and work as a whole. One representative of such
nonlinear optimization, mixed-integer program- methods is the Linnhoff “pinch” method, see
ming, gradient and search procedures). → Pinch Technology. This technique uses the
The large number of variables in a plant de- H/T diagram with cumulative curves for the
sign and the high degree of interaction in plants quantities of heat dissipated and absorbed in var-
with many process loops mean that a facility ious sections of the plant at defined tempera-
Next Page
tures. The method can be applied to utility sys- The boundaries between “routine” optimization
tems and to the integration of thermal engines during process design and a special, supplemen-
[58]. Software is available for the design of heat- tal optimization study are not clearcut. The prac-
exchanger networks by this method (e.g., Hex- tical operability of a plant should never be ig-
tran and Advent). An alternative method for nored. Overly complicated circuits, highly com-
heat-exchanger/utility networks is based on the plex control systems, dewpoints and corrosion
mixed-integer method [59]. limits that are too close together, and increased
Synthesis-gas processes offer an example of maintenance costs can all wipe out calculated
integrated loops. These reactions are mostly cost savings.
exothermic, and an attempt is made to transfer Continuous optimization is needed through-
the excess heat of reaction to steam instead of out the service life of a plant. Digital process
cooling water. Use of waste heat from gas pro- monitoring and control systems allow appropri-
duction to supply the heat required for gas purifi- ate data acquisition, storage, and archiving. Pro-
cation and converting processes has led to a va- cess data processing systems print data in the
riety of integrated loops with significant reduc- form of diagrams, graphs, and tables. They are
tions in operating costs, for example in ammonia an indispensable aid in the commissioning and
and methanol synthesis and in the production of optimal operation of plants. Process-based sim-
nitric, sulfuric, phthalic, and maleic acids. ulation programs allow on-line and off-line bal-
Another optimization possibility is the use ancing and prompt detection of abnormal occur-
of heat pumps. The mechanical compression of rences.
vapors and their condensation at higher pres-
sure offers interesting solutions with relatively
low investment costs, for example in the distilla- 3.3.2. Safety Aspects and Environmental
tive separation of components with similar boil- Control
ing points (e.g., such as ethylene – ethane and In the following section the essential ele-
propene – propane). ments of safety and environmental control are
The operability and economics of integrated treated – relevant to the design and construc-
loops must be checked during process design. tion of a chemical plant, using Germany as an
This can be done by using Linnhoff’s method example. The laws and decrees cited are only
of heat integration analysis [60], [61]. valid in Germany, however, there are similar
laws in other countries, e. g., those issued by the
Process Synthesis. The development of op-
EPA and OSHA in the United States and the
timal combinations of unit operations is an it-
“Stoomwezen” in The Netherlands.
erative process that is now carried out with the
The materials present in a chemical plant,
aid of simulation programs. An advanced pro-
their processing, and processing equipment con-
gram performs computer-aided process synthe-
stitute a source of risk to persons and property
sis by automatically generating design variants
in the plant area and its surroundings. The level
and selecting the best ones under consideration
of risk depends on the nature, extent, and prob-
of uncertain data, i.e., when material properties,
ability of occurrence of injury or damage [66].
thermodynamic data, and kinetics of partial pro-
Safety engineering institutes measures that re-
cesses are incomplete. Results can be applied
duce (limit) the risk to a degree acceptable to
to some practical problems [62–64] especially
the public require that:
to heat-exchanger networks (HENs) and utility
systems. 1) Potential hazards must be identified
The design of separation processes is much 2) Effective safety standards against these haz-
more difficult because of the great number of ards must be established
species present. Process synthesis has therefore 3) The standards must be transformed to engi-
not reached a comparable level. A survey of the neering and/or management safety practices
design of column cascades appears in [65]. 4) It must be proved that the safety level meets
Optimization has to be customized for every requirements
application, key points can be identified only by 5) The effectiveness of the adopted measures
economic and technical analysis of a process. must be evaluated and improved [67]
Previous Page
Safety-related functions are the responsibil- The “hazard and operability study” (HAZOP)
ity of governmental supervisors, the plant op- is often used and can reveal weak points in plant
erator, and the engineering contractor. In ap- equipment and operation while the facility is still
proving the plant, the regulatory authorities not under design. This method of risk analysis has
only ratify the safety objectives but also evalu- been proven in years of use [79–81].
ate the scope and quality of the safety measures.
The operator is responsible for correct execution Wastewater. The wastewater generated in a
of these measures. The design and construction plant is collected and treated in systems classi-
firms must assist the operator in complying with fied according to water quality (e.g., severely
the standards [68–70]. contaminated, moderately contaminated, un-
contaminated, rain water). If the systems are
properly designed, the treated wastewater can
3.3.2.1. Protection Against Emissions be released into a system approved by the local
authority [82], [83].
The following important environmental protec- Wastewater produced in case of fire (fire
tion goals are necessary for the approval of a new fighting water) must be collected in a retention
plant and are therefore the concern of authority basin whose capacity is usually sufficient to hold
engineering: the water used in 1 h against the design fire- case
[84].
Landscape and Surroundings. The erec-
tion of a plant on a site not expressly intended Soil. Soil protection is afforded by sealing all
for industrial use can run into difficulties [71]. plant areas that might be contaminated by haz-
It is also necessary to clarify in advance what ardous liquids or solids under normal operating
effects the plant will have on nearby residential conditions or in an accident [85].
areas and what levels of emissions and noise are
acceptable in industrial areas [72–75]. Waste. “Waste” denotes all those substances
The appearance of the plant must be appropri- and parts that cannot be recycled to the produc-
ate for the surroundings. This factor is governed tion process or otherwise reused.
by restrictions on building height, design, mate- As early as the process selection step, spe-
rials, color, the construction of visual barriers, cial attention must be paid to waste prevention
and landscape plantings. because waste is difficult to dispose of. In large
chemical complexes, wastes from one process
Air Pollution. Pollution control begins with can often be used as feedstocks in other pro-
the classification of hazardous substances and cesses. This alternative should be investigated
prevention or minimization of emissions to the closely in feasibility studies performed at a very
atmosphere. Release under normal operating early stage of the project [86–88].
conditions is prevented by using appropriate de-
3.3.2.2. Noise Control
sign and process conditions (e.g., gas collection
and recovery systems, use of low-polluting burn- The primary objectives of noise- control design
ers, catalytic gas purification, use of high-quality are in compliance with contractual and legal pro-
flange connections and seals) [76–78]. visions while ensuring that the plant is easy to
Safe operation of a chemical plant must be maintain and runs economically. Noise can be
ensured to prevent or minimize the hazard to the controlled at the source by selecting low-noise
surroundings. Possible sources of danger (acci- products and processes. Low-noise equipment
dents) include release of large amounts of haz- often has the welcome side effect that it offers
ardous substances (gases, liquids, solids), fire in low energy consumption and longer service life.
the plants, and explosions [72]. Basic concepts and research in acoustics are
Safety aspects must be taken into considera- discussed as examples in [89–92].
tion in process design, plant layout, and equip-
ment selection; in the construction, operation, Regulations. Noise- control regulations are
and maintenance of the plant; and in the training intended to protect the surroundings and the
of plant personnel [69]. plant personnel.
Protection of the Surroundings . The basis Measurement of noise at DIN 45 635 part 1,
for immission noise limits in Germany is the machines and following parts
Bundes-Immissionsschutzgesetz (Federal Im- Average level and assessed level DIN 45 641
temporal fluctuating sound processes
mission Control Act) and the TA Lärm (Engi- Sound propagation in the open VDI 2714
neering Directive on Noise Control) contained Assessment of working noise in the VDI 2058 sheet 1
neighborhood
in it [93]. The directive lays down permissible at workplace regarding danger to VDI 2058 sheet 2
immission noise levels as a function of land use hearing
(Table 2). The site of measurement varies; as a with regard to various occupations VDI 2058 sheet 3
Sound projection from industrial VDI 2571
rule, it is 0.5 m in front of an open window of the construction
residence. Regulatory practice has been to treat Noise from piping VDI 3733
Noise abatement for ventilation and air VDI 2081
the permissible levels cumulatively: if several conditioning plants
plants emit to one receiver, the maximum level Personal soundproofing VDI 2560
must be distributed among all the emitters. Fur- Soundproofing by mufflers VDI 2567
Soundproofing by shielding VDI 2720 sheets 1 + 2
thermore, if a plant is expanded, its permissible Soundproofing by metal cladding VDI 2711
noise-level contribution must not be exceeded.
Table 2. Permissible noise immission levels Design. The engineering firm must guaran-
tee compliance with noise regulations at the
Type of builtup area Standard value, dB(A) workplace and in residential areas. The contract
Day Night should also stipulate the type of noise measure-
ment and the operating conditions at the time of
Exclusively industrial utilization 70 70
Mainly industrial utilization 65 50 measurement.
Equal housing and industrial 60 45 Planning for noise control begins in the pre-
utilization liminary design phase and continues through ba-
Mainly housing areas 55 40
Exclusively housing, health resorts, 50 35 sic and detail engineering. The engineer must
and hospitals carry out the following activities:
1) Calculate the permissible sound level for the
entire plant on the basis of the maximum
level allowed in the residential area and avail-
This approach ensures that the permissible able studies on the workplace noise-level
total noise level in the residential area is not ex- limits.
ceeded. On the other hand, new plant sections 2) List noise-producing components and estab-
are only approved if they meet strict noise stan- lish their permissible sound levels. Noise-
dards. protection practices are dictated by practical
Protection of Plant Personnel. The basis for and economic considerations.
noise regulations at the workplace in Ger- 3) Prepare noise specifications (including per-
many comprises the Arbeitsstätten Verordnung missible sound levels) as part of the bid spec-
(Workplace Regulation) [94] and the relevant ifications for all noise-emitting equipment.
sections of the Unfallverhütungsgesetz Lärm 4) Check the bids (e.g., for machinery, control
(Accident Prevention Code) [95] which contain valves) to ensure that noise requirements are
references to DIN standards and VDI guide- satisfied.
lines. These regulations set a maximum per- 5) Compile specifications for silencers, hoods,
sonal noise level of 85 dB(A) for an 8-h shift and and insulation; check bids and orders for
recommend the use of personal hearing protec- these items.
tion above 85 dB(A). Personal hearing protec- 6) Compile noise specifications for the build-
tion must be worn at levels over 90 dB(A). ing.
The most important regulations for plant de- 7) After the design is complete, write a design
sign follow: report on residential and workplace noise
levels.
8) Inspect installation of equipment at the con-
struction site.
9) Measure noise levels of noise-generating Plant safety and reliability must not be im-
equipment at the workshop where it is manu- paired by noise- control measures. Low-noise
factured, and also later when it is installed in machines must therefore be preferred over loud
the plant and the plant is on stream. machines with soundproof enclosures. If hoods
10) Prepare a final report. or enclosures cannot be avoided, accessible ar-
eas inside noise enclosures on gas-handling de-
Manufacturers of noise-generating equip- vices must be provided with adequate ventila-
ment have many ways of reducing noise. Ex- tion, gas alarms, and possibly fire fighting sys-
amples follow: tems. Noise- control barriers and shielding must
Electric motors: Reduction of cooling air re- not block escape routes.
quirement, use of low-noise cooling fans, use
of improved insulation.
Control valves: Division of large-expansion 3.3.2.3. Occupational Safety and Health
cross sections into smaller areas (perforated
cage), division of pressure release into mul- The principal requirement in occupational safety
tiple stages, optimized flow control. and health is that physiological and psychologi-
Air coolers and small cooling towers: Re- cal burdens on the employees caused by working
duction of rotor peripheral velocity, modifi- and other conditions must be limited to a gener-
cation of blade profile, increase in number of ally accepted level. Measures must also be taken
blades, use of low-noise gears. to prevent or control risks in case of an accident
Pumps: Optimization of impeller design, [70].
avoidance of cavitating conditions, reduc- The occupational safety and health authori-
tion of impeller peripheral velocity (below ties have defined general conditions for ventila-
45 m/s). tion, lighting, and ambient temperatures at work-
Steam generators and process furnaces: places, protection against weather and noise,
Low-noise, forced-air burners; use of and the safe use of traffic routes inside the
ceramic-fiber linings on interior walls. plant. Accident insurance regulations are es-
Compressors: Frequency- controlled drives, pecially important for plant layout and pro-
low-noise oil systems, direct drives (no cess design of chemical plants. These rules
gears), low-noise surge-limit control. concern: harzardous operations, work involving
hazardous substances [77], [78], use of special
Important secondary practices of noise abate- auxiliary equipment, and ergonomic design of
ment include: the workplace [96]. Suitably equipped “social”
facilities such as rest and changing rooms, wash-
1) Soundproof enclosures rooms, toilets, and medical stations must also be
2) Soundproof hoods and barriers included in the design [94].
3) Soundproofing insulation on piping, ducts, Warning of unavoidable dangers must be
and machine housings given, and appropriate protective measures must
4) Silencers in the form of absorbers, res- be instituted (e.g., signs marking fire or explo-
onators, or combinations of both types sion hazard zones and appropriate safeguards
against ignition). Escape routes and protected
In most chemical plants, on-battery sound areas with emergency lighting, fixed personal
pressure levels can be held to 85 dB(A) by means protection facilities (emergency showers), and
of careful design. Large compressor sections are alarm systems must be provided [94], [97].
an exception; levels up to 100 dB(A) can be ex- Appropriate layout of buildings and appara-
pected and such areas must be designated as tus or enclosures around particularly dangerous
high-noise areas. equipment help to minimize injuries and damage
Investment costs for noise control normally [96].
range from 0.5 to 3 % of total plant material Effective fire fighting measures include short
and installation costs. These percentages are ex- access routes as well as fixed or mobile fire-
ceeded if residential restrictions make it neces- extinguishing equipment with an assured supply
sary to enclose the entire plant.
of extinguishing media and an adequate action Emergency power-generating units are

radius. needed to maintain safety-relevant drive and
Occupational safety and health measures also control functions (including emergency lighting,
apply during construction of the plant. They re- communication facilities, and computer-aided
late to the structural design and size of the plant process control systems) during power outages.
and the construction methods. As much as pos- In the case of particularly critical equipment, a
sible of the equipment used in subsequent nor- separate power source (e.g., battery, instrument-
mal operation of the plant must be available dur- air reservoir, nitrogen reservoir) must be pro-
ing commissioning for protection of the workers vided to bridge the startup time of the emergency
[96]. generator.
Control functions and process control sys-
tems play a vital role in reliability and safety.
3.3.2.4. Plant Availability Relevant process parameters and the points
where they are to be measured must be de-
Capacity and profitability calculations for a fined during process design so that indicators
chemical plant are normally based on 8000 h/a and alarms will warn the operating person-
on-stream (corresponding to roughly 330 d/a). nel promptly whenever operating conditions be-
Shutdowns are generally planned at intervals come abnormal.
of one or two years to allow cleaning of heat ex- Allowance must also be made for opera-
changers, apparatus, and piping; charging of new tor error so that consequential damage (e.g.,
catalysts and chemicals; replacement of worn overheating or pressure buildup in uncontrolled
mechanical parts; and prescribed inspections by exothermic reactions) can be avoided. Auto-
regulatory authorities. matic emergency-shutdown devices are pro-
Unplanned shutdowns are usually caused vided for such cases. They are often redundantly
by mechanical defects or automatic emergency included in both the measurement and shutdown
shutdowns when operating parameters are out- systems. They must be regularly inspected by the
side the limits for normal plant operation. plant operator or the regulatory authorities.
Important items of equipment are dupli-
cated (standby equipment) to ensure continuous
operation between scheduled shutdowns. This 3.3.2.5. Authority Engineering
is standard practice for continuously operated
pumps and reciprocating compressors. Standby The construction and operation of chemical
turbine compressors are not necessary because plants are affected by many legislative provi-
of their longer maintenance intervals. In auxil- sions and regulations that are concerned with
iary systems (e.g., the lubrication system), how- environmental protection and plant safety [68].
ever, the necessary reliability is provided by in- These requirements have major consequences
stalling standby pumps and filters. for plant design and construction. It is no longer
If operating conditions make regeneration or sufficient to comply with all laws, standards, and
cleaning necessary during production, standby specifications applicable to a given plant at a
equipment is again used (e.g., fixed-bed reactors, given site. Instead, a formal approval process,
molecular-sieve adsorbers, dryers, and filters). usually with public participation, must be gone
Piping (as used to convey suspended solids or through in the design phase. Only then can con-
powders) may be susceptible to plugging. Instal- struction of the plant begin [98], [99].
lation of standby piping or flushing connections The length of the approval process depends
may be desirable. on the type of plant, the environmental sensitiv-
Measures to ensure reliable plant operation ity of the plant site, and the nature of the approval
during power outages must be considered at an procedure. Another important point is whether
early stage (emergency planning). the project involves expansion of an existing fa-
The drives of important process equipment cility or an entirely new “grass-roots” plant on a
(e.g., cooling-water pumps, instrument-air com- previously nonindustrial site.
pressors, boiler feedwater pumps) are usually The time taken for an application for a con-
dual (electric motor plus steam turbine). struction permit to be approved is usually six
months to a year, but sometimes longer. This is In order to clarify these points, informal con-
preceded by a lead time of about a year, dur- tact with the regulatory authorities should be ini-
ing which the conditions for the plant are dis- tiated as soon as the initial concept of the plant
cussed and preliminary talks are held with the is set.
regulatory authorities. The total span from the
investment decision to groundbreaking is there- Process Design/Basic Engineering. Re-
fore about 1.5 years. This is a substantial fraction sults obtained during the preliminary phase are
of a total project duration of 2 – 3 years. used for process design/basic engineering (e.g.,
The granting of construction and operational for planning off-gas collection and combustion
permits requires close collaboration between the systems and wastewater systems). A preliminary
plant owner, the engineering firm, and the au- safety analysis may be useful to identify poten-
thorities (Fig. 11). All activities aimed at devis- tial risks (e.g., threat to the environment due to
ing an approved plant concept are grouped under release of substances, or risk to the plant due
the heading “authority engineering” and are usu- to hazards in the vicinity). This kind of analy-
ally the responsibility of the engineering firm. sis is called an environmental impact study [73].
Typical activities carried out during the design The results of such an analysis may influence
phase are listed below. the plant layout [72], [75].
Feasibility Study/Preliminary Design . Detail Engineering, Construction, and

The feasibility study and preliminary design Commissioning. Many authority engineering
include technical and economic optimization of activities take place in the detail engineering
the process with minimization of environmen- phase. They include:
tally harmful factors. The following parameters
are established 1) Preparation of project documentation
2) Preparation of a detailed safety analysis
1) Nature and quantities of substances present 3) Engineering escort duty during approval pro-
2) Waste and residues ceedings
3) Wastewater 4) Implementation of design changes required
4) Emission of air pollutants during approval proceedings
5) Type and design of plant equipment 5) Management of partial approval procedures
6) Nature (open or closed) of processing sys- that take place in parallel with the main ap-
tems proval procedure
7) Safety and reliability standards [77], [78] 6) Selection of experts and technical cooper-
ation with them to clarify detail questions
As soon as site selection is complete, the fol- raised during approval proceedings
lowing questions must be answered:
The activities of engineering and authority
1) Which authorities are responsible for ap- engineering must be well coordinated if the
proving the construction and operation of the progress of work at the construction site is not
plant? to be held back.
2) Which laws must be observed? An important point for the success of a project
3) Which regulations, especially local ones, is that the engineering activities concerned with
must be complied with? early civil work activities should be taken care
4) What is the public opinion at the intended of early. This is especially important for the plot
location? plan and buildings; escape, emergency and ac-
5) Has any nearby project gone through ap- cess routes; and fire fighting concept.
proval proceedings recently? If so, with what The authorities grant partial approvals (e.g.,
result? How much time did the proceedings for civil work, erection, and commissioning of
take? plant sections) so that progress is not unneces-
6) Will special restrictions over and above nor- sarily delayed. They also check that relevant reg-
mal legislation and regulations apply to the ulations and provisions are observed during con-
site? [75], [100], [101]. struction and installation. When construction is
Figure 11. Principle flow scheme of German authority approvals procedure
complete the entire plant is examined by the au- (The main elements of basic engineering docu-
thorities. Deficiencies must usually be remedied mentation are described in Section 5.1).
immediately. The authorities only grant permis-
sion for commissioning when the acceptance re-
port has been made. 3.4.1. Equipment Specification from the
During commissioning proof of compliance Process Engineering Standpoint
with approved levels of emissions, wastewater
Equipment dimensions and capacities are dic-
values, etc. must be submitted. Measurements
tated by the process. Data from the process flow
are difficult to perform and time consuming. If
sheet can be used for the sizing of process equip-
improvements to the plant are required at this
ment, machinery, piping, etc. Examples of data
stage, they may be very expensive.
that can be derived in this way are the diameter,
number of trays, and tray spacing for distillation
towers. These design data are entered in pro-
3.4. Basic Engineering cess engineering data sheets (Fig. 12) that con-
tain all relevant specifications for the specialist
The focus has so far been on process design engineer. For example, the data sheet for pro-
(process flow diagrams and parameters such as cess equipment includes a schematic drawing
operating temperatures and pressures and flow with overall dimensions, operating and design
rates). Now the geometric dimensions of indi- pressures and temperatures, number and nom-
vidual equipment items, the design temperatures inal diameters of nozzles and manholes, mate-
and pressures, the materials of construction, and rial of construction, corrosion allowance, insula-
the layout of the entire plant must be established. tion thickness, etc.: in short, the information that
the equipment design engineer needs in order 1100 ◦ C and pressures from vacuum to several
to perform strength calculations and prepare a hundred bar.
more detailed drawing. For pumps, the data sheet The selection of a material is dictated by three
must show normal, maximum, and minimum criteria: mechanical stress, thermal stress, and
flow rates, inlet and outlet pressures, operating chemical attack. Seldom do these three types of
temperature, material of construction, type of stresses occur singly; the usual case, in which
medium, and physical properties of the medium. two or all three are present at once, governs ma-
On the basis of this information the mechanical terial selection.
engineer can select the optimal pump with the The most important ferrous materials used in
best efficiency. plant construction, are the following steels:
Specifications are prepared similarly for con-
Predominantly mechanical stress:
trol systems, safety valves, and all other items of
Structural steels
plant equipment. The nominal diameters of pip-
Fine-grained structural steels
ing are calculated for the specified flow rates,
Quenched and tempered steels
physical properties of the streams, and econom-
Steels for low-temperature service
ically acceptable pressure drops.
Coexisting mechanical and thermal stresses:
Steels for high-temperature service
High-strength alloy steels for high-
3.4.2. Materials of Construction
temperature service
Heat-resisting steels
See also → Construction Materials in Chemical
Steels for hydrogen service at elevated
Industry.
temperature and pressure
Materials of construction in chemical plants
Chemical attack together with thermal and
must be able to withstand mechanical, chemical,
mechanical stresses:
and thermal stresses and must not be attacked by
Ferritic chromium alloy steels
the medium with which they come in contact.
Austenitic chromium – nickel steels
Two criteria must be met:
Ferritic/austenitic steels (duplex steels)
1) Materials must be approved for use in pres- The selection of steels for predominantly
sure-bearing parts under the pertinent regula- mechanical stress depends on strength, tough-
tions, i.e., their guaranteed values, process- ness, and weldability. States of mechanical
ing, and permissible service conditions are stress in individual parts are often incompletely
defined and can be reproduced at any time. known. Design is therefore based on approxi-
2) Materials must be suitable from the corro- mate rules derived from simple loading modes
sion standpoint. Their behavior and proper- (tension, crushing, bending). The time depen-
ties should show little or no change under the dence of load (e.g., static or cyclic) must also be
action of the media with which they come in considered.
contact. The operating pressure, operating tempera-
ture, and number of load cycles are crucial for
Material selection should be solved by close
strength calculations of apparatus and piping.
collaboration between the materials specialist,
The temperatures determine the strength (yield
the designer, and the process engineer or chemist
point). The use of fine-grained structural steels,
[102–109]. The materials most commonly em-
with higher yield points than normal carbon
ployed in process engineering are unalloyed,
steels allows design of equipment with thinner
low-alloy, and high-alloy steels. Both solid steel
walls and thus results in significant savings in
and cladded steel fabricated by rolling, weld
weight and welding work.
overlaying, or explosion bonding are used in
Equipment must be sized so that it does not
vessels, towers, heat exchangers, storage tanks,
fail by ductile fracture, brittle fracture, fatigue,
piping, and other equipment.
or creep (Table 3).
The choice of steels for chemical service, or
Stresses. Materials of construction must where chemical attack occurs together with ther-
withstand temperatures from ca. − 180 to mal and mechanical loads, is difficult because
Figure 12. Data sheet with process information for a deethanizer

several types of corrosion are possible, each re- with the desired properties can be produced with
sulting in a different type of failure. The problem these systems.
of material selection in this case is often very Other metals and alloys used in plant con-
complicated because corrosion is due to multi- struction are aluminum, titanium, zirconium,
component systems. and tantalum. See also → Construction Mate-
Table 3. Nature of failure of materials rials in Chemical Industry.
Nature of fault Cause Measure
Ductile fracture unacceptably high calculation with

loads elasticity limit or
safety correction
values
Brittle fracture stress also below the calculation of the
permissible elasticity brittle fracture safety
limit by influences with fracture
from mechanical values on
the basis of
1) multiaxial state of the combined effect
stresses of material faults and
2) thermal stress stresses
3) state of material highly dependent on
4) state of defect 1) material
production
5) geometry of 2) quality of
component manufacture
3) fault finding and
4) fault description
with nondestructive
testing
Fatigue introduction of crack calculation with
and crack conventional strength
propagation by values for alternating
alternating stress stress (e.g., fatigue
limit) taking into
account all stresses as
with the danger of
brittle fracture
fatigue crack consideration of Figure 13. Alloy systems most commonly used in chemical
propagation at mechanical fracture plant construction
existing fault sites principles and their
mathematical
utilization Corrosion. For a detailed description of cor-
Creep, time interval time-dependent
deformations and
1) calculation with
creep strength rosion, see → Corrosion. Corrosion phenomena
fractures at high (e.g., selective corrosion, diffusion, crevice cor-
temperature and 2) calculation of rosion, and pitting) must be given special atten-
stresses below the time yield limit
elasticity limit 3) crack propagation tion but are not amenable to design calculations.
by existing defects The most frequent form, general corrosion,
can be dealt with by appropriate corrosion al-
lowances of ca. 1 – 5 mm. The corroded mate-
Alloys. Corrosion-resistant alloy systems rial must not, however, interfere with the pro-
have been developed which form a passive layer cess or affect the product (discoloration or flavor
that affords protection against corrosion. Such changes in the pharmaceutical, beverage, and
alloys must remain stable during subsequent food industries).
treatment (e.g., welding) so that phase precipita- Charts, tables, empirical values, and process-
tion does not affect the passivity of the material. ing guidelines are available for material se-
The most commonly used alloy systems for lection according to corrosion criteria. Carbon
chemical plant construction are those based on steel, for example, is attacked only slightly by
iron, nickel, and copper. Figure 13 shows these water, but severely by water in the presence
three groups schematically, with the maximum of air. Pitting occurs if air-containing water is
concentrations of the alloying elements singly heated, or if oxygen is present in steam and con-
or in combination. A great number of alloys densate piping; this often rules out the use of car-
bon steel. Although stainless steels resist many the presence of organic substances, especially at
media, they also suffer pitting or stress corrosion elevated temperature.
cracking in the presence of halogen compounds.
Material selection has to take into account
both the chemical nature and the flow of the 3.4.3. Plant Layout
medium. Rapid motion of a liquid along a pipe
wall can accelerate corrosion, whereas a protec- The layout becomes a high-priority item during
tive film often forms on the surface when the basic engineering [111].
velocity is low. For large plants, the planner begins with
Intergranular stress corrosion cracking may 1: 500 layout sketches that merely show the
be caused, for example, by alkaline solutions space required for individual units. Such pre-
above 100 ◦ C under pressure in welded vessels liminary layouts are used to determine the most
of unalloyed steels. expedient arrangement with possible transfer
Transgranular stress corrosion cracking can points at battery limits for material and energy
occur in equipment made of austenitic Cr – Ni streams. Conventional layout techniques em-
steels, while crevice corrosion results from im- ploy adhesive films and overlaying of transpar-
proper fastening of tubes in tube sheets; these ent sketches; PC and CAD programs are also
types of corrosion are both accelerated by vi- finding use.
brations (corrosion fatigue). The layout should include approximate data
Electrolytic corrosion can take place when on the positions and sizes of storage areas for raw
metals widely separated in the electrochemical materials, intermediates, and end products, as
series (e.g., copper, iron, and aluminum) are not well as pipe bridges, roads, underground piping,
insulated from one another in the same piece of and sewerage. Control room and electrical sub-
equipment apparatus and come in contact with stations, compressor buildings and service fa-
conductive liquids. cilities, and road and rail connections are shown
Other corrosion-related problems are hydro- with their overall dimensions. The accessibility
gen embrittlement, embrittlement at low temper- of plant equipment for repair and maintenance,
ature, and high-temperature corrosion. construction aspects, safety, and inspection must
The same degree of corrosion protection can be considered from the very start. The conse-
often be obtained with several materials. In such quences of later expansion must also be taken
cases, price, service life, and profitability must into account.
be balanced [110]. If the existing information is adequate, the
Costs can be saved by applying more noble layout should be drawn to scale. The layout and
materials as a coating or cladding. Electroplated the process flow diagram then permit assessment
coatings cannot be employed in chemical plant of the production sequence, mass transport, and
apparatus because they do not offer long-term storage (Fig. 14).
protection. Claddings of nonferrous metals, their On the basis of the layout and specifications,
alloys, or austenitic steels can be used if the con- buildings should be inserted next as needed
tact between the corrosive stream and the load- (ground plan, number of floors, height between
bearing steel shell of an apparatus can be pre- floors).
vented by appropriate design.
In simpler cases, plastic coatings can be Layout Model. The layout can also be made
employed in place of cladding. Stoving fin- into a block model (Fig. 15). Layout models
ishes (duroplastic) have proved suitable for have proved especially useful for complicated
contaminated cooling water and weak acids installations such as refineries and petrochem-
in heat exchangers (service up to 240 ◦ C). ical plants. They convey a general impression
Polytetrafluoroethylene coatings are highly re- of the final appearance of the plant, even at
sistant to acidic and alkaline substances (up to an early stage. Approximate 1 : 100 or 1 : 50
300 ◦ C). Rubber and hard rubber, respectively, models of equipment items are made of foamed
are effective against weak acids and salt solu- polystyrene or a similar material and can then
tions up to ca. + 100 ◦ C. It should be kept in mind be moved around to establish suitable positions
that plastic coatings tend to swell and unbond in and spacings.
Figure 14. Plant layout plan

a) Steam generation; b) Process steam generation and fuel oil system; c) Oil wash with dispersed oil separator; d) Propene – pro-
pane separation; e) Debutanizer; f ) Depropanizer; g) Deethanizer; h) Condensate and slop system; i) Hydrogen methanization;
j) Hydrogenation; k) Propene refrigeration; l) Ethylene refrigeration; m) Charge gas compressor; n) Caustic wash; o) Water
wash with gasoline stripper; p) Cracking furnaces; q) Substation, transformer station; r) Control room; s) Social facilities;
t) Ethylene – ethane separation; u) Charge gas dryer; v) Acetylene conversion; w) Demethanizer; x) Cold box; y) Compressor
house; z) Pumps, compressors
The layout model includes steel structures cesses involving flammable materials. The out-
but does not cover the details of pipe runs. It door setting, however, entails more expense for
mainly serves as a basis for discussion, permit- shelter against weather, heat, and cold.
ting a number of fundamental questions to be For some types of plant equipment, the layout
clarified. criteria are nearly always the same. For exam-
At this stage of basic design (at the latest), the ple, turbocompressors, reciprocating compres-
design engineer is thus able to decide which parts sors and their drives; coolers and oil circulation
of the plant will be outdoor or enclosed facilities, lines should be located in sheds or compressor
and whether it will be on one or more levels. A buildings. Pumps, in contrast, are usually placed
process plant should be outdoors unless there are outdoors; they are installed in pump houses only
pressing reasons to enclose it. This allows sub- if this is necessary on environmental grounds
stantial savings in construction costs; machinery (e.g., for noise protection).
and equipment remain more accessible; and the Production facilities that are sensitive to am-
danger of fire and explosion is reduced for pro- bient conditions (e.g., film and fiber produc-
Figure 15. Layout model (hydrocracker complex), courtesy of Lurgi AG
tion, paper mills, pharmaceutical plants, catalyst 2) Nominal diameter, pressure, material of con-
plants, packaging facilities) must be set up inside struction, and design information of piping
buildings. Raw materials and products that are 3) Field instruments, control devices, and con-
sensitive to moisture and sunlight must be stored nections between them
in covered areas or enclosed buildings. 4) Special fittings required for process control
In contrast to the solidly constructed build- and safety, e.g., check valves, safety valves,
ings required in Europe, buildings in tropical re- level gauges, condensate drain lines
gions can be lightly constructed. Sheds open on 5) Significant dimensions of equipment and
two sides, affording protection against wind and machinery
rain only, may be adequate if the process does 6) Essential data on materials of construction
not call for climate control.
3.5. Calculation of Plant Costs
3.4.4. Preliminary Piping and Once the engineering documents for the calcula-
Instrumentation Diagram tions at the requisite accuracy are available, plant
costs can be determined. It is useful to employ
A piping and instrumentation diagram, based a scheme as shown in Table 4 for this. A “stan-
on the process flow diagram, is needed for dard” scheme has been proposed by Aries and
more accurate calculations at the preliminary de- Newton [112] and other authors. The calcula-
sign stage. For the basic engineering package it tion is subdivided into three groups of items:
should contain the following information: equipment, bulk materials, and indirect costs;
each has to be calculated differently.
1) All equipment and machinery, drives, piping The equipment group includes all itemized
or transport routes, and fittings (including in- plant equipment such as towers, reactors, and
stalled spares) heat exchangers, vessels and machinery that are
Table 4. Example of a calculation scheme for plant costs
Designation % of 1 % of 1 + 2 % of 1 to 3 % of 1 to 4
Equipment
Columns 12.5 7.4 4.7 3.4
Reactors 6 3.5 2.2 1.6
Heat exchangers 22.5 13.3 8.4 6.1
Tanks 18 10.6 6.7 4.8
Furnaces 10 5.9 3.7 2.7
Machines 26 15.3 9.6 7
Other equipment 5 3 1.9 1.4
Total 1 100 59 37.2 27
Bulk material
Steel structures 8.3 4.3 3.1 2.2
Piping 25 14.7 9.3 6.7
Control systems 15 8.8 5.5 4
Electricals 9.5 5.6 3.5 2.5
Noise abatement 0.7 0.4 0.3 0.2
Catalysts 2.5 1.5 0.9 0.6
First charges 1.2 0.7 0.4 0.3
Spare parts 7.5 4.4 2.8 2
Total 2 69.7 41 25.8 18.5
Total 1 + 2 100
Package units
Erection (including material for 43 27 19.5
insulation and painting)
Civil work 16 10 7.2
Total 3 59 37 26.7
Total 1 + 2 + 3 100
Other costs
Packing 3 2.2
Transport 2 1.4
Insurances 1.5 1.1
Planning costs 14 10.1
Supervision of construction 5 3.6
Commissioning 4 2.9
Allowance for inflation 4 2.9
Unforeseen 5 3.6
Total 4 38.5 27.8
Total 1 to 4 = project costs 100
calculated ex factory without packaging. These 3.5.1. Equipment

items are normally specified individually in en-
gineering design allowing a rapid, detailed, pre- Because most pieces of equipment are “tailor-
liminary calculation to be made. made,” manufacturers’ price lists are not often
The bulk materials group covers items such available for cost calculations. The best way to
as pipes, control systems, electrical equipment get accurate prices is to submit enquiries to the
and materials, insulation, and paint. Exact de- manufacturers. This can be done on the basis
termination of these costs is expensive and time of the design specifications, but applicable stan-
consuming and can be done only on the basis of dards (e.g., DIN or ASA), design specifications,
detailed material takeoffs (MTOs). This group and acceptance conditions (e.g., AD-Merkblatt
also takes in civil work, structural steel and erec- documents, ASME Code, TÜV, Lloyd’s) must
tion work. be indicated. Such inquiries are, however, time-
consuming and make a great deal of work for
Other costs include engineering, procure-
the vendors; they are accordingly unwelcome.
ment, construction supervision, commissioning,
Therefore inquiries are only made with compli-
travel costs; price inflation during the construc-
cated equipment and machinery. Simpler items
tion period; insurance, duties, and contingen-
are estimated on the basis of in-house docu-
cies. These items can be only calculated for the
ments.
project as a whole and cannot be determined un-
An engineering firm normally has a data base
til the equipment and bulk materials costs are
containing important data (including weights
known.
and prices) on all equipment and machinery cov- costs. It should therefore be employed only when
ered by orders and inquiries in recent years. The a highly accurate estimate is needed.
data base must be kept up to date, this requires The engineering documents available in the
close cooperation with the purchasing depart- design stage are usually incomplete. The trend
ment. Armed with such a system, the firm can in bulk materials estimation is therefore toward
make fairly accurate estimates, for example, of applying multiplication factors to the estimated
the cost of heat exchangers per square meter total equipment costs. The latter can be obtained
or per kilogram, given the size, type, pressure, only, however, by analyzing projects already re-
and material of construction. The same holds alized. In order to achieve satisfactory accuracy,
for towers, reactors, and vessels; here also the separate multiplication factors must be derived
size, pressure, temperature, and material must for each plant type and each process. The larger
be known. The costs of simple machinery can the number of facilities evaluated, the more ac-
be determined similarly. The use of computer curate are the multiplication factors. The per-
programs makes it an easy matter to calculate centages given in Table 4 represent multiplica-
the weights of equipment items. tion factors for the individual cost items of a
Before such prices are incorporated into the typical chemical plant; normally, material and
estimate, correction factors must be determined construction costs for a bulk item are determined
so that current prices can be obtained. There are separately. Other multiplication factors are pub-
two reasons for such a correction: lished in [7].
1) The figures stored in the data base cannot be If the required accuracy is ≤ ± 10 %, how-
completely up to date, and there may be a ever, these two estimation approaches are com-
lag of half a year or more before the order is bined.
issued
2) Purchase prices depend not only on market Civil Work and Structural Steel. For
trends but also on the economic situation of structures such as compressor houses, control
the manufacturer rooms, laboratories, and workshops the enclosed
volume is usually determined and the costs esti-
The use of such a data base system neces-
mated by using unit costs. In the case of adverse
sitates the availability of appropriate cost-index
soil conditions or heavy structures, it may be
figures for price adjustment. More information
necessary to perform a preliminary static cal-
on cost-index figures is given in Section 2.2.1.4.
culation so that the foundation size and/or the
number of piles needed can be determined more
3.5.2. Bulk Materials accurately. The other civil-work items are often
handled by means of multiplication factors.
Provided the engineering documentation (lay- The same holds for structural steel, although
out, piping and instrumentation diagrams etc.) is here the costs are found in terms of the weight
exact enough (see Fig. 7, Section 3.1), bulk ma- and the price per tonne for heavy, medium, and
terial costs can be calculated fairly accurately light steel construction.
by applying unit prices (per piece, m, m2 , m3 ,
kg, etc.) to material takeoffs. Installation costs Control Systems. The trend toward plant au-
are also derived from takeoffs classified accord- tomation and increasingly strict safety standards
ing to functional disciplines (unit prices for con- have increased the contribution of control sys-
struction activities plus costs of site prepara- tems to plant costs. The degree of sophistication
tion, erection equipment, materials, etc.). If unit of the control system of a chemical plant de-
prices from an in-house data base system are pends strongly on the future operator. Accord-
used for bulk materials, they must be adjusted ingly, it is often impossible to work with gen-
in the same way as equipment prices (see Sec- eral multiplication factors. Costs are therefore
tion 3.5.1). calculated from the number of control circuits,
Another option is to obtain detailed current required computer capacity, number of displays
unit prices from the manufacturers or construc- and control panels, etc. Multiplication factors
tion contractors. This method yields accurate re- are used only for installation materials.
sults, but is time consuming and involves high
Electricals. Since the number and sizes of equipment, scaffolds, site roads, fencing, secu-
electric motors are normally known from the de- rity, first aid, and other items.
tailed equipment estimate, it is relatively simple
to determine cost-intensive electrical items such 3.5.3. Other Costs
as motors, transformers, switchgear, and cables.
Costs for other items, such as grounding, light- Bulk material costs are commonly determined
ning protection, lighting, and installation mate- for each section of the plant, whereas “other”
rials are handled with multiplication factors. costs are calculated for the project as a whole.
Multiplication factors are employed for items
Erection. The determination of equipment such as packaging, shipping, insurance, price es-
installation costs on the basis of unit-weight for- calation, and contingencies.
mulas gives adequate accuracy; it is also simple Before the contingency factor is established,
because the cost of major equipment (other than it is necessary to make certain that the calcula-
machinery) is usually based on weight. A sim- tions for the various functional disciplines do not
ilar method can be used for machinery, but the contain any multipliers of this type, since other-
calculation process is often divided into equip- wise contingency amounts grow out of control.
ment setting (unit-weight formulas) and equip- Engineering, procurement, construction super-
ment alignment (hourly basis). vision, and commissioning costs are, however,
Installation costs for bulk material items (e.g., usually determined individually.
control systems, electrical, insulation, and paint)
and for catalysts and first charges are usually de- Engineering and Procurement Costs. In
termined by applying multiplication factors to addition to the approximate method of obtain-
the material costs. ing engineering and procurement costs by ap-
The civil work discussed above normally in- plying multiplication factors to plant costs, two
cludes installation costs. Erection costs for struc- more accurate methods are available: calculation
tural steel are established on the basis of unit- of engineering hours and procurement hours on
weight installation formulas and subdivided into the basis of equipment items or the documents to
heavy, medium, and light steelwork. be prepared for each functional discipline. The
Serious difficulties arise in the accurate esti- latter is more accurate.
mation of piping installation because the exact
material takeoff and the exact routes of pipe runs Itemized Equipment Approach. The num-
are seldom known. The labor cost of installation ber of hours per equipment item can be referred
depends on the number of welds and flange con- to the work done on each item; all equipment
nections, pipe diameters, wall thicknesses, ma- items are then added together with multiplica-
terials of construction, and installation heights. tion factors for other functional disciplines. Al-
Estimation is therefore done with unit-weight ternatively, a total number of hours per equip-
prices tabulated for each nominal diameter or ment item can be determined for all functional
nominal-diameter group. A separate calculation disciplines. This total number of hours varies
is needed for each material of construction. widely, depending on the processes employed,
Installation costs can also be estimated from the scope of authority engineering, and exist-
the number of welds per meter of straight pipe ing design documents. It generally lies between
and the nominal diameter but this requires de- 600 and 1200 h per equipment item. This method
tailed knowledge of the piping design. can be used only if experience has been gathered
Vendors normally offer package units, such with existing plants of the same type.
as cooling towers and refrigeration units, includ-
ing installation; the entire scope of supply and Calculation Based on Documents to be
installation costs given in the bid specifications Prepared. The estimation of man-hours based
can therefore be incorporated in the calculation on the number and size of drawings and docu-
as a lump sum. ments presupposes a great deal of experience in
The calculation of the construction of a plant project execution and the availability of docu-
must also cover the costs of site preparation, ment breakdowns from earlier projects (includ-
utilities, construction equipment, transportation ing empirical figures for the hours spent on all
other activities, such as procurement and expe- 3) An on-call installation crew who remedy
diting, dealing with vendors, and inspection of mechanical problems and/or reinforce the
equipment). This procedure also calls for an ex- shift crew in the workshop
act definition of the individual services (service 4) Specialists assigned by vendors for commis-
catalog) so that the various functional disciplines sioning special equipment and machinery
can be clearly isolated from one another. In prac- 5) Consulting or supervision by licenser’s per-
tice, a blend of the two methods of calculation sonnel
is often used. 6) Possible increased deployment of process
After the man-hour requirements for engi- and specialist engineers from the operator’s
neering and procurement of a project have been engineering department
determined, they are subdivided into categories 7) Consultation or supervision by personnel be-
and multiplied by appropriate hourly rates to de- longing to the engineering contractor
termine the costs. Travel, communications, re-
production, computer costs, and the cost of the Other Commissioning Costs. These costs have
model must be added. to be estimated case by case. For routine pro-
cesses where most products are directly mar-
Construction supervision costs are often ketable, raw material, auxiliary, and fuel costs
obtained by applying multiplication factors to can be virtually neglected. In larger, more inno-
the equipment and bulk materials groups or to vative plants running difficult processes, these
the engineering hours. A better, slightly more costs may be very high. Further difficulties may
complex method is to determine the costs on the arise if the market for a new product has to be
basis of construction and manpower schedules. created. Other commissioning costs are divided
The manpower schedules include supervi- into
sory personnel for the functional disciplines 1) Training of company personnel (possibly in
used by the operator and the engineering con- the licenser’s facility)
tractor; also the installation specialists provided 2) Raw materials and auxiliaries as well as util-
by the manufacturers of complex apparatus, ma- ities needed to replace defective charges or
chinery, and package units; and supervisory per- product not up to specification
sonnel, if any, assigned by the licenser. 3) Travel expenses for personnel not belonging
In contrast to engineering costs, estimates are to the company
based not on hours but on person-days and daily
rates. These rates normally include accomoda-
tion and food costs for personnel. The calcula-
tion must also cover overtime, travel expenses,
and costs for the construction office and its op- Indirect Costs. Other indirect costs can ac-
eration. count for a large portion of investment costs.
They are:
Commissioning Costs. The costs of com-
missioning relate to the time from the end of 1) Licensing fees
erection to the start of production. They are also 2) Land costs
classified as investment and must therefore be 3) Land development costs
incorporated into the estimate. Commissioning 4) Fees for government inspections and ap-
usually lasts one to three months, but up to six provals
months for very large multistage plants. This 5) Financing costs
cost group includes the following items: 6) Administrative costs and costs for possible
Personnel Costs. Personnel costs are generally expansion of sales organization to market the
determined in the same way as installation su- product
pervision costs. 7) Public relations work to inform the public
about the new plant
1) Operating personnel on a rotating shift basis 8) Working capital, such as raw materials
2) Laboratory personnel on a rotating shift ba- stocks and finished product storage
sis
3.6. Conclusion of Preliminary Design and 4.1.3), and straight transfers of know-how
Phase for processes not protected by patent (Sec-
tion 4.1.4).
The last step in preliminary design is the prepa-
ration of a report containing the following infor- 4.1.1. Patent Licenses
mation:
Suppose chemical company A has developed a
1) The updated feasibility study.
process that is under patent protection but is
2) Profitability calculation with graphs of ac-
wholly or partly covered by the earlier protection
cumulated revenues and expenses, the break-
of chemical company B. Company A will seek
even point, and profits (similar to Fig. 6, Sec-
to join B by exchanging patent rights, a mutual
tion 2.3.1). If a clear decision in favor of one
grant of rights to use the patents, or the purchase
of the alternative investments is possible, the
of a patent license from B. Usually, company
profitability calculation is limited to a single
B asks for compensation in an amount that de-
proposal. If, however, entrepreneurial ques-
pends on the age, the importance of its rights, and
tions figure in the analysis, the report should
the degree of overlap. This fee only covers the
include the two best alternatives.
particular use in question. The licenser does not
Inaccuracies in the primary documents and
disclose experience above and beyond the pub-
the amounts added to allow for these should
lished contents of the patents. If the fee asked
be established and specified in all calcula-
is too high for A or there are doubts about the
tions.
validity of B’s patents, then in the absence of an
3) Schedule for financing requirements.
agreement A can either seek to have the courts
4) Schedule for personnel requirements.
declare B’s patents invalid or can disregard them
5) Time schedule for the phases of execution up
and risk legal action by B.
to the start of production.
6) The project manual containing all the studies
and results from preliminary design (basic 4.1.2. Process Licenses
engineering documentation), including the
estimate. As a further example, B has plant-scale experi-
ence while A only has experience with a pilot
plant for the same or a similar process. Even if
the new process is clearly an improvement, it is
4. Contract Writing and Forms of expedient for A to purchase B’s experience be-
Contracts cause inevitable setbacks and lost time on going
from the pilot plant to a first production-scale
4.1. Licensing Agreements facility (“scaleup risk”) usually cost more than
a process license.
Process development has become so expensive In acquiring a process license, company A
that development costs can seldom be covered will commonly be confronted with one or more
by royalties. Aside from government-funded re- of the following possiblities:
search, new processes are developed chiefly
by production-oriented chemical companies or Case 1. To date, company B has only built
petrochemical concerns, which regard license its own full-scale plant. It has not yet granted
fees as incidental income. In cases where en- any licenses to third parties and therefore has no
gineering firms hold licensing rights, they either design documentation on plants with different
arise from license agreements with production feedstocks and utilities, as needed by A for its
companies or represent improvements to estab- plant. B is not prepared to guarantee third-party
lished processes. plants, but only to offer a patent and know-how
Licensing agreements may relate to patent contract. Once such a contract has been signed,
licenses (rights to use granted patents, Sec- it permits A to examine the operating records
tion 4.1.1), process licenses (which include and assemble the documentation needed for the
patent rights and all know-how, Sections 4.1.2 projected plant.
Case 2. Company B is interested in world- For profitable processes, royalties amount to

wide licensing of the process, maintains a 1 – 4 % of the product value for the life of the
large in-house engineering department, and has patent, but for at least 10 years. A running roy-
worked out the complete process design. In addi- alty is a license fee levied on a specific mea-
tion to the license and know-how contract, B will surable quantity of production from a specified
offer guarantees, and may even be ready to un- technology. A paid-up royalty generally repre-
dertake engineering, procurement, construction sents the current value of 10 years’ royalties and
supervision, and commissioning with separate is thus equal to 5 – 6 times an annual royalty. If
billing for these services. supply contracts are in effect, the royalty may
A variant of this case is when B has devel- also be calculated in terms of the plant value
oped the process in collaboration with an engi- (e.g., 5 % of the value of the entire facility or
neering contractor and granted exclusive use or 10 % of the value of the process facility proper)
construction rights to that company. Here again, or as a fixed amount per unit product, often with
licensee A cannot seek competing bids because price escalator clauses.
the process is a “monopoly.”
Case 3. As in case 2, B owns the process de- 4.1.3. Process Licenses via Engineering
sign and is prepared to give guarantees in the Contractors
context of a license and know-how contract. B
leaves it to licensee A, however, to select an engi- Cooperation with engineering contractors often
neering contractor to construct the plant. Com- increases the licenser’s chances of obtaining ad-
pany A requests competitive bids from several ditional revenue by licensing its entire operat-
engineering firms, each of which must enter into ing know-how. The licenser simultaneously re-
a confidentiality agreement regarding the work- duces the load on in-house engineering capac-
ing documents delivered to it. Licenser B will ity because the external engineering firm bears
opt for this procedure when its patents have the main load of establishing engineering docu-
given it the lead on the market for a long enough mentation, interpretation, and training. Licens-
time and disclosure to several engineering con- ing is therefore being increasingly handled by
tractors will lead to the wider use of the process engineering firms who check and extend the pro-
and generate royalties. cess documentation and may also optimize some
equipment items or process steps. Improvements
Case 4. Since patent protection for processes are possible when new operational know-how
declines in value with age, it is in B’s interest has not yet been implemented as redesigns in
to secure its know-how to the maximum extent. the licenser’s first full-scale plant; this is difficult
Accordingly, B will hand over the acquisition with good processes because of market require-
and licensing rights to one or two trusted en- ments (supply contracts for products). Engineer-
gineering firms in the form of a license agree- ing firms are able to undertake all design, sup-
ment (which may be exclusive or nonexclusive, ply, and plant construction tasks, including com-
for stated countries or for the world). Licensee A missioning. Competitors offering the same pro-
can then acquire process rights, engineering, and cess will design different plants because of their
plants only by contracting with one of these en- different design and construction experience. In
gineering companies. comparing bids, the customer must therefore
Process licensers usually give limited guaran- consider not only the price, but also the refer-
tees on the functioning of the process and prod- ences, guarantees, and quality of the bidders.
uct quality, but their liability commonly extends Production companies granting licenses only
only to half of the license fee. Commissioning tend to guarantee the typical basic features of
assistance is generally given – in special cases, the process (yield and product quality). They
after training of the operating personnel in B’s never take responsibility for plants erected by
own plant or another licensee’s plant. In devel- third parties. Engineering firms thus see an op-
oping countries, licenses are only granted with portunity to guarantee the whole plant. This is,
long-term management contracts, which many of course, only possible when the company has
banks require as a condition of financing. built many plants and has wide experience and
knowledge. The licenser generally remunerates 4.2. Design and Supply Contracts with
the engineering firm for this aid by paying it part Engineering Contractors
of the royalty in return for the additional respon-
sibility. Should an investor bring in an engineering firm
If the engineering firm has no special expe- to construct its plants? This question arises
rience, it will supplement the licenser’s process whenever the investor does not have adequate
guarantee with a guarantee of correct engineer- in-house engineering capacity. In the following
ing design; in the case of supply contracts, it sections it is assumed that the investor needs an
will relieve the customer of some risk by giving outside engineering contractor for a construction
a material and price guarantee. Depending on project.
experience, the firm may also guarantee the ca-
pacity of the plant and the utilities consumption 4.2.1. Selection of Engineering Contractors
within stated tolerances. When processes are li-
censed from the licenser either directly or via an 4.2.1.1. Importance of Risk in the Plant
engineering firm, it is important for the licenser Business
to ensure that “secret know-how” remains se-
cret and that the exchange of experience, includ- The intention to build a chemical plant presents
ing supplementary discoveries of the licensee the investor and the candidate engineering firm
(feedback), remains confidential. Naturally, the not only opportunities for success but also risks.
licenser will compensate the licensee for eco- The erection of a large plant entails above-
nomically valuable improvements. average, qualitative and quantitative risks. The
following features of the large-plant business are
crucial in risk assessment:
4.1.4. Know-How Contracts via Engineering
Contractors 1) Complexity and duration of the project
2) Responsibility for long-term operation of the
The know-how contract is a modification of the plant
process license agreement. When patent protec- 3) Transfer of investor’s entrepreneurial risks to
tion ceases, the process licenser attaches great the engineering firm and vice versa
importance to keeping its undisclosed know- 4) Priority of the project in investor’s and engi-
how secret. This know-how is given to a few neering firm’s business results
engineering firms under strict confidentiality 5) High financing budget
agreements, which are binding on the firms’ em- 6) Heavy dependence on market development
ployees. Companies interested in the construc- of the product
tion of plants may be told solely what has already
been published. They can only obtain more pre- A unique feature of the plant design and con-
cise information after having signed a secrecy struction business is that these risks are gener-
agreement. ally cumulative, so that both the investor and the
The texts of know-how contracts are compa- engineering contractor must practice risk man-
rable to those of license agreements, but the fee agement, i.e., measures aimed at identifying, as-
is lower. The activity of engineering firms and sessing, and limiting risks.
any guarantees they might give are similar to Since the investor and the engineering con-
those discussed under license agreements. tractor deal with potential risks in different ways,
Some engineering companies have often the formulation of a plant construction contract
managed to improve current processes that are between these parties is extremely important:
no longer protected so that new applications re- both parties must be satisfied that their interests
sult. In most cases, however, the activity of such are protected.
firms is limited to simpler processes (e.g., gasi- Generally, there is no benefit to the investor
fication and gas purification), unit operations, or in looking too hard for every competitive advan-
improvements in thermal economy, automation, tage. This is especially so when the engineering
environmental protection, and disposal technol-
ogy.
contractor may fall into the danger of trading off manner so that the potential bidder can precisely
plant quality for savings as a result of accept- identify the task to be performed.
ing below- cost prices and unsatisfactory con- In order to make bids comparable, all bidders
ditions; such shortcuts often become apparent must be given the same documents and informa-
only after the plant is on-stream. As a rule, sharp tion. The bid invitation should always include
competition forces engineering firms to seek an the following:
optimal outcome at minimum cost. These con-
1) General description of project with site lay-
siderations have promoted cooperation between
out plan.
investor and engineering contractor and have be-
2) Services and deliveries desired (e.g., basic
come crucial points in contract drafting.
engineering and know-how, complete en-
gineering, complete engineering plus pro-
4.2.1.2. Selection and Award Criteria curement assistance, delivery with or with-
out construction and commissioning).
The investor develops his own criteria for select- 3) Precise data on the process or process
ing an engineering firm to carry out a construc- stages to be covered by the bid. If the bid-
tion project. Bid invitations and bid comparisons der does not have rights to the process, the
are used to award a contract that is acceptable to invitation must state whether the process li-
both parties. The most important criteria follow: cense is also to be covered or whether this
will be handled by the investor directly with
1) Does the engineering firm have experience or the process licenser.
references relevant to the tasks it may have 4) Production capacity and product quality.
to perform? 5) Available feedstocks, auxiliaries, and utili-
2) Does the firm have experience in the coun- ties (composition and quantity available).
try and locality where the plant is to be built 6) Availability of electric power and water for
(logistics)? construction purposes.
3) Is there a danger of communications prob- 7) Available infrastructure (e.g., workshops,
lems during execution of the project (lan- laboratories, warehouses, and social facili-
guage barrier)? ties).
4) What kind of staff situation exists within the 8) Overall time schedule.
engineering firm? Will it be able to organize 9) Guarantees desired for production, quality,
good project management? consumption rates, materials, date of com-
5) What standards and specifications will gov- pletion.
ern the work? Can the engineering firm en- 10) Pricing terms of payment desired.
sure compliance with standards that may be 11) Standard codes and guidelines to be ap-
new and unfamiliar to it? plied.
6) What references does the firm offer with re- 12) Deadline for bid submission.
gard to the quality of supply and services and 13) Period for which bid must remain binding.
compliance with time schedules? 14) General conditions.
7) Is the firm’s credit rating adequate for the
requirements of a large contract? A qualified engineering firm may still decide,
not to submit a bid – possibly because it sees too
In the bid invitation, the investor states what little chance of realization of the project or a
is wanted and required with regard to the tech- chance of success in the face of stiff competi-
nical concept (process technology, scope of de- tion.
livery and services, quality requirements, etc.) The simplest approach to bid comparison is
and the commercial concept (type and contents to prepare schedules of prices, delivery times,
of contract, financing, marketing, etc.). terms of payment, terms of delivery, exclusions,
A thorough, detailed bid represents a signif- and miscellaneous conditions. Large investor
icant cost to the bidder. A company will only companies send preformulated tables to bid-
make this investment if it has a good chance of ders, especially for standard processes; the bid-
winning the competition. The bid invitation must der merely has to enter the services, exclusions,
therefore be written in a clear, understandable and miscellaneous conditions.
The differences found in the bid comparison of decision. The person in charge of the nego-
should be analyzed and then discussed with the tiations must therefore know when the limits of
bidder. Discussions are often time consuming his jurisdiction have been reached. The decision
and should be carefully planned. An efficient whether to accept or reject conditions proposed
negotiating program should cover the following by the other party must then be passed on to an
topics, in order: appropriately higher level in the company hier-
archy.
1) Fundamentals, infrastructure, overall con- Second, there are modifiable (dispositive)
cept, process engineering, economics goals for the negotiating parties. The limits of
2) Equipment, material, and services to be pro- negotiability (breaking points) are reached when
vided; exclusions one or the other party’s willingness to make com-
3) Special and general conditions; guarantees promises has been exhausted or when accep-
4) Price tance of the other party’s proposals would result
5) Time schedule, including intermediate tar- in incalculable risks.
gets As a rule, the engineering contractor has to
decline to accept liability for indirect and con-
sequential damages. Furthermore, the contractor
4.2.2. Form and Content of Contracts cannot be held responsible if postponements of
deliveries and services occur as a result of cir-
4.2.2.1. Basic Concerns in Contract Writing cumstances beyond his control (e.g., war, revo-
lution, strikes). Other possible breaking points
In writing the contract, both the party inviting include excessive guarantee requirements.
bids and the bidder can propose, negotiate, and The engineering contractor will reject a pro-
conclude agreements. The elements of the con- posal for unlimited liability. Limitations on lia-
tract must therefore cover all those aspects that bility include:
the potential contracting parties deem not satis-
factorily governed by other provisions (usually 1) Limitation of total liability for delays and/or
by relevant legislation). nonattainment of process guarantees and/or
Efforts to reach contractual agreement aside for costs incurred for the correction of design
from relevant legislation are primarily devoted errors in equipment or during construction
to making the potential risks manageable. De- and installation.
tails on contract drafting can be found in [37], 2) Time limits on the guarantee for materials,
[38], [113–115]. typically x months after commissioning of
Since the profit margins of the engineering the plant; if commissioning is delayed and
contracting business are small, it is important this is not the fault of the engineering con-
to identify, assess, and allot all risks. For a tractor, a “not later than” date must be agreed
multimillion-dollar project differences of a few on.
tenths of a percent can decide whether a bid is 3) The liability provisions set forth in the con-
accepted or rejected. tract should bar recourse to liability laws
Often the only other possibility for absorbing because these do not make appropriate al-
risks is the contractor’s profit, which averages lowance for the special features of the plant
ca. 2 – 4 % of contract value in the plant design construction business.
and construction business. Such a small margin 4) No liability for indirect or consequential
can only cover limited cost overruns on a single damages, such as lost profits, loss of use,
project. and loss of production. From the engineering
Methods of dealing with potential risks at the contractor’s standpoint, this is a nonnego-
contract drafting stage can be classified into two tiable clause. If such liability were accepted,
groups. First, each of the parties must consider the existence of even financially sound con-
the well-established policies of its company. The tracting companies might be endangered.
extent of potential risk for the company resulting
from deviation from such a policy governs which
person in the company hierarchy has the power
Next Page
4.2.2.2. Contract Types and Provisions Reimbursable Contract with Target Price. In
this type of contract, the engineering contractor
Although there are many types of contracts, the accepts a share of the risk for staying within the
following are particularly important: calculated service costs. A target price is set on
the basis of the calculated costs; the engineering
Engineering Contract. An engineering contractor generally takes a certain percent par-
contract normally governs compensation for ticipation in any overrun, but receives a bonus if
engineering and procurement services, and the the work comes under the target price.
supervision of construction, and commission- The target-price provision can also extend to
ing. It usually provides for reimbursement of equipment and construction costs. A sufficiently
incidental costs such as travel, communications, exact definition of the services is required so that
computer support, and accomodation. a fairly reliable calculation is possible. The in-
The contract can be for complete engineer- vestor gains the advantage of better budget con-
ing, including procurement and supervision at trol.
the construction site up to the successful com- Lump-Sum Engineering Contract. If the bid
pletion of the guarantee run. invitation for a chemical plant defines the scope
The contract may, however, be limited to par- of work well enough, a lump-sum bid can be pre-
tial services, such as basic engineering, detailed pared. This type of contract has the advantage for
engineering, procurement services, supervision the investor that the budget is set in advance (pro-
of construction, supervision of commissioning, vided no additional work is needed in the course
and supervision of third-party engineering ser- of the project). The engineering contractor has
vices. much better control over the project with regard
An engineering contract does not include de- to costs (man hours) and schedules. In contrast
livery of plant equipment or the performance to the reimbursable contract, the investor has a
of plant construction. The procurement services limited say in decisions taken during the project.
that may be included are generally carried out
“in the name and on behalf of ” the investor. Supply Contract, Turnkey Contract. As a
The contractor’s liability in an engineering rule, a supply contract commits the engineering
contract extends to correcting design errors at contractor to provide engineering, and supply of
no cost to the investor, and often includes a per- all plant equipment and materials needed for the
centage of costs incurred as a result of correcting construction of a complete chemical plant. The
problems in equipment or during construction. contract must define the limit of responsibility
Reimbursable Contract. In the reimbursable of the engineering contractor for plant equip-
contract, every hour of work performed by the ment; the boundary may be the ship, railroad
engineers and procurement staff is paid for, plus car, or truck used to transport the equipment to
all incidental costs. Proof of working hours is the construction site. The engineering contrac-
required. tor’s responsibility can, however, extend to the
A reimbursable contract offers an advantage receipt of equipment on site.
when the scope of work is not well-defined (so A turnkey contract includes the provisions of
that it is impossible to determine a fixed price) or the supply contract, plus construction services. If
when abandonment of the project is anticipated. the engineering contractor does not have the per-
The hourly or daily rates specified in the con- sonnel resources for construction work, it gen-
tract are often classified by category. The con- erally subcontracts this work to specialist firms
tract must state what is included in the hourly but assigns its own management and supervisory
rates (e.g., salary, other payroll costs, workplace personnel to maintain single-line responsibility
costs, profit). to the investor.
An important drawback of this type of con- In supply and turnkey contracts, all goods
tract is that the investor can strongly influence and services are procured in the name and on
the contractor’s execution of the project. Be- behalf of the engineering contractor. The con-
cause the scope of engineering services is gen- tractor thus assumes liability to the investor
erally not adequately defined, control of the ser- for the mechanical functioning of equipment as
vice budget is difficult. provided by the contract. In turn, the liability
Previous Page
risks associated with this material guarantee are The list of services should give a detailed de-
shifted to the relevant suppliers and subcontrac- scription of technical and commercial services
tors. Similarly, the engineering contractor will to be performed, indicating what design docu-
impose penalties on the suppliers and subcon- mentation is to be prepared (e.g., drawings, data
tractors for late delivery or installation to reduce sheets, specifications, flow sheets and schemat-
its own time risk. ics, lists, approval documents).
Supply and turnkey contracts are based on a Moreover, it must be stated which of the ser-
lump-sum price, sometimes with a provision for vices will be performed by the engineering con-
price escalation. In order to keep the price risk tractor, the investor and third parties.
quantifiable, the bid must be based on a detailed,
accurate definition of the scope of deliveries and Scope of Delivery/Delivery Boundaries. A
services for the plant to be erected. supply contract must describe the equipment and
materials to be supplied; a turnkey contract must
also define the construction services. In addition,
4.2.2.3. Essential Elements of a Contract the scopes of delivery and work must be delim-
ited with respect to third parties.
The structure and delimitation of scopes of de- The description of the scopes of delivery and
livery and work are very important, especially work should contain the most complete list pos-
because these factors affect liability questions, sible of apparatus and machinery; a description
contractual provisions, and the negotiation proof electrical equipment and materials and control
cess. They are expressed in the form of systems; approximate quantity requirements for
1) Specifications of services piping, concrete, cables, and structural steel; and
2) Description of the scope of delivery with de- a description of construction services. It is not,
livery boundaries however, expedient to set down exact numbers
3) Guarantees and liabilities because final data on equipment size, pipe rout-
4) Criteria for handing the plant over to the in- ing, etc. cannot be made until the design work
vestor is under way. Establishing the details too early
could hinder subsequent optimization of the de-
Specification of Services. Although the sign, this would not be in the investor’s interest.
specification of technical and commercial ser-
vices is not usually problematic from the stand- Guarantees. Forms of guarantee for chemi-
point of contract law, it is often highly relevant cal plants have been devised that are technically
as a basic fact and for later reference. Since this meaningful and can be verified at a reasonable
specification normally comprises a very large cost.
set of documents, it should be formulated as Mechanical (material) guarantees relate
one or more appendices to the contract. Much solely to individual pieces of equipment, but
unnecessary discussion between the contract- not parts subject to wear. A period (e.g., 12 or
ing parties can be avoided if the specification 18 months) is defined in which repair or replace-
of services is carefully prepared in detail and ment is undertaken by the contracting party or
states clearly what services must be performed suppliers at no cost to the investor.
by whom. Process guarantees generally relate to the
It is useful to prepare a list of services for capacity of the plant, product quality, and the
the project, which can be based on the specifi- consumption figures for utilities such as steam,
cation services contained in the bid invitation, cooling water, and electric power.
as well as in the bid. Any modifications made The contract should state the conditions used
in the course of contract negotiations must be to verify the process guarantee (e.g., analysis
incorporated. of feedstock, quality of utilities). Furthermore,
The specification of services must also con- it should define the measurement and analysis
tain the detailed conditions and constraints methods used in the guarantee run and its dura-
needed to carry out the assignment, a procedural tion.
description, and a list of relevant regulations and The forms of guarantees are different for util-
standards. ities (steam, electric power, fuel gas), where a
certain amount of over- and underconsumption 5.1. Scope of Work

can offset each other, and for plant capacity and
product quality, where shortfalls result in penal- Work on total chemical plant project comprises
ties. basic engineering, detail engineering, procure-
If the plant does not meet the agreed figures ment, civil work and erection, and commission-
in the guarantee run, the engineering contractor ing. (The “authority engineering” activity, in
is given an opportunity to make improvements. which documents are prepared for submission
If these are not successful either, the relevant to the authorities having jurisdiction, is gener-
contractual consequences take effect. ally carried out during both basic and detail en-
gineering.)
Handing Over the Plant. The criteria for Depending on its engineering capabilities and
handing the plant over to the investor are usually resources the investor may execute part of the
stated in the contract. The plant is often handed project (basic engineering and/or procurement,
over section by section and/or in phases. Several and/or construction). The remaining activities
forms of handover are employed: (or the whole project) are executed by an en-
gineering firm under contract.
1) Transfer to the operational custody of the Basic engineering is based on process de-
investor: This, as a rule, takes place at the sign (Section 3.3) which is performed during the
beginning of test operation. The investor’s preliminary design phase by the investor, by the
personnel run the plant under the direction licenser, or by an engineering firm in close co-
of the engineering contractor. operation with the investor. Process design is a
2) Provisional handover: Provisional handover component of basic engineering.
takes place after a report on the successful Basic engineering documentation includes
guarantee run has been signed, or after a “not the process flow diagrams, piping and instru-
later than” date has passed (if the guarantee mentation diagrams, plant layout, equipment list
run has not been done for reasons that the (broken down according to plant sections), util-
investor has to justify). ities distribution scheme, process engineering
3) Final handover: Final handover comes after data sheets, noise protection concept, electri-
all defects listed in the report made after the cal equipment list, summary of electrical con-
provisional handover have been corrected. sumers (one-line diagram), data sheets for con-
Final inspection of the plant, performed by trol equipment and instrumentation, functional
both parties, completes the handover procedure. process control and instrumentation plan, de-
scription of the process control system, and soil
report.
The content and level of detail in basic engi-
5. Execution of the Project neering documentation is such that detail engi-
neering can be done (possibly by another engi-
Design and construction of chemical plants are
neering firm) without significant difficulties.
complex operations comprising many interre-
lated activities (Fig. 16). Plant design and the
Detail Engineering. In detail engineering
procurement of equipment occupy workers from
the engineering and procurement teams prepare
nearly a dozen special engineering and procure-
detailed plans, drawings, specifications, calcu-
ment disciplines.
lations, and descriptions so that the following
Medium-sized to large projects [contract
steps can be carried out:
value (50 – 250)×106 DM; (30 – 170)×106 $]
have a design period of approximately 15 – 18 1) Preparation of bid invitations for all plant
months and a total project duration (up to equipment, material, and services such as
commissioning) of ca. 18 – 24 months. Some civil work and erection of plant equipment
100 – 150 engineers and procurement staff are 2) Selection of manufacturers, vendors, sub-
involved at the peak of such a project in the de- contractors; placing of orders
sign offices alone. 3) Execution of quality assurance operations at
manufacturers’ and vendors’ workshops
Figure 16. Main tasks of project execution
4) Shipping of plant equipment to the plant site Commissioning of a plant comprises all the
5) Execution of civil work and erection of plant work done after “mechanical completion” up
equipment to certification of the guarantees embodied in
6) Commissioning the contract. The term “mechanical completion”
should be defined unambiguously and in de-
Procurement services include all activities tail. Once “mechanical completion” has been
in connection with preparation of bid invita- certified, the plant passes into the custody of
tions, evaluation of bids and bid comparisons, the builder. Preparatory work for commissioning
and placing of orders. They also involve ensur- and commissioning itself are usually performed
ing on-time performance of manufacturers and by employees of the future operator under the di-
vendors (expediting), as well as the planning and rection of the engineering contractor or licenser.
supervision of the shipping of plant equipment When the guarantee tests defined in the contract
to the plant site. have been passed, the plant is handed over to the
owner. Minor activities remain that are carried
Civil work and erection of a facility are out by the engineering and/or construction con-
generally subcontracted to specialist firms by the tractor. This work is specified in a punch list and
engineering contractor or by the investor. The must be completed within a stated time.
work is often supervised by the same organiza-
tion that does the detail engineering. It must not
be overlooked that the construction documenta- 5.2. Project Organization and
tion prepared by the engineering contractor will Management
not be free of errors, so that corrections have
to be made on-site. Such corrections should be The design and construction of a chemical plant
carried out by the engineering contractor’s spe- within a predefined time and budget calls for
cialists. careful organization of the people working on
The contract should state which partner is re- the project, a clear definition of their respon-
sponsible for construction execution time and sibilities and competences, and an appropriate
costs: the investor, the engineering contractor, management concept.
or (as at large, complex plants) a general con- A chemical-plant engineering firm usually
tractor accepting overall responsibility. executes many such projects, differing in size,
duration, and complexity, at any one time. The Such an organization represents the best solution
contracting firm is geared to this kind of assign- for integration of temporary project teams into
ment; it often develops its own set of “tools” and the company organization. It also ensures that
is organized exclusively for these activities. the projects are optimally executed.
The following description of the relatively Matrix project management is character-
complex steps in the execution of a chemical ized by division of competences (Fig. 17). The
plant project is given from the viewpoint of an project manager is responsible to company man-
engineering contractor. It should not, however, agement for the realization of project targets.
be forgotten that investors and/or operators of The managers of the functional departments
chemical plants also follow a similar procedure (engineering and procurement) involved in the
to design and construct plants in their own areas project are responsible for delegating appropri-
of expertise. ate persons to the project team. The managers
also carry the technical responsibility for the per-
formance of these team members. The project
5.2.1. Matrix Project Management [116], manager determines the “what” and “when” of
[117] a task in the project, while the department man-
The first powerful management concepts for the agers determine the “who” and “how.”
execution of complex, single projects were de- For smaller, simpler projects and projects of a
vised in the United States during the last years repetitive character, which do not keep a project
of World War II. It was recognized that exist- manager busy full-time with management tasks,
ing forms of organization were not suited to the the matrix system can easily be modified so that
solution of complicated armaments assignments project management is taken over by a qualified
on a crash basis. This management philosophy person from a functional department, who also
was subsequently employed in the space pro- carries out the required specialist work.
gram, and later found use in the industries of
Western Europe. It can be defined as follows:
“Project management is a management concept 5.2.2. The Project Manager
for the solution of a well-defined problem within
a predefined time subject to a cost framework The execution of a project in the matrix or-
specified for the project” [117]. ganization concept places heavy demands on
Personnel from a wide range of disciplines the project manager [117], [118]. He assumes
within a company work on a defined project in “project responsibility” to company manage-
an interdisciplinary setting and must be coordi- ment for the assigned project: compliance with
nated and directed. This means: budgeted project costs, agreed time schedules,
and all contractual conditions, particularly the
1) Assignment of appropriate personnel to the attainment of the agreed quality level.
project from functional organizations in the For the customer, the project manager is the
company first representative of the engineering firm for the
2) Organization of the personnel into a project project, and also his first partner in discussions.
team for a defined period of time The management tasks of the project manager
3) Designation of a project manager are to set targets, establish guidelines, promote
4) Establishment of responsibilities and com- information flow, supervise, analyze and correct,
petences for the duration of the project motivate, and report. He must accord the same
The organization of the project team and, weight to the interests of the customer as he does
above all, the responsibility and competences to his own company.
of the project manager and his colleagues, have The technical capabilities of the project man-
three basic forms: functional, matrix, and au- ager should include not only specialized knowl-
tonomous project management. edge of the project and the technology, but
The matrix form of project management, ei- also knowledge of how design and construction
ther in pure or modified form, is the most suit- work is executed and ability in engineering, pro-
able concept for engineering contractors be- curement, contract drafting, and project control.
cause they perform “multiproject” management.
Figure 17. Matrix project management
These capabilities should be complemented by cial. An effort is therefore made to separate

familiarity with the client’s language, country, the project team members physically from their
and the client, as well as skill in giving presenta- functional departments within the company and
tions and in moderating discussions. Other qual- locate them close together.
ities include analytical ability, leadership and ne- The team members remain subordinate to
gotiation skills, ability to work under physical the project manager in regard to project re-
and psychological stress, ability to make deci- quirements and for the duration of their partic-
sions, and at the same time ability to integrate ipation in project execution. They continue to
and to make compromises. make their technical and functional “residence”
In larger projects, project engineers are put in their home departments.
under an experienced project manager; they take
responsibility for the execution of portions of the
project. 5.2.4. The Start Phase of a Project
The most important phase in the execution of a

5.2.3. The Project Team project is the start phase [119], [120]. The first
1 – 3 months are crucial to the success of the
A project team comprises employees from tech- project. In this period all basic decisions must
nical and procurement departments. If they are be made; all project-specific documents needed
not fully occupied by a project (e.g., as it winds by the team members and the project manager
down), they may also belong to a team work- must be generated.
ing on another project at the same time. The The essential decisions and documentation
organization of a project team (Fig. 18) must include:
be adapted to the specific needs of the project.
Tasks, responsibilities, and competences are 1) Selection of project manager and key per-
unambiguously defined. The project manager sonnel
bears responsibility for meeting targets until the 2) Creation of project team and its organiza-
project is handed over to the owner, he is there- tion
fore placed above the construction site manager, 3) Working out project structure, including
who in turn heads the construction site organi- definition of subprojects and work pack-
zation. ages
Efficient coordination, with short lines of 4) Planning of project execution and prepara-
communication within the project team, is cru- tion of project execution guidelines
Figure 18. Organization of a project team
5) Identification of codes and standards gov- outstanding activities, expected time consump-
erning the project (usually included in the tion, and cost and man-hours up to the end of
contract) the project is used to update these values. A
6) Preparation of detailed time schedules (bar comparison of the actual/expected/target values
charts and network diagrams) as a basis for shows the reliable status of the project, enabling
time scheduling and control the project manager to identify problems at an
7) Drawing up a detailed budget as a basis for early stage. After appropriate analysis, he and
cost control his coworkers devise solution options, which
8) Preparation of a detailed man-hour budget then lead to decisions about further steps. This
for each of the technical and procurement procedure generally allows corrective measures
disciplines to be implemented so that the target status can
9) Determination of nominal progress curves be regained.
for all disciplines involved, as a basis for
monitoring compliance work progress 5.3.1. Time Scheduling
10) Manpower planning (office and construc-
tion site) Time scheduling and control involve the use of
bar charts or network diagrams. The choice is
5.3. Project Control (Schedules, made at the start of execution and depends on the
Progress, Costs) size, complexity, and criticality of the project,
and the customer’s requirements. Schedules
(Project control during the construction phase are usually prepared and updated by computer
is described in Section 5.6.2.2). The control of (mainframe and/or PC).
project execution is one of the most important
tasks of the project manager. As early as possi- Bar Charts. Bar charts are used for planning
ble, the project control team (schedule and cost and control of small, simple projects employ-
control engineers) provides information about ing established processes and involving little
the time situation, the progress of work, and the time risk. These charts show the planned elapsed
consumption of man-hours in relation to due time for each discipline and their important ac-
dates and determines the cost situation for de- tivities. In general, the following areas are in-
liveries and services [121]. Regular analysis of cluded: process engineering, plant layout, civil
work and structural steel, mechanical equipment Activity-on-arrow plan: The network is formu-
(furnaces, process equipment, machinery), pip- lated mainly in terms of activities, which are rep-
ing, electrical, and control systems. resented by arrows.
The schedules cover the full span of the con- The following network methods based on the
tract period and are broken down into the follow- above approaches were devised independently
ing activities: engineering (specifications, draw- of one another.
ings); procurement (bid invitations, bid compar- The Program Evaluation and Review Tech-
isons, orders, delivery time, shipping); construc- nique (PERT) is an event-on-node method and
tion and commissioning. was devised in 1958 by the U.S. Navy in collab-
Figure 19 shows an example. A “dual-bar” oration with the Boots & Hamilton consulting
system is employed to check the status of indi- firm and Lockheed. The impetus for its develop-
vidual activities with respect to the due dates at ment was the program to design and construct
any time during execution. The upper bar shows nuclear submarines. PERT uses three time es-
the planned duration of the activity. The lower timates for each activity: optimistic, probable,
bar indicates, as of the cutoff date, the actual and pessimistic. The analysis is run with each
or expected start and end of the activity. The estimate and the results are averaged.
progress of the activity is indicated by filling in The Critical Path Method (CPM) was also
the lower bar. developed in the United States in 1957. It is an
If needed, bar charts for individual disciplines activity-on-arrow network method that was de-
can be expanded to show more detail. This is vised by Du Pont and Remington Rand. It was
done, for example, when an early activity plan first used for planning maintenance and conver-
is prepared for the first three months of project sion work in the chemical industry.
execution, or when a detailed chart is drawn up The Metra Potential Method (MPM) was first
if the status of work in one area is critical. used in the design of nuclear power plants and
was developed in 1958 by the French consulting
Network Diagrams. The network technique firm SEMA. It is an activity-on-node technique.
is widely used in industrial operations research Several other network methods have since
[116], [121–124]. According to DIN 69 900, been worked out. The Precedence Diagram
the term “network diagram technique” includes Method (PDM) was developed from MPM and
all methods used to analyze, describe, plan, allows greater flexibility in the way precedences
oversee, and control processes on the basis of are represented.
graph theory; considered parameters include The advantages of network diagram planning
time, costs, and materials. The main applica- can best be exploited with computers. By the
tion of network diagrams is in project planning end of the 1970s, these techniques had been op-
and supervision. The project is broken down into timized for mainframe systems. Since the be-
steps (activities), which are placed in a network ginning of the 1980s, a variety of personal com-
diagram according to their logical dependences puter programs have been written, and network
(precedences). diagram techniques have come into wide use.
Formal representation employs arrows and Mainframe and PC software are capable of out-
nodes (a node may be represented by a rectangle putting the results of network calculations in the
or a circle). Network diagram techniques differ form of due date lists, bar charts, and network
in how the logical conditions “event” and “activ- plots.
ity” are assigned to these fundamental elements. To control progress effectively, the actual sta-
Event-on-node plan: The network is formulated tus of project execution must be determined at
mainly in terms of events, which are represented regular intervals, the results compared with the
by nodes. An event is the start or finish of an ac- target data from the network chart, and the con-
tivity and has no duration. sequences ascertained by recalculating the net-
Activity-on-node plan: The network is formu- work to the end of the project.
lated mainly in terms of activities, which are
represented by nodes.
Figure 19. Bar chart

Event-oriented network systems play a sec- sis for control of actual work progress and actual
ondary role in project planning and control. consumption of work units (e.g., man-hours).
Activity-on-node and activity-on-arrow charts Actual work progress(physical progress)is
are about equally important in the planning and determined by scheduling engineers who query
control of all kinds of projects, including re- the discipline engineers and evaluate the work
search and development. performed. An example of such a work progress
Some engineering firms have their own soft- chart is shown in Figure 21. The positions of
ware for calculating network plans. Lurgi, for the curves of physical progress and work units
example, uses the PDM method to prepare consumed, relative to the target curve, give the
network charts (unless the customer requires project manager a clear indication of the time
otherwise). The calculation is done with the compliance situation and the efficiency of the
Lurgi Netzplan System, which was developed personnel involved. If there are significant devi-
in-house and is specially adapted to the condi- ations from the target curve, the causes should
tions of chemical plant construction. Network be analyzed and appropriate corrective measures
diagrams are used for large, complex projects, taken.
chiefly when there is a great time risk. The
project is broken down into individual activities 5.3.3. Cost Planning and Control
of the various divisions involved, similar to the
procedure for bar charts (see above). The level Costs. The objective of cost control is to pro-
of detail is predefined by the project manager vide correct information, as early as possible,
and scheduling engineer. The stored data can on the cost status for equipment, materials, ser-
be quickly updated on screen (interactive op- vices, and indirect costs, and to identify reliable
eration) and the network diagram immediately trends in cost development.
recalculated. The project manager instructs the cost control
When the network calculations are com- engineers to analyze planned orders for equip-
plete, the results can be output as lists of due ment and services so that cost budgets are met.
dates sorted under all kinds of criteria, or bar This “cost engineering” already involves the cost
charts with or without interdependence. Fig- engineer at the stage of bid invitation, price com-
ure 20 shows the steps involved in project control parison, and assignment of order stages.
with network planning. Cost control is used throughout the entire
project for engineering and procurement, as well
as for construction. All costs connected with the
5.3.2. Progress Planning and Control project are considered, such as costs of equip-
ment and bulk materials (mechanical, electrical,
Progress planning and control is performed control systems, structural steel); spare parts;
for each discipline involved. For management civil work and erection; third-party services; in-
needs, these individual plans are assembled into direct costs (e.g., travel, computer services, com-
an overall plan. munications); and costs for engineering, pro-
The progress plan is generally plotted graph- curement, and construction supervision.
ically. A “target” curve for the planned progress Figure 22 illustrates the operation of a
of work, for example of engineering, is drawn computer-supported project cost control system.
up in the following way. The work of each en- Cost control is based on the calculation used
gineering discipline is broken down into indi- to obtain the contract price. A detailed budget is
vidual activities. The duration and the expected prepared at the start of project execution. In the
monthly consumption of work units (e.g., man- course of project execution, this budget will be
hours) available from experience is specified for modified if change orders are received from the
each activity. The sums of the monthly work client. The project team members responsible
units planned for individual activities are ex- for each of the disciplines involved, in collab-
pressed as a fraction of the total number of work oration with the cost engineer, keep a continual
units required to give a target progress curve. watch on the technical and cost developments of
These planning curves are prepared at the start of the project in their respective areas of responsi-
the project. During execution, they form the ba- bility.
Figure 20. Project control with network system
Figure 21. Engineering work progress

Figure 22. Principles of cost controlling
A data link between purchasing and cost con- a decisive influence on the project. The effects
trol allows updating of actual costs. Cost control, of these risks on costs and their probability of
however, is based on comparison of calculated occurrence cannot generally be clearly defined.
and expected values, i.e., the calculated values One approach to risk quantification is the Lurgi
are always compared with the costs forecasted “project risk analyis” concept [125], [126]. The
up to the end of the project. This forecast is re- concept is based on the risk profile developed
peatedly updated for each discipline by the spe- during expert conferences.
cialist engineer and the cost engineer. Forecasts
are based on the order values at the cutoff date, Cashflow Schedule. Knowledge of how to
the calculated values of equipment not yet or- procure funds for equipment and services at the
dered, and expected cost increases or decreases. appropriate time is important for the investor, but
The cost control cycle closes when data for the also for the engineering firm working on supply
forecast and costs for approved changes are in- or turnkey contract. A project cashflow schedule
put to the cost control system. is a combination of cost planning, time schedul-
ing, and progress planning. The following pro-
Risk Analysis. The analysis of orders still cedure is used to prepare such a schedule:
to be carried out and services still to be per- 1) Planning of deliveries and services, includ-
formed is fed into the latest forecast. This anal- ing payment modalities agreed on with the
ysis often reveals potential risks that may have suppliers of equipment and subcontractors
2) Determination of relevant actual figures tions 3.3 and 3.4). In addition, the process engi-
3) Deviation analysis (e.g., postponements) neers devise the plant control concepts in collab-
4) Revision of the plan oration with the control system engineers. The
contribution of process engineers to the comple-
Figure 23 is a graphical representation of a
tion of piping and instrumentation diagrams ex-
cashflow schedule. Payments can be read off in
tends far into the detail engineering phase. The
detail from the associated lists.
process engineers also prepare the process de-
scription, which states how the process operates
5.3.4. Project Report and identifies important control functions and
special features.
The preparation of regular reports for the man-
In cooperation with the appropriate specialty
agement of the engineering firm and the investor
engineers, the process engineers write detailed
is the task of the project manager. These project
startup instructions which are needed for com-
status reports should provide comprehensive in-
missioning. The process engineers responsible
formation; information on cost and man-hours
for process design should also be involved in
should not, however, be included in the report to
commissioning because they are familiar with
the investor in the case of a lump-sum contract.
the process and control details of the plant. They
The report should contain the following
can also gain considerable expertise in operation
items:
of a plant, know-how that they can use in future
1) Text design.
a) Summary (highlights): project status, If the engineering firm is responsible for “au-
trends, problems thority engineering,” the process engineer also
b) Detailed information makes a significant contribution to the approval
– Progress of individual disciplines documentation (see also Section 3.3.2.5), which
(process engineering;civil engineer- includes specifications for products, byproducts,
ing,structural steel;apparatus; piping, residues, and wastes; emissions; safety analyses;
machinery, electrical, control sys- and HAZOP studies.
tems, procurement civil work, and
construction)
– Problems in execution and recom- 5.4.2. Plant Layout
mended remedies
– Forecast for the following month and Plant layout is an interdisciplinary activity. Its
key points most important components are the layout (plot
2) Graphs and lists plan) and the piping and instrumentation dia-
– Time schedules gram. Both documents are created, in prelimi-
– Progress curves (for individual disciplines nary form, during basic engineering (see Sec-
and the project as a whole) tions 3.4.3 and 3.4.4). They are continually up-
– Network diagrams and lists dated in the course of detail engineering.
– Procurement lists
3) Cost report Plot Plan [38], [111]. The layout of, for ex-
– Analysis and assessment ample, a petrochemical plant is usually drawn to
– Status of costs and man-hours 1: 100 scale. It shows the outlines of equipment
– Cost report (computer printout), summary items, pipe bridges, and buildings, all dimen-
– Cost report (computer printout), detailed sioned. In the case of buildings and platforms
on tanks and towers, horizontal projections in
appropriate planes and vertical sections are also
5.4. Detail Engineering included (see Fig. 24).
An experienced erection engineer should be
5.4.1. Process Engineering involved in the layout planning so that allowance
can be made for erection operations, in particular
Most of the process engineering of a project is the space required for the installation of heavy
performed at the basic engineering stage (Sec-
Figure 23. Cashflow schedule
apparatus. Other factors that must be considered The final P & I diagram describes the whole
include maximal exploitation of available space, plant in detail (by use of coding). The contents
placement of heavy apparatus on the ground of the P & I diagram from the basic engineering
floor, operability of important block valves, easy stage (Section 3.4.4.) are supplemented during
maintenance of machinery, and short runs of detailed engineering by:
pipes with large diameters and/or made from ex- 1) Operating data and dimensions of equipment
pensive materials. There must be adequate safety 2) Design data for machinery
distances between pieces of equipment, escape 3) Data on insulation and heating of equipment,
routes for operating personnel, and access for machinery, and piping
fire fighting vehicles. 4) Elevation of machinery and equipment
It is also advisable to discuss the basic plot 5) Information on noise abatement
plan with the client’s personnel (plant operators, 6) Delivery boundaries
maintenance personnel) at an early stage. The 7) Codes for equipment nozzles
progress of construction and new detailed infor- 8) Codes for fittings
mation provided by equipment vendors during 9) Detailed information on electricals and con-
detail engineering necessitate continual changes trol systems
in the layout. In order to avoid delays in the
The utility systems (e.g., steam, instrument
start of construction, an attempt must be made
air, and condensate systems) are diagrammed
to “freeze” the building dimensions and the po-
separately from the process systems. In larger,
sitions of heavy apparatus as early as possible.
more complicated chemical plants, P & I dia-
The final layout is the result of design work
grams may comprise > 100 DIN A2 sheets.
performed by all the disciplines involved in the
The P & I diagram contains all essential in-
execution of the project.
formation developed by the individual disci-
plines: process engineering; equipment, ma-
Piping and Instrumentation Diagram.
chinery, piping engineering; engineering for
The piping and instrumentation (P & I) diagram
electricals and control systems. It must also in-
or mechanical flow diagram is based on the pre-
clude data provided by the manufacturers of
liminary P & I diagram from basic engineering.
equipment and machinery (e.g., the control sys-
The latter is developed and elaborated in de-
tem of a compressor). This information becomes
tail engineering, as new information is acquired
available over a prolonged span of time.
from the engineering disciplines and equipment
The P & I diagram is therefore revised sev-
vendors.
eral times in the engineering stage (Fig. 25 is a
Figure 24. General arrangement drawing
portion of a P & I diagram). An attempt should the document reflects the “as built” state of the
be made to review the P & I diagram with all plant.
responsible persons (and, if possible, represen-
tatives of the client). After this review, the P & I
diagram is “frozen” and only essential changes 5.4.3. Apparatus and Machinery
should be subsequently allowed (e.g., changes
concerned with plant safety). Minor changes are All important process engineering data for ap-
often made during commissioning; these should paratus (e.g., heat exchangers, reactors, tow-
be incorporated into the P & I diagram so that ers, vessels, tanks) and machinery (e.g., pumps,
blowers, compressors, turbines) are specified
Next Page
Figure 25. Section of a piping and instrumentation (P & I) diagram

(e.g., LIC = level control; TE = local temperature indicator; TI = temperature indicator in the control room; TIC = temperature
control)
Previous Page
during basic engineering. Data sheets pre- trast to apparatus, which is usually custom-built
pared in this stage contain essential informa- and thus individually designed and drawn, an
tion on overall dimensions, pressures, tempera- attempt is made to use off-the-shelf machinery.
tures, quantities, materials of construction, etc., There are two reasons for doing so: to minimize
of each piece of apparatus and machinery. In de- engineering costs and to hold down the purchase
tail engineering the apparatus and machinery en- price.
gineers complete this information. The result of The machinery engineers prepare specifica-
this work is a set of specifications in the form of tions for every machine to be procured. The
drawings and descriptions, which enable quali- specifications are based on the data sheets com-
fied manufacturers to submit bids for apparatus piled by the process engineers, which contain
and machinery. all information relevant to the process (operat-
The equipment engineers prepare so- called ing conditions, materials of construction). As an
guide drawings, which are scaled drawings in- example, Figure 27 shows a data sheet for cen-
dicating all dimensions dictated by process en- trifugal pumps taken from the bid specification.
gineering (e.g., number and diameter of trays in The machinery manufacturer supplements the
a tower, spacing of trays, and tower height). All data sheet with further information on the model
dimensions of importance for shipping are also he has selected for the bid.
shown. Relevant legal provisions must be taken An important element of order handling is the
into account. Nozzle tabulation and other impor- time schedule according to which the machinery
tant design data are attached to the guide drawing manufacturer is to submit information about the
(see Fig. 26). The wall thickness is estimated so machine (e.g., dimensions, weight, vibratory be-
that the weight of the apparatus can be calculated havior). It is important for the engineering firm
The number and dimensions of the nozzles, and to obtain this information as early as possible to
frequently their elevations, are stated. The hor- avoid delays in the design of footings and foun-
izontal orientation of the nozzles is determined dations, buildings, and piping. Such information
later when the exact position can be ascertained should also be finalized as soon as possible to
from the piping design. avoid duplication of work.
The guide drawings and supplementary in- For noise-abatement design see Section
formation form the technical portion of the bid 3.3.2.2.
invitation, which is sent to selected manufac- Spare parts required for plant startup and the
turers. The information in the bid invitation must first two years of on-stream operation are com-
be presented in such a way that the bidders can monly ordered at the same time as the machin-
submit comparable bids (see also Section 5.5.1). ery. The manufacturer recommends the type and
The design office of the manufacturer pre- quantity of spares. The subsequent operator of
pares detailed workshop drawings and calculates the plant makes the final decision once the spe-
the final wall thicknesses. The workshop draw- cialist engineer has checked the bid.
ings are checked by the engineering firm who
also fixes the position of the nozzles and informs
the manufacturer of any changes. 5.4.4. Piping
Once the drawings have been approved, pro-
duction can begin. The manufacturer is respon- The objective of piping design is to prepare all
sible for compliance with legal provisions. drawings and specifications needed for procure-
Specialist engineers periodically inspect ment and installation of the piping components.
complicated equipment, even during its produc- The engineering of piping systems is closely
tion. Such inspections are independent of those linked with the engineering of all other disci-
per-formed by a third party (e.g., one of the Ger- plines. In the initial phase of engineering, infor-
man TÜV organizations or Lloyds) when man- mation is incomplete and often preliminary. The
dated by law (e.g., for pressure vessels). The data become more complete and exact as work
equipment is cleared for shipping only after final progresses. Because the need for on-time avail-
acceptance by the same specialist engineers. ability of piping data requires early information
The specification and procurement of ma- from the other engineering disciplines, a step-
chinery are similar to that for apparatus. In con- by-step procedure is employed. Often the first
Figure 26. Guide drawing for a vessel

Figure 27. Data sheet for a centrifugal pump

steps are based on assumptions, so that frequent basis of flowing media, pressures, and tempera-
corrections are required later. tures that occur in the plant.
Piping accounts for a relatively high propor- A piping class comprises the expected di-
tion of chemical plant costs and piping engi- mensions of components and their materials of
neering may represent as much as 20 – 40 % of construction for a given set of media, pressures,
total engineering. Refineries and petrochemical and temperatures. The classification is based on
plants lie at the upper end of this range. pressure – temperature diagrams from DIN 2401
Piping engineering can begin once the fol- or ANSI B 16.5 (see Fig. 28). Each of the ar-
lowing information (at least in preliminary form) eas represents one piping class. All components
is available: within one such area are uniformly sized. Fit-
tings and flanges are standardized according to
1) Standards and codes (of the investor or the pressure level. Wall thicknesses are calculated
engineering firm) from the pressure and temperature. Once the pip-
2) P & I diagram ing classes have been worked out, the figures
3) Layout model are stored in a data base and can be retrieved
4) Plot plan as needed. The use of such a data base greatly
5) Guide drawings for apparatus reduces the amount of work to be done in spec-
6) System drawings for machinery ifying the piping system for a plant.
7) Preliminary civil and structural steel draw-
ings Piping List. All pipe runs are identified by a
8) Data on electricals and control systems code number and a piping class, and are com-
piled in a piping list. The associated data are
Piping Specification. For the sake of effi- stored in a data file. The piping list is prepared
ciency in engineering, procurement, and piping at the same time as the P & I diagram.
installation, and in view of the wide variety of
piping components and design, a piping specifi- Isometric Piping Drawings and Piping
cation is first prepared. This document is based Model. Drawings that show both the geometry
on the standards and codes applicable to the plant of the run and its location in the plant are needed
and relevant engineering regulations. The piping for the prefabrication and installation of piping.
specification also contains special piping design It used to be common to plot every pipe run and
guidelines for the project. every fitting in a piping diagram with plan, ele-
vation, and section views. This method has been
largely replaced by a diagram of a single pipe
run and its components, along with measure-
ment and control devices and piping supports.
The initial piping studies and the final iso-
metric drawing of a pipe run are done in paral-
lel with the construction of a piping model. A
bill of materials containing all piping compo-
nents is drawn up for every pipe run. Figure 29
gives an example of such an isometric drawing.
Computer-aided design (CAD) techniques are
used increasingly in preparing isometrics.
The isometric drawings are supplemented by
plans for pipe bridges and underground pipe
Figure 28. Piping classes (pressure – temperature diagram) runs.
The model shop uses the plot plan to make
An important element in the piping specifi- a basic model at 1 : 33 1/3 or 1: 25 scale that
cation is the piping classification which mini- includes all apparatus, buildings, frameworks
mizes the different types of piping components for equipment, stairs, ladders, platforms, and
required. All piping components (pipe, fittings, pipe bridges (Fig. 30). The piping model forms
flanges, bolts, seals, etc.) are classified on the
Figure 29. Isometric piping drawing

Symbols and designations mark piping components (e. g., valves, flanges, reducers), dimensions, position of the pipe run
the center for coordination of all detail designs Piping Calculations. Piping calculations
[127]. cover strength calculations for individual el-
Installation work carried out on the model ements (wall thicknesses, flanged joints) and
in parallel with piping includes air condition- stress analysis of the piping system.
ing and cable ducts, control panels, hoists, and Wall thicknesses are calculated from the pres-
cranes. sure and temperature ratings of the piping class.
A piping model has the following advan- The safe functioning of a piping system de-
tages: pends on correct sizing and proper layout. Spe-
cial attention should be given to the elasticity
1) Piping routes are easy to check for collisions
of the piping and the use of supports and an-
with other equipment
chors. Temperature changes give rise to stresses
2) The plant operator can check ease of opera-
in piping systems, which in turn generate forces
tion and maintenance
and moments at connection and support points.
3) The model can serve as a training facility for
Computer-aided elasticity calculations are per-
operating personnel and as a form of instruc-
formed to make certain that the strains resulting
tion during installation
from stresses in a given piping layout are within
The completed model should be thoroughly the elastic range. If the stresses are too high, a
assessed by all discipline engineers, the later different configuration must be selected or com-
maintenance engineer, and the operator. Any pensators must be inserted. For small-diameter
necessary changes made at this stage are much pipes and moderate temperatures, these expen-
less costly than if they are made later on the con-
struction site.
Figure 30. Piping model (fluid catalytic cracker complex, courtesy of Lurgi AG)
sive calculations are often superfluous, since ex- material takeoff is worked out after all isomet-
perienced piping engineers lay out such piping rics and piping plans are complete.
with adequate elasticity. The preparation of the material takeoffs is
computer-aided. Sorting and condensing pro-
Material Takeoff and Procurement. A grams calculate the quantities that have to be
first rough material takeoff can be performed ordered [128]. An integrated materials manage-
when the P & I diagram has reached a certain ment system allows the print out of lists and
level of completeness and the plot plan has been calculations for every step (e.g., bid invitation,
drawn up so that fittings can be counted and the ordering, expediting, and material handling on
lengths of the main pipe runs can be estimated. site). The efficient use of such a system requires
The objective of this preliminary takeoff step is a consistent high-order data structure as well as
to invite bids and place orders for piping com- the unambiguous definition of piping compo-
ponents with long delivery times. Sufficient ma- nents in terms of piping classes.
terial can thus be made available on site when
piping installation begins. Insulation and Coatings. The thickness of
As piping design advances, isometrics and insulation needed on equipment and piping must
piping plans with bills of material are generated. be established at a fairly early stage since this
Another (not yet final) material takeoff is then value may influence other parameters such as the
prepared and has a higher degree of accuracy length of nozzles and the width of pipe bridges.
than the preliminary takeoff. Further orders are Insulation thicknesses are entered on the P & I
then placed. At this stage, bid invitations can be diagram and in the piping list. Thermal insula-
sent for the installation work, and the piping in- tion for pipes carrying hot media generally con-
stallation contractor can be selected. The final sists of mineral wool enclosed in galvanized or
aluminum jackets. Polyurethane foam enclosed
in sheet metal is widely used for pipes carrying tional investment is amortized after as little as
cold media to prevent icing and cold bridges. one to two years. Complicated analytical sys-
Uninsulated surfaces of tanks, piping, and tems, however, have higher costs for mainte-
steel structures must be painted to protect them nance, which is performed by specially trained
against corrosion. As a rule, machinery is deliv- personnel.
ered with the specified prime and topcoats. Rust Analytical instruments are built in prefabri-
must be removed from the surface before appli- cated enclosures and tested at the vendor’s work-
cation of the prime coat. In many cases, a second shop. Installation simply involves connecting
prime coat is needed before the first and second the process loop lines, utilities, and data cables.
topcoats are applied.
Underground pipe is either coated with as- Plant Safety and Availability. Regulations
phalt or jacketed in plastic. on plant safety and environmental protection
have rapidly become more stringent, influenc-
ing the choice of automation hardware and sys-
5.4.5. Control Systems [129–133] tem structure. Safety control requires the use of
redundant systems approved by the regulatory
Automation of chemical plants is increasing. authorities. Interfaces connect these systems to
Rapid progress in microprocessor technology the process control system, special attention
has led to the development of distributed control should be paid to transmission time between the
systems (DCS) that can meet the increasingly different systems.
stringent requirements of modern process op-
eration. The objectives are to improve the avail- Process Monitoring and Control Sys-
ability of operating process plants, enhance their tem. In petroleum refineries and petrochem-
reliability, and optimize their operation. ical plants, it is often necessary to operate
The distributed functions facilitate the engi- 3000 – 4000 loops and give the plant operator
neering, operation, and maintenance when bro- access to these in a meaningful order.
ken down into levels (Fig. 31). Sensor signals relating to the process and
Centralization of process control systems control functions, along with signals to motor
means that plants are chiefly fitted with elec- control centers (MCC) and valve actuators, are
tronic devices, since this kind of equipment with handled in the processing stations, which per-
its reliable signals is suitable, even for explosion form configured tasks such as signal condition-
hazard areas. Pneumatic instrumentation is lim- ing, control, and signal processing. The process-
ited to pneumatically actuated controllers and ing stations are assembled from modules and
low-order local control loops. tailored to individual functions. Process infor-
With the help of process monitoring and con- mation is transmitted to the operating and mon-
trol systems, advanced control strategies can be itoring system via serial busses.
built up in modular form. The modules perform The chemical plant is controlled with ex-
both computing and dynamic functions, so that tended software functions for graphical display,
a variety of signal processing algorithms can be along with process graphics overlays. The hi-
selected for optimal control strategy. erarchical information structure of data repre-
The control of material streams, plant opti- sentation leads the operator to the proper level
mization, and balancing is implemented by pro- in the information structure. The alarm func-
cess control computers at a level above the pro- tions notify the operator directly of the inititating
cess control systems. These computers may have measuring point in the process. The automation
an on-line function or a data management func- structure is governed by the following important
tion. Software vendors offer appropriate modu- criteria:
lar software. Such programs are linked together 1) Size of process plant
to permit control of products by centralized pro- 2) Continuous or batch process
grams. 3) Behavior of process over time
Optimization programs did not gain wide use – Steady and stable
until stable on-line analytical instruments with – Product output or quality strongly affected
short response times were developed. The addi- by load variations and/or perturbations
Figure 31. Levels of distributed control systems (DCS)
4) Complexity of process uously updated record of alarm and condition re-

– Simple control strategies ports, series of measurements, balances, and op-
– Complex interdependences erator actions. Trend displays of the process vari-
– Frequently changing recipes ables are replacing conventional chart recorders.
5) Local or central process control The latter are needed only as required by the
6) Startup and shutdown strategies regulatory authorities (e.g., emission measure-
7) Upgradability ments) or to record guaranteed values (e.g., tem-
8) Amenability to changes peratures in a catalyst bed).
9) Capability of linking with automation The workstations and peripherals should be
systems at other plants, other monitor- arranged so that the operator sees the whole
ing/control levels, or information systems working field as a closed area and operators
10) Type of reporting can exchange information in order to coordinate
11) Safety, availability their actions in case of abnormal occurrences
12) Standardization (Fig. 32).
13) Environmental restrictions
14) Maker and service capabilities Engineering of Control Systems. It is use-
15) Personnel considerations (crew size, qualifi- ful to break the engineering of modern mea-
cations) surement and control equipment into field de-
16) Economic and management aspects vices and central control rooms (process control
systems). Different levels of detailed knowledge
Only close collaboration between process en- are needed for these two areas. The high rate
gineering and process control specialists belong- of innovation in process monitoring and control
ing to the staff of the engineering contractor and systems demands continuous retraining of the
the owner can ensure proper decisions. design engineers.
In the central control room, the operating and The main activities involved in engineering
monitoring devices collect all needed process follow and make use of computer-aided engi-
information. All signals from the plant (flow, neering (CAE) systems with different software
pressure, temperature, etc.) are dynamically dis- requirements:
played on a screen. Two to three screens per
workstation, with the necessary operating fea- 1) Preparation of basic documents such as cod-
tures (touch screen, light pen, keyboard), have ing system, power supply and distribution,
proved optimal with regard to cost and volume materials of construction, P & I diagrams,
of information. The process control system in- control strategy, functional diagrams for pro-
cludes reporting features that maintain a contin- cess and device control systems, instrument
Figure 32. Control room, courtesy of Lurgi AG
list, quantity structure list, requirements for cilitate plant maintenance and the remedying of
process measurement and control system malfunctions.
2) Preparation of instrument specifications Information on reliability, maintenance cost,
such as data sheets for all instruments to be spare parts management, experience, availabil-
installed, with information on designation of ity over an extended time, and service are impor-
measurement location, process data, manu- tant factors in the selection of instruments and
facturer’s data, materials of construction systems. Ease of access to instruments and sys-
3) Engineering of process measurement and tems greatly reduces the number of plant mal-
control system: configuration documenta- functions and thus increases profits.
tion, process graphics, loop sheets, descrip-
tion of process measurement and control sys-
tem 5.4.6. Electrical Design
4) Planning of central facilities such as power
distribution, instrument cabinets, monitoring The objective of electrical design is to supply
rooms electric power reliably and economically to all
5) Preparation of installation documents such consumers. The designer does not create iso-
as cable run plans, cable lists, hookups, and lated solutions component by component but
list of installation materials must find the optimal solution for the system
as a whole.
The pareparation of as-built documents once Design begins where high-voltage power
the plant has been commissioned and the main- enters the plant, and may include medium-
tenance of important documents thereafter fa- and low-voltage switchgear, transformers, gen-
erators, emergency backup systems, lighting,
grounding, and communications. It covers three Installation Planning. Electrical installa-

areas: tion accounts for a significant fraction of invest-
ment costs, so detailed planning is a prerequisite
1) Planning of power generation and distribu- for economic execution. At this stage access to
tion a plant model is extremely helpful.
2) Planning of electric utilities The installation plans are drawn up by CAD
3) Installation planning methods on the basis of layout plans and com-
prise:
Planning of Power Generation and Dis-
tribution. The operator wants to optimize use 1) Position plan for electrical consumers
of the electric power and to insure that the 2) Cable run plan
system can handle short- circuit loads, that the 3) Cable run sections
power grid can handle short- circuit loads, that 4) Grounding position plan
the power grid offers the necessary reliability, 5) Lighting layout plan
that investment costs are minimized, and that 6) Hazardous area classification
operating costs are held down. 7) Layout plan for communication systems
The following points therefore have to be ex-
amined carefully in the design of the distribution On the basis of the designs and documents
grid: prepared, the quantities needed are determined
and bid invitations are prepared for bulk mate-
1) Selection of voltage levels rials and installation. The ordered equipment is
2) Determination of transformer ratings inspected at the workshops to check for compli-
3) Location of load centers ance with the specifications.
4) Location of distribution stations (with al- The cost of electrical equipment and mate-
lowance for danger zones) rials makes up 6 – 10 % of the total chemical
5) Reliability of supply from electric utilities plant costs. The high end of the range applies
and/or in-plant generating capacity to grass-roots plants where a new infrastructure
6) Materials of construction must be created. For further information, see
[134], [135].
The elements of the electrical grid must be
selected and sized. The use of powerful com-
puter programs is indispensable (to keep the
consumer list, perform short- circuit/load – flow
5.5. Procurement
calculations, determine the run up behavior of
Procurement activities consist of three main
motors, and carry out the sizing of cables). The
tasks:
results of these steps are entered in the block
diagram. 1) The purchase of plant components and ser-
The list of electrical consumers gives a devices
tailed description of energy consumption and 2) Expediting during the fabrication of plant
provides the basis for the energy balance, in components (i.e., supervising the fabrication
which the installed power and net power demand sequence of plant components according to
are calculated. an agreed time schedule)
3) The shipping of plant components to the con-
Planning of Electric Utilities. Once the re- struction site
sults of the above activities are available, docu-
ments needed for specifying the electrical utili- In U.S. oriented regions, workshop inspec-
ties are prepared. These include technical spection of plant components also comes under this
ifications, engineering data sheets, circuit dia- heading.
grams, cable lists, terminal diagrams, and mimic Depending on the terms of the contract, the
diagrams. These technical procurement docu- engineering firm procures plant equipment in its
ments form the basis for bid comparisons and own name or in the name and on behalf of the in-
order specifications. The plans are prepared by vestor. The procurement department of an engi-
CAD methods. neering firm is acquainted with the world market
and carefully observes trends. The procurement covered by the bid invitations is important so that
and engineering activities are closely linked to- bids from competing vendors are comparable as
gether. The purchasing and shipping agents as to content and thus price.
well as the expediters are also members of the The above procedure is also followed in the
project team, and thus subordinate to the project procurement of services. The technical docu-
manager. Procurement man-hours make up 8 – mentation (e.g., for installation of piping) is pre-
12 % of total engineering hours spent on project pared by the specialist engineers responsible for
execution. piping, in close cooperation with the erection
planning department. This documentation in-
5.5.1. Purchase of Equipment and Services cludes the piping material takeoff, plant layout,
specifications for piping installation, informa-
The main steps in purchasing are: tion on material storage capabilities, and sched-
ules. The received bids for plant components
1) Preparation of a vendor list, possibly in col- and services are examined by the responsible
laboration with the investor engineers to insure that they are comparable and
2) Preparation and dispatch of bid invitations conform to the requirements stated in the bid
based on requisitions written by the special- invitations. Bidders may often be asked to cor-
ist engineers rect their scope of delivery and services. The bid
3) Handling queries from bidders, checking on- price may be adjusted as a result.
time receipt of bids, checking received bids Technical bid comparison is followed by
for completeness commercial bid comparison and an order rec-
4) Checking bids for comparability by the en- ommendation. Often, the final decision is only
gineer made after verbal negotiations with two or three
5) Preparation of bid comparison and order rec- bidders. Decision criteria include not only low-
ommendation by the purchasing department est price but also the technical reliability of the
6) Checking the order recommendation (by cost plant component covered by the bid, the experi-
engineers, specialist engineers, and possibly ence and reliability of the manufacturer, and the
the project manager) vendor’s solvency and workshop capacity uti-
7) Negotiations with the assistance of the spe- lization.
cialist engineer and possibly the project man-
ager
8) Preparation of order documents Orders. Especially in the case of compli-
9) Checking order confirmation cated plant components and large service pack-
10) Approval of bill payments after confirmation ages, the order often goes out in abbreviated
from the specialist engineer form by Telex, to make the best possible use
11) Compilation of lists of bid invitations, bid of the agreed-on lead time. The detailed order
comparisons, and orders document follows immediately. The order is pre-
pared by computer-aided techniques so that, for
Bid Invitations and Comparisons. The en- example, the value of the order is transferred di-
gineer responsible for a particular discipline pre- rectly into the computer-aided cost control sys-
pares specifications for the components he needs tem.
in the form of data sheets, guide drawings, de- If the plant components are clearly defined,
scriptions, and information on when each item the specification used for the bid invitation can
will be needed. These documents are sent to also be employed for ordering. For larger and
the purchasing department, which adds relevant more complicated items, the scope of delivery
business conditions and sends the packages to or service must be unambiguously described
selected bidders. The potential bidders are cho- with a statement of exclusions. Imprecision at
sen by the responsible engineers and purchas- this point can result in unpleasant confronta-
ing agents when the vendor list is drawn up. If tions with the vendor. Receipt of the order is
goods are purchased in the name and on behalf of confirmed in writing by the vendor.
the investor, the investor commonly has a say in
the process. Good definition of equipment items
5.5.2. Expediting 5.6. Planning and Execution of Civil

Work and Erection
The engineering firm has an obligation to the
investor to erect the plant within a certain time. The main execution phases of a project up to
The time schedule agreed between the engineer- mechanical completion (engineering, procure-
ing firm and the vendor must therefore also be ment, civil work, erection) overlap one another
complied with. The engineering firm establish a in time. The sequence of engineering work
production schedule monitoring system for this should guarantee that
purpose. Supervision begins as soon as stocks 1) Plant equipment with long delivery times
of material are ordered, it covers the manufac- (e.g., compressors, complicated apparatus)
turer’s design work (workshop drawings) and can be ordered as early as possible
other production steps. Expediters from the en- 2) Civil work (e.g., foundations, cable ducts,
gineering firm carry out their checks by tele- buildings) is begun early so that equipment
phone calls and regular visits to material ven- erection is not delayed
dors and the manufacturers of plant equipment. Civil work should be begun as soon as the
They report regularly to the expediting engineer engineering work is 25 – 30 % complete.
and the project manager. By way of example, Figure 33 shows the
When delays are expected, corrective mea- project master schedule for the design and con-
sures must be instituted in collaboration with the struction of the expansion of a refinery complex
manufacturer (e.g., changing material vendors, including the progress curves for engineering
weekend work, night shifts). and construction. The time to mechanical com-
pletion is 30 months if basic engineering (which
must be performed by the licenser) is complete
at the outset. Usually the time required for basic
5.5.3. Shipping engineering is four to six months. Figure 33 also
shows that engineering office work is only com-
The packaging and shipping of plant compo- plete by the time of “mechanical completion.”
nents to the construction site may be included The remaining work includes the preparation of
in the order given to the vendor, or may be final documentation.
the responsibility of the engineering firm. In
larger projects, the engineering firm should take
responsibility for coordinating and supervising 5.6.1. Planning of Civil Work and Erection
packaging and shipping. The principal activities The planning of civil work and erection is part
of the shipping department are: of detail engineering.
1) Checking the specifications for packaging,
shipping, payments, and duties (these are 5.6.1.1. Planning of Civil Work (Including
usually part of the contract with the investor) Structural Steel Work)
2) Drawing up plans for the delivery of equip-
ment As a rule, engineering for civil work and struc-
3) Issuing standard invoices for import licenses tural steel is done by engineers in the civil engi-
4) Obtaining packaging bids and issuing orders neering department assigned to the project team.
5) Checking container lists and obtaining trans- Often, however, their activity is limited to basic
port approval for large and heavy containers civil design, while detailed civil design is as-
signed to engineering firms in the country where
Further activities include booking freight the plant will be built. These firms are famil-
space, procuring insurance, and supervising iar with local conditions, know the local regu-
loading and transport. Shipping, customs, and lations, and have short lines of communication
bank documents (including invoices) must also to the construction site and the firm performing
be prepared. Finally, damage and faults must be the civil work.
taken care of. Important information required at the start of
basic civil design includes:
Figure 33. Project master schedule (refinery expansion project)
1) Soil evaluation report that contains, data on piping, sewers, wastewater systems, and heat-
the subsurface soil conditions at the plant ing/ventilation/air conditioning systems. They
site, water table, water analysis, and soil are the basis for detailed planning by the civil
bearing capacity. It should also give settle- engineering subcontractor or in the office. To-
ment calculations so that plant components gether with the estimated quantities determined
subjected to severe dynamic loads can be cal- for steel and concrete, these documents are used
culated and designed. in inviting bids. The detail engineering for struc-
2) Data on the proposed wastewater system. tural steel is usually carried out by the structural
3) An approved layout. steel supplier.
4) Geological and climatic figures such as After the submitted bids have been evaluated,
earthquake factor, prevailing wind direction, the contractors for civil work and structural steel
and severe snow conditions. are selected on the basis of qualitative and price
5) Static and dynamic load data for the foun- aspects.
dations of machinery, equipment, furnaces,
and steel structures.
6) Footprint dimensions of machinery and 5.6.1.2. Erection Planning
equipment: piping and cable cutouts in
floors, platforms, and walls. Planning the installation of plant equipment
starts at a relatively early stage in the engineer-
On the basis of this information, prelimi- ing process. The sequence of installation activi-
nary plans are drawn for foundations, build- ties can strongly influence the detailed schedul-
ings, steel frames, traffic routes, underground ing of engineering and procurement. The sched-
ule for overall project execution should be de- sponsibility for all site activities belongs to the
veloped backward from the agreed mechanical construction manager, as specified in the con-
completion date and specifically for equipment tract, relevant codes, and regulations. The con-
with long delivery times. In large plants, sepa- struction manager is answerable to the project
rate schedules are worked out for each plant sec- manager and is the engineering firm’s principal
tion. Erection schedules are revised at intervals representative to the investor on the site. The
throughout detail engineering and procurement organization of the construction team must take
as the agreed equipment delivery times are in- account of the size and complexity of the project,
corporated into the schedules. time schedule, local conditions, and contractual
Drawing up the plot plan calls for the co- obligations.
operation of an experienced erection engineer, Figure 34 shows a typical site organization
who must consider in particular the erection for a large project. Commonly the investor main-
requirements for heavy components (space retains a similar, but smaller organization so that
quirement, accessibility). discussions can be carried on at all technical lev-
The land on which the plant will later be built els.
must be prepared prior to construction work. The The main tasks of the construction site team
planning of temporary facilities is generally the are:
responsibility of the engineering firm. Besides
surveying and leveling, it is necessary to plan for
the delivery of utilities and the removal of runoff 1) To plan, coordinate, and manage all site ac-
and sewage. Other facilities include construc- tivities
tion offices, stores, open-air storage areas, site 2) To arrange for site offices and establish site
roads, site fencing, piping prefabrication shops, security systems
communication facilities, toilets, first-aid sta- 3) To organize and oversee materials manage-
tion, guardroom, changing rooms, and accom- ment
modation for subcontractor personnel. 4) To perform scheduling and progress con-
The engineering firm subcontracts installa- trol
tion work to qualified firms specializing in the 5) To define working methods
erection of structural steel, apparatus, machin- 6) To prepare and carry out quality control
ery, and installation of piping, electricals, and 7) To establish and supervise work safety pro-
control systems. Subcontracting takes place in cedures
the detail engineering stage as soon as suffi- 8) To coordinate and oversee the work of con-
ciently exact information is available on the struction subcontractors
plant components and bulk materials. This is es- 9) To manage and clarify the construction
pecially important when installation is covered documentation
by a fixed-price contract. 10) To implement a cost control system and ar-
range payments
11) To prepare construction-site orders
5.6.2. Execution of Construction 12) To prepare deficiency reports and control
insurance cases
The construction work performed by specialist
13) To prepare as-built drawings
subcontractors is generally directed by the en-
14) To implement a change order management
gineering firm. If the contract provides for the
system
investor or a third party to do the construction,
15) To submit reports to the investor and the
the engineering firm only supplies technical ad-
project manager
visory services.
16) To direct and oversee functional tests
17) To initiate and direct the final plant inspec-
5.6.2.1. Construction-Site Organization and tion and, when the plant is mechanically
Management complete, to pass it on to the commission-
ing manager or turn it over to the custody
The construction manager and his team super- of the future plant operator
vise, coordinate, and direct construction. Re-
Figure 34. Organization of a construction team
5.6.2.2. Time Scheduling and Progress Progress of Work. Regular evaluation of

Control progress in construction provides reliable infor-
mation about the current status of the project.
Time Schedules. An overall construction Schedule changes show up and measures can be
schedule is created during detail engineering. planned and carried out early enough to insure
This plan is continually refined as new infor- on-time completion of the plant.
mation becomes available. Progress planning is based on a detailed
Construction work calls for more detailed, in- schedule, list of plant components, material
dividual schedules for on-site activities, which takeoffs, and specific rating factors. A specific
allow better monitoring of individual jobs and rating factor is an empirical number of hours
fast response to schedule changes. required for a specified activity (e.g., hours per
Experience shows that detailed construction tonne, m3 , or piece). If there are no rating fac-
network diagrams are unwieldy because of the tors, the hours required for stated activities are
large quantity of data. Individual schedules for estimated in advance.
use at the construction site are therefore usually
The total number of hours thus found for each
prepared as bar charts that also show the inter-
activity is allotted to the planned execution time
dependencies between the various activities.
for individual activities. Expressing such allot-
Two types of bar charts are usually used:
ments in percent allows a target progress curve
1) Detail schedules for plant sections, subdi- to be determined for each functional discipline
vided according to functional disciplines. in each plant section; this curve serves as a ref-
These charts form the basis for assessing erence for monitoring construction progress.
progress of work. Progress in each special discipline is evalu-
2) Detailed schedules for each functional dis- ated every two to four weeks. Activities not com-
cipline that include all plant sections. These pleted at the time of progress assessment must be
charts are used for capacity planning for con- included. The activities of the special disciplines
struction personnel and their tools, equip-
ment, materials, and consumables.
are therefore divided into steps and evaluated. A cannot be shipped in one piece. Tall towers are
breakdown for above-ground piping installation divided into sections, while large tanks are de-
serves as an example: livered in the form of prefabricated pieces. The
Prefabrication: tools needed for assembly (e.g., welding and cut-
Pick up material 2%
Prepare and tack parts 16 %
ting machines) and facilities for stress-relief an-
Weld 16 % nealing of the welds must be provided at the site.
Fit up and weld small parts 6% If possible, the delivery of heavy units should
Installation:
Transport 5% be scheduled so that they can be placed on their
Install, tack 20 % foundations or supported in their frames imme-
Weld 11 %
diately. Specialists provided by the manufac-
Attach clamps, supports 9% turer usually assist in the installation of pumps,
Inspection: compressors, and turbines, as well as “package
Do preliminary tests, remedy 6%
deficiencies units” such as refrigeration systems and compli-
Pressure test, flush 7% cated conveyors; these experts later commission
Do final test and prepare 2%
report
the components installed.
Total 100 % Piping installation at a chemical plant is of-
ten the most labor intensive and longest phase
Assessments of individual operations result of installation. It starts with the placement of
from years of experience. The progress values underground pipelines,the mounting of straight
found for each discipline are then summarized piping on bridges, and the prefabrication of pip-
for each plant section, yielding the progress ing. When the number of connection points to
for each plant section or the plant as a whole. apparatus and machinery is great enough (i.e.,
These values are compared with the planned tar- when the devices have been delivered and put in
get progress values. If there are deviations, the place), the prefabricated piping sections are con-
causes are analyzed and appropriate measures nected. Satisfactory progress in prefabrication
taken. and smooth installation of piping depends on
The progress report contains the above infor- skillful scheduling of the preparation of isomet-
mation and is an essential part of the regularly ric drawings and the observance of this schedule.
updated construction-site report. Furthermore, the procurement of piping material
should be scheduled so that the material for pre-
fabrication arrives at the site on time. Computer-
5.6.2.3. Construction Work [123] aided integrated material management systems
are a great help in the handling of bulk material.
Work at the construction site begins with prepa- Weld inspection is carried out by X-ray meth-
ration of the terrain. The plot must be sur- ods. Which piping is to be inspected depends on
veyed, graded, and terraced if necessary. Access the quality assurance specifications.
roads must be laid out and old structures demol- After a pipe run has been installed, it is pres-
ished. Utilities for construction must be brought surized with water to reveal any leaks. The pres-
in. Construction-site offices, storage areas, and sure test is documented in a report and the piping
workshops must be built. Accomodation (con- is approved for painting or insulation.
tainers) for construction personnel must be pro- Insulation work starts at vessels, towers, and
vided. reactors and often requires the construction of
The construction work begins with excava- complex scaffolds. Pipes should not be insulated
tion and foundation work. If the soil quality ne- until a given plant section has a sufficiently large
cessitates driving piles, this must be done first. number of pipe runs that have been approved for
The sequence of pouring foundations depends insulation.
on the order in which equipment is to be deliv- The installation of electronic devices and
ered and installed. control systems takes place after a section of
The first step in erection is the erection of piping has been completed. Devices in control
heavy equipment (reactors, towers) and steel rooms and substations can, however, be installed
structures (pipe bridges and equipment support- independent of other work as soon as the build-
ing frames). Very large process equipment often ings have been completed. Underground electri-
cal cables are layed after piping. Electrical and Figure 35 shows a three-train reformer plant
pneumatic cables for measurement and control under construction.
are installed in cable ducts after the completion
of underground work. The laying of cables on
cable trays is put off until as late as possible to 5.7. Commissioning
prevent damage during simultaneous piping in-
stallation. The same applies to the installation 5.7.1. Plant Design and Commissioning
and junctions of field instruments.
Furnaces are lined with refractories before Commissioning must be considered even dur-
shipping to the site or on site. Trays are installed ing basic and detail engineering in the design of
in towers after access to the towers has been pro- equipment, piping, and control systems. Faulty
vided by platforms and ladders. Lightning pro- process design can have serious effects on the
tection and grounding wires are installed at an time required for commissioning and the amount
early stage, during the fill work of foundation of corrective work needed. The start of produc-
excavations. tion may be significantly delayed and the owner
Functional tests of the installed equipment may suffer a substantial loss of production and
mark the end of erection work. These tests are revenue.
done with the plant in the cold condition and Difficulties in commissioning and causes of
with no product. delays have been identified as [136]:
The contract must precisely define “mechan-
26 – 29 % faulty design
ical completion,” since the contractual obliga- 56 – 61 % failure of plant components
tions of the engineering contractor to the in- 13 – 15 % errors by operating personnel
vestor often end at this point. Responsibility for
the commissioning of the plant may lie with the Commissioning costs as a percentage of total
investor, the licenser, or the engineering con- plant investment are:
tractor. Generally speaking, a plant is mechani- 5 – 10 % for established processes
cally completed when subsequent commission- 10 – 15 % for relatively new processes
15 – 20 % for novel processes
ing will not be delayed or disrupted by installa-
tion work and that the safety of the plant is fully Commissioning should be a special consid-
guaranteed. eration when the piping and instrumentation di-
The certificate of mechanical completion is agram is designed. A commissioning engineer
usually accompanied by a “punch list” that de- with relevant experience should be brought in
fines all installation work that is still outstanding during the planning work. This engineer should
and to be done in the commissioning phase. The prepare the complete operating manual which
certificate is generally granted when the follow- should be available before the final version of
ing activities have been performed: the piping and instrumentation diagram.
1) Pressure testing of equipment and vessels The experienced commissioning engineer
with air, water, or nitrogen along with specialists (and maintenance engi-
2) Purging and, if necessary, chemical cleaning neers) working for the future plant operator
and pressure testing of piping should also be involved in checking the piping
3) Testing of stress-free piping connections to model. Errors in pipe routing and poor access for
machinery and checking of rotation direction the servicing, installation, and removal of equip-
and coupling seating ment can thus be remedied at an early stage.
4) Brief trial run of pumps (with water) and of
machinery and motors (as possible without 5.7.2. Operating Manual
product)
5) Calibration of measuring instruments, The operating manual is a condensed “reference
alarms, interlocks, and cutoff points book” for the entire plant. It should contain all
6) Functional checking of electrical equipment important details about the design and operation.
and control systems The typical contents of an operating manual for
a chemical plant follow [123], [136], [137]:
Figure 35. Reformer plant during construction, courtesy of Lurgi AG
Part I. Operating Instructions 2.4. Process principles and guidelines for

1. Design Principles plant operation explain the theoretical ba-
Statement of the type, purpose, and capac- sis of the process, as well as the process
ity of the plant; specification of quality and variables and their effects on product quality
quantities of feedstocks and products (in- or composition. Diagrams, formulas, nomo-
cluding waste streams); utilities and consum- graphs, and tables allow estimation of these
ables. variables (e.g., raw-materials composition,
2. Description of the Process and the Plant cooling water temperatures).
2.1. Description of the process with its prin- 3. Special Equipment
ciples (e.g., chemical and physical princi- This chapter contains an in-depth descrip-
ples of the process stages). The process itself tion of special-purpose or critical equip-
is demonstrated by process flow diagrams ment (e.g., reactors, compressors, turbines).
showing equipment, machinery, and instru- A subchapter deals with particularly impor-
ments and important process conditions. tant or complex control loops or interlock-
Auxiliary systems such as refrigeration, ings and emergency shutdown systems.
steam, or slop (wastewater) systems are sim- 4. Preparation of the Plant for Commission-
ilarly shown. The delivery and disposal of ing
utilities and consumables is also discussed. This chapter lists the preparatory steps re-
2.2. The plant description covers the designs quired for commissioning (e.g., flushing,
of the individual plant sections, the functions cleaning, and neutralizing of piping, equip-
of their components, and the control of the ment, and plant sections; inspections; pres-
installed unit operations. sure and leak tests; inspection of safety de-
2.3. Material balances. vices; mechanical tests of machinery; drying
of furnace refractory or reactor linings; and havior of the operating personnel is rec-
specifications for charging catalysts and con- ommended or prescribed. Information about
sumables). safety facilities and the locations of first-aid
5. Plant Startup stations is given.
An outline of the overall plan for starting 10. Miscellaneous
up the plant is first given. All startup oper- List of blinds, setpoints for alarm and switch-
ations are then described in detail step-by- ing functions.
step. Special precautions and unusual design
Part II. Drawings and Equipment Specifi-
conditions are highlighted.
cations
The startup instructions are broken down as 1. Drawings
follows: This chapter contains drawings that relate to
a) Initial startup after installation is com- the process or to the plant as a whole:
plete. a) Process flow diagrams and P & I diagram
b) Startup after a prolonged shutdown. b) Plant layout plan
c) Restart after a brief shutdown when the c) Underground plan
plant is still warm. d) Selected overall drawings of important
d) Procedures for catalyst regeneration or equipment (e.g., reactors)
replacement. 2. Specifications
e) Measures to be taken after abnormal Equipment design specifications are com-
occurrences. Possible disturbances are piled. Relevant drawing numbers, technical
listed together with their effects and procurement specifications, and other doc-
countermeasures. This section discusses uments containing supplementary informa-
how to remedy problems during operation are also noted.
tion; how to keep plant sections in opera- 3. Equipment Manufacturers Operating In-
tion while problems are being remedied; structions
and how to perform restart afterward.
6. Plant Shutdown Part III. Technical Documentation and
This chapter describes procedures for Drawings
planned and unplanned shutdown of the Manuals are prepared for each engineering
plant. It is subdivided as follows: discipline. These manuals show all specifica-
tions and drawings relating to plant compo-
a) Partial shutdown for periodic catalyst re-
nents and their operation and maintenance.
generation or removal of cracking de-
posits from furnace tubes
b) Procedure for brief shutdown 5.7.3. Responsibility and Organization
c) Procedure for extended shutdown
d) Shutdown on utilities outage Responsibility for commissioning generally lies
e) Emergency shutdown and special pre- with the party granting the process license: the
cautions investor/owner, licenser, or the engineering firm.
7. Analysis Specifications The commissioning team is led by the commis-
Analysis specifications: required or recom- sioning manager. The key positions are occu-
mended number of analyses during commis- pied by experienced startup engineers. Startup
sioning under steady-state operating condi- operation goes on around the clock, so that an
tions and exceptional operating conditions. adequate number of startup engineers must be
8. Operating Report available for shift work.
This chapter describes which data are to be In large plants involving two or more process
recorded during plant operation. A standard steps, it is desirable to break the plant down into
form for reporting during steady-state oper- sections and assign responsibility for each to a
ation or commissioning is recommended. smaller startup team.
9. Safety Practices On mechanical completion of the plant most
The safety regulations are summarized. Po- of the installation personnel leave. Some special-
tential hazards are discussed, and the be- ist engineers remain on site, however, especially
those involved with piping, electricals, control time, lined furnaces are dried and heated in ac-
systems, and machinery, who solve problems cordance with the vendor’s specifications. The
that arise during commissioning. catalyst is charged, reduced when necessary,
The actual manual commissioning activities and brought up to reaction temperature. Plants
are generally performed by personnel of the opin which combustible media circulate must be
erator who have already gone through classroom purged with inert gas so that they are oxygen-
training. The operating personnel can often be free before charging. Steam lines must be care-
trained in similar plants operated by associated fully dewatered.
firms. All measurements are recorded and balances
are run so that incorrect behavior of the plant
5.7.4. Preparation for Commissioning can be quickly detected and corrective measures
instituted.
The commissioning manager must ensure that Initial disorders are almost always encoun-
the plant is supplied with the necessary quan- tered: these result, for example, from utilities
tities and qualities of feedstocks, utilities, con- outages, mechanical damage, and hot running
sumables, and energy in time for the planned of bearings or stuffing boxes. An attempt should
start of commissioning. Spare parts and a fully be made, however, to get the plant running first
equipped repair shop must also be available. The and start up all systems, provided the safety of
cooperation of specialists provided by the manu- personnel and equipment is not endangered. The
facturers is essential for the commissioning of defects can then be remedied during the first
complicated equipment (e.g., compressors, re- scheduled shutdown of the plant.
frigeration plants). After operation has stabilized, conditions are
The plant laboratory has a vital function dur- optimized. When the planned values of product
ing commissioning. Analytical data are an im- quantity and quality, utilities consumption etc.,
portant input to process control. Sampling and have been attained, the guarantee test is carried
analysis programs must be prepared and dis- out. Guarantee values and conditions for per-
cussed with the laboratory. forming the guarantee test are stipulated in the
The commissioning team should be present contract.
on site during the final installation phase. While If the test results are satisfactory, a report for
the installation team performs function tests, handover of the plant to the owner is signed. Re-
the commissioning engineers perform a detailed sponsibility for the plant and its operation now
check of the plant, focusing on process design shifts to the owner. Any defects still to be reme-
and operation (e.g., inspection of towers, inter- died are entered in a punch list and a deadline
nals, and control systems). Changes requested for corrective action is established. Generally the
by the commissioning team can then be carried service life of plant equipment is guaranteed for
out by the installation team. a further, contractually agreed period (parts sub-
When the commissioning manager is con- ject to wear are usually exempt from this guaran-
vinced that the plant is ready for operation, he tee). Whether this guarantee is the responsibility
takes over responsibility for further activities of the manufacturers or the engineering firm de-
from the erection management. pends on the contract. Figure 36 shows part of a
plant complex for olefin production.
5.7.5. Plant Startup

6. Computer Support
The measures described in Sections 5.7.3 and
5.7.4 apply to chemical plants in general, Most engineering contractors have invested
whereas activities during the initial startup of heavily in computerization, with the emphasis
a plant depend on the type of process. on computer-aided design (CAD), computer-
Commissioning takes place step by step as aided engineering (CAE), design calculations,
specified in the operating manual. The first units data-base management,and office communica-
to be started are utilities and off-sites (e.g., cool- tion sys-tems [138]. Decisions on the use of
ing water loop, steam generation). At the same such systems, in particular CAD and CAE, are
Figure 36. Section of an olefin complex, courtesy of Lurgi AG
driven by benefits, chiefly reductions in costs large plants, dynamic simulation, and plant op-
and turnaround times, gains in the transparency timization.
of methods used, and systematic support for Project management uses computer software
project procedures. with a high degree of integration for schedul-
ing, cost planning, and project control. These
systems are generally accessible on both main-
6.1. Role of Computers in Project frames and PCs.
Execution The specific applications of computer sys-
tems vary. Graphical documents (e.g., process
A variety of systems based on discrete and flow diagrams, P & I diagrams, loop diagrams)
closed mathematical models are employed in are prepared with CAD systems which are
process engineering for the simulation and de- being increasingly linked to engineering data
sign of processes. They can be accessed from bases. Two-dimensional design instruments are
mainframe computers, workstations, or personal in widespread use for site layout planning and
computers (PCs). plant design; three-dimensional design systems
For special processes, firms use internally de- are occasionally used in special piping-intensive
veloped programs and modules based on stan- projects [139].
dard PC software. Internationally recognized The advantages of graphics in plant design
simulation programs are employed to prepare are the consistent and systematic use of mod-
mass and energy balances and to optimize heat- els and overlays and the reuse and evaluation
exchanger systems. Powerful systems are also of graphical elements with variable intelligence
available for computer-aided process analysis in [140].
CAD use improves collaboration between in- sign and engineering of plant equipment. The
dividual disciplines. For example, if plant and following general-purpose programs are also
civil engineering both use the same CAD sys- commercially available:
tem, plant design can be optimized “at the PROCESS, ASPEN PLUS simulation programs, flow sheeting
source.” SDC material data compiler
Engineering calculations can be performed HTRI design of heat exchangers
ROHR2 strength calculations for piping
with PC programs developed in-house or with PROBAD/FEZEN strength calculations for apparatus
internationally recognized standard software ANSYS, STRUDL finite-element method (FEM)
programs for structural analysis and
products. material and heat flow
Standard systems are predominant in direct
daily use by engineers. In subfields, such as Data-Base Management Systems. The fol-
finite-elements design, tasks are delegated to lowing list includes systems developed by Lurgi
specialists who can perform optimizations with from relational data-base systems:
special computer tools. ANSY mechanical equipment
Every step in the procurement of equipment LUPREA electrical equipment
is computer-aided. All data and functions are in- MASY control systems
MVS/LUROMAK piping
tegrated into a system that performs bid invita- DISPO disposition of bulk materials
tion, bid comparison, ordering, expediting, and MOSY management of materials on-site
shipping. Relevant data are available not only to BISAM bid invitation and ordering
VERONA shipping
the cost control system but also to accounting. ATERM expediting
As a rule, the entire accounting process is also KAPAZ capacity planning
KOKO cost control
computer-aided. DOSY documentation and archiving
Specialized relational data-base systems are REPRÜ accounting
widely used in the procurement of plant com-
ponents and bulk materials. These systems are Graphics. Standard systems for graphics ap-
linked by interfaces. plications include:
Administrative functions are supported by in- CADAM/AEC two- and three-dimensional plant
tegrated office communications systems. Cleri- layout and design
INTERGRAPH/IGDS, preparation of P & I diagrams
cal staff work with PC support connected to laser CADEX
printers. AUTOCAD preparation of P & I diagrams in
special fields
6.2. EDP Infrastructure and Systems

Progressive engineering companies strive for 6.3. Coordination and Interfaces
complete system integration so that engineering,
commercial, and management data can be uti- Growing importance is now attached to the fast,
lized in interlinked modules. In addition to main- error-free transfer of information generated in
frame computers, PCs are increasingly used for computer-aided operations of the engineering
individual support at engineering workstations. firm during project execution, to the owner and
The growing demand for “distributed intel- to engineering partners (and vice versa). Ac-
ligence” and advances in computer capabilities cordingly, the partners must arrive at a good
are now leading to the use of interconnected, de- understanding as to the content of documents
centralized workstations with alphanumeric ap- and data files to be transmitted; standards and
plications (data bases, calculations) and graph- codes (data structures, nomenclature, symbols);
ical ones (CAD). Extensive standardization of and data formats and EDP procedures.
the data-processing infrastructure is desirable. The definition of interfaces between two dif-
The variety of software systems used in ferent EDP systems is an important factor in data
project execution are illustrated by the following transfer. Standardization of interfaces to a reli-
examples: able extent does not yet exist for plant design
and construction. Various engineering compa-
Design Calculations. Many software sys- nies have devised interfaces for two-dimensional
tems are developed in-house for the process de- plant layout and design so that drawing data can
be flexibly transmitted to any computer system.
7. Quality Assurance Management tasks

Company quality assurance system
The primary goal in the design and construction Marketing
of chemical plants is to satisfy quality require- Research and development, engineering,
ments. These are defined by agreement between project management
the investor and the engineering contractor, by Documentation
legal regulations, and by objectives set by the Procurement
engineering firm. The quality requirements are Fabrication, civil work, erection, commis-
generally specified in the contract between the sioning
investor and the engineering firm. Measuring and test equipment, inspection
Quality assurance is ensured by installation status, corrective action
of relevant systems. These quality assurance sys- Quality records
tems cover all technical and organizational prac- Internal quality audits
tices needed to achieve the desired quality. Education and training
Requirements for quality assurance systems
are defined in standards. The international stan- The quality assurance system must not
dards ISO 9000 – 9004 have already been incor- be regarded as a fixture that schematizes all
porated into most national standards systems procedures – it needs to be continuously im-
[141]. Increasing numbers of quality assurance proved in the light of practical knowledge.
systems have been developed, introduced, and An engineering firm does not usually have its
documented in production and service compa- own fabrication capacity or perform construc-
nies. Certification of these quality assurance sys- tion services. Equipment as well as construc-
tems by neutral organizations is in development. tion and installation services must therefore be
The idea behind the creation of quality as- procured. Suppliers of equipment and firms per-
surance systems is that the quality of a product forming construction work must demonstrate
should not only be established after its produc- their own quality assurance systems to the en-
tion, but rather that the entire production process gineering firm and allow them to be verified. In
should be subjected to appropriate quality assur- addition to this, employees of the engineering
ance practices on a phase-by-phase basis. Qual- firm monitor the fabrication of equipment and
ity assurance practices must be defined and im- the construction work in accordance with estab-
plemented for all services performed by the en- lished rues to ensure that delivery and perfor-
gineering firm itself (e.g., project management, mance are in accordance with quality require-
engineering, procurement, supervision of con- ments and planned schedules. Such supervision
struction, commissioning). does not, however, release a manufacturer or a
The company quality assurance system is construction contractor from its contract obliga-
usually documented in a “quality assurance tions.
manual” which contains information on orga- In the normal case, a project can be executed
nizational structure and processes, as well as the and meet the quality requirements if the provi-
procedures, means, and methods used to assure sions of the quality system are satisfied. In com-
quality. It may also include references to inter- plicated projects or those involving a high de-
nal procedures and work instructions which are gree of risk or innovation, a quality assurance
not part of the manual. plan must be drawn up [142]. This sets forth in
The manual gives the owner and third par- detail the quality practices to be followed dur-
ties a summary of the company’s quality policy ing execution of the project. A quality assurance
and quality system. It is also an instrument for manager is designated for the project who, af-
communicating the company’s quality policy to ter consultations with the project manager and
management and employees. the heads of the functional divisions, directs the
A typical table of contents follows: quality assurance activities. He is independent
of the project team, reports directly to company
1) Quality policy of the company management, and confers with the investor on
2) Brief description of the company all questions of quality assurance.
3) Elements of quality assurance:
Many quality assurance practices are in- firms the transfer of operating and maintenance
volved in the execution of a project, a few ex- knowledge to their specialists, supervisors, en-
amples follow: gineers, and technicians. Training covers tech-
nical and commercial jobs as well as middle and
1) Checking contracts against checklists
upper management.
2) Defining the degree of checking of technical
The following questions should be explored
specifications and drawings for equipment
at the feasibility study stage:
3) Implementing design change control
4) Instituting design reviews to check, for ex- 1) What level of education exists in the region?
ample, process flow diagrams, layout plans, 2) Will skilled labor be available in the region?
piping and instrumentation diagrams, and 3) Is the project a newly-built plant or an ex-
piping models pansion of an existing facility?
5) Selecting competent manufacturers for crit- 4) If it is an expansion, can skilled operating
ical equipment personnel be found?
6) Identifying “hold points” and intensity of in- 5) Is the plant a labor-intensive production fa-
spection for equipment during fabrication cility or one that can run automatically?
Quality obtained on the basis of an assurance 6) Can the plant operate autonomously (e.g., in
system “tailored” to the company results in sev- a virgin forest area or on an island) or does
eral important benefits: it require an industrial infrastructure?
1) After consultation of quality assurance doc- Training Plan. The training plan must be
uments, the customer of a production or ser- adapted to the needs of the plant and its sur-
vice company can convince himself of the roundings and should be workable regardless
company’s ability to achieve the agreed-on of the initial qualifications of the workers be-
quality of the product or service ing trained. It should also convey state-of-the-art
2) A company’s quality assurance systems, ex- knowledge.
amined and certified by a competent neutral The training plan comprises organizational
organization, can mean a competitive advan- charts, job descriptions, definition of mini-
tage mum qualifications of future jobholders, train-
3) If a quality assurance system is organized in ing schedules, and identification of facilities for
a meaningful and expedient manner, agreed- practical training. It may also include adminis-
on quality of a product can be obtained at trative topics (e.g., how to obtain a visa and res-
low cost and with little expenditure of time idence and work permits, assistance in finding
Quality assurance practices must already be accomo-dation, where to get work and safety
applied, for example, during the design stage clothing, personal insurance and medical care
for a piece of plant equipment. Expensive post- during the training period).
fabrication corrections on a wrongly specified The planning documents provide a basis for
device are then avoided. hiring tests and results are compared with the
profile of requirements in the job descriptions.
The tests should pose and evaluate technical
8. Training of Plant Personnel and management skills questions. If necessary,
an institute or an industrial psychologist can be
Preliminary Planning. The people who are brought in.
to operate and maintain a chemical plant must
have the necessary theoretical background, prac- Execution of Training. Every participant
tical training, and know-how. should receive a training schedule in which the
This applies in particular to personnel in subject, day/time, and discussion partner or in-
developing countries, who should participate structor are listed.
in specially developed know-how transfer pro- Training should take place as late as possible
grams. so that there is no lag between training and job
Many owners and operators of chemical assignment (fluctuation danger). However, train-
plants write into their contracts with engineering ing activities should be started early enough so
that the future operator’s personnel can see their 6. V. D. Herbert, A. Bisio: “The Risk and the
own plant demonstrated in the final installation Benefit,” part 2, CHEMTECH 6 (1976) no. 7,
phase and can perform some functions them- 422 – 429.
selves. This improves their sense of responsibil- 7. H. Kölbel, J. Schulze: Projektierung und
ity. Vorkalkulation in der Chemischen Industrie,
The training program is usually broken down Springer-Verlag, Berlin 1982.
as follows: 8. J. E. Haselbarth: “Updated Investment Cost for
60 Types of Chemical Plants,” Chem. Eng.
(N. Y.) 74 (1967) Dec. 4, 214.
Phase I. Presentation of basic information about the plant. 9. K. M. Guthrie: “Capital and Operating Cost
Phase II. Presentation of generally important instructions on for 54 Chemical Processes,” Chem. Eng.
plant operation, maintenance of machinery, safety
practices, and organization. (N. Y.) 77 (1970) June 15, 140 – 156.
Phase III. The trainees are divided into operating personnel, 10. J. Jung: “Detaillierte Vorausberechnung von
maintenance personnel, and administrative and Investitionskosten,” in GVT-Hochschulkurs:
management personnel. When possible, these groups
are trained on the same or similar facilities for the Angewandte Kosten- und
jobs they will later perform. Wirtschaftlichkeitsberechnungen bei der
Phase IV. During the final phase of installation, the plant Projektierung verfahrenstechnischer Anlagen,
personnel familiarize themselves in depth with their
own plant. The training period ends with active University of Dortmund 1984, pp. 115 – 137.
participation in plant commissioning. 11. F. Strailk: “Das Verfahrensschema als
Grundlage bei der Planung in der chemischen
Training Costs. Training costs comprise Technik,” Chem. Appar. 92 (1968) 419 – 434.
personnel, nonpersonnel, and incidental costs. 12. H. C. Lang, Cost Engineering in the Process
Personnel costs are incurred for the people Industries, McGraw-Hill, New York, 1960,
who prepare, execute, and coordinate training, pp. 7 – 14.
as well as the trainees salaries. Nonpersonnel 13. C. H. Chilton, Chem. Eng. (N. Y.) 73 (1966)
costs include payments to the operators of facil- 184 – 190; C. H. Chilton: Cost Engineering in
ities where training takes place and the outfit- the Process Industries, McGraw-Hill, New
ting of training rooms on the construction site. York 1960.
Incidental costs comprise costs for accomoda- 14. W. E. Hand, “From Flowsheet to Cost
tion, travel, work clothing, insurance, and util- Estimate,” Pet. Refin. 37 (1958) 331.
15. W. Burgert “Kostenschätzung mit Hilfe von
ities. These may make up a significant fraction
Kostenstrukturanalysen,” Chem-Ing.-Techn. 51
of total costs if the trainees are sent abroad.
(1979) 484 –487.
16. C. A. Miller: “Factor Estimating Refined for
the Appropriation of Funds,” Chem. Eng. Cost
9. References File, vol. 7, McGraw-Hill, New York 1965.
17. K. M. Guthrie: “Date Techniques for
1. H. Popper: Modern Cost Engineering
Preliminary Capital Cost Estimating,” Chem.
Techniques, McGraw-Hill, New York 1970.
Eng. (N. Y.) 76 (1969) Jan. 13, 138;76 (1969)
2. H. Kölbel, J. Schulze: Der Absatz in der
March 24, 114 –142;76 (1969) April 14,
chemischen Industrie, Springer-Verlag, Berlin
201 – 216. Chem. Eng. Cost File, vol. 11,
1982.
3. J. T. Thorngren: “Probability Technique
18. Chemical Engineering, McGraw-Hill, New
Improves Investment Analysis,” Chem. Eng.
York –Düsseldorf, published monthly.
Cost File, vol. 9, McGraw-Hill, New York
19. Chemische Industrie, Verlag Handelsblatt,
1967.
Frankfurt am Main (published monthly).
4. D. J. Massey, I. H. Black: “Predicting
20. P. M. Kohn: “CE Cost Indexes Maintain
Chemical Prices,” Chem. Eng. Cost File,
13-Year Ascent,” in: Modern Cost
vol. 11, McGraw-Hill, New York 1969.
5. J. Jung: “Globale Vorausberechnung von Engineering: Methods and Data,
Investitionskosten,” in GVT-Hochschulkurs: McGraw-Hill, New York 1979.
Angewandte Kosten- und 21. J. Schulze: “Modernisierter Preisindex für
Wirtschaftlichkeitsberechnungen bei der Chemieanlagen,” Chem. Ind. (Düsseldorf) 32
Projektierung verfahrenstechnischer Anlagen, (1980) no. 10, 657 – 663.
University of Dortmund 1984, 90 – 114.
22. J. Jung: “Globale Vorausberechnung von 40. A. Jaafari: “Management Know-how for
Betriebskosten,” in GVT-Hochschulkurs: Project Feasibility Studies,” Int. J. Project
Angewandte Kosten- und Management 8 (1990) no. 3, 167 – 172.
Wirtschaftlichkeitsberechnungen bei der 41. W. T. Nichols, Ind. Eng. Chem. 43 (1951)
Projektierung verfahrenstechnischer Anlagen, no. 19, 2295.
University of Dortmund 1984, pp. 90 – 114. 42. American Association of Cost Engineers: A
23. J. T. Sommerfeld, C. T. Lenk, Chem. Eng. 77 Guide to Capital Estimating (1988) 14.
(1970) May 4, 136 – 138. 43. R. J. Loring: “Cost of Preparing Proposals,”
24. H. Gaensslen, Chem. Ing. Tech. 48 (1976) Chem. Eng. (N. Y.) 77 (1970) Nov. 16, 126.
no. 12, 1193 – 1195. 44. P. Grassmann: Physikalische Grundlagen der
25. F. C. Vilbrandt, C. E. Dryden: Chemical Chemie-Ingenieur-Technik, Sauerländer,
Engineering Plant Design, McGraw-Hill, Frankfurt 1983.
New York 1959. 45. E. U. Schlünder: Heat Exchanger Design
26. ICI “Factest,” Eur. Chem. News 21 (1972) Handbook, Hemisphere Publ. Corp.,
March 17, 32. Washington 1983.
27. ASPEN: TECHNOLOGY ASPEN plus 46. J. H. Perry: Chemical Engineers Handbook,
Costing Manual, Cambridge 1984. McGraw-Hill, New York 1984.
28. M. S. Peters, K. D. Timmenhaus: Plant Design 47. McGraw-Hill, New York: L. Clarke, R. L.
and Economics for Chemical Engineers, Davidson: Manual for Process Engineering
McGraw-Hill, New York 1980. Calculations, 1962; E. W. Comings: High
29. Verband der chemischen Industrie: Pressure Technology, 1956; D. L. Katz:
Kostenrechnung in der Chemischen Industrie, Handbook of Natural Gas Engineering, 1959;
Gabler, Wiesbaden 1962. A. L. Kohl, F. C. Riesenfeld: Gas Purification,
30. R. I. Reul: “Which Investment Appraisal 1960; W. L. Nelson: Petroleum Refinery
Technique Should You Use?” Chem. Eng. Cost Engineering, 1958; M. van Winkle:
File, vol. 10, McGraw-Hill, New York 1968. Distillation, 1967. H. Harnisch, R. Steiner, K.
W. R. Park: “The Investment Profit-Prophet,” Winnacker: Chemische Technologie, C.
Chem. Eng. Cost File, vol. 10, McGraw-Hill, Hanser Verlag, München 1984.
New York 1968. 48. Gulf Publ. Co., Houston: R. N. Watkins:
31. D. Spethmann: “Flexibilitätsüberlegungen bei Petroleum Refinery Destillation, 1979; E. E.
Investitionsprogrammen,” Vortrag auf dem Ludwig: Applied Process Design for Chemical
22. Deutschen Betriebswirtschaftler Tag, and Petrochemical Plants, 1964.
Deutsche Gesellschaft für Betriebswirtschaft, 49. R. H. Perry: Perry’s Chemical Engineers’
Berlin 1971. Handbook, McGraw-Hill, New York 1984.
32. H. Jonas: Investitionsrechnung, De Gruyter, 50. K. Weissermel, H.-J. Arpe: Industrial Organic
Berlin 1964. Chemistry, VCH Verlagsgesellschaft,
33. J. Leibson, C. A. Trischmann: “When and Weinheim 1993.
How to Apply Discounted Cash Flow and 51. L. B. Evans: Foundations of Computer-Aided
Present Worth,” Chem. Eng. (N. Y.) 78 (1971) Chemical Process Design, vol. 1, Engineering
Dec. 13, 97 – 106. Foundation, New York 1981, 425 – 469.
34. A. Fletscher, G. Clarke: Mathematische 52. R. Raman: Chemical Process Computations,
Hilfsmittel der Unternehmensführung, Verlag Elsevier Appl. Sci. Publ., London 1985.
W. Dummer & Co., München 1966. 53. DECHEMA, DETHERM-SDC
35. H. Müller-Merbach: “Operations (Stoffdaten-Compiler), Frankfurt, updated
Research/Rev. 1,” Methoden und Modelle der regularly. Design Institute of Physical Property
Optimalplanung, 3rd ed., München 1973. Data (DIPR), American Institute of Chemical
36. H. F. Rase, M. H. Barrow: Project Engineering Engineers (AIChE), DIPPR Data Compilation,
of Process Plants, J. Wiley, New York 1957. uptated regularly. Thermodynamics Research
37. B. Aggteleky: Fabrikplanung, Hanser Verlag, Center (TRC), Vapor Pressure Datafile,
München 1987, 1990. updated regularly.
38. E. Mach: Planung und Errichtung chemischer 54. Landolt-Börnstein: Zahlenwerte und
Fabriken, Sauerländer, Frankfurt 1971. Funktionen aus Naturwissenschaft und
39. A. Franke: “Risk Analysis in Project Technik, Springer-Verlag, Berlin 1985.
Management,” Int. J. Project Management 5 55. D’Ans-Lax: Taschenbuch für Chemiker und
(1987) no. 1, 29 – 34. Physiker, Springer-Verlag, Berlin 1970.
56. D. Behrens, R. Eckermann: Chemistry Data 74. Gesetz über die Umwelthaftung,
Series, DECHEMA, Frankfurt 1977 ff. Bundesgesetzblatt (BGBl) F (1990), 2634.
57. M. Munsch, T. Mohr, E. Futterer, Chem. Ing. 75. Abstände zwischen Industrie- bzw.
Tech. 62 (1990) 995 – 1002. Gewerbegebieten und Wohngebieten im
58. D. W. Townsend, B. Linnhoff, AIChE J. 29 Rahmen der Bauleitplanung (Abstandserlaß),
(1983) 742 – 771. Minister für Umwelt, Raumordnung und
59. M. A. Duran, I. E. Grossmann, AIChE J. 32 Landwirtschaft, March 21 1980 (MBl.NW,
(1986) 123 – 138. 504 / SM Bl. NW, 283).
60. B. Linnhoff: “New Concepts in 76. Erste Allgemeine Verwaltungsvorschrift zum
Thermodynamics for Better Chemical Process Bundes-Immissionsschutzgesetz (Technische
Design,” Chem. Eng. Res. Des. 61 (1983) Anleitung zur Reinhaltung der Luft – TA
207 – 223. Luft), Feb. 27, 1986.
61. B. Linnhoff: “Wärme-Integration und 77. DIN 52 900,Feb. 1983, DIN Safety Data Sheet
Prozeßoptimierung,” Chem. Ing. Tech. 59 for Chemical Substances and Preparations,
(1987) no. 11, 851 –857. Beuth Verlag, Berlin 1983.
62. A. W. Westerberg, Comput. Chem. Eng. 13 78. T. Redeker, W. Möller: “Chemsafe-Datenbank
(1989) 365 – 376. für sicherheitstechnische Kenngrößen,” TU 29
63. V. Hlavacek, Comput. Chem. Eng. 2 (1978) (1988) no. 5, 174, VDI Verlag, Düsseldorf.
67 – 75. 79. V. Pilz: “Sicherheitsanalysen zur
64. N. Nishida, G. Stephanopoulos, A. W. systematischen Überprüfung von Verfahren
Westerberg, ALChE J. 27 (1981) 321 – 351. und Anlagen – Methoden, Nutzen und
65. A. W. Westerberg, Comput. Chem. Eng. 9 Grenzen,” Chem. Ing. Tech. 57 (1985) no. 4,
(1985) 421. 289 – 307.
66. G. Hosemann: “Methodisches Grundkonzept 80. A Guide to Hazard and Operability Studies,
technischer Sicherheit,” DIN-Mitteilung 70, Chemical Industry Safety and Health Council
no. 3, Beuth Verlag, Berlin 1991. of the Chemical Industries Association,
67. E. Tröster: “Sicherheitsbetrachtungen bei der Alensbie House, 93 Albert Embankment,
Planung von Chemieanlagen,” Chem. Ing. London SE 1 7TU. Reprinted 1985.
Tech. 57 (1985) no. 1, 15 – 19. 81. Risikobegrenzung in der Chemie,
68. Bundes-Immissionsschutzgesetz vom May 14, PAAG-Verfahren (HAZOP), ISSA Prevention
1990 (BGBl I, 880) Series No. 2002, May 1990. Published by:
69. Zwölfte Verordnung zur Durchführung des IVSS Internationale Vereinigung für soziale
Bundes-Immissionsschutzgesetzes Sicherheit, Berufsgenossenschaft der
(Störfallverordnung) vom September 20, 1991 chemischen Industrie, Geisbergstraße 11,
(BGBl I 1991, 1891) D-6900 Heidelberg.
70. Gewerbeordnung, Jan. 1, 1987 (BGBl. I, 1987, 82. Wasserhaushaltsgesetz Sept. 23, 1986
925). Amended by Gesetz zur Änderung der (BGBl. I, 1986, 1529)
Gewerbeordnung, April 5, 1990 (BGBl. I, 83. Allgemeine Rahmen-Verwaltungsvorschrift
1990, 706) and Gesetz zur Änderung der über Mindestanforderungen an das Einleiten
Gewerbeordnung Nov. 9, 1990 (BGBl. I, 1990, von Abwasser in Gewässer (Rahmen Abwasser
2442) VwV) vom Sept. 8, 1989 (GMBI, 1989, 518).
71. Bundesnaturschutzgesetz (Mar. 12, 1987) 84. H.-O. Braubach, E. Sommer, K. Zellmann:
Bundesgesetzblatt (BGBl) I (1987), 889. “Anforderungen an verfahrenstechnische
72. G. Hohe: “Sicherheitsabstände – Definition Anlagen durch die Weiterentwicklung der
und Bedeutung in Rechtsvorschriften und Gewässerschutz-Vorschriften,” Chem. Ing.
Technischen Regelwerken,” Berichtsband zum Tech. 57 (1985) no. 3, 113 –118.
BPU-Seminar: “Sicherheitsabstände bei 85. Allgemeine Verwaltungsvorschrift über die
Planung und Betrieb industrieller Anlagen,” nähere Bestimmung wassergefährdender
BPU GmbH, Berlin 1990. Stoffe und ihre Einstufung entsprechend ihrer
73. Gesetz zur Umsetzung der Richtlinie des Gefährlichkeit (VwV wassergefährdende
Rates, June 27, 1985 Concerning Stoffe), Mar. 9, 1990 (GMBI, 1990, 114).
environmental compatibility testing in public 86. Gesetz über die Vermeidung und Entsorgung
and private projects (85/337/EWG). (BGBl. I, von Abfällen (Abfallgesetz – AbfG), Aug. 27,
1990, 205). 1986 (BGBl I, 1986, 1410).
87. Verordnung zur Bestimmung von Abfällen der Genehmigung von Vorhaben
nach § 2 Abs. 2 des Abfallgesetzes (Planungserlaß), Minister für Landes- und
(Abfallsbestimmung-Verordnung – AbfBestV) Stadtentwicklung, Minister für Arbeit,
April 3, 1990 (BGBl. I, 1990, 614). Gesundheit und Soziales und Minister für
88. Allgemeine Abfallverwaltungsvorschrift über Wirtschaft, Mittelstand und Verkehr, July 8,
Anforderungen zum Schutz des Grundwassers 1982 (MBl. NW, 1366 /SM Bl. NW, 2311).
bei der Lagerung und Ablagerung von 101. Die Beteiligung an der Bauleitplanung
Abfällen, Jan. 31, 1990 (GMBI, 1990, 74). (Beteiligungserlaß), Minister für Landes- und
89. MAGS-Lärmschutz beim Raffineriebau, Stadtentwicklung, July 16, 1982 (MBl. NW,
Minister für Arbeit, Gesundheit und Soziales 1375 / SM Bl. NW, 2311).
des Landes Nordrhein-Westfalen, 1977. 102. A. Rahmel, W. Schenk: Korrosion und
90. Forschungsbericht 79-105-03-302, Stand der Korrosionsschutz von Stählen, Verlag Chemie,
Technik bei der Lärmminderung in der Weinheim 1977.
Petrochemie, commissioned by the 103. U. Heubner et al.: Nickellegierungen und
Bundesumweltamtes, Dec. 1979. hochlegierte Sonderstähle; Kontakt und
91. H. M. Bohuy: Lärmschutz in der Praxis, R. Studium, vol. 153, Expert-Verlag, Sindelfingen
Oldenbourg Verlag, München 1986. 1985.
92. M. Heckl, H. A. Müller: Taschenbuch der 104. H. Gräfen et al.: Die Praxis des
Technischen Akustik, Springer-Verlag, Berlin Korrosionsschutzes; Kontakt und Studium,
1975. vol. 64, Expert-Verlag, Grafenau 1981.
93. Allgemeine Verwaltungsvorschrift über 105. U. R. Evans: Einführung in die Korrosion der
genehmigungsbedürftige Anlagen nach § 16 Metalle, Verlag Chemie, Weinheim 1965.
der Gewerbeordnung GewO, Technische 106. DIN Taschenbuch 219: Korrosion und
Anleitung zum Schutz gegen Lärm (TA Lärm), Korrosionsschutz, Beuth-Verlag, Berlin 1987.
July 16, 1968 (Beilage zum BAnz Nr. 137, 107. H. Gräfen et al.: Kleine Stahlkunde für den
July 26, 1968) Chemieapparatebau, VDI Verlag, Düsseldorf
94. Verordnung über Arbeitsstätten, March 20, 1978.
1975 (BGBl. I, 729). Modified by decrees 108. VDI-Berichte 385: Schadensverhütung durch
passed on Jan. 2, 1982 (BGBl. I, 1) and Aug. 1, Qualitätssicherung von Werkstoffen und
1983 (BGBl. I, 1057) Bauteile-Optimierung des Bauteilhaltbarkeit.
95. Unfallverhütungsvorschrift Lärm (UVV-Lärm) Tagung, München 1980, VDI-Verlag,
Oct. 10, 1990, Hauptverband der gewerblichen Düsseldorf.
Berufsgenossenschaft. 109. D. Behrens: DECHEMA Corrosion Handbook,
96. Gesetz über Betriebsärzte,
VCH Verlagsgesellschaft mbH, Weinheim
Sicherheitsingenieure und andere Fachkräfte
1988 ff.
für Arbeitssicherheit, Dec. 12, 1973 (BGBl. I,
110. J. R. Brauweiler: “Economics of Longlife –
965). Modified by law passed on April 12,
Shortlife Material,” Chem. Eng. (N. Y.) 70
1976 (BGBl. I, 965)
(1963) no. 2, 128.
97. Verordnung über Druckbehälter,
111. R. E. Meissner, D. C. Shelton, Chem. Eng.
Druckgasbehälter und Füllanlagen
(N.Y.), April 1992, 81 – 85, 89 – 94.
(Druckbehälterverordnung), Feb. 27, 1980
112. R. S. Aries, R. D. Newton: Chem. Eng. Cost
(BGBl. I, 173). Modified by decree passed on
Estimation, New York (1955) 2, 77.
April 21, 1989 (BGBl. I, 830)
113. J. T. Gallagher: “A Fresh Look at Engineering
98. M. Pütz: Die Genehmigungsverfahren nach
Construction Contracts,” Chem. Eng. Cost File,
dem Bundes-Immissionsschutzgesetz.
vol. 9, McGraw-Hill, New York 1967, p. 23.
Handbuch für Antragsteller und
114. J. in ’t Veld, W. A. Peters: “Keeping large
Genehmigungsbehörden, Erich Schmidt,
Projects under Control: The Importance of
Berlin 1986.
Control Type Selections,” Int. J. Project
99. Neunte Verordnung zur Durchführung des
Management 7 (1989) no. 3.
Bundes-Immissionsschutzgesetzes
115. A. Morna, N. J. Smith: “Project Managers and
(Grundsätze des Genehmigungsverfahrens –
the Use of Turnkey Contracts,” Int. J. Project
9. BImSchV), Feb. 18, 1977 (BGBl. I, 274)
Management 8 (1990) no. 3, 183 – 189.
and May 19, 1988 (BGBl. I, 608, 623)
100. Berücksichtigung von Emissionen und 116. J. Madauss: Projektmanagement, 3rd ed.,
Immissionen bei der Bauleitplanung sowie bei C. E. Poeschel Verlag, Stuttgart 1989.
117. E. Mosberger: “Projektmanagement im Technik, 3rd ed., vol. V, Springer-Verlag,

Anlagenbau,” Chem. Ing. Tech. 63 (1991) Berlin 1985.
no. 9, 921 – 925. 130. VDI 3546 – Konstruktive Gestaltung von
118. D. Arnold: “Projektmanagment im Prozeßleitwarten, Beuth-Verlag, Berlin
internationalen Großanlagenbau und 1987 – 90.
Konsequenzen für die Aus- und Weiterbildung 131. VDI 3683 – Beschreibung von
von Führungskräften,” Zfbf Sonderheft 24 Steuerungsaufgaben, Pflichtenheft,
(1989) 55 – 77 (Verlagsgruppe Handelsblatt, Beuth-Verlag, Berlin 1986.
Düsseldorf-Frankfurt). 132. VDI 3693 – Verteilte Prozeßleitsysteme,
119. D. Kumar: “Developing Strategies and Prüfliste für den Einsatz, Beuth-Verlag, Berlin
Philosophies Early for Successful Project 1985.
Implementations,” Int. J. Projekt Management 133. VDI 2180 – Sicherung von Anlagen in der
7 (1989) no. 3. Verfahrenstechnik, Bl. 1 bis 5, Beuth-Verlag,
120. L. F. Rolstad: “Project Start-Up in Tough Berlin 1984 – 88.
Practice,” Int. J. Project Management 9 134. ABB (ed.): Schaltanlagen, 8th ed.,
(1991) no. 1, 10 – 14. Cornelsen-Verlag, Düsseldorf 1988.
121. H. Reschke, H. Schelle, R. Schnoop: 135. Siemens (ed.): Handbuch der Elektrotechnik,
Handbuch Projektmanagement, vol. 1, Verlag 3rd ed., Verlag Girardet, Essen 1971.
TÜV Rheinland, Köln 1989. 136. J. Matley: “Keys to Successful Plant
122. N. Thumb: Grundlagen und Praxis der Start-Ups,” Chem. Eng. (N.Y.) 76 (1969)
Netzplantechnik, Verlag Moderne Industrie, Sept. 8, 110 – 130.
München 1969. 137. W. Langhoff: “Inbetriebnahme,” Beitrag im
123. G. Bernecker: Planung und Bau
Kursushandbuch “Planung und Bau von
verfahrenstechnischer Anlagen, 3rd ed., VDI
Großanlagen der Chemischen Industrie,”
Verlag, Düsseldorf 1984.
DECHEMA, Erfahrungsaustausch, D.
124. H. Groh, R. Gutsch: Netzplantechnik, 3rd ed.,
Behrens, K. Fischbeck, Frankfurt 1969.
VDI Verlag, Düsseldorf 1982.
125. A. Franke: “Risikobewußtes 138. VDI-Richtlinien, Datenverarbeitung in der
Projektcontrolling, Risikomanagement als Konstruktion, Einführungsstrategien und
Element eines integrierten Wirtschaftlichkeit von CAD-Systemen,
Projectcontrollings,” Dissertation, Universität VDI 2216 (October 1990, draft).
Bremen 1991. 139. W. Hilkert, R. Pfohl: Anlagenkonstruktion mit
126. S. C. Ward, C. B. Chapman, B. Curtis: “On the CAD/CAE-Werkzeugen – ein
Allocation of Risk in Construction Projects,” Erfahrungsbericht – VDI-Berichte Nr. 861.5,
Int. J. Project Management 9 (1991) no. 3, 1990.
140 – 147. 140. H. Schmidt-Traub: “Integrierte
127. E. Diegelmann, H. Benesch: “Industriemodelle Informationsverarbeitung im Anlagenbau,”
– Methodik, Abwicklung,” 3 R International Chem. Ing. Tech. 62 (1990) no. 5, 373 – 380.
(1983) no. 11, 535 – 541. 141. R. Gareis: Projektmanagement im Maschinen-
128. E. Diegelmann: “Erfassung, Beschaffung und und Anlagenbau, Manz-Verlag, Wien 1991.
Montage von Rohrleitungsteilen,” Chem. Ing. 142. S. J. Heisler: “Project Quality and the Project
Tech. 54 (1982) no. 4, 303 – 313. Manager,” Int. J. Project Management 8
129. J. Hengstenberg, B. Sturm, O. Winkler: (1990) no. 3, 133 – 137.
Messen, Steuern, Regeln in der Chemischen
Pinch Technology 1075
Pinch Technology
Bodo Linnhoff, University of Manchester Institute of Science and Technology, Manchester, United Kingdom
Vimal Sahdev, Linnhoff March Ltd., Manchester, United Kingdom
1. Introduction . . . . . . . . . . . . . . . . . 1075 5.2. Cogeneration . . . . . . . . . . . . . . . . 1078

2. Composite Curves and Energy Targets 1075 5.3. Flexibility . . . . . . . . . . . . . . . . . . 1078
3. Pinch Principle . . . . . . . . . . . . . . . 1076 6. Specific Examples . . . . . . . . . . . . . 1079
4. Energy – Capital Tradeoff . . . . . . . . 1077
6.1. Modification of a Continuous Process 1079
5. Process Modifications and
Applications . . . . . . . . . . . . . . . . . 1077 6.2. Integration of a Batch Operation . . . 1080
5.1. Batch Processes . . . . . . . . . . . . . . . 1078 7. References . . . . . . . . . . . . . . . . . . 1080
1. Introduction 2. Composite Curves and Energy

Targets
The discovery of the pinch principle by
Linnhoff has provided engineers with a sci- All processes consist of hot and cold streams. A
entific design methodology which has achieved hot stream is defined as one that requires cooling,
outstanding results across the range of process and a cold stream as one that requires heating.
industries [1]. The way in which industrial pro- For any process, a single line can be drawn on
cesses are designed and retrofitted has been rev- a temperature – enthalpy plot which represents
olutionized. Using the pinch principle, engineers either all the hot streams or all the cold streams
can obtain a better understanding of the funda- of the process. A single line representing all the
mentals of a particular process. Some of the orig- hot streams and a single line representing all the
inal applications in ICI [2] and Union Carbide cold streams are called the hot composite curve
[3] showed energy savings and capital savings in and the cold composite curve, respectively.
new designs. The technology has evolved to in- The construction of a composite curve is il-
corporate cogeneration schemes [4], to improve lustrated in Figure 1. Two hot streams are shown
plant flexibility [5], [6], increase production ca- on a temperature – enthalpy diagram.
pacity [5], and reduce the effect of fouling [7] in Stream 1 is cooled from 200 ◦ C to 100 ◦ C. It
both new designs and existing plants. has a CP (i.e., mass flow rate times specific heat
The early applications were in the oilrefin- capacity) of 1; therefore, it loses 100 kW of heat.
ing, petrochemical, and bulk chemical plants, Stream 2 is cooled from 150 ◦ C to 50 ◦ C. It has
but the technology has also been proved across a CP of 2; therefore, it loses 200 kW of heat.
a wide range of process industries, including The hot composite curve is produced by sim-
pharmaceuticals, food, pulp and paper, cement, ple addition of heat contents over temperature
brewing, coffee making, and ice-cream and dairy ranges. Between 200 ◦ C and 150 ◦ C, only one
products. Pinch technology has been used in var- stream exists and it has a CP of 1. Therefore, the
ious kinds of processes including batch, semi- heat loss across that temperature range is 50 kW.
continuous, and continuous operations incorpo- Between 150 ◦ C and 100 ◦ C, two hot streams ex-
rating various operating parameters, such as dif- ist, with a total CP of 3. The total heat loss from
ferent feedstocks, seasonal demand fluctuations, 150 ◦ C to 100 ◦ C is 150 kW. Since the total CP
multiple utilities, quality constraints, and envi- from 150 ◦ C to 100 ◦ C is greater than the CP
ronmental constraints. from 200 ◦ C to 150 ◦ C, that portion of the hot
composite curve becomes flatter in the second
temperature range from 150 ◦ C to 100 ◦ C. Be-
1076 Pinch Technology
tween 100 ◦ C and 50 ◦ C, only one stream exists, The point at which the curves come closest to
with a CP of 2. Therefore, the total heat loss is touching is known as the pinch. At the pinch the
100 kW. LIVE GRAPH curves are separated by the minimum approach
Click here to view
temperature ∆ T min . For that value of ∆ T min ,
the region of overlap shows the maximum possi-
ble amount of process-to-process heat exchange.
Furthermore, QH, min and QC ,min are the min-
imum utility requirements.
Figure 1. Two hot streams plotted on a temperature –

enthalpy diagram
Figure 2 shows the hot composite curve for

the problem. The cold composite curve is con-
structed in the same way. In practical applica-
tions the number of streams is generally much
greater, but these streams are constructed in ex-
Figure 3. Composite curves showing the pinch and the en-
actly the same way. Figure 3 shows the hot and ergy targets
cold composite curves plotted on the same tem-
perature – enthalpy diagram. The diagram repre-
sents the total heating and cooling requirements 3. Pinch Principle
of the process. LIVE GRAPH
Click here to view Once the pinch and utility targets of a process
have been identified, the three “golden rules”
of pinch technology can be applied. The pro-
cess can be considered as two separate systems
(Fig. 4) – a system above the pinch and a system
below the pinch. The system above the pinch
requires only residual heat and is, therefore, a
heat sink, whereas the system below the pinch
has heat to reject and is, therefore, a heat source.
The three rules are as follows:
1) Heat must not be transferred across the
pinch.
Figure 2. Hot composite curve
2) There must be no outside cooling above the
pinch.
Along the enthalpy axis the curves over- 3) There must be no outside heating below the
lap. The hot composite curve can be used to pinch.
heat up the cold composite curve by process-to- If the amount of heat traveling across the pinch is
process heat exchange. However, at either end α, then an extra amount (α) of hot utility must be
an overhang exists such that the top of the cold supplied and an extra amount of cold utility α is
composite curve needs an external heat source required (Fig. 5). Similarly, any outside cooling
(QH , min ) and the bottom of the hot composite of the heat sink and any outside heating of the
curve needs external cooling (QC , min ). These heat source increases the energy requirements.
are known as the hot and cold utility targets. Thus:
simply by shifting one or both of the compos-

T =A−α ite curves horizontally relative to the other. Ver-
where tical movement of the composite curves is not
allowed since temperatures are governed by the
T = target energy consumption, process.
A = actual energy consumption If ∆ T min is increased, the overlap decreases
α = cross-pinch heat flow and the energy target increases. However, capital
cost decreases.
To achieve the energy targets, cross-pinch heat
If ∆ T min decreases, capital cost increases
flows must be eliminated.
but energy cost decreases. Therefore, a tradeoff
between energy and capital and, thus, a cost opti-
mum exists. Figure 6 shows the effect of ∆ T min
on energy, capital, and total cost.
Pinch technology provides the value of
∆ T min with the minimum total cost prior to de-
sign. This is determined by a procedure known
as supertargeting [8].
Figure 4. Schematic representation of the systems above

and below the pinch
Figure 6. Energy cost, capital cost, and total cost plotted

against ∆ T min
5. Process Modifications and

Applications
Figure 5. Heat transfer across the pinch from heat sink to
heat source The insight into the thermodynamics of the pro-
cess provided by pinch technology enables an
experienced practitioner to identify potentially
4. Energy – Capital Tradeoff advantageous process changes. For example, by
alteration of the temperatures or pressures, it
The composite curves can be moved anywhere may be possible to reduce substantially the en-
parallel to the enthalpy axis, because the com- ergy bill without an adverse effect on the product
posite curves represent changes in enthalpy bet- or process. Proper modification of the process
ween certain temperatures, and not absolute val- also leads to other benefits, such as the removal
ues. Thus, ∆ T min can be increased or decreased of bottlenecks and the improvement of process
operability.
A systematic search of the data for such op- the projects identified by pinch technology have
portunities is an essential element in any pinch been implemented, in whole or part, in all in-
technology survey. This can be an iterative pro- stances mentioned in Table 1.
cedure: once any beneficial changes are high-
lighted, the composite curves must be redrawn
and the minimum energy needs recalculated, 5.1. Batch Processes
which may then open the way to further process
changes [3], [9]. In the early days pinch technology achieved its
most impressive results in continuous processes,
Table 1. Savings from some applications of pinch technology ∗ but Table 1 includes a number of processes with
exceptionally successful studies in batch opera-
Process description Savings
tions. The key to applying pinch technology in
Crude oil unit savings of ca. $ 1.75×106 at 1.6 year noncontinuous processes lies in the data extrac-
payback
Large petrochemical savings over ca. $ 7.00×106 with
tion. There are no shortcuts; detailed measure-
complex manufacturing paybacks from 12 to 20 months ments and timings of all the process streams are
ethylene, butadiene, essential if cost-saving opportunities are to be
HDPE, LDPE, and
polypropylene found. Where the technology has been applied to
Tailor-made chemicals, savings of ca. $ 0.45×106 at existing operations, there have frequently been
batch process with 30 paybacks of 3 months to 3 years wider process benefits, as well as lower energy
reactors and over 300
products bills. By improved integration of the plant, ca-
Sulfur-based speciality 30 % savings to total site energy bill pacity has often been increased, without ad-
chemicals, batch and (worth ca. $ 0.18×106 at paybacks of
continuous 9 – 16 months
versely affecting operability [10].
Edible oil refinery, batch savings of 70 % of process energy
operation, wide range of equivalent to ca. $ 0.79×106 with
feedstocks paybacks from 12 to 18 months and
debottlenecking equivalent to 15 %
5.2. Cogeneration
increased capacity
Batch processing of dairy savings of 30 % (equivalent to ca. $ The principles governing the correct siting of
products and dried 0.20×106 ) with payback of less than cogeneration systems were established several
beverages 1 year
Brewery savings from 12 % to 25 % of energy
years ago [11], [12]. A pinch study uncovers
costs with paybacks from 9 months to opportunities for introducing such equipment or
2 years optimizing existing units.
“State-of-the-art” whisky significant debottlenecking and
distillery savings of ca. $ 0.35×106 with In the pulp and paper industries, for example,
paybacks from 18 months to 2 years power generation is an important element, and
Paper mill savings of 8 – 20 % of energy bill at pinch technology has been applied successfully
paybacks from 1 to 3 years
Continuous cellulose savings of ca. $ 0.28 × 106 at 1 year to improve performance and to evaluate alterna-
acetate processing payback tives. Some of the examples in Table 1 feature
Continuous dry cement large energy savings the use of cogeneration schemes.
process
∗ Savings mentioned above are concerned primarily with
energy costs. The majority of the companies also benefited from
increased throughput and improved process flexibility and 5.3. Flexibility
operability; the economic value of these benefits is not included
in the table above. A well-integrated plant need not be less flexi-
ble [5], [6]. In fact, the opposite is the case, with
Since 1983, pinch technology has achieved techniques having been developed to ensure that
energy savings in the range of 10 – 70 %, reduc- flexibility is incorporated into the process design
tions in the capital cost of new plants by up to in the most cost-effective way. For example, it
25 %, increased process capacity by the removal is possible to allow for changes in feedstock and
of bottlenecks, and greater flexibility and oper- product specifications, turndown requirements,
ability. The projects summarized in Table 1 in- and seasonal variations.
dicate the variety of industries in which pinch In a study for Shell, UK, where flexibility
technology has been successfully applied: food, was of paramount importance, an integrated de-
paper, dairy products, whisky, cement, special- sign was produced that included twelve operat-
ity and bulk chemicals, and oil refining. To date, ing modes [13]. Throughput was also increased
Figure 7. Example of a process flow diagram

a) Fractionation column; b) Furnace; c) Reactor; d) Stabilizer column; e) Benzene column; f) Toluene column
and energy savings of ca. $ 2×106 were achieved which are mixed with a preheated hydrogen-rich
within a 1.6 year payback period. stream before entering the main reactor. The re-
actor product is cooled and partially separated
before being fed to the first of a series of three
distillation columns, each fitted with a reboiler
and a condenser.
The pinch analysis without process modifi-
cations showed that the utility energy target was
22 % lower than the actual use. The pinch point
occurred at 150 ◦ C on the hot curve.
When the aspect of process modification was
included, it was obvious that on all four of the
columns (the initial fractionation column and the
three distillation columns), the reboiler tempera-
ture was above the pinch and the condenser tem-
Figure 8. Original flow diagram of distillery cooker system perature was below it. If the possibility existed to
a) Water tank; b) Cooker; c) Fermenter; d) Ejector reduce the reboiler temperature to below 150 ◦ C,
where excess heat is readily available, then the
requirement for heating above the pinch would
6. Specific Examples be correspondingly reduced, thus offering sig-
nificant savings. In fact, practical considerations
The two examples that follow give some indi- limited the scope for this change, but change was
cation of the way in which pinch technology is achieved on one of the columns by a reduction
applied to specific problems and help to show of the operating pressure.
why it has had such an impact on every industry
that has used it. The next step was to examine the furnace,
which supplied most of the process heating. The
flue gas exit temperature was well above 150 ◦ C;
6.1. Modification of a Continuous
therefore, recovery of this heat above 150 ◦ C
Process would reduce the heating target. After composite
Figure 7 shows a simplified flow sheet of an or- curves had been redrawn and process modifica-
ganic chemicals plant. The crude feed is sep- tions incorporated, the revised energy target was
arated into residue and light aromatic fractions, less than half the former energy use.
The implementation of these proposals pro- need for steam to be brought in. The resulting
duced an integrated design that used 45 % less energy savings were only part of the benefit; the
energy than before, with the investment that was cooking cycle was shortened because the cool-
involved being paid for in less than one year. ing was faster and, thus, a process bottleneck
was removed and the production capacity of the
plant increased. The revised design of the batch
cooker is shown in Figure 9.
7. References
1. B. Linnhoff., D. W. Townsend, D. Boland,
G. F. Hewitt, B. E. A. Thomas, A. R. Guy,
R. H. Marsland: User Guide on Process
Integration for the Efficient Use of Energy,
IChemE (Rugby, UK) 1982.
2. B. Linnhoff, J. A. Turner: “Heat Recovery
Networks – New Insights Yield Big Savings,”
Chem. Eng. November 2, 1981 pp, 56 – 70.
3. B. Linnhoff, D. R. Vredeveld: “Pinch
Technology Has Come of Age,” Chem. Eng.
Prog. July 1984, pp. 33 – 40.
Figure 9. Distillery cooker system after integration 4. B. Linnhoff, A. R. Eastwood: Combined Heat
a) Water tank; b) Cooker, c) Buffer tank; d) Interchanger; and Power and Process Integration,
e) Fermenter Institution of Gas Engineers, 51st Autumn
Meeting, London, November 1985.
5. E. Kotjabasakis, B. Linnhoff: “Sensitivity
6.2. Integration of a Batch Operation Tables for the Design of Flexible Processes,”
Chem. Eng. Res. Des. 64 (1986) 197 – 211.
The batch cooking operation in a distillery is 6. E. Kotjabasakis, B. Linnhoff: Flexible Heat
shown in Figure 8. Preheated water and grain Exchanger Network Design: Comments on the
are cooked by steam injection; cooling begins Problem Definition and on Suitable Solution
by venting steam at above atmospheric pressure Techniques, paper presented at IChemE
to the water preheat tank and is then speeded Symposium “Innovation in Process Energy
by a steam ejector that evaporates water from Utilisation” Bath, 16 – 18 September 1987.
the cooker under vacuum. The cooled batch then 7. E. Kotjabasakis, B. Linnhoff: “Better System
moves to the fermentation stage. Design Reduces Heat Exchanger Fouling
The pinch analysis of the distillery as a whole Costs,” Oil Gas J. September 1987, pp.
had identified the pinch point at 90 ◦ C, which 49 – 56.
8. B. Linnhoff, S. Ahmad: Supertarget: Optimal
meant that a substantial cross-pinch heat trans-
Synthesis of Energy Management Systems,
fer existed within the batch cooking process.
presented at the ASME Winter Meeting,
Vent steam hotter than the pinch was heating the Anaheim, December 1986.
process water below it, and the ejector exhaust 9. B. Linnhoff, H. Dunford, R. Smith: “Heat
steam was being condensed by cooling water. Integration of Distillation Columns into
The cross-pinch heat transfer was eliminated Overall Process,” Chem. Eng. Sci. 38 (1983)
by a series of modifications. By introduction of no. 8, 1175 – 1188.
a buffer tank between the cooker and the fer- 10. B. Linnhoff, G. J. Ashton, E. D. A. Obeng.
menter, the process water could be preheated Process Integration of Batch Processes, paper
from the cooling cooked grain, which was be- presented at the 79th AIChE Annual Meeting,
low the 90 ◦ C pinch, thus eliminating the in- New York November 1987, pp. 15 – 20.
appropriate steam ejector. The vent steam, no 11. D. W. Townsend, B. Linnhoff: “The
longer needed for preheating the process water, Preliminary Design of Networks in Process
was utilized elsewhere on the site to reduce the Design,” Part 1: ‘Criteria for placement of heat
Pinc

Ullmann's Chemical Engineering and Plant Design - Vol. 1 Mathematics and Physics in Chem. Eng. - Fundamentals - Vol. 2 Plant and Process Design - Wiley-VCH PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Ullmann's Chemical Engineering and Plant Design - Vol. 1 Mathematics and Physics in Chem. Eng. - Fundamentals - Vol. 2 Plant and Process Design - Wiley-VCH PDF

Uploaded by

Copyright:

Available Formats

ULLMANN’S

Mathematics and Physics

c 2005 WILEY-VCH Verlag GmbH & Co. KGaA,

Composition: Steingraeber Satztechnik GmbH,

Printed in the Federal Republic of Germany.

Volume 1 Nondestructive Testing . . . . . . . . . . . . . . . . 785

Mathematics and Physics in Process Development . . . . . . . . . . . . . . . . . 873

Mathematics in Chemical Engineering

1. Solution of Equations . . . . . . . . 6 7. Ordinary Differential Equations as

10.5.2. Simplex Algorithm . . . . . . . . . . . 132 11.4. Factorial Design of Experiments

Symbols h set of m equality constraints for an opti-

problem, the independent time-varying optimization problem, the Lagrange mul-

1. Solution of Equations 1.1. Linear Algebraic Equations

it may be more difﬁcult to ﬁnd the x satisfying enddo

Then two matrices are formed. The upper matrix for i = n − 1, 1 do

for k = 2, n do where the norm is deﬁned as

for all x and the equality holds only if x = 0

Then the linear equations are solved by

Generally, the inverse is not used in this way

When a matrix is ill-conditioned the LU decom- A x(i) =b(i)

Solutions of Special Matrices. Special ma-

The LU decomposition algorithm for solving

other methods, other special patterns arise. So- and

Figure 4. Structure of arrow matrix

Sparse matrices are ones in which the major-

using the triangular matrices. The symbolic fac- Guess x0

supply various x until f (x) = 0. Another alterna-

This method converges if the following inequal-

one quick method for ﬁnding a root is to program  d2 f 

h (x, t) =t f (x) + (1 −t) g (x) ∂h dx ∂h dt

here for solving difference equations. More xn+1 −fn xn = 0

xn+1 −xn = fn the general solution is

xn = xn,P + xn,H A laborious way to ﬁnd the eigenvalues of a ma-

The eigenvalues of a certain tridiagonal ma- Pm (x) = c j xj

x 2 . Likewise, Pijk...r is the unique polynomial b

These entries are deﬁned by using b

(x − xi+m ) Pi(i+1)...(i+m−1) + (xi − x) P(i+1)(i+2)...(i+m)

Pi(i+1)...(i+m) agrees with the function at all

a b W (x) Name Recursion

−1 1 1 Legendre (i+1) Pi +1 =(2 i+1)xPi − i Pi −1

Pµ (x) p0 + p1 x+ . . . +pµ xµ 2.3. Piecewise Approximation

  and the ﬁnite interpolation formula through the

The interpolation polynomial of order n through NI=1 = 1 − u , NI=2 = u

y (x) = ci NI=1 (u) + ci+1 NI=2 (u) , with ceI = y (xi ) , i = (e − 1) 2 + I

xi < x < xi+1 , 0 < u < 1 in the e−th element

Splines. Splines are functions that match

Figure 6. Finite elements approximation – quadratic ele-

H3 = u2 (3 − 2u) Ci−1 (xi ) = Ci (xi ) =f (xi )

and integrated once to give Orthogonal Collocation on Finite Elements.

1 The actual points xi are taken as the roots of the

Figure 8. Notation for orthogonal collocation on ﬁnite elements

2 N + 1, with a = x 0 , a + ∆x = x 1 , a + 2 ∆x = x 2 , If the quadratic expansion is used (Eq. 3), the

Mathematics in Chemical Engineering 23

For many elements, with different ∆xe , N xi Wi

quadratic elements : 1 0.5000000000 0.6666666667

24 Mathematics in Chemical Engineering

The following description of maximum likeli-

will cause round-off errors for a smaller M than

The notation akl means the l-th component of a

and the constant chosen somehow to decrease

Sometimes, particularly in two-dimensional ∂χ2 yi − y (xi ; a) ∂y (xi ; a)

The second term in the second derivative is

The fast Fourier transform (FFT ) is used to The inverse transformation is

one quick method for ﬁnding a root is to program d2 f

and the ﬁnite interpolation formula through the

where n denotes the residue of f (z) at zn . − π < θ < π, r > 0

1 Applied to the differential equation