13/06/2017

Lecture 1 – Thursday 1/10/2013

• Introduction

• Definitions
CINETICA QUIMICA
• General Mole Balance Equation
• Batch (BR)
• Continuously Stirred Tank Reactor (CSTR)
• Plug Flow Reactor (PFR)
• Packed Bed Reactor (PBR)

Smog (Ch. 1)
Wetlands (Ch. 7 DVD-ROM)

Hippo Digestion (Ch. 2)

Oil Recovery Cobra Bites

(Ch. 7) (Ch. 8 DVD-ROM)

Lubricant Design Plant Safety

3 Chemical Plant for Ethylene Glycol (Ch. 5) (Ch. 9) (Ch. 11,12,13) 4

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Let’s Begin CRE

• Chemical Reaction Engineering (CRE) is the field that studies
Materials on the Web and the rates and mechanisms of chemical reactions and the design
of the reactors in which they take place.
CD-ROM
http://www.umich.edu/~essen/

5 6

Chemical Identity Chemical Identity

• A chemical species is said to have reacted when it has lost its • A chemical species is said to have reacted when it has lost its
chemical identity. chemical identity.
• The identity of a chemical species is determined by the kind, • There are three ways for a species to loose its identity:
number, and configuration of that species’ atoms.
1. Decomposition CH3CH3  H2 + H2C=CH2
2. Combination N2 + O2  2 NO
3. Isomerization C2H5CH=CH2  CH2=C(CH3)2

7 8

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Reaction Rate Reaction Rate

• The reaction rate is the rate at which a species looses its
chemical identity per unit volume.
• The rate of a reaction (mol/dm3/s) can be expressed as either:
• The rate of Disappearance of reactant: -rA
or as
• The rate of Formation (Generation) of product: rP
Consider the isomerization
AB
rA = the rate of formation of species A per unit volume
-rA = the rate of a disappearance of species A per unit
volume
rB = the rate of formation of species B per unit volume

9 10

Reaction Rate Reaction Rate

EXAMPLE: AB • For a catalytic reaction we refer to –rA’ , which is the rate of disappearance
If Species B is being formed at a rate of of species A on a per mass of catalyst basis. (mol/gcat/s)
0.2 moles per decimeter cubed per second, i.e.,
rB = 0.2 mole/dm 3/s NOTE: dCA/dt is not the rate of reaction

Then A is disappearing at the same rate:

-rA= 0.2 mole/dm3/s
The rate of formation (generation of A) is:
rA= -0.2 mole/dm3/s

11 12

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Building Block 1:
Reaction Rate General Mole Balances
System
Consider species j: Volume, V

1. rj is the rate of formation of species j per unit volume [e.g. mol/dm3s]

Fj0 Gj Fj
2. rj is a function of concentration, temperature, pressure, and the type of
catalyst (if any)
3. rj is independent of the type of reaction system (batch, plug flow, etc.)
Molar Flow Molar Flow  Molar Rate  Molar Rate 
4. rj is an algebraic equation, not a differential equation  Rate of   Rate of   Generation    Accumulation
       
(e.g. -rA = kCA or -rA = kCA2)
Species j in  Species j out  of Species j  of Species j 
dN j
Fj 0  Fj  Gj 
dt
 mole   mole   mole   mole 
          
13  time   time   time   time  14

Building Block 1: Building Block 1:

General Mole Balances General Mole Balances
If spatially uniform: n

G j  r jV G j   rji Vi
i 1

If NOT spatially uniform:

Take limit
V1 n

V2 Gj   rjiVi   r dV j
r j1 i1 lim V  0 n  
rj 2
G j1  rj1V1
G j 2  r j 2 V2

15 16

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Building Block 1:
General Mole Balances Batch Reactor - Mole Balances
System
Volume, V
Batch
FA0 GA FA

dN A
FA0  FA   rAdV 
General Mole Balance on System Volume V dt
FA0  FA  0
In  Out  Generation  Accumulation
dN A
Well-Mixed r A dV  r AV
FA 0  FA   rA dV  dN A
dt  rAV
17
18 dt 18

Batch Reactor - Mole Balances Batch Reactor - Mole Balances

dN A
Integrating dt  NA
dN A
rAV t 
N A0
 rAV
t  0 N A  N A0
when
t  t NA  NA

NA NA
dN A
t N  rAV
A0

Time necessary to reduce the number of moles of A from N A0 to NA.

19 20 t

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CSTR - Mole Balances CSTR - Mole Balances

CSTR
Well Mixed  r dV  r V
A A

FA 0  FA  rAV  0

dN A
FA 0  FA   r dV  FA 0  FA
V
A
dt
rA
Steady State dN A
0 CSTR volume necessary to reduce the molar flow
dt rate from FA0 to FA.
21 22

Plug Flow Reactor - Mole Balances Plug Flow Reactor - Mole Balances
V

FA FA

V V  V

 In  Out  Generation
at V   at V  V   in V 0
     
FA V  FA V  V  rA V 0
23 24

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Plug Flow Reactor - Mole Balances Plug Flow Reactor - Mole Balances
Rearrange and take limit as ΔV0 PFR

FA V  V  FA V FA0  FA   rAdV 
dN A
lim  rA dt
V  0 V
dN A
dFA Steady State 0
 rA dt
dV

This is the volume necessary to reduce the entering molar FA0  FA   rA dV  0

flow rate (mol/s) from FA0 to the exit molar flow rate of FA.
25 26

Alternative Derivation
Plug Flow Reactor - Mole Balances Packed Bed Reactor - Mole Balances
W
Differientiate with respect to V PBR

0
dFA
  rA
dFA FA FA
dV
 rA
dV
W W  W
FA
dF A dN A
FA W   FA W  W   rA W 
The integral form is: V  
FA0
rA dt
Steady State dN A
0
This is the volume necessary to reduce the dt
entering molar flow rate (mol/s) from FA0 to the FA W  W  FA
exit molar flow rate of FA. lim W
 r A
27
W  0 W 28

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Packed Bed Reactor - Mole Balances Reactor Mole Balances Summary

Rearrange: The GMBE applied to the four major reactor types
dFA (and the general reaction AB)
 rA
dW Reactor Differential Algebraic Integral
NA NA
dN A
The integral form to find the catalyst weight is: Batch dN A
 rAV t 
N A 0 rAV
dt t
FA
dFA FA 0  FA
W 
FA 0 rA
CSTR V 
rA
FA
FA
dFA dFA
PFR
dV
 rA V 
FA 0
drA
PBR catalyst weight necessary to reduce the V
entering molar flow rate FA0 to molar flow rate FA. PBR dFA
FA FA
dFA W 
 rA rA
dW FA0
29 30
W

Lecture 2 – Tuesday 1/15/2013 Define conversion, X

Consider the generic reaction:
• Review of Lecture 1
a A bB
 c C  d D
• Definition of Conversion, X
• Develop the Design Equations in terms of X Chose limiting reactant A as basis of calculation:
• Size CSTRs and PFRs given –rA= f(X) b c d
A B
 C  D
• Conversion for Reactors in Series a a a
• Review the Fall of the Tower of CRE
Define conversion, X
moles A reacted
X 
moles A fed

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Batch Batch
dN A rV t0 X 0
Moles A  Moles A Moles A  A
remaining   initially   reacted 
dt N A0 t t X  X
     
NA  N A0  N A0 X Integrating,

dN A  0  N A0 dX X
dX
t  N A0 
dN A dX  rAV
  N A0  rAV 0
dt dt
The necessary t to achieve conversion X.

33 34

CSTR CSTR
Consider the generic reaction:
Steady State dN A
a A bB
 c C  d D 0
dt
Chose limiting reactant A as basis of calculation:
b c d
A B
 C  D
a a a FA 0  FA
Well Mixed V
rA
Define conversion, X

X 
moles A reacted
moles A fed
 r dV  r V
A A

35 36

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CSTR PFR
 Moles A  Moles A   Moles A dFA
leaving   entering    reacted   rA
      dV
FA  FA0  FA0 X
FA  FA0  FA0 X
FA 0  FA   rA dV  0
FA 0  FA 0  FA 0 X 
V Steady State dFA  0  FA0 X
rA
FA0 X dX  rA
V 
 rA dV FA0
CSTR volume necessary to achieve conversion X. 37 38

PFR Reactor Mole Balances Summary

in terms of conversion, X
V 0 X 0 Reactor Differential Algebraic Integral
X
V V X  X X
dX
Batch N A0
dX
  r AV t  N A0 
dt 0
 rAV
Integrating, t
F X
X
FA0 CSTR V  A0
rA
V  dX
0
 rA X
dX FA0 dX
PFR FA 0  rA V 
dV  rA
PFR volume necessary to achieve conversion X. 0

X
X
dX FA0 dX
PBR FA 0   rA W 
dW 0  rA
39
W 40

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Levenspiel Plots Levenspiel Plots

Reactor Sizing
Given –rA as a function of conversion, -rA= f(X),
one can size any type of reactor. We do this by
constructing a Levenspiel plot. Here we plot
FA 0
either (FA0/-rA) or (1/-rA) as a function of X. For
(FA0/-rA) vs. X, the volume of a CSTR and the rA
volume of a PFR can be represented as the
shaded areas in the Levenspiel Plots shown as:
X
FA0
 g( X )
 rA
41 42

CSTR PFR

Area = Volume of CSTR

FA 0
 rA F 
V   A0  X 1
  rA  X1
X1

43 44

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Numerical Evaluations of Integrals

Levenspiel Plots • The integral to calculate the PFR volume can be
evaluated using method as Simpson’s One-
Third Rule: (See Appendix A.4)
X
FA0 x  1 4 1 
V dX  FA0    
1  rA
0
3   rA (0)  rA ( X / 2)  rA ( X ) 
 rA ( X 2 )
1
 rA
Other numerical methods are:
1  Trapezoidal Rule (uses two
 rA ( X 1 )
data points)
1  Simpson’s Three-Eight’s
 rA (0) 0 X1 X2 Rule (uses four data points)
 Five-Point Quadrature
Formula
45 46

Reactors in Series Reactors in Series

Given: rA as a function of conversion, one can also
design any sequence of reactors in series by
defining X:
total moles of A reacted up to point i
Xi 
moles of A fed to first reactor

Only valid if there are no side streams.

Molar Flow rate of species A at point i:

FAi  FA0  FA0 X i

47 48

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Reactors in Series Reactors in Series

Reactor 1: Reactor 2:

FA1  FA0  FA0 X 1 X2

FA0
V2    r dX
FA0  FA1 FA0  FA0  FA0 X 1  FA0 X 1 X1 A
V1   
 rA1  rA1  rA1

FA0 V2
FA 0 V1  rA
 rA

X1 X2
X1 X
X 49 50

Reactors in Series Reactors in Series

Reactor 3:
FA2  FA3  rA3V3  0
FA0  FA0 X 2   FA0  FA0 X 3   rA3V3  0
FA 0 X 3  X 2 
V3 
rA 3

V3
FA 0
 rA

X1 X X2 X3 51 52

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Reactors in Series Lecture 3 – Thursday 1/17/2013

Space time τ is the time necessary to process 1
reactor volume of fluid at entrance conditions. • Review of Lectures 1 and 2
• Building Block 1
V • Mole Balances (Review)

0 • Size CSTRs and PFRs given –rA= f(X)
• Conversion for Reactors in Series
• Building Block 2
• Rate Laws
• Reaction Orders
• Arrhenius Equation
• Activation Energy
• Effect of Temperature
53 54

Reactor Mole Balances Summary

a A  b B c C  d D
The GMBE applied to the four major reactor types
(and the general reaction AB)
Choose limiting reactant A as basis of calculation
Reactor Differential Algebraic Integral
NA
NA
dN A b c d
Batch dN A
 rAV t  A B
 C  D
dt N A 0 rAV a a a
t
CSTR FA 0  FA
V 
rA FA
FA moles A reacted
PFR dFA
 rA V 
dFA X
dV FA 0
drA moles A fed
V
FA FA
PBR dFA dFA
 rA W 
dW FA0
rA
55 56
W

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Reactor Mole Balances Summary Levenspiel Plots

In terms of Conversion
Reactor Differential Algebraic Integral
X
X
dX
Batch N A0
dX
  r AV t  N A0 
dt 0
 rAV
t
F X
CSTR V  A0
 rA
X
dX dX
PFR FA0   rA V  FA0 
dV 0  rA
X
X
dX dX
PBR FA0   rA W  FA0 
dW 
0  rA
W 57 58

Reactors in Series Reactors in Series

moles of A reacted up to point i

Xi 
moles of A fed to first reactor

Only valid if there are no side streams

59 60

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Building Block 2: Rate Laws Building Block 2: Rate Laws

2A  B  3C
Power Law Model:
α order in A
 rA  kC A C B A reactor follows an elementary rate law if the
β order in B reaction orders just happens to agree with the
stoichiometric coefficients for the reaction as written.
Overall Rection Order  α  β
e.g. If the above reaction follows an elementary rate
law
 rA  k AC AC B
2

2nd order in A, 1st order in B, overall third order

61 62

Building Block 2: Rate Laws Relative Rates of Reaction

2A+B3C aA  bB  cC  dD
If  rA  kC A
2

b c d
› Second Order in A A B C D
› Zero Order in B a a a
› Overall Second Order
rA  kACA2 CB rA r r r
 B  C  D
rB  kBCA2 CB a b c d
rC  kC CA2 CB

63 64

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Relative Rates of Reaction Reversible Elementary Reaction

2A  B  3C kA
A+2B
mol k-A
 rA  10 3C
dm 3  s
Given
rA r r  CC3 
 B  C  rA  k AC A2 C B  k ACC3  k A C A2 C B 
Then  2 1 3  k A k  A 
 rA mol  2 C3 
 rB  5  k A C A C B  C 
2 dm 3  s Ke 

3 mol
rC  rA  15
2 dm 3  s
65 66

Reversible Elementary Reaction

kA
A+2B Reaction is: First Order in A
k-A
3C
Second Order in B

Overall third Order

moles
 rA   moles CA 
3
dm s dm3

k     rA 
 
mole dm 3 s

dm 6
2

 C AC B  mole dm mole dm
3 3
 
2
mole 2 s
67 68

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Algorithm Arrhenius Equation

k is the specific reaction rate (constant) and is
How to find  rA  f  X 
given by the Arrhenius Equation.

Step 1: Rate Law  rA  gCi  where:

k  Ae  E RT
Step 2: Stoichiometry Ci   h X 
T  k  A
k T 0 k 0
Step 3: Combine to get  rA  f  X 
A  1013
T
69 70

Arrhenius Equation Reaction Coordinate

where: The activation energy can be thought of as a barrier
E = Activation energy (cal/mol) to the reaction. One way to view the barrier to a
R = Gas constant (cal/mol*K) reaction is through the reaction coordinates. These
coordinates denote the energy of the system as a
T = Temperature (K)
function of progress along the reaction path. For the
A = Frequency factor (same units as rate constant k) reaction:
(units of A, and k, depend on overall reaction order) A  BC  A ::: B ::: C  AB  C

The reaction coordinate is:

71 72

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Collision Theory

73 74

Why is there an Activation Energy? Distribution of Velocities

We see that for the reaction to occur, the reactants We will use the Maxwell-Boltzmann
must overcome an energy barrier or activation Distribution of Molecular Velocities. For a
energy EA. The energy to overcome their barrier species af mass m, the Maxwell distribution of
comes from the transfer of the kinetic energy from velocities (relative velocities) is:
molecular collisions to internal energy (e.g.
32
Vibrational Energy).  m 
f U , T  dU  4 
2

 e  mU 2 kBT
U 2 dU
1. The molecules need energy to disort or stretch
 2 k BT 
their bonds in order to break them and thus form
new bonds
2. As the reacting molecules come close together f(U,T)dU represents the fraction of velocities
they must overcome both stearic and electron between U and (U+dU).
repulsion forces in order to react.
75 76

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Distribution of Velocities Distribution of Velocities

32
 m 
Given f U , T  dU  4 
2

A plot of the distribution function, f(U,T), is shown  e mU 2 kBT

U 2 dU
as a function of U:  2 k BT 
T1 Let E  1 mU 2
T2 T2>T1 2
E
2
, f  E , T  dE  E 1 2 e kBT dE
 2 k BT 
32

f(E,T)dE represents the fraction of collisions

that have energy between E and (E+dE)
U
Maxwell-Boltzmann Distribution of velocities.
77 78

f(E,T)dE=fraction of molecules with energies between E+dE

One such distribution of energies is in the following figure:

ANALISIS DE DATOS DE
VELOCIDAD

79

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Lecture 11 – Thursday 2/14/2013 Integral Method

• Block 1: Mole Balances Consider the following reaction that occurs in a constant volume Batch
• Block 2: Rate Laws Reactor: (We will withdraw samples and record the concentration of A as a
function of time.)
• Block 3: Stoichiometry
A  Products
• Block 4: Combine dNA
Mole Balances:  rAV
dt
• Determining the Rate Law from Experimental Data Rate Laws: rA  kC A
• Integral Method
• Differential (Graphical) Method Stoichiometry: V  V0
• Nonlinear Least Regression
dC
Combine:  A  kCA
dt
81 82

Finally we should also use the formula to plot reaction

rate data in terms of conversion vs. time for 0, 1st and
2nd order reactions. Integral Method
Derivation equations used to plot 0th, 1st and 2nd order
reactions.
Guess and check for α = 0, 1, 2 and check against experimental
These types of plots are usually used to determine the plot.
values k for runs at various temperatures and then used  0  1  2
to determine the activation energy. C  1 1
rA  C A 0  kt ln A0   kt   kt
 CA  C A C A0
Zeroth order First Order Second Order
dCA dCA dCA
 rA  k  rA  kC A  rA  kC A2 CA ln(CA0/CA) 1/CA
dt dt dt

at t  0, C A  C A 0 at t  0, C A  CA 0 at t  0, C A  C A 0
C  1 1
 CA  CA 0  kt  ln A 0  kt    kt
 CA  CA CA 0 83
t t t 84

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Differential Method Methods for finding the slope of log-log and semi-
log graph papers may be found at
 dCA 
Taking the natural log of   kCA 
 dt 
http://www.physics.uoguelph.ca/tutorials/GLP/
 dC 
ln   A   ln k   ln C A
 dt 
 dCA  However, we are usually given concentration as a
The reaction order can be found from a ln-ln plot of:   vs C A
 dt  function of time from batch reactor experiments:
dC A ln

dt time (s) 0 t1 t2 t3
 dC A  concentration CA0 CA1 CA2 CA3
dC A  

dt Slope = α  dt  p (moles/dm3)
P
k
C Ap
ln
C AP CA 85 86

Three ways to determine (-dCA/dt) from concentration-time data C A

• Graphical differentiation

t
• Numerical differentiation formulas
• Differentiation of a polynomial fit to the data
1. Graphical dC A 
 
dt  0
C A
 
dC A 

t dt  t1
dC A 
 
dt  t2

t
0 t1 t2
The method accentuates measurement error!
t 87 88

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Example – Finding the Rate Law Example – Finding the Rate Law
C A
t(min) 0 1 2 3 Find f(t) of  using equal area differentiation
t
CA(mol/L) 1 0.7 0.5 0.35

C A
CA 1 0.7 0.5 0.35
 0.3 0.2 0.15
t -dCA/dt 0.35 0.25 0.175 0.12

C A Areas equal for both Plot (–dCA/dt) as a function of CA


t .3 sides of the histogram ln
.2
dCA/dt
.1 Slope = α
t ln
1 2 3 CA
89 90

Example – Finding the Rate Law Non-Linear Least-Square Analysis

Choose a point, p, and find the concentration and
derivative at that point to determine k. We want to find the parameter values (α, k, E) for which the sum
of the squares of the differences, the measured rate (rm), and the
calculated rate (rc) is a minimum.
ln dCA/dt
 dC A 
  2 
n
Cim  Cic 2 
S2
 dt  p  dC A 
  Slope = α i 1 N K N K
k  dt  p
C Ap
ln CA That is, we want 2 to be a minimum.
CAp

91 92

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Non-Linear Least-Square Analysis Non-Linear Least-Square Analysis

For concentration-time data, we can combine Now we could use Polymath or MATLAB to find the values of α and k
the mole balance equation that would minimize the sum of squares of differences between the
rA for
 kCA to measured (CAm) and calculated (CAc) concentrations.
obtain:
dC A That is, for N data points,
 kC A
dt
t  0 C A  C A0
Similarly one can calculate the time at a specified concentration, tc
C A10  C1A  (1   ) kt

Rearranging to obtain the calculated and compare it with the measured time, tm, at that same concentration.
concentration as a function of time, we obtain: That is, we find the values of k and α that minimize:
C Ac  C A  [C1A0  (1   )kt ]1/(1 )
93 94

Non-Linear Least Squares Analysis Non-Linear Least Squares Analysis

Guess values for α and k and solve for measured
data points then sum squared differences:
CAm 1 0.7 0.5 0.35
CAc 1 0.5 0.33 0.25
(CAc-CAm ) 0 -0.2 -0.17 -0.10
(CAc-CAm )2 0 0.04 0.029 0.01 0.07

for α= 2, k = 1 → s2 = 0.07
for α = 2, k = 2 → s2 = 0.27
etc. until s2 is a minimum 95 96

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Non-Linear Least Squares Analysis

 
N N
1 1 2
s 2   CAmi  C Aci   CAmi  C1
A 0  1   kt i 
2 

i1 i1

We find the values of alpha and k which minimize s2

Minimum Sum of Squares

97

99 100

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Residuals

101 102

End of Lecture 11

103

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