Lecture Note - Chemical Reaction Engineering

VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY
UNIVERSITY OF TECHNOLOGY
FACULTY OF CHEMICAL ENGINEERING
Chemical Reaction Engineering

(Homogeneous Reactions in Ideal Reactors)
Mai Thanh Phong, Ph.D.
FCE – HCMC University of Technology Chemical Reaction Engineering

References
1. Octave Levenspiel, “Chemical Reaction Engineering”, John Wiley&Sons, 2002.
2. H. Scot Foggler, “Elements of Chemical Reaction Engineering”,International

students edition, 1989.
3. E.B.Nauman, “Chemical Reactor Design”, John Wiley & sons, 1987.
4. Stanley M. Walas, “Reaction Kinetics for Chemical Engineers”,Int. Student

Edition, 1990.
5. Coulson & Richardsons, “Chemical Engineering – Vol 6”,Elsevier, 1979.
6. Richard M. Felder, “Elementary Principles of Chemical Processes”, John Wiley &

sons, 2000.
Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 2

Chapter 1. Introduction
• Topic of the lecture „Chemical Reaction Engineering“ is the quantitative

assessment of chemical reactions. The selection of suitable reactor types and
their design will be discussed.
• Reactor design uses information, knowledge, and experience from a variety of

areas: thermodynamics, chemical kinetics, fluid mechanics, heat transfer, mass
transfer, and economics. Chemical reaction engineering is the synthesis of all
these factors with the aim of properly designing a chemical reactor.
• Thermodynamics tell us in which direction a reaction system will develop and

how far it is from its equilibrium state.
• Analyses of kinetics provide information about the rate with which the system will
approach equilibrium.

I. Basic Parameter
Description of the amount of a substance i:
mi
Number of moles: ni = Mi = molecular weight
Mi
ni
Molar concentration: ci = V = volume
V
ni
Mole fraction: xi =
∑ nj j

Progress of chemical reactions:
ni 0 − ni
Conversion: Xi =
ni 0
ci 0 − ci
If V = const: Xi =
ci 0
ni − ni 0
Extent of reaction: ξ=
νi
Performance criteria:
produced amount of product P

Productivity: n& P =
operating time

II. Stoichiometry of chemical reactions:
Stoichiometry is based on mass conservation and thus quantifies general laws

that must be fulfilled during each chemical reaction.
Starting point of a quantitative analysis is the following formulation of a chemical

reaction:
N
∑ν A = 0
i =1
i i
This equation describes the change of the number of moles of N components

A1, A2, ... AN. The νi are the stoichiometric coefficients of component i. They have
to be chosen in such a way that the moles of all elements involved in the chemical
reaction remain constant.
A convention is that reactants have negative stoichiometric coefficients and products

have positive stoichiometric coefficients.

As an example the stoichiometric equation for the oxidation of carbon monoxide

is given by:
2CO + O2 → 2CO2
with νCO = -2, vO2 = -1, vCO2 = 2
To calculate changes in the mole number of a component i due to reaction, the

following balance has to be respected:
ni = ni 0 + ν iξ
From this equation results the important stoichiometric balance:
ni 0 − ni Δni nk 0 − nk Δnk
= = =
νi νi νk νk
Using the conversion X of a component k, the above equation becomes:
νi
ni = ni 0 − nk 0 X k
νk
III. Chemical thermodynamics:

Chemical thermodynamics deal with equilibrium states of reaction system. This
Section will concentrate on the following two essential areas:
a) The calculation of enthalpy changes connected with chemical reactions, and
b) The calculation of equilibrium compositions of reacting systems.
3.1 Enthalpy of reaction
The change of enthalpy caused by a reaction is called reaction enthalpy ∆HR.

This quantity can be calculated according to the following equation:
N
ΔH R = ∑ν i ΔH Fi
i =1
∆HFi is the enthalpy of formation of component i
∆HR < 0, the reaction is exothermic

∆HR > 0, the reaction is endothermic

It is simple to calculate the reaction enthalpy at a certain standard state ∆HR0 from
the corresponding standard enthalpies of formation ∆HFi0. The standard enthalpies
of formation are available from databases for P = P0 = 1 bar and T = T0 = 298 K.
For pure elements like C, H2, O2,...: ∆HFi0 = 0.
The reaction enthalpy is a state variable. Thus, a change depends only on the
Initial and the end state of the reaction and does not dependent on the reaction
parthway.
3.2 Temperature and pressure dependence of reaction enthalpy
⎛ ∂ΔH R ⎞ ⎛ ∂ΔH R ⎞
d (ΔH R ) = ⎜ ⎟ dP + ⎜ ⎟ dT
⎝ ∂P ⎠T ⎝ ∂T ⎠ P
The pressure dependence is usually very small. For ideal gas behaviour, the
reaction enthalpy does not depend on pressure.

The correlation of reaction enthalpy and temperature is related to the isobaric

heat capacities of all species involved in the considered reaction, cPi.
N T
ΔH R (T ) = ΔH R0 + ∑ν i ∫ c (T )dT
Pi
i =1 T = 298 K
Assuming that the reactants and the products have different but temperature
independent heat capacities, the temperarue dependence of the reaction
enthalpy can be estimated as follows:
ΔH R (T ) = ΔH R0 + (T − T0 )(cP ,products − cP ,reactants )

3.3 Chemical equilibrium

• Chemical reactions approach to an equilibrium, when the product and reactant
concentrations do not change anymore.
• A reacting system is in chemical equilibrium if the reaction rates of the forward
and backward reactions are equal.
• The basic quantity required to indentify the equilibrium state is the Gibbs free
enthalpy of reaction GR.
• The change of this quantity becomes zero when the equilibrium is reached (i.e.
dGR = 0)
For constant pressure and temperature, the change of free Gibbs enthalpy of
reaction can be described as follows:
N
⎛ dGR ⎞ N
dGR = ∑ν i μi dξ or ⎜⎜ ⎟⎟ = ∑ν i μi
i =1 ⎝ dξ ⎠T , P i =1

In Figure 1-1 is shown the course of free

Gibbs enthalpy of reaction as a function
of the extent of reaction.
Free Gibbs enthalpy

The equilibrium is reached when the free
⎛ ∂GR ⎞ ⎛ ∂GR ⎞
Gibbs enthalpy of reaction is minimum. ⎜⎜ ⎟⎟ < 0 ⎜⎜ ⎟⎟ > 0
⎝ ∂ξ ⎠T , P ⎝ ∂ξ ⎠T , P
Thus, for the chemical equilibrium:
⎛ dGR ⎞
⎜⎜ ⎟⎟ = 0
⎝ dξ ⎠T , P
⎛ ∂GR ⎞
⎜⎜ ⎟⎟ = 0
Or dGR=0 (or in an integrated form: ∆GR = 0) ⎝ ∂ξ ⎠T , P
Thus, the equilibrium is characterized by:

ξ
N Fig. 1-1: Changing of free Gibbs enthalpy
∑ν μ
i =1
i i =0 for a chemical reaction

3.3.1 Reation free Gibbs enthalpy, ∆GR

N
ΔG = ∑ν i ΔGFi0
0
R
i =1
ΔGFi0 free Gibbs energy of formation
Relation between ∆GR and ∆HR
(
d ΔGR0 T )
ΔH R0
=− 2
dT T

3.3.2 Equilibrium constant and temperature dependence
Relationship between the free Gibss enthalpy and the equilibrium constant:
ΔGR0 (T ) = − RT ln K
⎛ ΔGR0 ⎞
K = exp⎜⎜ − ⎟⎟
⎝ RT ⎠
Van‘t Hoff equation describing the temperature dependence of the equilibrium
constant:
d (ln K ) ΔH R0
=−
dT RT 2
For a small temperature range, ∆HR is constant, thus:
ΔH R0 ⎛1 1⎞
ln K (T2 ) = ln K (T1 ) − ⎜⎜ − ⎟⎟
R ⎝ T2 T1 ⎠
4. Reaction rate
Based on unit volume of reacting fluid:
1 1 dni • VR is volume of the reaction mixture
r= • ni is mole number of component i
ν i VR dt • t is reaction time
If VR is constant:
1 dci • ci is molar concentration of component i
r=
ν i dt
Based on unit mass of solid in solid-liquid systems:
1 1 dni
r= • W is mass of solid
ν i W dt
Based on unit solid surface of solid-liquid or solid-gas systems:
1 1 dni
r= • S is solid surface area
ν i S dt
5. Standard Reactors
To carry out chemical reactions discontinuously operated reactors or
continuously operated reactors can be used.
• Discontinuously: more frequently applied to produce fine chemicals
• Continuously: more advantageous for the production of larger amounts of bulk
chemicals.
To study the different behavior of these types of reactors another important criterion
serves to distinguish two limiting cases: mixed flow and plug flow behavior
For theoretical studies and to compare the different reactors, four different ideal
reactors can be defined using the above classification:
a) Batch Reactor (BR, perfectly mixed, discontinuous operation):
Features:
• All components are in the reactor before the reaction starts
• Composition changes with time
• Composition throughout the reactor is uniform

Adv.:
• Simple, flexible, high conversion…
Disadv.:
• Dead times for charging, discharging, cleaning,…
• Difficult to control and automate
•…
BR are applied in particular for:

• Relatively slow reactions
• Slightly exothermic reactions
Areas of application for BR are:

• Reactions in pharmaceutical industry
• Polymerisation reactions
• Dye production
• Speciality chemicals

b) Semi-batch Reactor (SBR): perfectly mixed, semi continuous operation
Features:
• One reactant is introduced first and then the
second is dosed in a controlled manner.
• Composition changes with time
Adv.:
• Controlled reaction rate and heat generation
• ...
Disadv.:
• Same as BR
• More complicated than BR
•…

c) Continuously Stirred Tank Reactor (CSTR): perfectly mixed, continuous operation
Features:
A,B A,B,products • Reactants are continuously introduced,
products (+ unconverted reactants) are
continuously withdrawn
• Composition does not change with time
Adv.:
• Controlled heat generation
• Easy to control and automate
• No dead times
• Constant product quality,...
Disadv.:
• Complicated
• Can become unstable
• Large investmnent cost,...

d) Plug Flow Tubular Reactor (PFTR): no mixing, continuous operation
A, B tubular reactor A, B,
products
Features:
• Composition varies from point to point along a flow path
Adv.:
• High conversion
• Easy to automate
• No dead times
• Better to cool (compare to stirred tanks)
•…
Disadv.:
• Complicated
• Danger of “hot spot”
•…

FCEMai ThanhUniversity
– HCMC Phong - HCMUT
of Technology Chemical Reaction
Chemical Engineering
Reaction Engineering 3-Feb-09 21
Chapter 2. Interpretation of Batch Reactor Data
1. Rates of reaction
1.1. Description of reaction rates
Reaction rates depend usually in a complex manner on the concentrations, the
temperature and often on the effect introduced by catalysts:
r = f ( ci ,T, catalyst)
The order of a reaction is related to the concentration dependence. Typical

examples are:
Irreversible Reactions:
• First order:
A → Products: r = k(T)CA k in [s-1]
• Second order:
A + B → Products: r = k(T)CACB k in [m3 mol-1s-1]
2A → Products: r = k(T)CA2 k in [m3 mol-1s-1]

Reversible Reactions:
• First order:
A ' R: r = k1CA – k2CR k in [s-1]
• Second order:
A + B ' R + S: r = k1CACB – k2CRCS k in [m3 mol-1s-1]
2A ' 2R: r = k1CA2 – k2CR2 k in [m3 mol-1s-1]
2A ' R + S: r = k1CA2 – k2CRCS k in [m3 mol-1s-1]
A + B ' 2R: r = k1CACB – k2CR2 k in [m3 mol-1s-1]
The dependency of the reaction rate on the temperature can be described using
Arrhenius law:
• EA is the activation energy of the reaction.
⎛ EA ⎞
k (T ) = k0 exp⎜ − ⎟ • ko is the pre-exponential factor (not dependent on
⎝ RT ⎠ the reaction temperature

1.2. Rate laws of simple reactions

In this section, rate equations of simple reactions and the corresponding
temporal change of concentration are analyzed. A closed system (isothermic,
batch reactor) and aconstant volume are assumed.
1.2.1. Irreversible first-order reactions (Decomposition reactions)
A → Products
1 dCi
The rate equation is: r= = kCi (2.1)
ν i dt
dC A
With i is A and vi = -1, then: r = − = kC A (2.2)
dt
CA t
dC A CA
The integration form: − ∫
C Ao
CA
= k ∫ dt or − ln
0
C A0
= kt (2.3)

The eq. (2.3) leads to the temporal course of concentration cA.
C A = C A0 e − kt (2.4)
C A0 − C A
With XA = , the eq. (2.3) leads to: (2.5)
C A0
− ln(1 − X A ) = kt or X A = 1 − e − kt (2.6)
1.2.2. Irreversible bimolecular-type second-order reactions
Consider the reaction (A + B → Products) with corresponding rate equation
r= (2.7)

Noting that the amounts of A and B that have reacted at any time t are equal and
given by CA0XA, eq. (2.7) can be written in terms of XA as
r= (2.8)
(2.9)
(2.10)

After breakdown into partial fractions, integration, and rearrangement, the final
result in a number of different forms is
(2.11)
For the reaction: 2A → Products, the defining second-order differential

equation becomes
r= (2.12)
which on integration yields
(2.13)

1.2.3. Empirical rate equations of nth order

When the mechanism of reaction is not known, we often attempt to fit the data
with an nth-order rate equation of the form
(2.14)
which on separation and integration yields
(2.15)
1.2.4. Zero-order reactions
Integrating and noting that CA

can never become negative, (2.16)
we obtain directly:

1.2.5. Irreversible Reactions in Parallel

Consider the simplest case, A decomposing by two competing paths
The rates of change of the three components are given by
(2.17)
(2.18)
(2.19)

The k values are found using all three differential rate equations. First of all,
eq. (2.17), which is of simple first order, is integrated to give
(2.20)
Then dividing eq. (2.18) by eq. (2.19) we obtain the following
(2.21)
which integrated gives simply
(2.22)

1.2.6. Irreversible Reactions in Series
Consider the reaction
Rate eqautions for the three components are
(2.23)
(2.24)
(2.25)

Assuming that at t = 0, concentration of A is CA0, and no R or S present,

integration of eq. (2.23) gives
(2.26)
To find the changing concentration of R, substitute the concentration of A from

eq. (2.26) into the differential equation governing the rate of change of R, eq.
(2.24); thus
(2.27)
Solving the above differential equation gives
(2.28)

Noting that
which eqs (2.26) and (2.28) gives
(2.29)
If k2 is much larger than k1, Eq. (2.29) reduces to

(2.30)
If k1 is much larger than k2, then

(2.31)
Thus, in general, for any number of reactions in series it is the slowest step that has
the greatest influence on the overall reaction rate.
By differentiating Eq. (2.28) and setting dCRldt = 0, the maximum concentration of

R and the time at which it occours can be found:
(2.32)
(2.33)

Figure 2.1 shows the general

characteristics of the
concentration-time curves Eq. (2.26)
for the three components:
• A decreases exponentially, Eq. (2.29)
• R rises to a maximum and
then falls,
• and S rises continuously, the
greatest rate of increase of S Eq. (2.33) Eq. (2.28)
occurring where R is a
maximum.
Eq. (2.30)
Figure 2.1. Typical concentration-time

curves for consecutive first-order reactions.

1.2.7. First-Order Reversible Reactions

The simplest case is the opposed unimolecular-type reaction
(2.34a)
Starting with a concentration ratio M = CR0/CA0 th e rate equation is
(2.34b)
At equilibrium dCA/dt = 0. Hence from Eq. (2.34) we find the fractional

conversion of A at equilibrium conditions to be
(2.35)

and the equilibrium constant to be
(2.36)
Combining the above three equations we obtain, in terms of the equilibrium

conversion gives
(2.37)
Taking integration of the above equation, the following relation can be found:
(2.38)

1.2.8. Second-Order Reversible Reactions

For the bimolecular-type second-order reactions
(2.39a)
(2.39b)
(2.39c)
(2.39d)
with the restrictions that CA0 = CB0, and CR0 = CS0 = 0, the integrated rate
equations for A and B are all identical, as follows
(2.40)

2. Determination of kinetic parameters

2.1. Integral method
For the integral method, the concentration-time-course of one commponent is
measured.
A tipycal measurement is depicted in CA
Figure 2.2.
After this measured data are compared CA0 *
with theoretical integrated reaction rate
*
equation, for example: *
− kt
*
C A = C A0 e *
*
the unknown parameters can be calculated *
*
by non-linear regression or using the * *
linearised form of the integrated rate * * *
equation: t
CA Figure 2.2. Typical experimental
− ln = kt concentration-time-course
C A0
The measured data can be inllustrated in a ln(CA/CA0) vs. T diagram. The slope
of the straight line leads to the reaction rate constant (Figure 2.3).
2.6 of 2.3
Figure 2.3. Determination of the reaction rate constant k using the

integrated method in a linearised formulation
2.2. Differential method

For the differential method, also measurements of concentration-time courses are
necessary.
By means numerical and/or graphic differentiation of all measuring data of
concentration CA(t) the derivative dCA/dt can be determined. The measured data
can be approximated as a straight line in the reaction rate-concentration-diagram.
The procedure is as follows:
1. Plot the CA vs. t data, and then by eye carefully draw a smooth curve to
represent the data.
2. Determine the slope of this curve at suitably selected concentration values.
These slopes dCA/dt = r, are the rates of reaction at these compositions.
3. Search for a rate expression to represent this rA vs. CA data, either by
(a) picking and testing a particular rate form, rA = kf (CA), see Fig. 2.4, or
(b) testing an nth-order form rA = kCAn by taking logarithms of the rate equation
(see Fig. 2.5).

log(rA)
Figure 2.4. Test for the particular rate Figure 2.5. Test for an nth-order rate
form rA = kf(CA) by the differential method by the differential method.
form.

Problems
1. Aqueous A at a concentration CA0 = 1 mol/liter is introduced into a batch reactor
where it reacts away to form product R according to stoichiometry A Æ R. The
concentration of A in the reactor is monitored at various times, as shown below:
a) For CA0 = 500 mol/m3 find the conversion of reactant after 5 hours in the batch
reactor.
b) Find the rate for the reaction.
2. For the elementary reactions in series
find the maximum concentration of R and when it is reached.

3. In the presence of a homogeneous catalyst of given concentration, aqueous

reactant A is converted to product at the following rates, and CA alone determines
this rate:
We plan to run this reaction in a batch reactor at the same catalyst concentration
as used in getting the above data. Find the time needed to lower the concentration
of A from CA0 = 10 mollliter to CAf = 2 mol/liter.


FCEMai ThanhUniversity
– HCMC Phong - HCMUT
of Technology Chemical Reaction
Chemical Engineering
Reaction Engineering 3-Feb-09 45
Chapter 3. Ideal Reactors for a Single Reaction
1. Material and energy balances

The starting point for all design is the material balance expressed for any
reactant (or product).
Figure 3.1 Material

balance for an element
of volume of the reactor.
Thus, as illustrated in Fig. 3.1, we have

In nonisothermal operations energy balances must be used in conjunction with

material balances.
Figure 3.2 Energy balance for

an element of volume
of the reactor.
Thus, as illustrated in Fig. 3.2, we have

In this chapter we develop the performance equations for a single fluid reacting
in the three ideal reactors shown in Fig. 3.3. We call these homogeneous
reactions.
Figure 3.3 The three types of ideal reactors: (a) batch reactor, or BR; (b) plug
flow reactor, or PFR; and (c) continuously stirred tank reactor, or CSTR.

2. Batch reactor (BR)

Make a material balance for any component A. Noting that no fluid enters or
leaves the reaction mixture during reaction, the material balance written for
component A is
or
(3.1)

n n n (3.2)
By replacing these two terms in Eq. 3.1, we obtain
n (3.3)
Rearranging and integrating then gives
n (3.4)
If the density of the fluid remains constant, we obtain
with (3.5)

For all reactions in which the volume of reacting mixture changes

proportionately with conversion, Eq. 3.4 becomes
n (3.6)
3. Continuously stirred tank reactor (CSTR)
Figure 3.4 Notation for a CSTR
rAf = rA

By selecting reactant A for consideration, material balance for a CSTR can be

written as follows
(3.7)
As shown in Fig. 3.4, if FA0 = v0CA0 is the molar feed rate of component A to
the reactor, then considering the reactor as a whole we have
Introducing these three terms into Eq. 3.7, we obtain
(3.8)

More generally, if the feed on which conversion is based, subscript 0, enters

the reactor partially converted, subscript i, and leaves at conditions given by
subscript f, we have
(3.9)
For the case of constant-density systems XA = 1 – CA/CA0:
(3.10)

Figure 3.5 is a graphical representation of these mixed flow performance

equations.
Figure 3.5 Graphical representation of the design equations for CSTR.

Chapter 4. Design for Single Reactions
The reactor system selected will influence the economics of the process by
dictating the size of the units needed and by fixing the ratio of products (product
distribution) formed.
For single reactions, product distribution is fixed; hence, the important factor in
comparing designs is the reactor size.
1. Size comparision of single reactors

1.1. Mixed versus plug flow reactors: first- and second-order reactions
The ratio of sizes of mixed and plug flow reactors will depend on the extent of
reaction, the stoichiometry, and the form of the rate equation.
For the general case, a comparison of Eqs. 3.9 and 3.14 will give this size ratio.
Let us make this comparison for the reactions with the nth-order rate law:
(4.1)
where n varies anywhere from zero to three.

For mixed flow, Eq. 3.9 gives
(4.2)
whereas for plug flow, Eq. 3.14 gives
(4.3)
Dividing Eq. 4.2 by Eq. 4.3 gives
(4.4)

With constant density, or ε = 0, this expression integrates to
(4.5)
or
Equations 4.4 and 4.5 are displayed in graphical form in Fig. 4.1 to provide a
quick comparison of the performance of plug flow with mixed flow reactors.

Figure 4.1
Comparison of
performance of
single mixed flow
and plug flow
reactors for the nth-
order reactions

Figure 4.1 shows the following:
1. For any particular duty and for all positive reaction orders the mixed reactor
is always larger than the plug flow reactor. The ratio of volumes increases with
reaction order.
2. When conversion is small, the reactor performance is only slightly affected

by flow type. The performance ratio increases very rapidly at high conversion;
consequently, a proper representation of the flow becomes very important in this
range of conversion.
3. Density variation during reaction affects design; however, it is normally of

secondary importance compared to the difference in flow type.

1.2 Variation of Reactant Ratio for Second-Order Reactions

Second-order reactions of two components:
behaves as second-order reactions of one component when the reactant ratio is

unity. Thus
When a large excess of reactant B is used then its concentration does not change
appreciably (CB ~ CBO) and the reaction approaches first-order behavior with
respect to the limiting component A, or
Thus in Fig. 4.1, and in terms of the limiting component A, the size ratio of
mixed to plug flow reactors is represented by the region between the first-order
and the second-order curves.
2. Multiple-reactor systems
2.1. Plug flow reactors in series and/or in parallel
• Consider N plug flow reactors connected in series,
• X1, X2, . . . , XN is the fractional conversion of component A leaving reactor 1, 2, .
. . , N.
Basing the material balance on the feed rate of A to the first reactor, we find for
the ith reactor from Eq. 3.15
(4.6)
or for the N reactors in series
(4.7)

Hence, N plug flow reactors in series with a total volume V gives the same
conversion as a single plug flow reactor of volume V.
2.2. Equal-size mixed flow reactors in series

In plug flow, the concentration of reactant decreases progressively through the
system; in mixed flow, the concentration drops immediately to a low value.
Consider a system of N mixed flow reactors connected in series:

• The concentration is uniform in each reactor,
• The concentration changes as fluid moves from reactor to reactor.
This stepwise drop in concentration, illustrated in Fig. 4.2, suggests that the larger
the number of units in series, the closer should the behavior of the system
approach plug flow.

Figure 4.2 Concentration profile through an N-stage mixed flow reactor

system compared with single flow reactors.

Evaluate the behavior of a series of N equal-size mixed flow reactors. Density

changes will be assumed to be negligible; hence ε = 0 and t = τ.
Figure 4.3 Notation for a system of N equal-size mixed reactors in series.
First-Order Reactions:
For component A about vessel i, it can be written:
(4.8)

Because ε = 0 this may be written in terms of concentrations:
(4.9)
Or
(4.10)
The space-time r (or mean residence time t) is the same in all the equal-size
reactors of volume Vi. Therefore,
(4.11)
Rearranging Eq. 4.11 gives for the system:
(4.12)

For N Æ ∞, this equation reduces to the plug flow equation
(4.13)
With Eqs. 4.12 and 4.13 we can compare performance of N reactors in series with
a plug flow reactor or with a single mixed flow reactor. This comparison is shown
in Fig. 4.4 for first-order reactions in which density variations are negligible.

Figure 4.4 Comparison of performance of a series of N equal-size mixed flow

reactors with a plug flow reactor for the first-order reaction.
Second-Order Reactions
Consider reaction:
N reactors in series:
(4.14)
Whereas for plug flow:

(4.15)
A comparison of the performance of these reactors is shown in Fig. 4.5.

Figure 4.5 Comparison

of performance of a
series of N equal-size
mixed flow reactors
with a plug flow reactor
for elementary second-
order reactions

Example
1. At present 90% of reactant A is converted into product by a second-order reaction

in a single mixed flow reactor. We plan to place a second reactor similar to the
one being used in series with it.
(a) For the same treatment rate as that used at present, how will this addition
affect the conversion of reactant?
(b) For the same 90% conversion, by how much can the treatment rate be increased?
2. The following liquid-phase hydration reaction occurs in a 10,000 L CSTR:
A+H2O → B
with a first-order rate constant of 2.5 x 10-3 min-1.

a) What is the steady-state fractional conversion of A if the feed rate is 0.3 L/sec and
the feed concentration CAo = 0.12 mol/L?
b) If the feed rate suddenly drops to 70% of its original value and is maintained there,
what is the fractional conversion of A after 60 minutes, and what is the new
steady state fractional conversion?

2.3 Mixed Flow Reactors of Different Sizes in Series

2.3.1 Finding the Conversion in a Given System
Consider three mixed flow reactors in series as shown in Figure 4.6.
Figure 4.6 Notation for a series of unequal-size mixed flow reactors.

Noting that ε = 0, it can be written for component A in the first reactor:
(4.16)
or
(4.17)
Similarly, for the ith reactor we may write:
(4.18)

4.18)
4.18)
Figure 4.7 Graphical procedure for finding compositions in a series

of mixed flow reactors.
2.3.2 Determining the Best System for a Given Conversion
Suppose we want to find the minimum size of two mixed flow reactors in series to
achieve a specified conversion of feed which reacts with arbitrary but known
kinetics. It can be written for component A in the first and second reactor:
and (4.19)
These relationships are displayed in Fig. 4.8 for two alternative reactor
arrangements, both giving the same final conversion X2. Figure 4.8 shows that the
total reactor volume is as small as possible (total shaded area is minimized) when
the rectangle KLMN is as large as possible.

Figure 4.8 Graphical representation of the variables for two mixed flow reactors in
series.
Chapter 5. Design for Multiple Reactions
1. Multiple Reactions
• For multiple reactors, both the size requirement and the distribution of
reaction products are affected by the flow within the reactor.
• The distinction between a single reaction and multiple reactions is that the
single reaction requires only one rate expression to describe its kinetic behavior
whereas multiple reactions require more than one rate expression.
• Many multiple reactions can be considered to be combinations of two
primary types: parallel reactions and series reactions.
• In this chapter, expansion effects are ignored, thus ε = 0
1.1. Qualitative Discussion About Product Distribution

Consider the decomposition of A by either one of two paths:
(5.1)

with corresponding rate equations
(5.2a)
(5.2b)
Dividing Eq. 5.2a by Eq. 5.2b gives a measure of the relative rates of formation of
R and S. Thus
(5.3)
This ratio is expected to be as large as possible.

k1, k2, a1, and a2 are all constant for a specific system at a given temperature. Thus,
CA is the only factor in this equation which we can adjust and control.

• If a1 > a2: the desired reaction is of higher order than the unwanted reaction.
Eq. 5.3 shows that a high reactant concentration is desirable since it increases the
R/S ratio. As a result, a batch or plug flow reactor would favor formation of
product R and would require a minimum reactor size.
• If a1 < a2: the desired reaction is of lower order than the unwanted reaction.
A low reactant concentration is needed to favor formation of R. But this would
also require large mixed flow reactor.
• If a1 = a2: the two reactions are of the same order, Eq. 5.3 becomes
(5.4)
Thus, product distribution is fixed by k1/k2 alone and is unaffected by type of

reactor used.
Product distribution can be controlled by varying k1/k2 in two ways:

1. Changing the temperature. If the activation energies of the two reactions are
different, k1/k2 can be varied by changing temperature.
2. Using a catalyst. One of the most important features of a catalyst is its selectivity
in depressing or accelerating specific reactions. This may be a much more effective
way of controlling product distribution than any of the methods discussed so far.
When you have two or more reactants, combinations of high and low reactant
concentrations can be obtained by controlling the concentration of feed materials.
Figures 5.1 and 5.2 illustrate methods of contacting two reacting fluids in continuous
and noncontinuous operations that keep the concentrations of these components both
high, both low, or one high and the other low.

Figure 5.1 Contacting patterns for various combinations of high and low
concentration of reactants in noncontinuous operations.

Figure 5.2 Contacting patterns for various combinations of high and low
concentration of reactants in continuous flow operations.

1.2. Quantitative Treatment of Product Distribution and of Reactor Size

If rate equations are known for the individual reactions, we can quantitatively
determine product distribution and reactor-size requirements. For convenience
in evaluating product distribution we introduce two terms, φ and Φ.
Consider the composition of A:
The instantaneous fractional yield of R (φ) is defined as:
(5.5)

Lecture Note - Chemical Reaction Engineering

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Lecture Note - Chemical Reaction Engineering

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VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY

Chemical Reaction Engineering

Mai Thanh Phong, Ph.D.

FCE – HCMC University of Technology Chemical Reaction Engineering

1. Octave Levenspiel, “Chemical Reaction Engineering”, John Wiley&Sons, 2002.

2. H. Scot Foggler, “Elements of Chemical Reaction Engineering”,International

3. E.B.Nauman, “Chemical Reactor Design”, John Wiley & sons, 1987.

4. Stanley M. Walas, “Reaction Kinetics for Chemical Engineers”,Int. Student

5. Coulson & Richardsons, “Chemical Engineering – Vol 6”,Elsevier, 1979.

6. Richard M. Felder, “Elementary Principles of Chemical Processes”, John Wiley &

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 2

• Topic of the lecture „Chemical Reaction Engineering“ is the quantitative

• Reactor design uses information, knowledge, and experience from a variety of

• Thermodynamics tell us in which direction a reaction system will develop and

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 3

Description of the amount of a substance i:

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 4

Progress of chemical reactions:

produced amount of product P

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 5

II. Stoichiometry of chemical reactions:

Stoichiometry is based on mass conservation and thus quantifies general laws

Starting point of a quantitative analysis is the following formulation of a chemical

This equation describes the change of the number of moles of N components

A convention is that reactants have negative stoichiometric coefficients and products

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 6

As an example the stoichiometric equation for the oxidation of carbon monoxide

To calculate changes in the mole number of a component i due to reaction, the

III. Chemical thermodynamics:

3.1 Enthalpy of reaction

The change of enthalpy caused by a reaction is called reaction enthalpy ∆HR.

∆HFi is the enthalpy of formation of component i

∆HR < 0, the reaction is exothermic

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 8

For pure elements like C, H2, O2,...: ∆HFi0 = 0.

3.2 Temperature and pressure dependence of reaction enthalpy

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 9

The correlation of reaction enthalpy and temperature is related to the isobaric

ΔH R (T ) = ΔH R0 + (T − T0 )(cP ,products − cP ,reactants )

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 10

3.3 Chemical equilibrium

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 11

In Figure 1-1 is shown the course of free

Free Gibbs enthalpy

Thus, the equilibrium is characterized by:

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 12

3.3.1 Reation free Gibbs enthalpy, ∆GR

ΔGFi0 free Gibbs energy of formation

Relation between ∆GR and ∆HR

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 13

3.3.2 Equilibrium constant and temperature dependence

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 16

BR are applied in particular for:

Areas of application for BR are:

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 17

b) Semi-batch Reactor (SBR): perfectly mixed, semi continuous operation

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 18

c) Continuously Stirred Tank Reactor (CSTR): perfectly mixed, continuous operation

Mai Thanh Phong - HCMUT Chemical Reaction Engineering 3-Feb-09 19

d) Plug Flow Tubular Reactor (PFTR): no mixing, continuous operation

Chemical Reaction Engineering

Mai Thanh Phong, Ph.D.