Only study guide for

REE2601

University of South Africa

Pretoria
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REE2601/1/2021

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 CONTENTS

 Page

INTRODUCTION TO THE MODULEvii

LEARNING UNIT 1: INTRODUCTORY CONCEPTS AND REVIEW1

Learning outcomes1
1.1 Introduction1
1.2 General properties1
1.2.1 Definition of variables2
1.2.2 Total and partial pressure3
1.3 Reaction parameters5
1.3.1 Definition of terms5
1.4 Balancing chemical reaction7
1.5 Chemical equilibrium8
1.5.1 Equilibrium constant8
1.5.2 Gibbs free energy10
1.5.3 General formula of the Gibbs free energy11
1.5.4 Van't Hoff equation12
1.6 Summary12
Self-assessment problems12
Solutions to problems13
References15

LEARNING UNIT 2: MASS AND ENERGY BALANCES FOR REACTIVE SYSTEMS17

Learning outcomes17
2.1 Introduction17
2.2 Definition of terms18
2.3 System boundary20
2.4 Steady state and unsteady state processes21
2.5 Steady state material balances22
2.5.1 Component balance22
2.6 Mass balance for reactive systems25
2.7 Steady state energy balances29

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iii R EE 2 6 01/1
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2.8 Closed system chemical reaction energy balance32

2.9 Unsteady state material balances32
2.10 Summary35
Self-assessment problems35
Solutions to problems37
References41

LEARNING UNIT 3: BASICS OF REACTION KINETICS43

Learning outcomes43
3.1 Introduction43
3.2 Reaction order44
3.2.1 Determination of reaction order from experimental data45
3.2.2 Determination of reaction order using graphical method47
3.2.3 Zero order48
3.2.4 First order49
3.2.5 Second order51
3.2.6 Nth order equation54
3.3 Arrhenius equiation: The influence of temperature on reaction rate54
3.3.1 Single reaction54
3.4 Effect of pressure on reaction rates58
3.5 Variable volume60
3.5.1 For zero order reaction with variable volume62
Using C AO = 10, t = 1714.29 s = 28.6 mins
3.5.2 First order with variable volume63
3.5.3 Second order with variable volume64
3.5.4 Third order with variable volume64
3.6 Reversible reactions65
3.7 Multiple reactions67
3.7.1 Reactions in series67
3.8 Summary68
Self-assessment problems68
Solutions to problems70
References74

LEARNING UNIT 4: IDEAL REACTORS75

Learning outcomes75
4.1 Introduction75
4.2 Types of reactors75
4.2.1 Batch reactors76
4.2.2 Plug flow reactors (PFR)76
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4.2.3 Continuous stirred tank reactor (CSTR)77

4.3 Isothermal reactor design78
4.3.1 Design calculations for batch reactors79
4.3.2 Design calculations for CSTR82
4.3.3 Design calculations for plug flow reactor (PFR)84
4.4 Summary85
Self-assessment problems85
Solutions to problems86
References89

LEARNING UNIT 5: COMPARISON AND COMBINATION OF REACTORS91

Learning outcomes91
5.1 Introduction91
5.2 Comparison between batch reactor (BR), continuously stirred
tank reactor (CSTR) and plug flow reactor (PFR)91
5.3 Comparison of a batch reactor and plug flow reactor92
5.4 Comparison of a batch reactor and continuously stirred tank reactor93
5.5 Comparison of a plug flow reactor and continuously stirred tank
reactor94
5.6 Reactors in series95
5.6.1 CSTR in series95
5.6.2 CSTR in parallel100
5.6.3 PFR in series100
5.7 Conversion, selectivity, and yield101
5.8 Summary103
Self-assessment problems103
Solutions to problems105
References109

LEARNING UNIT 6: TEMPERATURE AND PRESSURE EFFECTS110

Learning outcomes110
6.1 Introduction110
6.2 Pressure drop in reactors (PFR)110
6.3 Temperature effects116
6.3.1 Energy balance for an adiabatic process117
6.3.2 Relationships for an adiabatic reactor117
6.3.3 Procedure to calculate – rA as a function of X alone117
6.4 Industrial processes121
6.5 Summary121

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Self-assessment problems121
Solutions to problems122
References126

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vi
 INTRODUCTION TO THE
MODULE

Welcome to the module: Reaction Engineering (REE2601). Please make sure

that you read this general introduction to the module because it contains
important information that you need to take note of.

Reaction engineering is a field of chemical engineering which deals specifically

with choosing and designing chemical reactors. We will focus on three types
of reactors, namely batch, plug flow and continually stirred reactors. These
are important for a chemical engineer in that reactors have to be designed to
operate at optimum levels in order to increase production and reduce costs.

This module forms part of the Diploma in Chemical Engineering. The purpose
of the module is to introduce you to the basic concepts of chemical reaction
engineering. You will first learn to perform unsteady state material balances
(for the basics of steady state material balances, see the CHF1501 study guide),
stoichiometric calculations and reaction equilibrium calculations before being
introduced to the basics of reaction kinetics that will be applied to derive ideal
reactor models.

Module Outcomes
On completion of this module you should be able to:

(1) Perform unsteady state material balances, stoichiometric calculations and

reaction equilibrium calculations. In learning to do so you will learn about:
•• Material balances review and unsteady state material balances
•• Thermodynamics (Equilibrium etc.)
•• Stoichiometry
(2) Perform chemical reaction kinetics calculations. In learning to do so you
will learn about:
•• Extent of reaction and conversion
•• Basic concepts of reaction rate: Rate law, reaction order
•• Reaction rate constant
•• Temperature dependence (Arrhenius equation) of rate constant
•• Experimental measurement of rate data
•• Analysis of rate data
(3) Perform modelling of ideal reactors under isothermal conditions. In
learning to do so you will learn about:
•• Isothermal reactor design, i.e. sizing calculations
–– Batch reactors
–– Continuous stirred tank reactors (CSTR)
–– Plug flow reactors (PFR)

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I N T R O D U C T I O N TO T H E M O D U L E

• Reactors in series and parallel

• Non-isothermal reactors (Energy balance, adiabatic)
• Pressure drop in reactors
• A brief introduction to industrial reactors

The diagram below gives an overview of the module content.

FIGURE 1
Overview of the module

Module structure
The module has been designed in such a way as to ensure that you can actively
engage with the learning content.

In order to simplify your studies, the learning units have been structured in
the same way:

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 I nt r o du c t i o n to t h e m o du l e

•• Each learning unit starts with a summary of the expected learning outcomes.
These outcomes detail what you should be able to do after you have studied
the learning unit.
•• Several practice examples with solutions are provided in each of the
learning units.
•• Some learning units may have activities that you can complete to assess
your own progress. Complete some of the activities, as indicated, under
Discussions on the module website on myUnisa.
•• At the end of each learning unit, you will find self-assessment problems
which will enable you to test whether you have accomplished the learning
outcomes. Look at the solutions only once you have attempted to solve
the problems on your own. Do not forget to do the applicable problems
in the prescribed textbook.

Module pre-requisites and co-requisites

You will need to have mastered (pre-requisites) Chemical Engineering
Fundamentals I (CHF1501), Mathematics I (Engineering) and Chemistry I
(Engineering). You will also use principles (co-requisites) from the following
modules to successfully understand this module: Chemical Engineering
Thermodynamics; Mathematics II (Engineering) and Chemical Engineering
Fundamentals II (CHF2601).

Prescribed and recommended textbooks for the module

The learning units in the study guide should be studied in conjunction with
the prescribed textbook:

Fogler, H.S. (2011). Essentials of Chemical Reaction Engineering. Prentice Hall

International series in the physical and chemical engineering sciences. Pearson.
International Edition, ISBN: 978-0-13-211936-8.

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I N T R O D U C T I O N TO T H E M O D U L E

We begin each learning unit with an outline of the relevant chapter of the
prescribed textbook, which forms the study material for REE2601. We then
give a more detailed description of the content of the specific learning unit.

Use the prescribed textbook and study guide as follows:

•• First study the relevant sections in the study guide.

•• Then consult the prescribed textbook if you need further explanations or
references to certain information.

The examination will be based on the information obtained from both this
study guide and the prescribed textbook.

Planning and managing your time

Because of your unique circumstances, each of you will plan and manage
your study programme during the semester/year differently. You may find the
following tips helpful for planning and managing your time:

•• Start by skimming through the study material to get an idea of what is covered
in the module. Use this information to divide the material into manageable
sections, and then schedule times at which you can study them. You may
need to revise the schedule as you delve deeper into the study material.
Also, schedule times for doing assignments and for examination revision.
Students in a contact setting are forced to interact with study material during
lectures. However, as you do not attend lectures, in order to be successful
you need to schedule times for interacting with the study material. Make
notes and summaries while you are studying, and use these when you do
assignments or prepare for the examination.
•• For suggestions on general time management and planning skills,
visit https://www.unisa.ac.za/sites/corporate/default/About/Service-
departments/Counselling-and-Career-Development/Manage-your-studies/
Time-management.
•• REE2601 is a year module offered over 30 weeks, and it requires at least
120 hours of study time. This means that you have to study for at least four
hours per week for this module.
•• Here is a suggested schedule that you could use as a guideline for studying
this module:

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ACTIVITY HOURS

Reading and rereading Tutorial Letter 101 and the module 3

overview

Skimming through the learning units and textbooks to get an 5

overview of the whole module

First reading of learning units and the textbook 10

In-depth study of learning units: study the content, work through 50

the examples and do the problems presented at the end of each
learning unit

Completing two assignments 20

Revising for the examination 30

Writing the examination 2

Total 120

Unlike contact students, you do not have regular contact with your lecturers,
but this should not stop you from asking for assistance if you need to as you
study. If you are struggling to understand a particular aspect, please contact
your lecturer. Provide as much detail as possible about your problem to enable
your lecturer to help you – for example, don’t simply say that you do not
understand learning unit 2. Instead, tell your lecturer which specific section
you do not understand, or explain where in a process you got stuck.

You may also find it helpful to discuss aspects of the study material with fellow
students or to make use of other resources. If you do that, though, always ensure
that your sources are reliable and that the facts they contain are correct and
in line with those listed in the study material. Many web-based resources are
not peer reviewed and do not give the correct facts.

We also recommend that you keep track of your progress throughout the
year: refer back to the original study plan and make sure that you are on track.
However you work, plan and manage your time, make sure that you are fully
prepared for the examination at the end of the year and that you have produced
high-quality assignments that will earn you a good year mark.

Final Word
It is our wish for you to do well in this module, therefore you need to have a
proper study timetable and to remember that, when you do not understand,
CONSULT your lecturer or e-tutor.

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xi R EE 2 6 01/1
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xii
 Study unit 1 1

INTRODUCTORY CONCEPTS AND REVIEW

LEARNING OUTCOMES
On completion of this learning unit, you should be able to:
• Define what a variable is.
• Calculate various variables in reaction engineering, including temperature, pressure,
volume, moles and concentration.
• Use the partial and total pressure method.
• Define and calculate the extent of reaction, conversion, yield and selectivity.
• Define and calculate chemical equilibrium and the Gibbs free energy.
This is an introductory unit and is based on Chapter 1 of your prescribed textbook. You
can also follow the links below to better understand some of the concepts.
• Chemical equilibrium (6:47): https://youtu.be/1GiZzCzmO5Q
• Balancing chemical equations (15:56): https://youtu.be/eNsVaUCzvLA
• Gibbs free energy (7:56): https://youtu.be/huKBuShAa1w
These links are also available on the module site under Additional Resources.

1.1 INTRODUCTION
A chemical reaction involves re-arrangement of molecules or atoms. During a chemical
reaction, many variables can change (Himmelblau & Riggs, 2004). A variable is an entity
(property) that can be measured or quantified during the reaction. These variables can
include temperature, pressure, volume, moles and concentration. If a reaction is
temperature, and/or pressure and/or volume dependent, then calculation and control of
these will help in getting the required products. For example if a reaction is endothermic,
then an increase in temperature will favour the reaction.

1.2 GENERAL PROPERTIES

We will now define each of the variables mentioned in 1.1

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1.2.1 Definition of variables

Temperature is the measure of the energy (mostly kinetic energy) that molecules possess
(Himmelblau & Riggs, 2004). Simply put, it measures how hot or cold a substance is. The
SI unit for temperature uses the absolute scale called the Kelvin (K) scale. Remember,
even though we commonly use °C, this is only a relative scale.
Pressure is the normal force per unit area (Himmelblau & Riggs, 2004). Figure 1.1
demonstrates atmospheric pressure. The arrows show the pressure exerted by the air on
a liquid surface. The SI unit for pressure is Pascals (Pa).

Air

Liquid

Figure 1.1
An illustration of atmospheric pressure on a liquid surface

Volume is the three dimensional space that a particular substance occupies. The SI unit
for volume is cubic metre (m3).
A mole is composed of 6.022 ×1023 (Avogadro's number) molecules. To simplify this, in
this module we will use kg mol (kmols). Each kmol contains 1000 moles. A mole can
also be related to the atomic weight or molecular weight of a substance. For example,
carbon has an atomic mass of 12, which means that 1 mole of carbon (C) contains 12 g,
whereas 1 kg mole of C contains 12 kg of C. Moles can be calculated as follows

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 𝑚𝑚
𝑛𝑛 =
𝑀𝑀
weight ( grams )
gmole =
atomicweight
NB: Atomic weights are determined from the periodic table.
Example 1.1: Number of moles in methane
Calculate the number of moles in 32 g of methane (CH4)
Solution:
The molecular mass of methane = (1 × 12) + (4 × 1) = 16
32
Number of moles = = 2 gmole (mols)
16
Concentration refers to the quantity of a particular substance per unit volume. This can
be mass per volume (kg/m3) or moles per unit volume (mol/m3):
𝑚𝑚 𝑛𝑛
𝑐𝑐 = 𝑉𝑉
or 𝑐𝑐 = 𝑉𝑉
NB: Do not confuse concentration (mass/volume) with density (mass/volume) of the
substance.

1.2.2 Total and partial pressure

The ideal gas law can be represented mathematically as:

PV = nRT , where P is the pressure (Pa), V is the volume (m3), n is the number of moles,
R is the gas constant and T is the temperature in Kelvins. You were introduced to this in
CHF1501 or Thermodynamics principles, as well as in matric. Total and partial pressure
for gaseous reaction are used to indicate the most likely species to be existing at the end
of the reaction.
Example 1.2: Pressure
Calculate the pressure exerted by 20 grams of oxygen gas confined to a 750.00 mL
container at 20.00 °C.
Solution:
The first step is to convert the volume and temperature to SI units.
750
1ml = 1 × 10 −6 m 3 ⇒ 750ml = = 0.00075m 3
1000000
20°C = 273 + 20 = 293K

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 20
Number of moles of oxygen gas = = 0.625 gmols
32
PV = nRT
nRT
P=
V
0.625 × 8.314 × 293
Using the ideal gas equation =
0.00075
= 2030001.7 Pa
= 2030kPa
= 2.03MPa
The partial pressure of each gas in a mixture is proportional to its mole fraction. The
pressure exerted by each gas in a gas mixture (its partial pressure) is independent of the
pressure exerted by all other gases present. Consequently, the total pressure exerted by a
mixture of gases is the sum of the partial pressures of the components (Dalton's law of
partial pressures). The amount of gas present in a mixture may be described by its partial
pressure or its mole fraction. The mole fraction of any component of a mixture is the ratio
of the number of moles of that substance to the total number of moles of all substances
present. In a mixture of gases, the partial pressure of each gas is the product of the total
pressure and the mole fraction of that gas. Mathematically:
Ptotal = P1 + P2 + ....... + Pn , where 𝑃𝑃1 is partial pressure for gas 1 and so on. The partial
pressure of an individual gas is equal to the total pressure multiplied by the mole fraction
of that gas.
Example 1.3: Total pressure
A 2.0 L container is pressurized with 25 kPa of oxygen gas and 60 kP of nitrogen gas.
What is the total pressure inside the container?
Solution:
Ptotal = P1 + P2 + ....... + Pn
Use the formula
Ptotal = 25 + 60 = 85kPa
Example 1.4: Mole fraction
A 3.0 L container contains 4 mol He, 2 mol Ne, and 1 mol Ar. What is the mole fraction
of neon gas?
Solution:
Total number of moles = 4 + 2 + 1 = 7 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚
2
Mole fraction of Ne = = 0.28
7

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Example 1.5: Partial Pressure
A mixture of 2 mol H2 and 3 mol He exerts a total pressure of 300 kPa. What is the partial
pressure of He?
Solution:

Partial pressure of He=, 𝒙𝒙𝑯𝑯𝑯𝑯 is the mole fraction of He

1.3 REACTION PARAMETERS

Stoichiometry is the theory of the proportions in which chemical species combine with
one another (Himmelblau & Riggs, 2004). The stoichiometric equation of a chemical
reaction is a statement of the relative number of molecules or moles of reactants and
products that participate in the reaction. Two reactants, A and B, are said to be present in
stoichiometric proportion if the ratio (moles A present)/(mole B present) equals the
stoichiometric ratio obtained from the balanced reaction. The reactant that would run out
if a reaction proceeded to completion is called the limiting reactant, and the other
reactants are termed excess reactants.

1.3.1 Definition of terms (Himmelblau and Riggs, 2004)

• Limiting reagent is the reactant which is present in the smallest stoichiometric amount.
• Excess reagent is the reactant which is present in excess above the stoichiometrically
required amount.
• Percentage excess is the ratio of excess moles to the theoretically required moles to
react with the limiting reagent.
• Conversion is the percentage of feed that is converted to products.
• Degree of conversion is the percentage of limiting reagent converted to required
product.
• Yield is the percentage ratio of the number of moles of limiting reagent undergoing
desired reaction to the number of moles of limiting reactant reacted.
• Selectivity is the ratio of the number of moles of reactant undergoing the desired
reaction to the ratio of moles of reactant undergoing an undesired reaction
Example 1.6: Limiting reagents
Two moles of benzene and three moles of chlorine react to give 1.8 moles of
monochlorobenzene and 0.1 moles dichlorobenzene. The reactions are as follows
C 6 H 6 + Cl 2 → C 6 H 5 Cl + HCl (1)
C 6 H 6 + 2Cl 2 → C 6 H 4 Cl 2 + 2 HCl (2)
If reaction 1 is the desired reaction:

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a) Identify the limiting reactant and the excess reactant.
b) Calculate % excess of excess reactant, degree of completion, conversion of limiting
reactant and excess reactant, yield and selectivity.
Solution:
Reaction (1) is the desired one. The stoichiometric ratio is 1:1, but the feed is 2:3 which
is 1:1.5 benzene: Chlorine. Therefore, the limiting reagent is Benzene. Chlorine is in
excess.
1
% Excess Chlorine= × 100 = 50%
2
1.8
Degree of completion = × 100 = 90%
2
1.9
Conversion of benzene= × 100 = 95%
2
2
Conversion of chlorine= × 100 = 66.67
3
1.8
Yield= × 100 = 94.74%
1.9
1.8
Selectivity= = 18
0.1
Example 1.7: Yield, Selectivity and Conversion.
Consider the following simultaneous parallel reaction where 100 moles of A is fed into a
batch reactor and the product contains 10 moles A, 160 moles B and 10 moles C.
A → 2B
A→C
Calculate
a) Fractional conversion of A
b) Yield of B
c) Selectivity of B
Solution:
90
a) Conversion of A =100 = 0.9
80
b) Yield of B 90 = 0.89
80
c) Selectivity =10=8

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1.4 BALANCING CHEMICAL REACTION
Chemical reactions show how molecules or atoms are interacting to produce products.
According to the mass balance rule, atoms on the left hand side should be the same in
number as right hand side of the equation. Let us look at the Haber process equation:
N 2 + H 2 → NH 3
By inspection, there are 2 nitrogen atoms on LHS and 1 on the RHS, 2 hydrogen atoms
on the LHS and 3 on the RHS. This means that the equation is not balanced.
Steps to balance
The following steps can be followed to balance the equation:
1. Give the representative letter of all reactant(s) and product(s) from A to Z
Therefore N2 is represented by A, H2 by B and NH3 by C
2. Write the equation for all atoms using the letters developed in step 1.
The equation for N is given by 2A=C, H is given by 2B=3C
3. Choose a value for either A, B or C and solve the equations in terms of A
Let us choose a value for A. Let A=1, then C=2 and then B=3
The balanced equation becomes
N 2 + 3H 2 → 2 NH 3
Example 1.8: Balancing Equations
Balance the following equations
Fe + O2 → Fe2 O3
Solution:
Step 1: Assign letters
Fe = A, O2 = B and Fe2O3 = C
Step 2: Balance for atoms –
Fe – A = 2C
O – 2B = 3C
Let A=1, then C=0.5 and B=0.75
However, fractions are not required, so we need to clear them by multiplying every
coefficient by 4.

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 3 1
Fe + O2 → Fe2O3
4 2
4 Fe + 3O2 → 2 Fe2O3
Now that we have looked at steady state systems, we also need to consider unsteady state
systems.

1.5 CHEMICAL EQUILIBRIUM

For a reversible chemical reaction when the forward reaction is equal to the backward
reaction, the reaction is said to be in dynamic equilibrium
reac tan ts ↔ products
Forward reaction is reactants to products, backward is products to reactants.

1.5.1 Equilibrium constant

Let us consider the reaction below:

aA + bB ↔ cC + dD
The equilibrium constant is given by:

K=
[C ]c [D]d
[A]a [B]b
where [C] is the concentration of product C and c is the coefficient of product C in the
balanced equation.
This equilibrium constant can be used by a chemical engineer to calculate the
composition of molecules in a reaction when they are at equilibrium.
NB: Please note that, depending on the reaction, K may have units or may not have
units. In this case, K has no units as they all cancel each other out.
Example 1.9: Equilibrium constant
For the reaction N 2 O4 ↔ 2NO2
Determine the equilibrium constant K. Also say if K will have units or not.
Solution:
The equilibrium constant is given by:

K=
[NO2 ]2
[N 2 O4 ]
K will have units of concentration (e.g. mol/L)

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Example 1.9: Equilibrium constant
For the reaction
2 HI ↔ H 2 + I 2
The equilibrium concentration of HI and I2 are 1.68 mol/L, 0.2 mol/L, respectively.
Calculate the equilibrium constant.
Solution:
From the balanced equation 1 mole of H2 needs 1 mole of I2, concentration of H2 = 0.2
mol/L
[𝐼𝐼2 ][𝐻𝐻2 ]
𝐾𝐾 = [𝐻𝐻𝐻𝐻]2

0.2 × 0.2
Therefore, K = = 1.4 × 10 − 2
1.68 2
NB: No units because they cancel out
Example 1.10: Equilibrium constant
The equilibrium constant for the reaction H 2 + I 2 ↔ 2 HI is 0.016.
If, initially, 1 mol of H2 and 1 mol of I2 are introduced into a 10 L container and allowed
to come into equilibrium, calculate the concentration of I2, H2 and HI at equilibrium
Solution:
NB. Concentration is mol/L therefore [H2]=1/10=0.1 mol/L.
Let x be the concentration of HI at equilibrium. Drawing a table to represent the situation at
start and at equilibrium gives:

H2 I2 2HI

Initial concentration (mol/L) 0.1 0.1 0

At equilibrium (mol/L) 0.1-x 0.1-x 2x

K=
[HI ]
2
= 0.016 =
(2 x) 2
=
2x
= 0.016 = 0.13
[H 2 ][I 2 ] (0.1 − x) 2 0.1 − x
2 x = (0.1 − x)(0.13)
x = 0.0061
[H2] = 0.1-0.0061=0.0939 mol/L
[I2] = 0.1-0.0061=0.0939 mol/L
[HI] = 2*0.0061=0.0122 mol/L

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Example 1.11: Equilibrium Constant
Calculate the equilibrium constant for the reaction below if 100 moles of A and 100
moles of B are fed into a batch reactor and there is 60 moles of A at equilibrium.
A + 2B ↔ C + D

A B C D

Initial concentration 100 100 0 0

(mol/L)

At equilibrium (mol/L) 60 20 moles 40 (40moles of 40 (40moles of A

(40 moles of A A reacted and reacted and
reacted and hence produce hence produce
hence need 80 40 moles of C) 40 moles of D
moles of B)

mol mol
40 × 40
K=
[C ][D] = L L = 0.067 L / mol
[A][B ]2 mol 2  mol 
2

60 × 20  
L  L 

1.5.2 Gibbs free energy

This is the thermodynamic potential that can be used to calculate thermodynamic work
that can be done by a system (Himmelblau and Riggs, 2004). It can be used to provide
information on the feasibility of a particular reaction. A negative value for the Gibbs free
energy implies that the reaction is spontaneous (it will occur in that direction) whilst a
positive value implies a non-spontaneous reaction. The equation for Gibbs free energy is
given by
∆G = ∆H − T∆S
where ΔG is the change in Gibbs free energy, ΔH is the change in enthalpy, T is the
temperature in Kelvins and ΔS is the change in entropy. The equation which links
equilibrium constant with Gibbs free energy is given as:
∆G = ∆G° + RT ln K
𝑊𝑊ℎ𝑒𝑒𝑒𝑒𝑒𝑒 𝑇𝑇 𝑖𝑖𝑖𝑖 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡, 𝑅𝑅 𝑖𝑖𝑖𝑖 𝑡𝑡ℎ𝑒𝑒 𝑔𝑔𝑔𝑔𝑔𝑔 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 , 𝐾𝐾 𝑖𝑖𝑖𝑖 𝑡𝑡ℎ𝑒𝑒 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
𝛥𝛥𝛥𝛥° 𝑖𝑖𝑖𝑖 𝑡𝑡ℎ𝑒𝑒 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 𝑜𝑜𝑜𝑜 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
The equation and its derivation can be found in the Chemical Engineering
Thermodynamics module.

10 REE2601/1
The values of ΔH and ΔS are found in the Thermodynamic tables.
Example 1.12: Gibbs free energy reactions
The Gibbs free energies of two reactions are -20.4 kJ/mol and -40 kJ/mol. Which one is
more spontaneous?
Solution: Both are spontaneous because ΔG is negative. But the more negative the value,
the greater the spontaneity hence the answer is -40 kJ/mol is more spontaneous.

1.5.3 General formula for the Gibbs free energy

There is also a general way to calculate Gibbs free energy from standard tables which is
given in example 1.13.
Example 1.13: Standard Free Energy
Calculate the standard free energy change for the reaction
2 NO ( g ) + O2 ( g ) → 2 NO2 ( g )

Substance ΔHºf (kJ/mol) ΔGºf (kJ/mol) Sº (J/mol⋅K)

NO(g) 90.4 86.7 210.62

O2(g) 0 0 205

NO2(g) 33.8 51.84 240.45

Solution:
ΔHº(rxn)=2x33.8 kJ/mol - (2x90.4 kJ/mol) = -113 kJ
ΔSº(rxn) = 2x240 J/mol⋅K - (2x210.62) - (1x205) = -146.24 J/K = -0.14624 kJ/K
Gibbs free energy at 298K
ΔGº(rxn) = -113 - (298)(-0.14624)= -69.4 kJ
For a reaction:
aA + bB → cC + dD
[ ] [
∆G° = c∆G° f (C ) + d∆G° f ( D) − a∆G° f ( A) + b∆G° f ( B ) ]
For the reaction:
2 NO ( g ) + O2 ( g ) → 2 NO2 ( g )
ΔGº = 2x51.84 - [(2x86.7) + 0] = -69.7 kJ.

11 REE2601/1
1.5.4 Van’t Hoff Equation

The assumption is that the temperature dependence of the equilibrium constant, K,

depends only on ΔH°. The equation is written as:

Example 1.14: Endothermic and Exothermic Reactions

Determine if a particular reaction is endothermic or exothermic if the equilibrium
constant at 100°C is 0.38 and at 300°C is 0.26.
Feedback

1.6 SUMMARY
In this learning unit we have learnt about a number of variables involved in chemical
reactions and how to balance chemical reactions. We will use these principles in later
chapters to solve chemical reactor problems. For now, it is best to test yourself by way of
the following problems, so as to gauge your understanding of these basic principles.

SELF-ASSESSMENT PROBLEMS
We have now learnt various principles and it is time to test yourself.
1.1 Calculate the number of moles in 560 g NaOH. Answer (14 g moles)
1.2 Calculate the mass of 15.0 L of NH3 at 27°C and 120 kPa. (12.27 g)
1.3 Write the equilibrium constant for the for the combustion of NH3
4 NH 3 + 5O2 → 4 NO + 6 H 2 O

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1.4 At a certain temperature, 4 Mols of PCl5 was placed in a 2 L flask. At equilibrium,
3.60 moles of PCl5 remained. Calculate the equilibrium constant for the reaction
PCl 5 ⇔ PCl 3 + Cl 2
(0.011)
1.5 Using Thermodynamic tables, calculate ΔG° for the reaction

(-818 kJ)
1.6 Acetaldehyde can be formed by oxidizing ethane, but a side reaction can occur
resulting in the production of carbon dioxide as shown in the equations below
C 2 H 6 + O2 → CH 3 CHO + H 2 0

7
C 2 H 6 + O2 + 2CO2 + 3H 2 0
2
If 65% (by mole) of the ethane feed stream forms acetaldehyde, 15% forms CO2 and
the remainder is unreacted, calculate
a) Yield (81.25%)
b) Selectivity (4.33)
c) Conversion (80%)
d) Degree of conversion (65%)

SOLUTIONS TO SELF-ASSESSMENT PROBLEMS

Compare your solutions with the solutions provided below.
1.1 Calculate the number of moles in 560 g NaOH Solution
Molecular weight of NaOH = 23 + 16 + 1 = 40

560
Number of moles= 40 = 14 gmoles
1.2 Calculate the mass of 15.0 L of NH3 at 27°C and 120 kPa

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Solution:
15 L = 0.015m 3
PV = nRT
PV
n=
RT
120000 × 0.015
=
8.314 × (273 + 27 )
= 0.72
Mass = 0.72 × 17 = 12.27 g

1.3

K=
[NO ] [H 2 O ]
4 6

[NH 3 ]4 [O2 ]5
1.4 Input the equilibrium concentrations.

Beginning Equilibrium

PCl5 4/2= 2 mol/L 3.6/2= 1.8 mol/L

PCl3 0 0.4/2=0.2 mol/L

Cl2 0 0.4/2=0.2 mol/L

0.2 × 0.2
K= = 0.011mol / L
1.8
1.5 Using thermodynamic tables calculate ΔG° for the reaction

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 ΔGº

H2O (l) -237.18

CO2 (g) -394.38

CH4 (g) -50.84

O2 0

∆G° = (2 × −237.18) + (− 394.38) − [− 50.84 + 0] = 818kJ / mol

NB only when ΔGº(rxn) is required do you use the formula ∆G = ∆H − T∆S

1.6 Acetaldehyde can be formed by oxidizing ethane, but a side reaction can occur
Solution:
Assume 100 mol of ethane

a) Yield= 65 /(65 + 15) = 81.25%

b) Selectivity= 65 / 15 = 4.33
c) Conversion= (65 + 15) / 100 = 80%
d) Degree of conversion=65%

REFERENCES
Fogler, HS. (2011). Essentials of Chemical Reaction Engineering. Prentice Hall
International series in the physical and chemical engineering sciences. Pearson.
International Edition, ISBN: 978-0-13-211936-8.
Himmelblau, DM & Riggs, JB. (2004). Basic Principles and Calculations in Chemical
Engineering, 7th ed Prentice Hall International.

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16 REE2601/1
 Study unit 1 2

MASS AND ENERGY BALANCES FOR REACTIVE SYSTEMS

LEARNING OUTCOMES
On completion of this learning unit, you should be able to:
• Perform basic mass balance calculations.
• Perform basic energy balance calculations.
• Balance chemical reaction equations.
• Derive integral equations for unsteady state mass balance.
• Calculate molecule concentration at equilibrium.
• Calculate equilibrium constant.
• Calculate the change in standard Gibbs free energy.
This learning unit is based on Chapters 1 and 3 of your prescribed book. You can also
follow the links below to better understand some of the concepts.
• Material balance (9:08): https://youtu.be/UGVEtzgR0lw
• Energy Balance (5:09): https://youtu.be/RF778F-D6p8?list=PL4xAk5aclnUiDazeSqz
59Zb9NC1a2AK0q
These links are also available on the module site under Additional Resources.

2.1 INTRODUCTION
Chemical reactions involve the re-arrangement of atoms to form new molecules or
products (Himmelblau & Riggs, 2004). An example of these reactions is the production
of ammonia from nitrogen and hydrogen gases;
𝑁𝑁2(𝑔𝑔) + 𝐻𝐻2(𝑔𝑔) → 𝑁𝑁𝐻𝐻3(𝑔𝑔)
By the Law of Conservation of Mass, mass cannot be created or destroyed and hence it
has to be conserved during the reaction. Therefore, the mass of components before the
reaction (reactants) must be equal to the mass after the reaction (products). This means
that you need to balance the chemical reaction equations. Basically, material

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conservation requires that the number of atoms of each element must be conserved in a
reaction. If this is achieved, chemical reaction equilibrium composition can then be
calculated for reversible reactions. This is important in that it allows chemical engineers
to fully control the process of chemical reactions within reactors, be they reversible or
irreversible reactions.

2.2 DEFINITION OF TERMS

• Material balance applies to the Law of Conservation of Mass. Matter or mass is neither
created nor destroyed.
• System is an arbitrary portion or the whole process you want to consider. For example,
in a refinery, a system maybe the whole plant or just the distiller. Figure 2.1 gives an
illustration of a system.

A C
MIXER Distiller

B E

Figure 2.1
Illustration of a system

• A closed system is the one with no interaction with the surrounding environment and
therefore no mass exchange. An open system is the one with interaction with the
surrounding environment and is also called a flow system. Figure 2.2 shows a closed
system. Solid lines mean there is no interaction with the outside; an example can be
a closed packet of biscuits!

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 Figure 2.2
A closed system

Figure 2.3 shows an open system. The top of the container is exposed to the outside
environment.

Figure 2.3
An open system

Activity 2.1: Open or closed system?

Answer the following question under Discussions on the module website on myUnisa
(Forum 3: learning unit 2 activities, Activity 2.1):

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Would you consider a closed can of Coca-Cola a closed system or an open system? Why do
you say so?

Feedback

A closed can of Coca-Cola is considered to be a closed system because there is no mass

transfer between it and the outside environment.

You will find feedback on this activity on the module site on myUnisa under Forum 3:
learning unit 2 activities, feedback on activity 2.1.

2.3 SYSTEM BOUNDARY

Figure 2.4 shows a distillation process

A C
MIXER Distiller

B E

Figure 2.4
Distillation process

Figure 2.4 illustrates that a system can consist of the mixer only, or the distiller, or the
entire process. Once the system is defined, one needs to draw a boundary around the
defined part as shown in Figure 2.5.

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 Outside of boundary or environment

A Mixer C

B
Boundary

Figure 2.5
Drawing of a system boundary around the mixer

2.4 STEADY STATE AND UNSTEADY STATE PROCESSES

Figure 2.6 shows an example of a steady state process

100 kg/h 100 kg/h

1000 kg

Figure 2.6
A steady state process

A steady-state process is a state where the conditions in the system (mass) does not change
since, as in Figure 2.6, inflow = outflow.
An unsteady state process is when the conditions in the system change with time. In the
example below (Figure 2.7), after 1 hour there will be 1020 kg in the system.

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 100 kg/h 80 kg/h
1000 kg

After one hour

100 kg/h 80 kg/h

1020 kg

Figure 2.7
Example of an unsteady state process

Now that we know the types of systems and how to make boundaries, let us consider
how to perform material balance calculation.

2.5 STEADY STATE MATERIAL BALANCES

The material balance equation is given as:
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 = 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 − 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 + 𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔 − 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
For a steady state process there is no accumulation and hence:
inflow + generation = outflow + consumption
If there is no chemical reaction involved, then
inflow = outflow
Please note that mass balances can be performed on the entire stream, or on one
component. The mass balance on the entire stream is governed by stream flow rates.

2.5.1 Component balance

Component balance has to do with the constituents of a stream. If, for example, the feed
and outlet contain water and salt, mass balance can therefore be in terms of salt solution
(stream) or water (component) or salt (component). If a stream has three components, A,

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B and C, and the stream mass flow rate is P kg/h, then the fractional compositions are as
follows:
𝐴𝐴 𝐵𝐵 𝐶𝐶
𝑥𝑥𝐴𝐴 = , 𝑥𝑥𝐵𝐵 = , 𝑥𝑥𝐶𝐶 = , 𝑥𝑥𝐴𝐴 + 𝑥𝑥𝐵𝐵 + 𝑥𝑥𝐶𝐶 = 1
𝑃𝑃 𝑃𝑃 𝑃𝑃
Example 2.1: Mass balance
Streams A and B flow into a mixing tank at the rate of 500 kg/h and 900 kg/h, respectively.
Assuming steady state and one outflow stream, calculate the outflow stream mass flow
rate.
Solution:
This can be solved in three steps, as follows:
Step 1 – Draw the system and its boundaries (Figure 1.5).

Boundary

A=500 kg/h ?
MixingTank
Mixing tank

B=900 kg/h

Figure 2.8
Drawing of boundaries

Step 2: Write the mass balance equation.

There are no chemical reactions involved, so:
Accumulation = inflow - outflow, but Accumulation = 0
Why is accumulation zero???
Step 3: Perform the calculation as per the diagram drawn and mass balance equation.
0 = 500 + 900 − out
out = 1400kg / h

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NB: Ensure that you always include units after each calculation on your answer!
Example 2.2: Product composition
A continuous mixer mixes NaOH and water to produce an aqueous solution of NaOH.
Determine the composition and flow rate of the product if the flow rate of NaOH is 900
kg/h and the ratio of the flow rate of water to the product is 0.7.
Solution:
This can be solved using a four step process:
Step 1: Draw the system diagram using information from the question (Figure 1.6).

P=?,
Water=?
NaOH=?
NaOH=900 kg/h MixingTank
tank
Mixing
NaOH=100%

Water=?
Water=100%

Figure 2.9
(System diagram)

Step 2: Start writing down all information given

Let NaOH stream be N, Water be W and Product be P
Step 3: Write the mass balance equation and component balance equation
Assuming steady state
N +W = P
We are also told that W/P=0.7 therefore W=0.7P
Substituting for W in the equation
N + (0.7 P ) = P
N = 0.3P ⇒ 900 / 0.3 = P = 3000kg / h
W = 3000 − 900 = 2100kg / h

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Remember: Water component in N=0, NaOH component in N=1 (100%), NaOH
component in W=0, water component in W=1 (100%)
Step 4: Do a component balance
For NaOH
1( N ) + 0(W ) = x NaOH P
900 = x NaOH × 3000
x NaOH = 900 / 3000 = 0.3 ⇒ x H 2O = 1 − 0.3 = 0.7
Therefore, Product is made up of 30% NaOH and 70% water.
This concludes steady-state mass balance basics. Let us now attempt mass balance for
reactive systems.

2.6 MASS BALANCE FOR REACTIVE SYSTEMS

We will now go through the processes involved in material balances for single
component reactive processes. The mass balance equation can be written as
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 = 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 − 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 + 𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔 − 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
or
molesAt 2 − molesAt1 = mole sin − molesout + molesgenerated − molesconsumed
𝑡𝑡1 𝑎𝑎𝑎𝑎𝑎𝑎 𝑡𝑡2 𝑎𝑎𝑎𝑎𝑎𝑎 𝑡𝑡𝑡𝑡𝑡𝑡 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
It is easier to work with moles and not mass, but moles can be converted to mass. The
term extent of reaction is very useful in solving material balances in a chemical reaction.
Extent of reaction denotes how many moles are reacting. It is given by:

ξ is the extent of reaction, 𝑛𝑛𝑖𝑖 𝑖𝑖𝑖𝑖 𝑡𝑡ℎ𝑒𝑒 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑜𝑜𝑜𝑜 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑖𝑖𝑖𝑖 𝑓𝑓𝑓𝑓𝑓𝑓 𝑖𝑖 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
𝑛𝑛𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖 𝑡𝑡ℎ𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑜𝑜𝑜𝑜 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑖𝑖 , 𝑣𝑣𝑖𝑖 𝑖𝑖𝑠𝑠 𝑡𝑡ℎ𝑒𝑒 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠ℎ𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑜𝑜𝑜𝑜 𝑖𝑖
𝑣𝑣𝑖𝑖 𝑓𝑓𝑓𝑓𝑓𝑓 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑖𝑖𝑖𝑖 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝, 𝑓𝑓𝑓𝑓𝑓𝑓 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛
Example 2.3: Extent of reaction for the Haber process
Calculate the extent of reaction for the Haber process reaction given the following
information:

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 Reactants Product

N2=100 g ?

H2= 50 g ?

NH3= 5 g 90 g

Solution:
The Haber process balanced equation is:
N 2 + 3H 2 → 2 NH 3
Looking at ammonia
5
ni o = = 0.29 gmole
17
90
ni = = 5.29 gmoles
17
Using the equation for extent of reaction
ni − ni o
ξ=
vi
5.29 − 0.29
= = 2.5molesreacting
2
Example 2.4: Mass balance of the composition of the exit gases
From example 2.3, do a mass balance of the composition of the exit gases.
Solution:
For N2
100
nio = = 3.57 gmoles
28
ni = nio + vi ξ
= 3.57 + (−1 × 2.5) = 1.07 gmoles

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For H2
50
nio = = 25 gmoles
2
ni = nio + vi ξ
= 25 + (−3 × 2.5) = 17.5 gmoles
The mass balance is given by multiplying number of moles by molecular mass.
H 2 (mass ) = 17.5 × 2 = 35 g
N 2 (mass ) = 1.07 × 28 = 29.96 g

Reactants Product

N2=100 g 29.96 g

H2= 50 g 35 g

NH3= 5 g 90 g

Example 2.5: Mass balance for the chlorination of methane

Perform a mass balance for the chlorination of methane. The mole % composition of the
feed is 40% methane, 50% chlorine and 10% nitrogen. The conversion rate for the
limiting reagent is 67%.
Solution:
CH 4 + Cl 2 → CH 3 Cl + HCl
The stoichiometric ratio for methane: chlorine is 1:1. Let there be 100 moles of feed, then
there is 40 moles CH4, 50 moles Cl2 and 10 moles N2. The feed ratio of methane: chlorine
is 4:5, therefore methane is the limiting reagent.
At 67% conversion then of methane,
For methane:
nio = 40moles
ni = 0.33 × 40 = 13.2mols
ni − ni o 13.2 − 40
ξ= = = 26.8molesreacting
vi −1

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For chlorine:
nio = 50moles
ni = nio + vi ξ
= 50 + (−1 × 26.8) = 23.2moles
For Products
moles(CH 3 Cl ) = nio + vi ξ = 0 + (1 × 26.8) = 26.8moles
moles( HCl ) = nio + vi ξ = 0 + (1 × 26.8) = 26.8moles
moles( N 2 ) = nio + vi ξ = 10 + (0 × 26.8) = 10moles
Mass balance

Product Moles (gmoles) Mass (g)

CH4 13.2 =13.2×16=211.2

Cl2 23.2 =23.2×71=1647.2

CH3Cl 26.8 =26.8×50.5=1353.4

HCl 26.8 =26.8×36.5=978.2

N2 10 =28×10=280

Example 2.6: Mass balance for nitration of benzene

Nitrobenzene is produced commercially by nitrating benzene with a mixed acid
containing 39% nitric acid, 53% sulphuric acid and 8% water. A charge is made up of
655 kg benzene and 1360 kg of mixed acid. The reaction is 95% complete. Calculate the
quantity of nitrobenzene produced and quantity and quality of spent acid. The reaction
is:
C 6 H 6 + HNO3 → C 6 H 5 NO2 + H 2 O
Solution:
Amount of benzene fed= 655 / 78 = 8.40kmol ,
1360 × 39 = 8.42kmol
Amount of nitric acid= 100 × 63

Benzene is limiting reagent, therefore amount reacted= 8.4 × 0.95 = 7.98kmol

Amount of nitrobenzene formed =7.98 kmol.
Excess nitric acid = 8.42 − 7.98 = 0.44kmol

28 REE2601/1
Water formed=7.98 kmol*18=143.64 kg.
1360 × 8 + 143.64 = 252.44
Total amount of water= 100 kg.
Composition of spent acid=27.72 kg unreacted nitric acid, 252.44 kg water, inter
sulphuric acid=720.80.
Now we will change focus to steady-state energy balances.

2.7 STEADY STATE ENERGY BALANCES

Energy conservation law states that the energy of the system and the surroundings can
neither be destroyed nor created (Himmelblau and Riggs, 2004). The need to reduce
energy consumption for particular reactions is important because one must do so in order
to be able to perform an energy balance. This, then, emphasises why energy balance is
important.
The total energy of a system has three components:
• Kinetic energy: Energy due to the translational motion of the system as a whole
relative to some frame of reference (usually the earth's surface) or to rotation of the
system about some axis. In this text, we will deal only with translational kinetic
energy.
• Potential energy: Energy due to the position of the system in a potential field (such as
a gravitational or electromagnetic field). In this text, we will deal only with
gravitational potential energy.
• Internal energy: All energy possessed by a system, other than kinetic and potential
energy, such as energy due to the motion of molecules relative to the centre of mass
of the system, to the rotational and vibrational motion and the electromagnetic
interactions of the molecules, and to the motion and interactions of the atomic and
subatomic constituents of the molecules.
Suppose a process system is closed, meaning that no mass is transferred across its
boundaries while the process is taking place. Energy may be transferred between such a
system and its surroundings in two ways:
1. As heat, or energy that flows as a result of temperature difference between a system
and its surroundings. The direction of flow is always from a higher temperature to a
lower one. Heat is defined as positive when it is transferred to the system from the
surroundings and negative when it is transferred from the system to the surroundings.
2. As work, or energy that flows in response to any driving force other than a temperature
difference, such as a force, a torque, or a voltage. For example, if a gas in a cylinder
expands and moves a piston against a restraining force, the gas does work on the
piston (energy is transferred as work from the gas to its surroundings, which include
the piston). In this text, work is defined as positive when it is done by the system on

29 REE2601/1
 the surroundings and negative when the surroundings do work on the system. The
energy balance for a closed system is:
∆ (U + E k + E p ) = Q − W

where U is internal energy, 𝐸𝐸𝑘𝑘 is kinetic energy, 𝐸𝐸𝑝𝑝 is the potential energy,
W is work, Q is the heat energy
When applying this equation to a given process, you should be aware of the following
points:
The internal energy of a system depends almost entirely on the chemical composition,
state of aggregation (solid, liquid, or gas), and temperature of the system materials. It is
independent of pressure for ideal gases and nearly independent of pressure for liquids
and solids. If no temperature changes, phase changes, or chemical reactions occur in a
closed system and if pressure changes are less than a few atmospheres, then ΔU = 0.
1. If a system is not accelerating, then ΔEk = 0. If a system is not rising or falling, then
ΔEp = 0.
2. If a system and its surroundings are at the same temperature or the system is perfectly
insulated, then ΔQ = 0. The process is then termed adiabatic.
3. Work done on or by a closed system is accomplished by movement of the system
boundary against a resisting force or the passage of an electrical current or radiation
across the system boundary. Examples of the first type of work are motion of a piston
or rotation of a shaft that projects through the system boundary. If there are no moving
parts or electrical currents or radiation at the system boundary, then ∆W = 0.
Example 2.7: Energy balance
A gas is contained in a cylinder fitted with a movable piston. The initial gas temperature
is 25 °C. The cylinder is placed in boiling water with the piston held in a fixed position.
Heat in the amount of 10 000 J is transferred to the gas, which equilibrates at 100 °C (and
a higher pressure). The piston is then released, and the gas does 100 J of work in moving
the piston to its new equilibrium position. The final gas temperature is l00 °C. Calculate
the change in internal energy for the initial rise in temperature for the gas. Calculate the
additional energy supplied to the gas as it moves the piston whilst expanding.
Solution:
This can be solved in three steps:
Step 1: Draw the initial increase in temperature without the piston moving, as shown in
Figure 2.10.

30 REE2601/1
 25 ºC 100 ºC

Figure 2.10
Initial state changes

Step 2: Write the energy balance equation and substitute given values
Δ(U+Ek+Ep)=Q-W
But ΔEk, W and ΔEp are zero. Why????
Remember the system is stationary, there is no vertical displacement and there is no
moving boundary.
Therefore
ΔU=Q
But Q = 10 000 J therefore ΔU= 10 kJ
Step 3
The second change is the movement of the piston as shown in Figure 2.7.

100 ºC 100 ºC

Figure 2.11
Movement of piston

31 REE2601/1
Δ(U+Ek+Ep)=Q-W
ΔU = 0 because it depends on temperature and there is no temperature change
ΔEp = 0 considered negligible
ΔEk = 0 system stationery at initial and final states
0 = Q - W, but W = 100 J
Therefore Q = 100 J
We now shift our focus to unsteady state balances starting with unsteady state material
balances.

2.8 CLOSED SYSTEM CHEMICAL REACTION ENERGY BALANCE

If a chemical reaction takes place in a closed system at constant volume then the energy
can be written in terms of internal energy as follows
 
∆U r = ∆H r − RT  ∑ vi − ∑ vi 
 gaseousproduct gaseousreac tan t 
Example 2.8: Energy balance in a closed system
Perform an energy balance for the following reaction taking place in a closed system at
constant volume given that the heat of reaction at 298 K is -420 kJ/mol.
19
C 6 H 14 (l ) + O2 ( g ) → 6CO2 ( g ) + 7 H 2 O( g )
2
Solution:
 
∆U r = ∆H r − RT  ∑ vi − ∑ vi 
 gaseousproduct gaseousreac tan t 
  19 
∆U r = −420 − 8.314 × 298 ×  6 + 7 − 
  2 
= −420 − 8.671
= −428.671kJ / mol

2.9 UNSTEADY STATE MATERIAL BALANCES

In real life, most processes are unsteady state and hence it is important for a chemical
engineer to understand what is happening and know how to control it. Unsteady state is
when the state and quantity of molecules change with time. The mass balance equation
can be written as:
Accumulation = Flow in – Flow out + Generation – Consumption

32 REE2601/1
We need to write the above equation in mathematical symbols for a very small time
interval Δt. Let the accumulation be positive in the direction in which time is positive,
that is, as time increases from t to t + Δt. Then, using the component mass balance as an
example, the accumulation will be the mass of A in the system at time t + Δt minus the
mass of A in the system at time t. The accumulation of A is then
Accumulation = ρ AV t + ∆t − ρ AV t

where ρA is the density of component of A and V is the volume of the system.

Example 2.9: Unsteady state balance
A tank holds 100 litres of a water-salt solution in which 4.0 kg of salt is dissolved. Water
flows into the tank at the rate of 5 litres/min and salt solution overflows at the same rate.
If the mixing in the tank is adequate to keep the concentration of salt in the tank uniform
at all times, how much salt is in the tank at the end of 50 mins? Assume that the density
of the salt solution is essentially the same as that of water.
Solution:
This can be solved in two steps:
Step 1: Draw the system

100 L, 4 kg salt 5 L/min salt

5 L/min solution

water, 100%
pure water

Step 2: Salt balance is given by:

Since there is no chemical reaction, generation and consumption are zero. Therefore:
Accumulation = Flow in – Flow out
5L x
x t + ∆t − x t = 0 − ∆t
min 100 L
Dividing by Δt we get
x t + ∆t − x t
= −0.05 x
∆t

33 REE2601/1
As Δt approaches 0, the equation becomes
dx
= −0.05 x , so at t = 0 x = 4.0 and at t = 50 mins, x is unknown
dt
X 50
dx
∫4 x = −0.05 ∫0 dt
X
ln = −0.05 × 50
4
X
ln = −2.5
4
X
ln
e = e − 2.5
4

X
= 0.082
4
X = 0.33kg
When there is a reactive mass balance, not all chemical reactions go to completion, but
they reach a state of equilibrium. Let us now look at chemical equilibrium.
Example 2.10: Unsteady state mass balance
A tank holds 75 000 litres of water and 60 000 kg of sugar. Pure water flows into the tank
at 20 000 L/h and the sugar solution flows out at 15 000 L/h. What is the weight of sugar
in the tank after 3 hours.
Solution:
Let y be the total mixture in the tank:
𝑑𝑑𝑑𝑑
= 20000 − 15000 = 5000
𝑑𝑑𝑑𝑑
dy
= 5000
dt
y t

75000
∫ dy = 5000 ∫ dt
0

y − 75000 = 5000t
y = 75000 + 5000t
Material Balance
Let x be the concentration of sugar in tank at time t, at t=0
60000
𝑥𝑥 = = 0.8 𝑘𝑘𝑘𝑘/𝐿𝐿
75000
Total amount of sugar I the tank is given by 𝑥𝑥𝑥𝑥 𝑘𝑘𝑘𝑘

34 REE2601/1
 𝑑𝑑𝑑𝑑𝑑𝑑
Rate of accumulation of sugar then is 𝑑𝑑𝑑𝑑
= 0 − 15000𝑥𝑥
dx dy
y +x = −15000 x
dt dt
dx
75000 + 5000t + x(5000) = −15000 x
dt
dx
75000 + 5000t = −20000 x
dt
dx − 20000 x
=
dt 75000 + 5000t
dx − 20000 x − 4x
= =
dt 5000(15 + t ) (15 + t )
X 3
dx −4
∫0.8 x = −∫0 15 + t dt
ln x − ln 0.8 = 4[ln 15 − ln 18]
x 15
ln = 4 ln = −0.729286
0.8 18
− 0.729286
x=e × 0.8 = 0.386
After three hours, the sugar in the tank is yx=
yx = (75000 + 5000 × 3)0.386
= 34740kg

2.10 SUMMARY
In this learning unit, you have been taught how to do basic mass and energy balances for
steady state systems. You have also learnt how to do a mass balance for an unsteady state
system. Remember, mass and energy cannot be created or destroyed, but simply
transferred. It is now time to test yourself to see if you have mastered the concepts in this
section. Work out the problems before looking at their solutions.

SELF-ASSESSMENT PROBLEMS
2.1 A continuous mixer mixes sugar and water to produce a syrup solution. Determine
the composition and flow rate of the product, if the flow rate of sugar is 900 kg/h
and the flow rate of the water is 80% of the product. (4500 kg/h, 0.2 sugar)
2.2 A slurry of sewage sludge is to be dried in an oven continuously. The slurry contains
60% sludge and 40% water. If the dried sludge is to contain 1% moisture determine
the flow rates of the dried sludge and evaporated water if the feed rate is 1000 kg/h.
(606.1 kg/h dry sludge rate, water rate =393.9 kg/h)

35 REE2601/1
2.3 A gas is contained in a cylinder fitted with a movable piston. The initial gas
temperature is 25 °C. The cylinder is placed in boiling water with the piston held
in a fixed position. Heat in the amount of 4 kcal is transferred to the gas, which
equilibrates at 100 °C (and a higher pressure). The piston is then released, and the
gas does 100 J of work in moving the piston to its new equilibrium position. The
final gas temperature is l00 °C. (ΔU= 16735 kJ, Q=100 J)
2.4 Balance the equation H 2 SO4 + NaOH → Na 2 SO4 + H 2 O
2.5 A tank holds 20 L of a water-salt solution in which 5 kg of salt is dissolved. Water
runs into the tank at the rate of 2 L/min and salt solution overflows at the same rate.
If the mixing in the tank is adequate to keep the concentration of salt in the tank
uniform at all times, how much salt is in the tank at the end of 60 min? Assume that
the density of the salt solution is essentially the same as that of water. (0.25 kg).
2.6 Write the equilibrium constant for the for the combustion of NH3
4 NH 3 + 5O2 → 4 NO + 6 H 2 O
2.7 At a certain temperature, 4 Mols of PCl5 was placed in a 2 L flask. At equilibrium
3.60 moles of PCl5 remained. Calculate the equilibrium constant for the reaction
PCl 5 ⇔ PCl 3 + Cl 2
(0.011)
2.8 Using thermodynamic tables calculate ΔG° for the reaction
CH 4 ( g ) + O2 ( g ) → CO 2( g ) + 2 H 2 O(l )
(-818 kJ)
2.9 Perform a mass balance and calculate the composition of the process of the
combustion of ammonia. Calculate the composition of the stack gases, given that
the reactants supplied in a mole ratio of 2:3. The feed is 100 moles.
4 NH 3 + 5O2 → 4 NO + 6 H 2 O

36 REE2601/1
SOLUTIONS TO SELF-ASSESSMENT PROBLEMS
2.1 Draw the system diagram.

P=?, Water
=?
Sugar=?
Sugar=900 kg/h MixingTank
tank
Mixing
NaOH=100%

Water=?
Water=100%

Let S=Sugar, W= Water and P=Product

S + W = P ⇒ W = 0.8 P
S + 0.8 P = P
900 = 0.2 P
P = 4500kg / h
Perform a sugar balance
S + 0(W ) = x s P
900 = x s × 4500
900
xs = = 0.2
4500
Therefore, the product has 20% sugar and 80% water.

37 REE2601/1
2.2 Draw the system diagram

Water?
P=?,
Water=0.01
Sludge=0.99

Feed=1000 kg/h Mixing Tank

Evaporator
Sludge=0.6

Do a mass balance
F =W + P
1000 = W + P
Do a component balance say for water
0.4 × 1000 = W + 0.01P
Solve the two equations simultaneously
400 = (1000 − P ) + 0.01P
− 600 = −0.99 P
P = 606kg / h
W = 394kg / h
2.3 This problem is very similar to example 1.3. Follow the steps there.
NB: convert kcal to Joules
2.4 Balance the equation H 2 SO4 + NaOH → Na 2 SO4 + H 2 O
Let H2SO4 be A, NaOH be B, Na2SO4 be C and H2O be D
H ⇒ 2 A + B = 2D
S ⇒ A=C
O ⇒ 4 A + B = 4C + D
Na ⇒ B = 2C
letA = 1, C = 1, B = 2, D = 2
H 2 SO4 + 2 NaOH → Na 2 SO4 + 2 H 2 O

38 REE2601/1
2.5 Draw the system diagram

20 L, 5 kg salt 2 L/min water

2 L/min
water, 100%
pure water

A salt balance is given by:

Accumulation=in-out
2L x
x t + ∆t − x t = 0 − ∆t
min 20 L
Dividing by Δt we get
x t + ∆t − x t
= −0.1x as Δt approaches 0 the equation becomes
∆t
dx
= −0.05 x , so at t=0 x=5.0, at t=60, x is unknown
dt
X 60
dx
∫5 x = −0,05 ∫0 dt
X
ln = −0.05 × 60
5
X
ln = −3
5
X
ln
e = e −3
5

X
= 0.0498
5
X = 0.249kg
2.6

K=
[NO ] [H 2 O ]
4 6

[NH 3 ]4 [O2 ]5

39 REE2601/1
2.7 Input the equilibrium concentrations.

Beginning Equilibrium

PCl5 4/2= 2 mol/L 3.6/2= 1.8 mol/L

PCl3 0 0.4/2=0.2 mol/L

Cl2 0 0.4/2=0.2 mol/L

0.2 × 0.2
K= = 0.011mol / L
1.8

2.8 Using thermodynamic tables calculate ΔG° for the reaction

ΔGº

H2O (l) -237.18

CO2 (g) -394.38

CH4 (g) -50.84

O2 0

∆G° = (2 × −237.18) + (− 394.38) − [− 50.84 + 0] = 818kJ / mol

NB: Only when ΔGº(rxn) is required do you use the formula ∆G = ∆H − T∆S
2.9 Perform a mass balance and calculate the composition of the process of the
combustion of ammonia. Calculate the composition of the stack gases, given that
the reactants supplied equimolar. The total feed rate 1s 100 moles.
4 NH 3 + 5O2 → 4 NO + 6 H 2 O
Solution:
2
At 100 mole of feed, then there is 5 × 100 = 40𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 NH3 and 60 moles O2. The
stoichiometric ratio of ammonia to water is 4: 5 but the feed rate is 2:3 therefore ammonia
is the limiting reagent.

40 REE2601/1
 O2
ni = nio + vi ζ
= 60 + (−5 × 10)
= 10moles
NO
ni = nio + vi ζ
= 0 + (4 × 10)
= 40moles
H 2O
ni = nio + vi ζ
= 0 + (5 × 10)
50moles

REFERENCES
Fogler, HS. (2011). Essentials of Chemical Reaction Engineering. Prentice Hall
International series in the physical and chemical engineering sciences. Pearson.
International Edition, ISBN: 978-0-13-211936-8.
Himmelblau, DM & Riggs, JB. (2004). Basic Principles and Calculations in Chemical
Engineering, 7th ed Prentice Hall International.

41 REE2601/1
42 REE2601/1
 Study unit 1 3

BASICS OF REACTION KINETICS

LEARNING OUTCOMES
On completion of this learning unit, you should be able to:
• Perform order of reactions calculations and represent these graphically.
• Use experimental data to calculate reaction order.
• Perform reaction rates calculations.
• Perform yield, selectivity and conversion calculations.
• Perform activation energy calculations.
• Perform first order constants calculations for reversible reactions (multiple reactions).
This learning unit is based on Chapters 1, 2 and 3 of your prescribed book. You can also
follow the links below to better understand the concepts:
• Reaction kinetics: (9:09) https://youtu.be/wYqQCojggyM
• Activation energy (17:20) https://youtu.be/16fFjAcxJSc
• Order of reaction: (10:38) https://youtu.be/6Ng8ayarWHw
These links are also available on the module site under Additional Resources.

3.1 INTRODUCTION
Reaction kinetics deals with the study of the rates at which chemical reactions occur (how
fast the reaction occurs) and the variables that affect these rates. Chemical reactions and
rates of reaction will be treated from an engineering point of view – in terms of physically
measurable quantities. All chemical reactions take place at a finite rate depending on the
conditions, the most important of which are the concentration of reactants and products,
temperature, and presence of a catalyst, promoter, or inhibitor. The first section on
reaction rates covers a broad spectrum of related topics. The definition of the rate of
reaction and the order of reaction will be presented. The variables affecting the rate will
also be discussed. The equations for many different situations will also be developed.

43 REE2601/1
3.2 REACTION ORDER
This is a number that relates the rate of reaction with the concentration of the reacting
substances (Fogler, 2011). The order gives information on how the reactants are depleted
(are being used up) in a particular reaction. It can be found only through experiments and
NOT by simply looking at the chemical reaction equation.
Consider a general equation
A→B
The rate of reaction involves the change in the amount of one of the components
participating in the reaction per unit time. The rate is proportional to the concentration of
the reactants and thus can be written as:
Rateα [A] ⇒ Rate = k [A]
n n

where k is the rate constant and 𝑛𝑛 is called the reaction order with respect to the
concentration of A, [A] means concentration of A and can also be written as 𝐶𝐶𝐴𝐴 .
Therefore, the order of a reaction with respect to a reactant is the power to which the
concentration of the reactant is raised in the rate law, and the overall order of reaction is
the sum of the powers of the concentrations of products involved in the rate law.
When: 𝑛𝑛 = 0, the reaction is zero order. This means that the reaction rate is not
dependent on the concentration of the particular species.
𝑛𝑛 = 1, the reaction is first order. The reaction rate is directly proportional to
the concentration of the species involved.
𝑛𝑛 = 2, it is called second order. For a single species reaction it means the rate
is proportional to the square of the concentration of the species.
𝑛𝑛 = 𝑛𝑛, the reaction is nth order. For a single species reaction it means the rate
is proportional to the nth power of the concentration of the species.
Activity 3.1: Reaction order

Answer the following question under Discussions on the module website on myUnisa
(Forum 4: learning unit 3 activities, Activity 3.1):

The rate equation of a particular reaction is written as follows

r = k [A] [B ]
2 2

What is the order with respect to A and B and the overall order of the reaction?

44 REE2601/1
Feedback

The order with respect to A is 2.

The order with respect to B is 2.

The overall order is 4. You simply add the powers (2+2).

Let us now look at experimental determination of reaction orders

You will find feedback on this activity on the module site on myUnisa under Forum 4:
learning unit 3 activities, feedback on activity 3.1.

Activity 3.2: Reaction order

The rate equation of a particular reaction is written as follows

r = k [A]

What is the order with respect to A?

Feedback

The order is 1.

Activity 3.3: Reaction order

The rate equation of a particular reaction is written as follows

r=k

What is the order of reaction?

Feedback

The order is 0

3.2.1 Determination of reaction order from experimental data

As mentioned in the previous section, reaction orders can be determined experimentally.

One will need the means to measure the concentration of different molecules at different
times. The example below illustrates how this is done.

45 REE2601/1
Example 3.1: Rate of reaction order from experimental data
Consider the following example:
Determine the rate order for the reaction between CO and NO2 using the experimental
information in Table 2.1.
Table 3.1
Reaction between CO and NO2

Experiment CO (initial mol/L) NO2 (initial mol/L) Initial Rate (mol/L.h)

1 5×10-4 0.35×10-4 3.4×10-8

2 5×10-4 0.7×10-4 6.8×10-8

3 5×10-4 0.175×10-4 1.7×10-8

4 1.02×10-3 0.350×10-4 6.8×10-8

5 1.53×10-3 0.350×10-4 10.2×10-8

Solution:
First consider experiments 1 and 2, [CO] is constant whilst [NO2] is doubled, leading to
doubling of the initial rate of reaction also
𝑛𝑛
𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟2 [𝑁𝑁𝑁𝑁2 ]2
=� �
𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟1 [𝑁𝑁𝑁𝑁2 ]1
𝑛𝑛
6.8𝑥𝑥10−8 0.7𝑥𝑥10−4
=� �
3.4𝑥𝑥10−8 0.35𝑥𝑥10−4
2 = 2𝑛𝑛
Therefore
𝑛𝑛 = 1
Hence the rate is first order with respect to [NO2].
Now consider experiments 1 and 4, they show that [NO2] is constant whilst [CO] is
doubled, also leading to a doubling of the rate. Hence, performing the same procedure
above, the rate is also first order with respect to [CO]. Therefore the rate equation
becomes
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = 𝑘𝑘[𝐶𝐶𝐶𝐶][𝑁𝑁𝑂𝑂2 ]

46 REE2601/1
This means that the order of reaction is first order with respect to NO2 and CO and that
the overall order of reaction is second order (1+1). Let us now look at graphical
determination of order of reactions.
Example 3.2: Order of reaction
The reaction between rate of the following reaction is shown in Table 3.2. Determine the
order of reaction. A + B → P .

A (mol/L) B (mol/L) Rate (mol/s)

Experiment 1 1 1 1

Experiment 2 1 2 2

Experiment 3 2 1 8

Solution:
With respect to A let us consider experiments 1 and 3:
2 8
( ) n = ⇒ 2 n = 23 ⇒ n = 3
1 1
With respect to B, let us consider experiments 1 and 2:
2 2
( ) n = ⇒ 2 n = 21 ⇒ n = 1
1 1
The overall order is 3+1 = 4

3.2.2 Determination of reaction order using the graphical method

We are going to look at graphical determination of reaction order, but first will introduce
a few basic concepts.
As stated earlier, rate of reaction is the measure of change in a reactant or appearance of
a product over a period of time. Remember that the reactant is being consumed during
the reaction whilst the product is being formed. Let us consider the reaction below:
A→ B
The rate of reaction with regards to the reactant A is given as
dC A
− rA =
dt
where rA is the reaction rate and CA is the concentration of A (as mentioned above).

47 REE2601/1
This applies for constant volume reaction. We will use constant volume reaction to better
understand the concepts. Remember also
rA = k [ A]
n

where n is the order of reaction and [A] is the concentration of A.

Combining the two equations and bearing in mind that the A is being consumed, and is
hence depleting, we end up having the following equation for the reaction rate at constant
volume:
dC A
= −rA = −k [A]
n

dt

We will now consider different orders of reaction and see how they look graphically.

3.2.3 Zero order

For zero order it means n=0. Then

dC A
= −k [A] = −k
0

dt

In order to find the relationship we then integrate between the following limits
t=0 to t=t and CA=CAO and CA, CAO is the initial concentration of A when t = 0.
dC A
= −k
dt
CA t

∫ dCA = −k ∫ dt ⇒
C AO 0

C A − C AO = −kt
C A = C AO − kt
Therefore, a plot of concentration of A, CA vs. time is a straight line with the rate constant
as the slope and initial concentration of A, CAO as the intercept.
Example 3.3: Zero order reaction graphically represented
Determine if the following reaction, the decomposition of hydrogen peroxide, is zero
order

48 REE2601/1
 Time (h) Concentration (mol/L)

0 10

1 8

2 6

3 4

4 2

5 0.1

Solution:
The first thing to do is to plot a graph of concentration vs. time and, if the plot is a straight
line, then the reaction is zero order.

12

10
Concentration (mol/L)

6 y = -1.9857x + 9.981
R² = 0.9999
4

0
0 1 2 3 4 5 6
Time (h)

The graph is a straight line; therefore the reaction is zero order. The rate constant is 1.99
mol/L.h and initial concentration is 9.98 (~10) mol/L.
NB: Remember how to determine units from your Chemical Engineering Fundamentals
I module

3.2.4 First order

For first order reaction r = k CA, where A is the reactant. Therefore, the rate is written as:

49 REE2601/1
 dC A
= −kC A
dt
dC A
= −kdt
CA
CA t
1
∫C C A dC A = −k ∫0 dt
AO

ln C A − ln C AO = −kt
ln C A = ln C AO − kt
A plot on a graph of 𝑙𝑙𝑙𝑙𝐶𝐶𝐴𝐴 𝑣𝑣𝑣𝑣 𝑡𝑡 should thus be a straight line where the slope is the reaction
constant and the intercept is ln CAO. The plot of ln (CA/CAO) vs. t should also be a straight
line.
Example 3.4: First order reaction graphically represented
From the experimental data, determine graphically the order of reaction with respect to
B.

Time (hr) CB (mol/L)

0 0.150

1 0.099

2 0.071

3 0.047

4 0.030

5 0.022

Solution:
First calculate the natural logarithm of [B]

Time (hr) CB (mol/L) ln CB

0 0.150 -1.90

1 0.099 -2.31

2 0.071 -2.65

50 REE2601/1
 3 0.047 -3.05

4 0.030 -3.50

5 0.022 -3.82

Then plot ln CB vs. t

The plot is linear; hence the rate equation is r = kCB.

The value of the rate constant is taken from the equation -0.3884 = -k
Therefore k = 0.3884/h
The rate equation is 𝑟𝑟 = 0.3884𝐶𝐶𝐵𝐵
Initial concentration: ln 𝐶𝐶𝐵𝐵𝐵𝐵 = −1.9017 and 𝐶𝐶𝐵𝐵𝐵𝐵 = 𝑒𝑒 −1.9017 = 0.149 (~0.15) mol/L

3.2.5 Second order

The general form of a second order rate expression is r = -kCA2. The mathematical
conversion of this equation into a linear form yields:

51 REE2601/1
 dC A 2
= −kC A
dt
dC A
2
= −kdt
CA
CA t
1
∫
C AO CA
2
dC A = −k ∫ dt
0

1 1
− + = −kt
C A C AO
1 1
− = −kt −
CA C AO
1 1
= kt +
CA C AO

1
Therefore, a plot of 𝐶𝐶 𝑣𝑣𝑣𝑣 𝑡𝑡 vs time should be a straight line with the rate constant as the
𝐴𝐴
gradient and inverse of CAO as the intercept.
Example 3.5: Second order reaction graphically represented
Determine if the following experimental conditions describe a second order equation
with respect to CA

Time (mins) CA (mol/L)

0 0.1300

4 0.0872

8 0.0650

12 0.0535

16 0.0453

20 0.0370

30 0.0281

52 REE2601/1
Solution:
First calculate 1/ CA

Time (mins) CA 1/ CA

0 0.1300 7.7

4 0.0872 11.5

8 0.0650 15.4

12 0.0535 18.7

16 0.0453 22.1

20 0.0370 27.0

30 0.0281 35.6

Then plot 1/ CA vs t

40
35 y = 0.9329x + 7.7189
R² = 0.9985
30
25
1/CA

20
15
10
5
0
0 5 10 15 20 25 30 35
t

The experimental data fits second order. The rate equation

2
r = 0.9329C A
Rate constant k = 0.9329 L⋅min/mol

53 REE2601/1
 1
Initial concentration: 𝐶𝐶 = 7.7189 and 𝐶𝐶𝐴𝐴𝐴𝐴 = 0.1296(~0.130) mol/L
𝐴𝐴𝐴𝐴

3.2.6 Nth order equation

If the rate equation is given by r = -k CAn via mathematical manipulation, the linear
equation becomes
dC A n
= −kC A
dt
dC A
n
= −kdt
CA
CA t
1
∫
C AO CA
n
dC A = −k ∫ dt
0

1 1 1
− ( n −1 − n −1
) = −kt
n +1 CA C AO
1 1 1 1
n −1
= kt +
n +1 CA n + 1 C AO n −1

A plot of 1 𝑣𝑣𝑣𝑣 𝑡𝑡
𝐶𝐶𝐴𝐴𝑛𝑛−1
should be a straight line with gradient as reaction constant and intercept as initial
concentration after some mathematical manipulations.

3.3 ARRHENIUS EQUATION: THE INFLUENCE OF TEMPERATURE ON

REACTION RATE

3.3.1 Single reaction

This equation shows the dependence of the rate constant on temperature, i.e. it is used
to show the effect of temperature on the reaction itself. The rate constant is temperature
dependent and is given by:
− EA
k = Ae RT

 −RTEA 
ln k = ln Ae 

 
−EA

ln k = ln A + ln e RT

E
ln k = ln A − A
RT

54 REE2601/1
where EA is the activation energy (kJ/mol), A is the pre-exponential term (units for k are
the same as units for A), R is the gas constant (=8.314 J/mol⋅K) and T is temperature in
Kelvins.
Example 3.6: Calculation of activation energy.
Calculate the activation energy of a reaction given the following experimental data.

k (s−1) ×10−8 4.53 59.3 197 613

T (◦C) 90 110 120 130

Solution:
Determine the natural logarithm of the rate constant and the inverse of temperature in
kelvins.

k (s−1) ×10−8 4.53 59.3 197 613

T (◦C) 90 110 120 130
ln k −16.910 −14.338 −13.137 −12.002
T (K) 363 383 393 403
1/T × 10−3 2.754 2.610 2.544 2.480

Now let us plot a graph of ln k vs 1/T (K)

1/T
0
0.00245
-2 0.0025 0.00255 0.0026 0.00265 0.0027 0.00275 0.0028

-4
-6
-8
ln k

-10 y = -17945x + 32.494

-12
-14
-16
-18

The activation energy is determined from the slope:

EA
− = −17945
R
E A = 8.314 × 17945
= 149194.73 J / mo1.K = 149kJ / mol − K

55 REE2601/1
For the pre-exponential term (A):
ln 𝐴𝐴 = 32.494
𝐴𝐴 = 𝑒𝑒 32.494 = 1.29𝑥𝑥1014 s-1
Therefore, for this reaction, the rate constant is given by:
𝑘𝑘 = 1.29𝑥𝑥1014 𝑒𝑒 −17945⁄𝑇𝑇 s-1
For 90 ≤ T ≤ 130oC
Example 3.7: Calculation of rate constant
The rate constant of a particular reaction at 273K is 7.78×10-7s-1 and at 338 K, the rate
constant is 4.87×10-3s-1. Calculate the activation energy and the pre-exponential constant
of the reaction.
Solution:
 EA 
ln k 273 =  ln A − 
 RT273 
 E 
ln k 338 =  ln A − A 
 RT338 
 E   EA 
ln k 338 − ln k 273 =  ln A − A  −  ln A − 
 RT338   RT273 
k 338 EA E E  1 1 
ln = − A = A  − 
k 273 RT273 RT338 R  T273 T338 
k 338  1 1 
ln × R = E A  − 
k 273  T273 T338 
k 338 4.87 × 10 −3
R ln 8.314 ln
k 273 7.78 × 10 −7 103kJmol −1
EA = ==
 1 1   1 1 
 −   − 
 T273 T338   273 338 

Taking the first equation:

103.2
ln 7.78𝑥𝑥10−7 = ln 𝐴𝐴 − 8.314𝑥𝑥10−3 (273)

ln 𝐴𝐴 = −14.07 + 45.46 = 31.39

56 REE2601/1
Therefore:
𝐴𝐴 = 𝑒𝑒 31.39 = 4.30𝑥𝑥1013 s-1
Therefore, the rate constant is:
𝑘𝑘 = 4.30𝑥𝑥1013 𝑒𝑒 −12338.7⁄𝑇𝑇 s-1
Example 3.8: Calculation of activation energy
The activation energy for the reaction
C2 H 4 + H 2 → C2 H 6
is 180.75 kJ/mol. Determine the effect on the reaction rate constant if the reaction
temperature is increased from 120 °C to 500 °C.
Solution:
EA EA
ln k120 = ln A − ln k 500 = ln A −
RT120 RT500

 E 
ln k 500 =  ln A − A 
 RT500 
 E 
ln k 200 =  ln A − A 
 RT120 
 E   EA 
ln k 500 − ln k 200 =  ln A − A  −  ln A − 
 RT500   RT200 
k 500 EA EA E  1 1 
ln = − = A  − 
k 200 RT500 RT200 R  T200 T500 
k 500 E A  1 1 
ln =  − 
k 200 R  T200 T500 
k 180750   1 1 
ln 500 =   − 
k 200 8.314   393 773  
k 500
ln = 27.19
k 200
k 500
= e 27.19 = 6.43 × 1011
k 200
Therefore, when the temperature changes from 120 to 500 oC, the reaction rate at 500 oC
increases by 6.43x1011 times that at 120 oC i.e. k500 = 6.43 x 1011 * k120.

57 REE2601/1
3.4 EFFECT OF PRESSURE ON REACTION RATES
You have been introduced to the ideal gas equation. If we make P the subject of the
formula, we have:
PV = nRT
n
P = RT
V
𝑛𝑛
But 𝑉𝑉 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 (𝑚𝑚𝑚𝑚𝑚𝑚/𝐿𝐿), 𝑅𝑅𝑅𝑅 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑎𝑎𝑎𝑎 𝑡𝑡ℎ𝑒𝑒 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡. Since:
𝑃𝑃
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 ∝ 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑡𝑡𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 ∝
𝑅𝑅𝑅𝑅
Therefore reaction rate becomes directly proportional to pressure, i.e., an increase in
pressure increases concentration increasing reaction rate.
Example 3.9: Effect of pressure on reaction rates
The decomposition of ethylene oxide at 690 K is monitored by measuring the total gas
pressure as a function of time. The data obtained are t =10 min, Ptot = 18.6 kPa 20 min,
20.22kPa; 40 min, 23.02 kPa; 60 min, 25.22 kPa; 100 min, 28.81 kPa; 200 min, 31.82
kPa ∞, 33.32 kPa. What is the order of the reaction:
(CH3)2O(g) → CH4(g) + CO(g)
Solution:
First define P = total pressure, Po = initial pressure of (CH3)2O, Pa = pressure of
(CH3)2O, Pb = Pc = pressure of CH4 = pressure of CO, and x = number of moles of
(CH3)2O consumed at a given time in the reaction. At "infinite" time, when you can
assume all the (CH3)2O has reacted, P = Pb + Pc = 2Pb = 33.32 kPa. C2H4O has
reacted, P = Pb + Pc = 2Pb = 249.88 torr. Therefore, Pb = 16.66 kPa. From the
stoichiometry of the reaction, this means the initial pressure Po = 16.66 kPa.
Now find an expression for Pa in terms of the initial pressure and the total pressure.
Pa = Po – x,
P = Pa + Pb + Pc = Pa + 2x
Plug in the expression for Pa to get
P = Po – x + 2x = Po + x. Solve this for x = P – Po.
Then plug this back into the expression for Pa to get
Pa = Po – (P – Po) = 2Po –P

58 REE2601/1
Plot the following table

Time 10 20 40 60 100 200 ∞

P 18.6 20.22 23.02 25.22 28.81 31.82 33.32

Pa 14.72 13.1 10.3 8.1 4.51 1.5 0

ln Pa 2.689207 2.572612 2.332144 2.091864 1.506297 0.405465

1/pa 0.067935 0.076336 0.097087 0.123457 0.221729 0.666667

Then plot ln pa vs t and also 1/pa vs t

2.5

2
ln Pa

1.5

0.5 y = -0.0121x + 2.8036

R² = 0.9977
0
0 50 100 150 200 250
Time

59 REE2601/1
 0.7
y = 0.0032x - 0.0192
0.6 R² = 0.944
0.5

0.4
1/Pa

0.3

0.2

0.1

0
0 50 100 150 200 250
Time (mins)

By inspection, the plot of ln(Pa) vs time is linear, and the plot of 1/Pa vs time is not.
Therefore, the reaction is first order in (CH3)2O.
Rate = k[(CH3)2O]
To find the rate constant k, use the first order integrated rate law
C A = C AO e − kt
You can use pressures instead of concentration since they are directly proportional with
the fixed volume and temperature assumed.
At 100 min:
C A = C AO e − kt
4.51 = 16.66 × e −100 k
4.51
= e −100 k
16.66
4.51
ln = −100k
16.66
4.51
ln
k = 16.66 = 1.3 ×10 − 2 min −1
− 100

3.5 VARIABLE VOLUME

All our examples have been on the assumption of a constant volume (which is the design
of most reactors), but there may be a variation of volume, particularly for some gas phase
reactions. However, these involve complex integral equations. We will now look at some

60 REE2601/1
of the simple ones, but first we will introduce some variables. The volume can vary as
given below:
P T NT
V = VO
PO TO N T O
𝑉𝑉 𝑖𝑖𝑖𝑖 𝑡𝑡ℎ𝑒𝑒 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣, 𝑃𝑃 𝑖𝑖𝑖𝑖 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝, 𝑇𝑇 𝑖𝑖𝑖𝑖 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑎𝑎𝑎𝑎𝑎𝑎 𝑁𝑁𝑇𝑇 𝑖𝑖𝑖𝑖 𝑡𝑡ℎ𝑒𝑒 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑜𝑜𝑜𝑜 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚
𝑇𝑇ℎ𝑒𝑒 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑂𝑂 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
δ is defined as the total number of moles per moles of A reacted for an irreversible reaction
aA + bB → cC + dD
d c b
δ= + − −1
a a a
Ɛ is defined as the change in total number of moles when reaction is complete per number
of moles initially fed into the reactor
ε = y AO δ where 𝑦𝑦𝐴𝐴𝐴𝐴 is the initial mole fraction of A.
If the pressure does not change much and the reaction is isothermal, then variation in
volume can be calculated as follows:
P T NT P T
V = VO ⇒ = =1
PO TO N T O PO TO
NT N
= VO ⇒ T = (1 + εX )
NT O NT O
V = VO (1 + εX )
𝑋𝑋 is the conversion of A.
Example 3.10: Reaction with variable volume
Consider an isothermal gas reaction A → 4 R , which is with a varying volume in a batch
reactor. Pure 10 moles/L A is put into the reactor. Determine the time needed for 60%
conversion, given that the rate constant is 0.005 mol/L.s.
Solution:
This activity will be used for cases where the reaction order is zero, first, second and third
order – all of them for variable volume.
The rate of disappearance A for a batch reactor is given as follows:

61 REE2601/1
3.5.1 For zero order reaction rate with variable volume

For a zero order reaction with variable volume, the following equation applies

N A N AO (1 − X ) N
CA = = ⇒ AO = C AO
V VO (1 + εX ) VO
1− X
C A = C AO
1 + εX
4
δ= − 1 = 3 ε = 1× 3 = 3
1
dC A 0
= −kC A
dt
CA t

∫ dCA = −k ∫ dt ⇒
C AO 0

C A − C AO = −kt
1− X
C A = C AO − kt ⇒ C A = C AO
1 + εX
1− X
C AO = C AO − kt
1 + εX
1 − 0.6
100 = 100 − 0.005t
1 + (3 × 0.6 )
14.29 − 100 = −0.005t
85.71
t= = 19985.71s = 5.6h
0.005
Using CA0 = 10, t = 1714.29 s = 28.6 mins

62 REE2601/1
3.5.2 First Order with variable volume

We will use the same problem as introduced in Example 3.10. The equation to be used
is the variation of
dN A
= −VkC A ⇒ dN A = − N AO dX
dt
− N AO dX = −VkC A
dX 1− X
N AO = kVO (1 + εX )C AO
dt 1 + εX
N AO dX
= kC AO (1 − X )
VO dt
dX
C AO = kC AO (1 − X )
dt
1
dX = kdt
1− X
X 0.6 t
1
∫
X0
1− X
dX = −k ∫ dt
0

− ln(1 − X ) = kt
− ln(1 − 0.6) = kt
0.92
t= = 183s = 3 min
0.005

63 REE2601/1
3.5.3 Second order with variable volume

We will use the same problem as introduced in Example 3.10.

dN A 2
= −VkC A ⇒ dN A = − N AO dX
dt
2
− N AO dX = −VkC A
2
dX 2 1− X 
N AO = kVO (1 + εX )C AO  
dt  1 + εX 
N AO dX 2 (1 − X )
2
= kC AO
VO dt 1 + εX
dX 2 1− X
C AO = kC AO
dt 1 + εX
1 + εX
dX = C AO kdt
(1 − X ) 2
X 0.6 t
1 + εX
∫
X0 (1 − X ) 2
dX = C AO k ∫ dt ⇒ ε = 3
0

 4  0.6
= [3 ln(1 − X )]0
0.6
+ = C AO 0.005t
1 − X  0
4 4
3 ln 0.4 + −
t= 0.4 1 = 65s
0.005 × 10
NB PLEASE REFER TO YOUR MATHEMATICS MODULE FOR INTERGRATION BY
PARTS AND BY SUBSTITUTION

3.5.4 Third order with variable volume

We will use the same problem as introduced in Example 3.10.

64 REE2601/1
When considering zero order, first order, second order and third order; the time required
to reach 60% reduces with an increase in reaction order, i.e. it takes less time to reach
60% when the reaction is third order than when it is zero order.

3.6 REVERSIBLE REACTIONS

Let us consider the simple reversible reaction given below:
nA ⇔ mB
where the forward reaction constant is kf and the reverse is kb
Concentration at initial point (t = 0) is A = a, B = 0; at time, t = t it is A = a-x, B = x
Therefore, rate of forward reaction = kf(a-x)n and Rate of reverse reaction = kb(x)m
dx
And net rate of reaction = = k f (a − x) n − k b ( x) m
dt
At equilibrium, net rate of reaction = 0, and x = xe
k f (a − xe ) n = k b ( xe ) m
Therefore m
k b = k f (a − xe ) n / xe

65 REE2601/1
Substituting for k2 in the original equation, we have:
dx m
= k f (a − x) n − k f (a − xe ) n x m / xe
dt
If both forward and reverse reactions are first order then:
dx k f a
= ( xe − x)
dt xe
x
1
t
kfa
∫0 ( xe − x) ∫0 xe dt
dx =

kfa
− ln ( xe − x ) = t
xe
xe x
kf = ln e
at xe − x

Example 3.11: Reversible reaction

Find the values of kf and kb for the given reaction, with the given information:
A⇔ B
if [A]0 = 0.30 mol dm–3 [A]e = 0.172 mol dm–3
[A]10 = 0.285 and [A]100 = 0.21 mol dm-3
Solution:
Let us consider first for t = 10:
xe xe 0.172 0.172
kf = ln = ln = 0.0052 s −1
at xe − x 0.3 × 10 0.172 − 0.015
kf a − xe k
= = 0.744 ∴ k 2 = f = 0.00703
kb xe 0.744

Now for t = 100:

𝑥𝑥 𝑥𝑥𝑒𝑒 0.172 0.172
𝑘𝑘𝑓𝑓 = 𝑎𝑎𝑎𝑎𝑒𝑒 ln 𝑥𝑥 = 0.3×100 ln 0.172−0.09 = 0.0042 s-1
𝑒𝑒 −𝑥𝑥
𝑘𝑘𝑓𝑓 𝑎𝑎−𝑥𝑥𝑒𝑒 0.3−0.172
= = = 0.744
𝑘𝑘𝑏𝑏 𝑥𝑥𝑒𝑒 0.172

Therefore:
𝑓𝑓 𝑘𝑘
𝑘𝑘𝑏𝑏 = 0.744 = 0.0057 s-1

66 REE2601/1
3.7 MULTIPLE REACTIONS
When a reactant in the reaction undergoes reactions in more than one pathway, giving
rise to different products, the reactions are termed as parallel or side reactions
A → B (1)
A → C (2)
If both reaction 1 and 2 are first order then
dC A
= − k1C A − k 2 C A
dt
dC A
= dt
− (k1 + k 2 )C A
CA t
dC A
∫ (k1 + k 2 )C A = ∫0 dt
C AO

1 C
ln A = t
− (k1 + k 2 ) C AO
Example 3.12: Multiple reactions
Two parallel reaction for A are first order with respect to A. The rate constant for reaction
1 is 0.4 s-1 and that for reaction 2 is 0.004 s-1. How long does it take for 70% conversion
of A into the products if 100 moles of A are fed into the reactor?
A → B (1)
A → C (2)
Solution:
1 C
ln A = t
− (k1 + k 2 ) C AO
1
ln 0.3 = t
− (0.4 + 0.004)
t = 2.98s

3.7.1 Reactions in series

To better understand the algorithm involved in these calculations we will use an

illustrative example.
Example 3.13: Series reaction
Consider the series reaction A → D → U , where A, D, and U represent the reactant, the
desirable product, and the undesirable product, respectively. The rate equation terms for

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the reactions are CAO = 2.0 mol/L, and CDO = CU0 = 0.0 with k1 = 0.2/h and k2= 0.4/h.
Calculate the maximum concentration of D that one can achieve in a batch reactor.
Solution:
The rate equations are as follows:
dC A
= − k1C A
dt
dC D
= k1 C A − k 2 C D
dt
dCU
= k 2C D
dt
The concentration is calculated as follows:
C A = C AO e − k1t
 k1  − k1t
C D = C AO  e − e − k2t
 k 2 − k1 
CU = C AO − C A − C D
dC D
= k1 C A − k 2 C D = 0
dt
k 2 C D = k1 C A
k2
𝑑𝑑𝐶𝐶𝐶𝐶 k1 k 2 − k1
Maximum D occurs when = 0, then C DMAX = C AO
𝑑𝑑𝑑𝑑 k2
0.5
0.2
= 2.0 ×
0.4
= 1.4mol / L

3.8 SUMMARY
In this learning unit, you have been taught how to calculate reaction order, activation
energy and reaction constants for various situations. Remember, before you plug in a
formula, determine whether the volume or pressure is variable or not. Usually this will
be stated in the question. Work out the problems before looking at their solutions.

SELF-ASSESSMENT PROBLEMS
3.1 A zero order reaction is 50% complete in 20 min. How much time will it take to
complete 90%? (36 mins).

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3.2 A first order reaction is 25% complete in 50 min. What would the concentration be
at the end of another 50 min if the initial concentration of the reactant is 5.0 × 103
mol dm–3? (2.81×103 mol/dm3)
3.3 A reactant reacts 30% in 30 min. If the reaction follows second order kinetics, find
the rate constant and remaining concentration of reactant after 60 min. Let initial
concentration be 100 mol. (1.42×10-4)(63.21%)
3.4 Acetaldehyde can be formed by oxidizing ethane, but a side reaction can occur
resulting in the production of carbon dioxide, as shown in the equations below:
C 2 H 6 + O2 → CH 3 CHO + H 2 0

7
C 2 H 6 + O2 + 2CO2 + 3H 2 0
2
If 65% (by mole) of the ethane feed stream forms acetaldehyde, 15% forms CO2 and
the remainder is unreacted, calculate:
a) Yield (81.25%)
b) Selectivity (4.33)
c) Conversion (80%)
d) Degree of conversion (65%)
3.5 Determine the reaction order using the following data:

Experiment Initial [NO] mol/L Initial [O2] mol/L Initial rate (mol/L.s

1 0.02 0.01 0.028

2 0.02 0.02 0.057

3 0.02 0.04 0.114

4 0.04 0.02 0.227

5 0.01 0.02 0.014

Answer r=k[NO]2[O2]

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3.6 The data for the decomposition of N2O5 is given below. Determine the order of
reaction.

[N2O5] t (min)

2.08 3.07

1.67 8.77

1.36 14.45

0.72 31.28

Answer first order

3.7 The reaction for the decomposition of NO2 has a rate constant of 2.7×10-2Mols-1 at
227 °C and of 2.4×10-1M-1s-1 at 277 °C. Calculate the activation energy. (Answer
9,99 ×104 J/mol).
3.8 Consider an isothermal gas reaction with a varying volume and in a batch reactor.
Pure 5 moles/L A is put into the reactor. Determine the time needed for 70%
conversion, given that the rate constant 0.05 mol/L.s. The reaction is given below
along with its zero order with respect to A (Answer=1.65 mins)
A → 2P

SOLUTIONS TO PROBLEMS
3.1 A zero order reaction is 50% complete in 20 min. How much time will it take to
complete 90%?
Solution – let initial concentration be 1 M/L.
C A = −kt + C AO
C AO − C A C − CA
k= ⇒ t = AO
t k
1 − 0.5 1 − 0.1
k= = 0.025mol / L. min ⇒ t = = 36 min
20 0.025
3.2 A first order reaction is 25% complete in 50 min. What would the concentration be
at the end of another 50 min if the initial concentration of the reactant is 5.0 × 103
mol dm3?

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 Solution: For a first order reaction, the following applies:
ln C A = ln C AO − kt
1 C 1 5 × 10 3
k = ln AO = ln = 0.00575
t CA 50 0.75 × 5 × 10 3
After another 50 minutes t=100 mins
ln C A = ln C AO − kt
CA
ln = −kt ⇒ C A = C AO e − kt = 5 × 10 3 e −0.00575×100 = 2.81 × 10 3 moldm −3
C AO
3.3 A reactant reacts 30% in 30 min. If the reaction follows second order kinetics, find
the rate constant and remaining concentration of reactant after 60 min. Let initial
concentration be 100 mol.
1 1 1 1 1  1  1 1 
− = kt ⇒ k =  −  =  −  = 1.42 × 10
−4

C A C AO t  C A C AO  30  70 100 
1 1
CA = = = 63.21%
1 −4 1
kt + 1.42 × 10 × 60 +
C AO 100

3.4 Acetaldehyde can be formed by oxidizing ethane, but a side reaction can occur
resulting in the production of carbon dioxide as shown in the equations below.
C 2 H 6 + O2 → CH 3 CHO + H 2 0

7
C 2 H 6 + O2 + 2CO2 + 3H 2 0
2
If 65% (by mole) of the ethane feed stream forms acetaldehyde, 15% forms CO2 and
the remainder is unreacted, calculate:
e) Yield
f) Selectivity
g) Conversion
h) Degree of conversion
Solution:
Assume 100 mol of ethane
a) Yield= 65 /(65 + 15) = 81.25%
b) Selectivity= 65 / 15 = 4.33
c) Conversion= (65 + 15) / 100 = 80%

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 d) Degree of conversion=65%
3.5 Determine the reaction order using the following data

Experiment Initial [NO] Initial [O2] Initial rate (mol/L.s

1 0.02 0.01 0.028

2 0.02 0.02 0.057

3 0.02 0.04 0.114

4 0.04 0.02 0.227

5 0.01 0.02 0.014

Answer: see example 2.1

3.6 The data for the decomposition of N2O5 is given below. Determine the order of
reaction.

[N2O5] T min

2.08 3.07

1.67 8.77

1.36 14.45

0.72 31.28

Solution:

[N2O5] T min Ln [N2O5]

2.08 3.07 0.732368

1.67 8.77 0.512824

1.36 14.45 0.307485

0.72 31.28 -0.3285

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Graph
0.8

0.6

0.4
Ln [N2O5]

0.2

0
0 5 10 15 20 25 30 35
-0.2
y = -0.0375x + 0.8463
R² = 0.9999
-0.4
time

Answer: First order

3.7 The reaction for the decomposition of NO2 has a rate constant of 2.7×10-2M-1s-1 at
227 °C and of 2.4×10-1M-1s-1 at 277 °C. Calculate the activation energy. (Answer
9,99 ×104 J/mol).
Answer

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 dC A 0
= −kC A
dt
CA t

∫ dCA = −k ∫ dt ⇒
C AO 0

C A − C AO = − kt
1− X
C A = C AO − kt ⇒ C A = C AO
1 + εX
1− X
C AO = C AO − kt
1 + εX
1 − 0.7
5 = 5 − 0.05t
1 + (1 × 0.6 )
0.9375 −`5 = −0.05t
4.0625
t= = 99.0625s = 1.65 min
0.05

REFERENCES
Fogler, HS. (2011). Essentials of Chemical Reaction Engineering. Prentice Hall
International Series in the Physical and Chemical Engineering Sciences. Pearson.
International Edition, ISBN: 978-0-13-211936-8.

74 REE2601/1
 Study unit 1 4

IDEAL REACTORS

LEARNING OUTCOMES
On completion of this learning unit, you should be able to:
• Describe and compare batch, plug flow and continuous stirred tank reactors.
• Calculate reaction time for batch reactors.
• Calculate residence time for plug flow and continuous stirred tank reactors.
• Calculate volume needed for specified conversion for plug flow and continuous
stirred tank reactors.
• Calculate activation energy.
This learning unit is based on Chapters 1, 4 and 5 of your prescribed book. You can also
follow the links below to better understand some of the concepts.
• Ideal reactors (6:26): https://youtu.be/XyLUVSfHL0Y
• Isothermal reactor design (19:17): https://youtu.be/t6um4T20sv0
These links are also available on the module site under Additional Resources.

4.1 INTRODUCTION
In this learning unit, we will introduce three types of reactors. These are batch reactors,
plug flow reactors and continuous stirred tank reactors. We will look at how to perform
various calculations on each reactor.

4.2 TYPES OF REACTORS

There are three types of ideal reactors that we will look at. These are batch reactors, plug
flow reactors and continuous stirred tank reactors.

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4.2.1 Batch reactors

1. A batch reactor is a discontinuous reactor (Fogler, 2011). It is essentially a stirred tank

that is filled with the reactants before the reaction starts and emptied after it has run
to completion (or to the extent of reaction that is needed). An example is the dilution
of syrup with water in bucket. One of the disadvantages of this type of reactor is that,
for large production quantities, the reaction has to be done multiple times in series.
This requires the emptying and refilling of the reactor, often accompanied by cooling
it off first and heating it up with the new batch (reactants). This large number of steps
takes time and attention, and thereby reduces the productivity of the reactor. On the
other hand, this type of reactor has the advantage that, if multiple similar but different
reactions are needed, the same equipment can often be used, and the additional effort
is comparatively small. Figure 4.1 is an illustration of a batch reactor.
2.

Figure 4.1
Batch Reactor

4.2.2 Plug flow reactors (PFR)

A PFR is a continuous reactor. It is a tubular in form, meaning that it consists of a long

cylindrical pipe through which the reaction mixture is flows steadily. Typically, the
assumption is made that the temperature, pressure, and composition do not vary radially
within the pipe, creating a “plug” that flows through the reactor. As the reactants flow
through the PFR, they are consumed, creating a concentration profile along the length of
the pipe. While these reactors can have a heating or cooling duty requirement that varies
along the reactor, the reactor volume necessary to reach a particular conversion is lower
than for a CSTR, while keeping the advantages of a continuous process. Figure 4.2 shows
an illustration of a PFR:

76 REE2601/1
 Figure 4.2
Plug flow reactor

4.2.3 Continuous stirred tank reactor (CSTR)

A continuous stirred tank reactor is like a batch reactor in that it consists of a tank and a
stirrer, however with the addition of an inlet and an outlet that allow for a constant flow
into and out of the reactor. Once the reactor is started up and reaches steady-state, it is
usually assumed to have a constant volume as well as constant and homogeneous
temperature, pressure, and composition. While continuous processes do not have the
variability of batch processes, and during start-up will produce product that does not meet
specifications, they have a number of advantages that make them attractive to use. For
one, continuous reactors do not have to be cooled off, emptied, cleaned, refilled, and
then heated to operating temperature. For another, if a reaction produces heat and the
reactor needs to be cooled, the cooling duty for a CSTR is constant, and can be tuned as
needed. For a batch reactor, the cooling duty needed would vary with the reaction rate,
and insufficient cooling could lead to a runaway reaction. Additionally, the product from
one reactor is often used in subsequent steps for other reactions. If multiple steps are
carried out in series in batch reactors, and each step takes a different amount of time, the
intermediate products need to be stored in buffer tanks. These tanks can be eliminated or
greatly reduced in size if each reactor produces a steady stream that can be fed to the
next reactor. If a process has to be carried out in batches, several reactors are often used
in parallel, shifted in time to give a continuous stream from the group of reactors. Figure
4.3 shows an illustration of a CSTR.

77 REE2601/1
 Figure 4.3
CSTR

4.3 ISOTHERMAL REACTOR DESIGN

We need to understand the mole balance for reactors before we design them. Conversion
is the number of moles of a limiting reactant that have reacted per mole of reactant added
at the beginning of reaction. It is defined in terms of the equation below:
MolesofAreacted
XA =
MolesofAfed
The derivation of the below equations can be found in detail in Chapter 1 of the
prescribed book.
The mole balance is given by:
N A = N A0 − N A0 X = N A0 (1 − X )
where NA0 is the moles of A fed at the start, NA is the moles of A at time t, X is the
conversion.
It then follows that the equation for concentration can also be written as:
C A = C A0 − C A0 X = C A0 (1 − X )
where CA0 is the concentration of A fed, CA is the concentration of A at time t, and X is
the conversion.
For continuous reactors, the term “residence time” is often used. It is given the symbol, τ

78 REE2601/1
Residence time is the average hold-up time spent in the reactor by reactants.

4.3.1 Design calculations for batch reactors

Because there is no spatial variation (perfect mixing) for batch reactors the mole balance
can be written as:
dN A
− = (−rA )V
dt
where rA is the rate of disappearance of A for a batch reactor, but also since NA0 is constant
dN A dX dX
= 0 − N AO = − N AO
dt dt dt
Therefore this reduces to:
dX
N A0 = −rAV
dt
And assuming a constant volume:
N AO dX
= −rA
V dt
dX
C AO = −rA
dt
Let us look at different cases of reaction rates (rA).
Irreversible first order reactions
For an irreversible first order reaction A → B where volume is constant and the rate law
is given by:
− rA = kC A
The design equation reduces to:
dX
C A0 = kC A ⇒ C A = C AO (1 − X )
dt
dX
C A0 = kC AO ((1 − X ))
dt
dX
= k (1 − X )
dt
1
dX = kdt
(1 − X )
1
( )dX = kdt
1− X

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Integrating the above from t = 0 to t = t and X = 0 to X = x
1
( ) dX = kdt
1− X
X t
1
∫0 1 − X dX = k ∫0 dt
ln (1 − X ) = kt
1  1 
t = ln 
k 1− X 

Irreversible second order reactions

For an irreversible second order reaction A → B where volume is constant and the rate
law is given by:
2
− rA = kC A
The design equation reduces to:
dX
= kC A ⇒ C A = C AO (1 − X )
2
C A0
dt
C A0
dX
dt
= kC AO (1 − X )
2
(
2
)
dX
= kC AO (1 − X )
2

dt
1
dX = kC AO dt
(1 − X )2
Integrating the above from t = 0 to t = t and X = 0 to X = x
1
dX = kC AO dt
(1 − X )2
X t
1
∫ (1 − X )
0
2
dX =kC AO ∫ dt
0

X
= kC AO t
1− X
1 X
t=
kC AO 1 − X
Example 4.1: Calculation of reaction time for a BR
Calculate the time required to achieve 90% conversion for a constant volume batch
reactor if the value of k is 10-4s-1 and CA0 is 10 mol/L for both first and second order
reactions.

80 REE2601/1
Solution:
From the batch design equation for first order we get:
1  1 
t= ln 
k 1− X 
1 1
= −4
ln
1 × 10 1 − 0.9
= 23025.85s = 6.4h
From the batch design equation for second order we get:
1 X
t=
kC AO 1 − X
1 0.9
= ×
0.0001 × 10 1 − 0.9
= 9000 s = 2.5h

The time required is less if it is second order reaction.

Example 4.2: Determination of half life
The half-life of a reactant is the time required for its concentration to decrease to one-half
of its initial value. The reaction of the hydration of ethylene oxide (A) to ethylene glycol
is given by the following reaction equation:
C 2 H 4 O + H 2 O → C 2 H 6 O2
The rate of reaction of dilute aqueous solution is proportional to the concentration of A,
with the proportionality constant being 4.11×10-5s-1 at 20°C. Determine the half-life of
(A) at if the reaction is carried out in a batch reactor.
Solution:
For half-life X=0.5, taking the design equation for first order, we get:
1  1 
t= ln 
k 1− X 
1  1 
= −5
ln 
4.11 × 10  1 − 0.5 
= 16864.89 s = 4.68h

81 REE2601/1
4.3.2 Design calculations for CSTR

The variation in volume for a CSTR can be written as:

FA 0 − FA
V = ⇒ FA = FA 0 − FA 0 X
− rA
FA 0 − FA 0 + FA 0 X FA 0 X
V = =
− rA − rA
FAO is the molar flow rate of reactant A when it is fed into the reactor, FA is the molar flow
rate at which A leaves the reactor. The equation calculates the volume required to achieve
a specified conversion.
Residence time is the time necessary to process one volume of reactor fluid at the
entrance conditions. The mean residence time provides a measure of how long the fluid
is in the reactor – which controls the conversion. The larger the residence time, the greater
V
the conversion. It is given by τ = Where v0 is the initial volumetric flow rate. FAO can
υ0
also be calculated from the volumetric flow as given below
FAO = ν O C AO
Irreversible first order reactions
For an irreversible first order reaction A → B where the rate law is given by
− rA = kC A
The design equation is
FA 0 X
V = ⇒ −rA = kC A
− rA
FA 0 X
= ⇒ C A = C AO (1 − X )
kC A
FA 0 X F
= ⇒ AO = ν O
kC AO (1 − X ) C AO
νOX
V =
k (1 − X )
V X
= =τ
ν O k (1 − X )
Irreversible second order reactions
For an irreversible second order reaction A → B where the rate law is given by
2
− rA = kC A

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The design equation is
FA 0 X 2
V = ⇒ −rA = kC A
− rA
FA 0 X
= 2
⇒ C A = C AO (1 − X )
kC A
FA 0 X FAO
= ⇒ =νO
kC AO (1 − X ) C AO
2 2

νOX
V =
kC AO (1 − X )
2

V X
= =τ
νO kC AO (1 − X )
2

Example 4.3: CSTR calculations for first order reactions

A first order irreversible reaction, A → B with k = 0.01 s−1 is required to reach 30%
conversion. Assuming constant volume, what CSTR reactor volume and residence time
would be required given a volumetric flow rate of 10−3 m3s−1?
Solution:
V X
=
νO k (1 − X )
νOX 1 × 10 −3 × 0.3
V = = = 0.043m 3
k (1 − X ) 0.01 × (1 − 0.3)
V 0.043
τ= = = 42.8s
ν O 1 × 10 −3
Therefore, CSTR volume required is 43 Litres and the residence time is 42.8 seconds.
Example 4.4: CSTR calculations for 2nd Order Reactions
A second order irreversible reaction, A → B with k = 0.01 M-1s−1 is required to reach
30% conversion. Assuming constant volume, what CSTR reactor volume and residence
time would be required given a volumetric flow rate of 10−3 m3s−1 given that pure 10 M
of A are fed?

83 REE2601/1
Solution:
νOX
V =
kC AO (1 − X )
2

1 × 10 −3 × 0.3
=
0.01 × 10 × (1 − 0.3)
2

= 0.006m 3
V 0.006
τ= = = 6s
νO 1 × 10 −3

4.3.3 Design calculations for plug flow reactor (PFR)

We will start with the mole balance for PFR and then calculate the mean residence time:
dFA dX X dX
− = − rA = FA0 = −rA ⇒ V = FA0 ∫
dV dV 0 −r
A

Irreversible first order reactions

For an irreversible first order reaction A → B where the rate law is given by
− rA = kC A
The mean residence time for PFR is calculated as follows for first order reactions:

X dX
V = FA 0 ∫ ⇒ − rA = kC A ⇒ C A = C A0 (1 − X ) ⇒ F A0 = C AOυ 0
0 − rA
FA 0 X dX ν 1
V =
kC A0 ∫ 0 1− X
= − 0 ln(1 − X ) ∴τ = − ln(1 − X )
k k

Irreversible Second Order Reactions

For an irreversible second order reaction A → B where the rate law is given by:
2
− rA = kC A
The design equation is:

84 REE2601/1
Example 4.5: PFR calculations for first order reactions
A first order irreversible reaction, A → B , what PFR reactor volume and residence time
would be required given a volumetric flow rate of 10-3 m3s-1?
Solution:

FA 0 X dX ν 0.001
V =
kC A0 ∫
0 1− X
= − 0 ln(1 − X ) = −
k 0.01
ln(0.7) = 0.036m 3

V 0.036
τ= = = 36 s
vo 0.001

Example 4.6: PFR calculations for second order reactions

A second order irreversible reaction, A → B with k = 0.01 M-1s−1 is required to reach
30% conversion. Assuming constant volume, what PFR reactor volume and residence
time would be required given a volumetric flow rate of 10−3 m3s−1 given that pure 10 M
of A are fed?
Solution:

υ0 1
V =
C A0 1− X
0.001 1
= × = 0.00014m 3
10 1 − 0.3
V 0.00014
τ= = = 0.14 s
υ0 0.001

4.4 SUMMARY
We have covered most of the characteristic equations associated with the three ideal
reactors. What is left is to practise how to tackle the questions. Remember, it is better to
know the characteristic equation by heart and then be able to integrate it, depending on
the obtaining conditions given in each question.

SELF-ASSESSMENT PROBLEMS
4.1 A first order irreversible elementary reaction
A→B
with a reaction velocity constant of 0.376 (min)-1 takes place in a constant volume
batch reactor. Calculate the time required to achieve a conversion of 80%.

85 REE2601/1
4.2 Consider the elementary irreversible reaction between benzoquinone (A) and
cyclopentadiene (B)
A + B → Pr oduct
Calculate the reactor size requirements for one CSTR. Assume isothermal operation
at 25 oC where the reaction rate constant is equal to 9.92 m3/(kgmol ks). Reactant
concentrations in the feed are each equal to 0.08 kgmol/m3, and the liquid feed rate
is equal to 0.278 m3 /ks. The desired degree of conversion is 87.5%.
4.3 It is proposed to decompose pure diethyl per­ oxide (A) at 225 ºC in a bench-scale
tubular reactor. The organic will be entering the reactor at a flow rate of 12.1 L/s. It
is desired to decompose 99.995% of the diethyl peroxide. The following data are
available: kA = 38.3 s-1 at 225 °C.
4.4 For a liquid-phase reaction of the type A → P an experimental CSTR of volume 1.5
L is used to measure the rate of reaction at a given temperature. If the steady- state
feed rate is 0.015 L/s and the feed concentration is 0.8 mol/L and A is 15%
converted on flow through the reactor, what is the value of the -rA?
4.5 The reaction A → P occurs in CSTR with 90% conversion and is second order with
respect to A. If k = 0.5 L/mol.min and CAO = 2 moles/litre, and ν = 4 L/m, what
residence time and the reactor volume that will be required?
4.6 The reaction occurs in PFR with 90% conversion and is first order with respect to
A. If k = 0.5 L/min and CAO = 2 moles/litre, and ν = 4 L/m, what residence time
and the reactor volume that will be required?
4.7 The reaction occurs in PFR with 90% conversion and is second order with respect
to A. If k = 0.5 L/L.min and CAO = 2 moles/litre, and ν = 4 L/m, what residence
time and the reactor volume that will be required?

SOLUTIONS TO PROBLEMS
4.1 A first order irreversible elementary reaction
A→B
with a reaction velocity constant of 0.376 (min)-1 takes place in a constant volume
batch reactor. Calculate the time required to achieve a conversion of 80%.
Solution:
1 1 1
t r = 1 ln = ln = 4.28 min
k 1 − X 0.376 1 − 0.8
4.2 Consider the elementary irreversible reaction between benzoquinone (A) and
cyclopentadiene (B)
A + B → Pr oduct

86 REE2601/1
 Calculate the reactor size requirements for one CSTR. Assume isothermal operation
at 25 ºC where the reaction rate constant is equal to 9.92 m3/(kgmol· ks). Reactant
concentrations in the feed are each equal to 0.08 kgmol/m3, and the liquid feed rate
is equal to 0.278 m3 /ks. The desired degree of conversion is 87.5%.
Solution:
− rA = kC A C B
= k [C AO (1 − X )C BO (1 − X )] ⇒ C BO = C AO
[
= k C AO (1 − X )
2 2
]
FA 0 − FA 0 + FA 0 X FA 0 X
V = =
− rA − rA
FA 0 X
=
[
k C AO (1 − X )
2 2
] ⇒ FAO = 0.08 × 0.278 = 0.02224 gmol / s
0.02224 × 0.875
= = 19.6m 3
[
9.92 0.08 2 (1 − 0.875) 2 ]
4.3 It is proposed to decompose pure diethyl peroxide (A) at 225 °C in a bench-scale
tubular reactor. The organic will be entering the reactor at a flow rate of 12.1 L/s. It
is desired to decompose 99.995% of the diethyl peroxide. The following data are
available: kA = 38.3 (s)- 1 at 225 °C

X dX
V = FA 0 ∫ ⇒ −rA = kC A ⇒ Ca = C A0 (1 − X ) ⇒ F A0 = C AOυ 0
0 − rA
FA 0 X dX ν 12.1
V =
kC A0 ∫ 0 1− X
= − 0 ln(1 − X ) = −
k 38.3
ln(1 − 0.99995) = 3.13L

4.4 For a liquid-phase reaction of the type an experimental CSTR of volume 1.5 L is
used to measure the rate of reaction at a given temperature. If the steady- state feed
rate is 0.015 L/s and the feed concentration is 0.8 mol/L and A is 15% converted on
flow through the reactor, what is the value of the -rA?
4.5 The reaction occurs in CSTR with 90% conversion and is second order with respect
to A. If k = 0.5 L/mol.min and CAO = 2 moles/litre, and ν = 4 L/min, what residence
time and the reactor volume that will be required?

87 REE2601/1
4.6 The reaction occurs in PFR with 90% conversion and is first order with respect to
A. If k = 0.5 L/min and CAO = 2 moles/litre, and ν = 4 L/m, what residence time
and the reactor volume that will be required?

4.7 The reaction occurs in PFR with 90% conversion and is second order with respect
to A. If k = 0.5 L/L.min and CAO = 2 moles/litre, and ν = 4 L/m, what residence
time and the reactor volume that will be required?

X dX
V = FA 0 ∫
0 − rA
X
dX
= FA 0 ∫ 2
⇒ C A = C AO (1 − X )
0 kC A
X
dX
= FA 0 ∫
C AO (1 − X )
2 2
0
X
FA 0 dX
=
kC AO
2 ∫ (1 − X )
0
2
⇒ FA0 = νC AO

X
νC AO dX
=
kC AO
2 ∫ (1 − X )
0
2

ν X 4 0.9
= = × = 36 L
kC AO 1 − X 2 × 0.5 1 − 0.9
V 36
τ= = = 9 min
ν 4

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REFERENCES
Fogler, HS. (2011). Essentials of Chemical Reaction Engineering. Prentice Hall
International Series in the Physical and Chemical Engineering Sciences. Pearson.
International Edition, ISBN: 978-0-13-211936-8.

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90 REE2601/1
 Study unit 1 5

COMPARISON AND COMBINATION OF REACTORS

LEARNING OUTCOMES
On completion of this learning unit, you should be able to:
• Calculate and compare the reaction times and residence times for batch, plug flow
and continuous stirred tank reactors.
• Calculate and compare volume needed for specified conversion for CSTR and PFR.
• Calculate the effect of reactor sequencing.
This learning unit is based on Chapters 2, 4, 5 and 7 of your prescribed book. You can
use the following links to better understand the concepts presented in this unit:
• Reactor comparison (7:59): https://youtu.be/b3Ejaip9wMQ
• Levenspiel plots (3:16): https://youtu.be/g820W4DuhdA
These links are also available on the module site under Additional Resources.

5.1 INTRODUCTION
Sequencing of reactors is an important practice in chemical engineering. In this learning
unit we will therefore look at the effect of reactor sequencing with regards to yield.

5.2 COMPARISON BETWEEN BATCH REACTOR (BR), CONTINUOUSLY

STIRRED TANK REACTOR (CSTR) AND PLUG FLOW REACTOR (PFR).
Table 5.1 shows a summarised comparison of the reactors.

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 TABLE 5.1
Comparison of advantages (A) and disadvantages (D) of BR, CSTR and PFR reactors

BR CSTR PFR

Reactor size for similar conversion A D A

Simplicity and cost A A D

Continuous operation D A A

Ability to handle large throughputs D A A

Instrumentation A D D

Flexibility A D D

5.3 COMPARISON OF A BATCH REACTOR AND PLUG FLOW REACTOR

Table 5.2 shows the calculation of reaction time and residence time for a batch reactor
and plug flow reactor respectively.
Table 5.2
Calculation of reaction and residence time for BR and PFR

Batch reactor Plug Flow Reactor

dX X dX
C A0 = −rA V = FA 0 ∫ ⇒ F A0 = C AOυ 0
dt 0 − rA
dX X dX V
C A0 = dt V = C AOυ 0 ∫ ⇒ =τ
− rA 0 − rA νO
t
dX X dX
C A0 ∫
− rA ∫0
= dt τ = C AO ∫
0 − rA
X
dX
t = C A0 ∫
0
− rA

The comparison shows that the reaction time for a batch reactor and residence time for
PFR is identical. In effect, and since the tubular reactor is assumed to operate in plug-
flow mode, the residence time of the reacting species is simply the reaction time for the
reacting species in a batch reactor. Since there is no difference one may conclude that
the performances in terms of the conversion, X, are identical.

92 REE2601/1
Example 5.1: Residence and reaction time for PFR and BR
Consider the following:
Compare the residence time or reaction time for a PFR and a BR for a first order
irreversible reaction, A → B , given a volumetric flow rate of 10−3 m3s−1, with a rate
constant of 0.5 s-1 to achieve a 90% conversion.
Solution:

BR PFR

1  1  V 1
t= ln  = τ = − ln(1 − X )
k 1− X  νO k
1 1 1
= ln =− ln(1 − 0.9 )
0.5 1 − 0.9 0.5
= 4.6 s = 4.6 s

The time is the same, meaning that the reaction time in BR is the same as the residence
time for PFR.
5.4 COMPARISON OF A BATCH REACTOR AND CONTINUOUSLY STIRRED
TANK REACTOR
Table 5.3 shows the time comparison between a BR and a CSTR.
Table 5.3
Time comparison between BR and CSTR
BR CSTR

dX FA 0 X
C A0 = − rA V = ⇒ −rA = kC A
dt − rA
dX FA 0 X
C A0 = dt = ⇒ C A = C AO (1 − X )
− rA kC A
X t
dX FA 0 X F
C A0 ∫
kC A ∫0
= dt = ⇒ AO = ν O
0 kC AO (1 − X ) C AO
X
dX νOX
t = C A0 ∫ V =
0
kC A k (1 − X )
C A0 dXX
V X
τ= =
C A0 ∫0 1 − X
=
ν O k (1 − X )
1
= ln
1− X

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The CSTR becomes extremely large with respect to volume and/or residence time when
compared to a batch reactor for high conversions for first order kinetics. This analysis can
be extended to other reaction orders.
Example 5.2: Residence and reaction time for a CSTR and BR
Compare the residence time of reaction time for a CSTR and a BR for a 1st order
irreversible reaction, A → B , given a volumetric flow rate of 10−3 m3s−1, with a rate
constant of 0.5 s-1 to achieve a 90% conversion.
Solution:
BR CSTR

1  1  V X
t= ln  τ= =
k 1− X  νO k (1 − X )
1 1 0.9
= ln =
0.5 1 − 0.9 0.5(1 − 0.9 )
= 4.6 s = 18s

The reaction time in BR is smaller than the residence time in CSTR. This means if you
want to react a conversion of 90%, use either a BR or PFR before considering a CSTR
reactor. However, other reasons will also need to be taken into account.
5.5 COMPARISON OF A PLUG FLOW REACTOR AND CONTINUOUSLY
STIRRED TANK REACTOR
Table 5.4 shows a comparison between a PFR and CSTR.
Table 5.4
Comparison between PFR and CSTR
PFR CSTR

dX X F X
V = FA 0 ∫ ⇒ − rA = kC A ⇒ C A = C A0 (1 − X ) ⇒ F A0 = C AOυ 0 V = A0 ⇒ −rA = kC A
0 −r
A − rA
F X dX ν 1 FA 0 X
V = A0 ∫ = − 0 ln(1 − X ) ∴τ = − ln(1 − X ) = ⇒ C A = C AO (1 − X )
kC A0 0 1 − X k k kC A
FA 0 X F
= ⇒ AO = ν O
kC AO (1 − X ) C AO
νOX
V =
k (1 − X )
V X
τ= =
ν O k (1 − X )

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The CSTR has certain advantages – such as near uniform temperature and concentration
because of mixing. However, for perfect mixing, the reaction occurs at a rate determined
by the concentration of the discharge (or exit) stream from the reactor. Since the rate
usually decreases with the extent of reaction (conversion), the CSTR operates in the range
between the high reaction rate corresponding to the concentration in the feed stream and
the (normally) lower rate corresponding to the concentration leaving the reactor. On the
other hand, the tubular flow reactor takes maximum advantage of the high reaction rate
corresponding to the high concentration(s) near the entrance to the reactor. The CSTR
therefore requires a larger volume than a tubular reactor to accomplish a given degree of
conversion. This statement applies to all positive reaction orders. The reaction/residence
time ratio for a zero order reaction is unity, i.e., both perform identically.

5.6 REACTORS IN SERIES

Next, we will consider several mixed chemical reactors in series.

5.6.1 CSTR in series

When CSTR are connected in series (one after the other), the feed to the first reactor is
CA0 and the effluent from the first reactor is CA1. This becomes the feed to the second
reactor, and the effluent from second reactor is CA2 which becomes the feed to the third
reactor and so on.
For a reaction A → P , which is first order, the mass balance can be written as:
C AO − C A1 = τ 1 rC A1
C A1 − C A 2 = τ 2 rC A 2
C A1, n −1 − C An = τ n rC An
The various different concentrations can then be calculated as:
C AO
C A1 =
1 + kτ 1
C A1 C AO
C A2 = =
1 + kτ 2 (1 + kτ 1 )(1 + kτ 2 )

Now, if each reactor has the same residence time and hence same volume:
τ total = ∑ nτ and
C AO
C An =
(1 + kτ n )n

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Example 5.3: CSTR in series
The reaction A → P and r = kC A occurs in equal volume CSTRs in series, each with
residence time 𝜏𝜏 with 90% overall conversion. If k = 0.5 min-1, CA0 = 2 moles/litre, and
ν = 4 L/min. What residence times and reactor volumes will be required for n = 1, 2, 3
and 4 reactors?
Solution:
C AO
C An =
(1 + kτ n )n
C An
= (1 + kτ n )
−n

C AO
1
 C An n
  = (1 + kτ n )
 C AO 
1
 C AOn
  − 1 = kτ n
 CA 
 1

n  C AO  n 
τ n =   −1
k  C A  
 
 1

1   2  1  
τ1 =   − 1 = 18s
0.5   0.2  
   
 1

2   2  2  
τ2 =   − 1 = 8.65s
0.5   0.2  
   
 1

3   2  3  
τ3 =   − 1 = 6.92 s
0.5   0.2  
   
 1

4   2  4  
τ4 =   − 1 = 6..22 s
0.5   0.2  
   

96 REE2601/1
The calculation for the volume
V = ντ
V1 = 4 × 18 = 72 L
V2 = 4 × 8.65 = 34.6 L
V3 = 4 × 6.92 = 27.68 L
V4 = 4 × 6.22 = 24.88 L
Example 5.4: CSTR in series
A three-stage CSTR is used for the reaction A → P . The reaction occurs in aqueous
solution, and is second-order with respect to A, with kA = 0.040 L/min.mol. The inlet
concentration of A and the inlet volumetric flow rate are 1.5 mol/L and 2.5 L/min,
respectively. Determine the fractional conversion obtained at the outlet, if V1 = 10 L, V2
= 20 L, and V3 = 50 L.
Solution:

V1 X1
=
νO kC AO (1 − X 1 )
2

10 X1
=
2.5 0.04 × 1.5 × (1 − X 1 )2
0.24 × (1 − X 1 ) = X 1
2

( 2
0.24 1 − 2 X 1 + X 1 = X 1 )
2
0.24 X 1 − 0.48 X 1 + 0.24 = X 1
2
0.24 X 1 − 1.48 X 1 + 0.24 = 0
1.48 ± 1.48 2 − 4 × 0.24 × 0.24
X1 =
2 × 0.24
X 1 = 0.17

97 REE2601/1
Calculation for the second conversion
FA 0 ( X 2 − X 1 )
V2 =
− rA
FA 0 ( X 2 − X 1 )
=
kC AO (1 − X 1 )
2 2

C AOν ( X 2 − X 1 )
=
kC AO (1 − X 1 )
2 2

ν (X 2 − X1)
=
kC AO (1 − X 1 )
2

2.5 × ( X 2 − 0.17)
20 =
0.04 × 1.5 × (1 − X 2 )
2

0.48 × (1 − X 2 ) = ( X 2 − 0.17)
2

( 2
0.48 X 2 − 2 X 2 + 1 = ( X 2 − 0.17) )
2
0.48 X 2 − 1.96 X 2 + 0.65 = 0
1.96 ± 1.96 2 − 4 × 0.48 × 0.65
X2 =
0.96
= 0.36
Calculation for the third conversion
F (X − X 2 )
V3 = A0 3
− rA
F (X − X 2 )
= A0 2 3
kC AO (1 − X 1 )
2

C AOν ( X 3 − X 2 )
=
kC AO (1 − X 3 )
2 2

ν (X 3 − X 2 )
=
kC AO (1 − X 3 )
2

2.5 × ( X 3 − 0.36)
50 =
0.04 × 1.5 × (1 − X 3 )
2

1.2 × (1 − X 3 ) = ( X 2 − 0.36)
2

( 2
1.2 × X 3 − 2 X 3 + 1 = ( X 3 − 0.36) )
2
1.2 X 2 − 3.4 X 2 + 1.56 = 0
3.4 ± 3.4 2 − 4 × 1.2 × 1.56
X2 =
2.4
= 0.58

98 REE2601/1
Example 5.5: Combined volume of two CSTRs in series
Find the combined volume of two CSTRs in series, where the first tank achieves 40%
conversion whilst the overall conversion is 80%, given the information below.
X -rA(mol/m3.s) FA0/rA

0 0.450 0.89

0.1 0.370 1.08

0.2 0.300 1.33

0.4 0.195 2.05

0.6 0.113 3.54

0.7 0.079 5.06

0.8 0.050 8.00

9
8
7
6
FA0/-rA

5
4
3
2
1
0
0 0.1 0.2 0.4 0.6 0.7 0.8
X

FA 0 X F
V1 = = A0 X = 2.05 × 0.4 = 0.82m 3 Remember for X=0.4 FA0/-rA=2.05
− rA − rA
FA 0 ( X 2 − X 1 ) FA 0
V2 = = ( X 2 − X 1 ) = 8 × (0.8 − 0.4) = 3.2m 3
− rA − rA
Total volume =4.02m3

99 REE2601/1
5.6.2 CSTR in parallel

If two CSTR of equal volume are fed by equal amounts of feed and are operating at the
same temperature, the conversion of each reactor will be the same and the reaction rate
will be the same in each reactor.
Example 5.6: CSTR in parallel
A feed of pure A (10 M/s) containing 5 M/L A is fed into two CSTR which are in parallel.
The feed is split into a ratio of 3:2 to the 30 L CSTR and 20 L CSTR respectively. Calculate
the conversion in each tank if the reaction is first order and irreversible with a rate
constant of 0.01 s-1.
Solution:
For 30 L CSTR
νOX FAO 0.6 × 10
V = ⇒ν = = = 1.2
k (1 − X ) C AO 5
1.2 X
30 =
0.01(1 − X )
0.3(1 − X ) = 1.2 X
1.5 X = 0.3
X = 0.2
For 20 L CSTR
νOX FAO 0.4 × 10
V = ⇒ν = = = 0.8
k (1 − X ) C AO 5
0.8 X
20 =
0.01(1 − X )
0.2(1 − X ) = 0.8 X
X = 0.2

5.6.3 PFR in series

For a number of PFR, N plug flow reactors in series with a total volume V gives the same
conversion as a single plug flow reactor of volume V.
For two PFR in series the following equations apply:
X2 X1 x2
dX dX dX
V = ∫F
0
AO
− rA
= ∫F
0
AO + ∫ FAO
− rA X 1 − rA
Where X1 and X2 are the conversion in reactor 1 and reactor 2 respectively.

100 REE2601/1
Example 5.7: PFR in series
Calculate the V1 and V2 for the following data, when intermediate conversion is 40% and
final conversion is 80%.

X 0 0.1 0.2 0.4 0.6 0.7 0.8

FAO/-rA 0.89 1.08 1.33 2.05 3.54 5.08 8.00

9
8
7
6
FA0/-rA

5
4
3
2
1
0
0 0.1 0.2 0.4 0.6 0.7 0.8
X

Using the Simpson rule to determine the area under the curve to X = 0.4:
h  FAO FAO FAO 
V1 =  + + 
3  − rA (0 ) − rA (0.2 ) − rA (0.4 )
0.2
= [0.89 + 4 × 1.33 + 2.05] = 0.551m 3
3
h  FAO FAO FAO 
V2 =  + + 
3  − rA (0.4 ) − rA (0.6 ) − rA (0.8) 
0.2
= [2.05 + 4 × 5.08 + 8] = 1.614m 3
3
V = V1 + V2 = 1.614 + 0.551 = 2.165m 3

5.7 CONVERSION, SELECTIVITY, AND YIELD

In the following sections we will consider only two sets of reactions in detail, the parallel
reaction system A → B and A → C ; and the series reaction system A → B → C . These

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are prototype reactions for most reaction systems, and their characteristics show many of
the features of any complex reaction system. The characteristics of these simple reactions
are:
1. There is a single reactant A,
2. There are two products B and C and we usually want to produce B and minimise C,
and
3. The stoichiometric coefficients of all species are unity. These stoichiometries require
that, if we feed pure A, it must react to form either B or C. Therefore, the loss of A is
equal to the gain in B and C,
N AO − N A = N B + N C
At constant density
C AO − C A = C B + C C
These relations assume that there is no B or C in the feed, CB = Cc = 0. With this simple
stoichiometry the definitions become simpler compared to more complex sets of
reactions.
Conversion is given as:
lossofA
Conversion =
feedofA

If we can identify a reactant A on which to base the selectivity, then we can define the
selectivity as (at constant density):
CB
SB =
C B + CC
Yield can be defined as:
CB
YB = X A S B =
C AO
Production rate is defined as:
FB = YB FAO = S B X A FAO
Example 5.8: Calculation of selectivity
Two parallel reactions for A are first order with respect to A. The rate constant for reaction
1 is 0.4 s-1 and that for reaction 2 is 0.004 s-1. If reaction 1 is the preferred reaction, and
at the end of 3 seconds there is 5 moles of product C, calculate the selectivity and yield
conversion of A. Assume this takes place in a batch reactor.
A → B (1)
A → C (2)

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Solution:
1 C
ln A = 3
− (k1 + k 2 ) C AO
1 C
ln A = 3
− (0.4 + 0.004) 100
C
ln A = −3 × 0.404
100
CA
= e −3×0.404
100
C A = 100 × e −3×0.404 = 29.76 ≈ 30

From the above calculation, 70 moles of A reacted but there is 5 moles of C, therefore
there is 65 moles of B.
70
Conversion =
100
= 0.7

Selectivity
65
SB = = 0.93
65 + 5
Yields
65
YB = X A S B = = 0.65
100

5.8 SUMMARY
In this learning unit, you have been taught how to compare different reactors for the same
reaction. This will help you to decide which reactor is economical for a particular
reaction. Selectivity and yield will also assist you in choosing the best reactor. Work out
the problems before looking at their solutions

SELF-ASSESSMENT PROBLEMS
There are various principles we have learnt. Now it is time to test yourself.
5.1 For the information below, and for the first order kinetic reactions, calculate:
a) The volume of CSTR and PFR to achieve 40% conversion (CSTR=24dm3.
PFR=72 dm3)
b) The maximum conversion for a 105 dm3 CSTR (0.7)

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 c) The conversion that will be achieved if a 24 CSTR dm3 is followed by a 45dm3
CSTR
If the flow rate is 300 mol/min
X 0 0.2 0.4 0.45 0.5 0.6 0.8 0.9

- 1 1.67 5 5 5 5 1.25 1.91

rA(mol/dm3.min)

5.2 Compound B is prepared from pure compound A according to the following liquid-
phase elementary reversible reaction:
A⇔ B
Determine the amount of time necessary to achieve a conversion of 40% if a
10-liter batch reactor is used to perform the reaction.
Additional information: CAo = 3.0 lbmol/L, kf) = 6.0/(h), kb= 0.53/(h)
5.3 A first order irreversible elementary reaction
A→B
with a reaction velocity constant of 0.376 (min)-1 takes place in a constant volume
batch reactor. Calculate the time required to achieve a conversion of 80%.
5.4 Consider the elementary irreversible reaction between benzoquinone (A) and
cyclopentadiene (B)
A + B → Pr oduct
Calculate the reactor size requirements for one CSTR. Also calculate the volume
requirements for a cascade composed of two identical CSTRs. Assume isothermal
operation at 25 oC where the reaction rate constant is equal to 9.92 m3/(kgmol· ks).
Reactant concentrations in the feed are each equal to 0.08 kgmol/m3, and the liquid
feed rate is equal to 0.278 m3 /ks. The desired degree of conversion is 87.5%.
5.5 It is proposed to decompose pure diethyl per­ oxide (A) at 225 °C in a bench-scale
tubular reactor. The organic will be entering the reactor at a flow rate of 12.1 L/s. It
is desired to decompose 99.995% of the diethyl peroxide. The following data are
available: kA = 38.3 (s)- 1 at 225 °C.
5.6 Consider the second order, liquid phase reaction A → Pr oducts which has a rate
constant k = 0.5 L/gmol min at 300°K. For isothermal operation at 300°K and the
following process conditions apply: FAO=100 gmol/min, CAO 1 gmol/L, XA=0.95.
a) What size plug flow reactor would be required?
b) What size CSTR would be required?

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SOLUTIONS TO PROBLEMS
5.1 For the information below and for the first order kinetic reactions, calculate:
a) The volume of CSTR and PFR to achieve 40% conversion (CSTR=24dm3.
PFR=72 dm3)
b) The maximum conversion for a 105 dm3 CSTR (0.7)
c) The conversion that will be achieved if a 24 CSTR dm3 is followed by a 45dm3
CSTR
If the flow rate is 300 mol/min

X 0 0.2 0.4 0.45 0.5 0.6 0.8 0.9

-rA(mol/dm3.min) 1 1.67 5 5 5 5 1.25 1.91

Answer

350

300

250

200
FA/-rA

150

100

50

0
0 0.2 0.4 0.45 0.5 0.6 0.8 0.9
X

FAO
a) CSTR volume = X = 60 × 0.4 = 24dm 3
− rA
240 × 0.4
PFR volume= + 60 × 0.4 = 72dm 3
2

105 REE2601/1
 b)

350

300

250

200
FA/-rA

150

100

50

0
0 0.2 0.4 0.45 0.5 0.6 0.8 0.9
X

By trial and error X=0.7, V= = 150 × 0.7 = 105dm 3

c) A 24dm3 reactor gives a conversion of 40% so intermediate conversion is 0.4.
By trial and error 0.7 is the final conversion
FAO
V2 = ( X 2 − X 1 ) = 150 × (0.7 − 0.4) = 45dm 3
− rA
5.2 Compound B is prepared from pure compound A according to the following liquid-
phase elementary reversible reaction
A⇔ B
Determine the amount of time necessary to achieve a conversion of 40% if a
10-liter batch reactor is used to perform the reaction.
Additional information: CAo = 3.0 lbmol/L, kf = 6.0/(h), kb= 0.53/(h)
Solution:
dX
C AO = k f C A − kbC B
dt
dX
C AO = k f C AO (1 − X ) − k b C AO X
dt
dX
= k f − k f X − kb X
dt
1 k f − k f X − kb X − 1 6 − (6 × 0.4 ) − (0.53 × 0.4 )
t=− ln = ln = 5.26 min
k f + kb kf 6.53 6

106 REE2601/1
5.3 A first order irreversible elementary reaction
A→B
with a reaction velocity constant of 0.376 (min)-1 takes place in a constant volume
batch reactor. Calculate the time required to achieve a conversion of 80%.
Solution:
1 1 1
t r = 1 ln = ln = 4.28 min
k 1 − X 0.376 1 − 0.8

5.4 Consider the elementary irreversible reaction between benzoquinone (A) and
cyclopentadiene (B)
A + B → Pr oduct
Calculate the reactor size requirements for one CSTR. Also calculate the volume
requirements for a cascade composed of two identical CSTRs. Assume isothermal
operation at 25oC where the reaction rate constant is equal to 9.92 m3/(kgmol· ks).
Reactant concentrations in the feed are each equal to 0.08 kgmol/m3, and the liquid
feed rate is equal to 0.278 m3 /ks. The desired degree of conversion is 87.5%.
Solution:
− rA = kC A C B
= k [C AO (1 − X )C BO (1 − X )] ⇒ C BO = C AO
[
= k C AO (1 − X )
2 2
]

107 REE2601/1
 FA 0 X F (X − X1)
V1 = andV2 = A0 2
− rA − rA
FA 0 X FA 0 ( X 2 − X 1 )
=
[
k C AO (1 − X 1 )
2 2
] k [C AO
2
(1 − X 2 )2 ]
X1 (X 2 − X1)
[(1 − X ) ] [(1 − X ) ] ⇒ X
1
2
=
2
2 2 = 0.875

X 1 = 0.7251

0.02224 × 0.7251
V1 = = 3.36m 3
2
[
9.92 0.08 (1 − 0.7251) 2
]
3
V2 = 3.36m
VT = 6.72m 3

5.5 It is proposed to decompose pure diethyl per­ oxide (A) at 225 °C in a bench-scale
tubular reactor. The organic will be entering the reactor at a flow rate of 12.1 L/s. It
is desired to decompose 99.995% of the diethyl peroxide. The following data are
available: kA = 38.3 (s)- 1 at 225 °C
X dX
V = FA 0 ∫ ⇒ −rA = kC A ⇒ Ca = C A0 (1 − X ) ⇒ F A0 = C AOυ 0
0 − rA
FA 0 X dX ν 12.1
V =
kC A0 ∫ 0 1− X
= − 0 ln(1 − X ) = −
k 38.3
ln(1 − 0.99995) = 3.13L

5.6 Consider the second order, liquid phase reaction A → Pr oducts which has a rate
constant k = 0.5 L/gmol min at 300°K. For isothermal operation at 300°K and the
following process conditions apply: FAO=100 gmol/min, CAO 1 gmol/L, XA=0.95.
a) What size CSTR would be required?
b) What size plug flow reactor would be required?

108 REE2601/1
Solution:
FA 0 X 2
V = ⇒ −rA = kC A
− rA
FA 0 X
= 2
⇒ C A = C AO (1 − X )
kC A
a)
FA 0 X
=
kC AO (1 − X )
2 2

100 × 0.95
= = 76000 L
0.5 × 12 (1 − 0.95)
2

b)

X dX
V = FA 0 ∫
2 2
⇒ − rA = kC A = kC AO (1 − X ) 2
0 − rA
X dX
V = FA 0 ∫ 2
0
kC AO (1 − X ) 2
X
FA 0 dX
=
kC AO
2 ∫ (1 − X )
0
2

FA 0 X
= ×
kC AO
2
1− X
100 0.95
= 2
× = 3800 L
0.5 × 1 1 − 0.95

REFERENCES
Fogler, HS. (2011). Essentials of Chemical Reaction Engineering. Prentice Hall
International Series in the Physical and Chemical Engineering Sciences. Pearson.
International Edition, ISBN: 978-0-13-211936-8.

109 REE2601/1
 Study unit 1 6

TEMPERATURE AND PRESSURE EFFECTS

LEARNING OUTCOMES
On completion of this learning unit, you should be able to:
• Calculate conversion in a PFR with pressure drop.
• Calculate conversion in a non-isothermal reactor.
This learning unit is based on Chapters 5 and 11 of your prescribed book. You can use
the following links to better understand the concepts presented in this learning unit:
• Adiabatic reactors (7:03): https://youtu.be/--cZwa2TXhY
• Pressure drop in PFR (4:14): https://youtu.be/RAIzVl7e-fo
These links are also available on the module site under Additional Resources.

6.1 INTRODUCTION
Not all processes are isobaric (constant pressure) and isothermal (constant temperature).
In this learning unit we will look at the effects of temperature and pressure change on the
conversion of different reactors.

6.2 PRESSURE DROP IN PLUG FLOW REACTORS (PFRS)

Gas phase reactions are affected by changes in pressure, due to pressure drops because
the concentration of reacting molecules is proportional to the total pressure. This means
that pressure effects are considered for gas phase reactions only. We will deal with PFRs
because they mostly work with gaseous reactions, as compared to BR and CSTR which
work with liquid and solid reactions.

110 REE2601/1
Definition of terms
• The usual notation applies.
– FA = molar flow rate of A, FT = total molar flow rate
– V = volume of reactor, 𝛾𝛾= volumetric flow rate
– D = diameter and A = cross-sectional area of PFR, L = length of PFR, z = distance
(between 0 and L)
– T = temperature, R = universal gas constant, P = pressure, PA = partial pressure
of A
– X = conversion, e = fractional increase in number of moles for 100% conversion,
for a given feed conditions.
– k = rate constant, CA = concentration of A
– ρ = density, µ = viscosity
– f = friction factor, Re = Reynolds number
– <Vav> = average velocity of the fluid in the PFR. Used sparingly.
The following equations apply:
FA = FAO (1 − X A )
FT = FTO (1 + εX A )
FA
CA =
ν
We will now deal with gas phase reactions.
FT RT FTO (1 + εX )RT
For ideal gas reaction ν = = at constant temperature it becomes
P P
(1 + εX )POν O
ν=
P
For gases the Reynolds number (Re) is given:
4νρ
Re =
πDµ
The fanning friction factor is given by:
16
f = if Re ≤ 2100
Re
f = 0.0014 + 0.125 Re (−0.32 ) for 3000 ≤ Re ≤ 3000000

111 REE2601/1
Material balance equation for PFR with a pressure drop (First order):
dX
FAO = −rA
dV
dX
FAO = kC A
dV
dX F F (1 − X A )
FAO = k A = AO
dV ν ν
(1 + εX )POν O
isothermal ⇒ ν =
P
dX (1 − X A ) k (1 − X A ) P
=k =
dV ν POν O (1 + εX )
dX Ak (1 − X A ) P Ak
⇒ = ⇒H =
dz POν O (1 + εX ) POν O
dX (1 − X A ) P
=H
dz (1 + εX )
For pressure drop we assume that viscosity remains the same:
dP 32 fρν 2 32 fρ Oν Oν 32 fρ Oν O POν O (1 + εX ) 32 fρ Oν O POν O
=− 2 5 =− =− ⇒G=
dz π D π D
2 5
π D2 5
P π 2 D5
dP
= −G
(1 + εX )
dz P
The pressure differential and material differential are solved simultaneously. For ease of
understanding of this, concept we will restrict ourselves to cases where:
∈= 0
In these cases, one solves the pressure differential then inserts the calculated P in the
material balance differential.
Example 6.1: Length of reactor with pressure drop
• Consider a gas phase reaction under isothermal conditions. (Isomerization) A B
Pin = 1013.25 kPa, ν = 0.005 m3/s, T = 300 K, Pure A is fed, k = 0.1 L/s, Molecular
weight M = 60 g/gmol, Viscosity of the gas = 10-5 Pa⋅s, Diameter is 2 cm.
a) What is the length of reactor that is required to achieve 40% conversion?
b) What is the pressure drop at this length?

112 REE2601/1
Solution:
Step 1:
dP
= −G
(1 + εX ) ⇒ ε = 0
dz P
dP 1
= −G
dz P
P z

∫ PdP = −G ∫ dz
PO 0
2
P 2 − PO
= −Gz
2
2 32 fρ Oν O POν O
P 2 = PO − 2Gz ⇒ G =
π 2 D5
2 32 fρ Oν O POν O
P 2 = PO − 2× ×z
π 2 D5
Step 2: Calculating density:
PO Mw
ρ=
RT
1013..25 × 60
= = 24.37kg / m 3
8.206 × 300
Step 3: Calculating Reynolds number to determine flow characteristics
4νρ
Re =
πDµ
4 × 0.005 × 24.37
= = 775721.19
π × 0.02 × 1 × 10 −5
Step 4: Determining fanning friction factor
f = 0.0014 + 0.125 × 775721.19 (−0.32 )
= 0.003
2 32 fρ Oν O POν O
P 2 = PO − 2 × ×z
π 2 D5
32 × 0.003 × 24.37 × 0.005 × 0.005 × 1013
= 1013250 2 − 2 z
π 2 × 0.02 5
= 1013250 2 − 3752871163.3 z
P = 1013250 2 − 3752871163.3 z

113 REE2601/1
Step 5: Calculating conversion term
dX Ak (1 − X A ) P Ak
= ⇒H =
dz POν O (1 + εX ) POν O
dX (1 − X A ) P
=H ⇒ε =0
dz (1 + εX )
1
= HPdz
1− X A
X
1
∫1− X
0 A
= HPz

1
ln = HPz
1− X A
1
= e HPz
1− X A
1
HPz
= 1− X A
e
1
X A = 1− HPz
e
0.02 × 0.02
0.0001 × π ×
Ak 4
H= = = 6.2 × 10 −9
POν O 1013 × 0.005
1
X A = 1− 6.2×10 − 9 Pz
e
Step 6: Put values of P and z to get X
Then one plugs in the values of P and z to get X as shown in Table 6.1.

P (Pa) 1013250 1009539 1005815 1002077 998325 994559 990778 986983 983173 979349 975509
z (m) 0 2 4 6 8 10 12 14 16 18 20
X 0 0.11766 0.22076 0.31118 0.39053 0.46024 0.52152 0.57544 0.62292 0.66477 0.70169

114 REE2601/1
 0.8
0.7
0.6
0.5
Conversion

0.4
0.3
0.2
0.1
0
0 5 10 15 20 25
z(m)

Figure 6.1
Conversion vs z

Step 7: Plotting a graph of pressure vs z and X vs z

1040000

1020000

1000000
Pressure (PaP

980000

960000

940000

920000

900000
0 5 10 15 20
z(m)

Figure 6.2
Pressure vs z

115 REE2601/1
Therefore:
a) Length from Fig. 6.2 is 8 m
b) From figure 6.1, Pressure for 40% conversion is 996000 Pa. The pressure drop is
1013250 − 996000 = 17250𝑃𝑃𝑃𝑃

6.3 TEMPERATURE EFFECTS

For a reaction 𝐴𝐴 → 𝐵𝐵, assuming that the reaction is exothermic and adiabatic, the
temperature will increase with conversion. If the conversion is 70%, how does one
calculate the volume needed? Table 6.2 shows some of the equation derivations for a first
order reaction using a CSTR.
Table 6.2
Some of the equation derivations for a first order reaction using a CSTR

Relationship Equation

Design Equation dX − rA
=
dV FAO

Rate law − rA = kC A

Stoichiometry v = vO
FA = C A v O
FAO = C AO vO
C A = C AO (1 − X )

Combining the above and cancelling dX k (1 − X )

=
dV vO

Arrhenius Equation  E  1 1 
k = k1 exp  −  
 R  T1 T  

Combining equations again  E  1 1 

k1 exp  −  (1 − X )
dX
=  R  T1 T  
dV vO

116 REE2601/1
We see that we need another relationship relating X and T or T and V to solve this
equation. The energy balance will provide us with this relationship. We thus add a further
step to our algorithm. This step is the energy balance. For an adiabatic relationship:
− ∆H Rx
T = TO + X
CP A

6.3.1 Energy balance for an adiabatic process

For a closed system 𝑑𝑑𝑑𝑑 = 𝛿𝛿𝛿𝛿 − 𝛿𝛿𝛿𝛿. The δs signify that the functions are not exact
differentials of a state function.

6.3.2 Relationships for an adiabatic reactor

NB 𝑸𝑸 = 𝟎𝟎. For CSTR, Batch and PFR the relationship between conversion (𝑋𝑋𝐸𝐸𝐸𝐸 ), and
temperature with 𝑊𝑊𝑠𝑠 = 0, constant 𝐶𝐶𝑝𝑝𝑝𝑝 ,∆𝐶𝐶𝑃𝑃 = 0

X EB =
∑ Θ C (T − T )
i Pi O

− ∆H Rx
− ∆H Rx
T = TO + X
∑ ΘiCP A
Definitions
𝐶𝐶𝑝𝑝𝑝𝑝 𝑖𝑖𝑖𝑖 𝑡𝑡ℎ𝑒𝑒 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 ℎ𝑒𝑒𝑒𝑒𝑒𝑒 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
−∆𝐻𝐻𝑅𝑅𝑅𝑅 𝑖𝑖𝑖𝑖 𝑡𝑡ℎ𝑒𝑒 ℎ𝑒𝑒𝑒𝑒𝑒𝑒 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟
𝑑𝑑 𝑐𝑐 𝑏𝑏
∆𝐻𝐻°𝑅𝑅𝑅𝑅 = 𝐻𝐻°𝐷𝐷 + 𝐻𝐻°𝐶𝐶 − 𝐻𝐻°𝐵𝐵 − 𝐻𝐻°𝐴𝐴
𝑎𝑎 𝑎𝑎 𝑎𝑎
𝑑𝑑 𝑐𝑐 𝑏𝑏
∆𝐶𝐶𝑝𝑝 = 𝐶𝐶𝑃𝑃𝑃𝑃 + 𝐶𝐶𝑃𝑃𝑃𝑃 − 𝐶𝐶𝑃𝑃𝑃𝑃 − 𝐶𝐶𝑃𝑃𝑃𝑃
𝑎𝑎 𝑎𝑎 𝑎𝑎
6.3.3 Procedure to calculate −𝒓𝒓𝑨𝑨 as a function of X alone

1. Choose X
− ∆H Rx
2. Calculate T using T = TO + X
CP A

 E  1 1 
3. Calculate k using k = k1 exp  −  
 R  T1 T  
 E  1 1 
4. Calculate -rA using − rA = k1 exp  −  C AO (1 − X )
 R  T1 T  

117 REE2601/1
 FAO
5. Then one needs to calculate
− rA
The adiabatic Energy balance is given as

X EB =
∑ Θ C (T − T )
i Pi O

− ∆H ° Rx (TR ) + ∆C P (T − TR )

where TR is the reference temperature. Usually ∆C P (T − TR ) is approximated to zero.

Example 6.2: Adiabatic reactions
A gas-phase decomposition A → R + S is to be conducted in a batch reactor, with initial
conditions of TO = 300 K, V, = 0.5 m3, and a (constant) total pressure of 500 kPa. The
values of CP, for A, R, and S are, respectively 185.6, 104.7, and 80.9 J mol-1K-l. The
enthalpy of reaction is -6280 J (mol A)-l, and the reaction is first-order with respect to A,
with kA = 1014exp(-10 000/T) h-l, T in K. Determine the profiles of XA and T versus t, if the
process is adiabatic, and T and t for XA = 0.99.
Solution:
kn A kn AO (1 − X )
− rA = kC A = = (Gas phase reaction)
V V
For first order batch reactor
1
( )dX = kdt
1− X
X
1
∫0 1 − X = kt
1 1
t= ln
k 1− X

− ∆H Rx
T = TO + X
CP A
6280
= 300 + X
185.6
= 300 + 33.8 X

118 REE2601/1
 X T (K) k (h-1) t (h)

0.10 303.38 0.483951 0.217709

0.20 306.76 0.695877 0.320665

0.30 310.14 0.992715 0.359292

0.40 313.52 1.405368 0.363482

0.50 316.90 1.974856 0.350986

0.60 320.28 2.755258 0.332561

0.70 323.66 3.817407 0.315390

0.80 327.04 5.253486 0.306356

0.82 327.72 5.595516 0.306459

0.84 328.39 5.958266 0.307570

0.86 329.07 6.342896 0.309971

0.88 329.74 6.750624 0.314084

0.90 330.42 7.182730 0.320572

0.99 333.46 9.467000 0.486000

Therefore, for a conversion of 0.99, the temperature must be 333 K after 0.48 h.
Example 6.3: Adiabatic reactions
A first-order liquid-phase reaction A → P , is conducted in a CSTR adiabatically. The feed
contains pure A, at a rate of 300 L/m with an inlet concentration of 4.0 mol/L. The reaction
is first order with regards to A. Calculate the temperature, residence time and volume for
80% conversion. The following additional data is available:
−12000
𝐽𝐽 𝑘𝑘𝑘𝑘 1015 𝑒𝑒
𝐶𝐶𝑝𝑝 = 350 , ∆𝐻𝐻 = −5 , 𝑘𝑘 = 2.4 × 𝑇𝑇 , 𝑇𝑇𝑂𝑂 = 290𝐾𝐾
𝑚𝑚𝑚𝑚𝑚𝑚. 𝐾𝐾 𝑚𝑚𝑚𝑚𝑚𝑚 𝐴𝐴 𝑚𝑚𝑚𝑚𝑚𝑚

119 REE2601/1
Solution:
− ∆H Rx
T = TO + X
CP A

Calculating final temperature: = 290 + 5000 X

350
= 290 + 14.29 × 0.8
= 301.43K
Calculating k:
- 12000
k A = 2.4 × 1015 e
301.43
= 0.0123 / min

Calculating volume:
FA 0 X
V = ⇒ −rA = kC A
− rA
FA 0 X
= ⇒ C A = C AO (1 − X )
kC A
FA 0 X F
= ⇒ AO = ν O
kC AO (1 − X ) C AO
νο X
V =
k (1 − X )
300 × 0.8
=
0.0123 × (1 − 0.8)
= 97561L
Calculating residence time:
V 97561
=τ = = 325.2 min
ν 300

120 REE2601/1
6.4 INDUSTRIAL PROCESSES
Industrial processes use a variation of the three reactors we have discussed in this learning
unit, and mostly with modifications. Table 6.3 below shows some industrial reactors. Be
sure to look them up on YouTube.
Table 6.3
Some industrial reactors

Process Reactor Type

Fisher-Tropsch reaction (SASOL) Packed and fluidised beds

Gas cleaning Absorption columns

Metal Extraction (Base metal recovery) Column and mixer settlers

6.5 SUMMARY
In this learning unit you have been taught to calculate the effect of temperature and
pressure variations. These can be used to choose the best reactor for different situations.

SELF-ASSESSMENT PROBLEMS
6.1 A second-order liquid-phase reaction A → P , is conducted in adiabatically. The
feed contains pure A, at a rate of 300 L/m with an inlet concentration of 4.0 mol/L.
Calculate the temperature, residence time and volume for 70% conversion for a
CSTR and PFR The following additional data are available:
−12000
𝐽𝐽 𝑘𝑘𝑘𝑘 1015 𝑒𝑒
𝐶𝐶𝑝𝑝 = 350 , ∆𝐻𝐻 = −5 , 𝑘𝑘𝐴𝐴 = 2.4 × 𝑇𝑇 , 𝑇𝑇𝑂𝑂 = 290𝐾𝐾
𝑚𝑚𝑚𝑚𝑚𝑚. 𝐾𝐾 𝑚𝑚𝑚𝑚𝑚𝑚 𝑚𝑚𝑚𝑚𝑚𝑚
6.2 Consider the problem in example 6.1, but the reaction is now second order with
respect to A.
Pin = 1013.25 kPa, ν = 0.005 m3/s, T = 300 K, Pure A is fed, k = 0.1 M-1s-1
Molecular weight M = 60 g/gmol, Viscosity of the gas = 10-5 Pa-s, Diameter is
2 cm.
What is the length to achieve 40% conversion?
What is the pressure drop at this length?

121 REE2601/1
SOLUTIONS TO PROBLEMS
6.1 CSTR solution
Temperature
− ∆H Rx
T = TO + X
CP A
5000
= 290 + X
350
= 290 + 14.29 × 0.8
= 301.43K
Calculating k
- 12000
k A = 2.4 × 1015 e
301.43
= 0.0123 / min
Volume
FA 0 X 2
V = ⇒ − rA = kC A
− rA
FA 0 X
= 2
⇒ C A = C AO (1 − X )
kC A
FA 0 X FAO
= ⇒ =νO
kC AO (1 − X ) C AO
2 2

νOX
V =
kC AO (1 − X )
2

300 × 0.7
=
0.0123 × 4 × (1 − 0.7 )
2

210
= = 47425.5 L
0.00442
Calculating residence time
V 47425.5
=τ = = 158.1 min
ν 300

122 REE2601/1
 PFR Solution
X
dX
V = FAO ∫ ⇒ −rA = kC A = kC AO (1 − X )
2 2 2

0
− rA
X
dX
= FAO ∫
kC AO (1 − X )
2 2
0

FAO X
=
kC AO
2
1− X
300 0.7
= × = 3557 L
0.0123 × 4 × 4 1 − 0.7
Residence time
V 3557
=τ = = 11.9 min
ν 300
6.2
PO Mw
ρ=
RT
1013..25 × 60
= = 24.37kg / m 3
8.206 × 300

f = 0.0014 + 0.125 × 775721.19 (−0.32 )

= 0.003

123 REE2601/1
 dX
FAO = − rA
dV
dX 2
FAO = kC A
dV
2 2
dX F  F (1 − X A ) 2
FAO = k  A  = k AO
dV ν  ν2
(1 + εX )POν O
isothermal ⇒ ν =
P
2
dX FAO (1 − X A ) k (1 − X A ) 2 P 2
=k = 2 2
dV ν2 PO ν O (1 + εX )2
dX Ak (1 − X A ) 2 P 2 Ak
⇒ = 2 2 ⇒H = 2 2
dz PO ν O (1 + εX ) 2
PO ν O
dX (1 − X A ) 2 P 2
=H ⇒ε =0
dz (1 + εX )2
dX
= H (1 − X A ) 2 P 2
dz

2 32 fρ Oν O POν O
P 2 = PO − 2 × ×z
π 2 D5
32 × 0.003 × 24.37 × 0.005 × 0.005 × 1013250
= 1013250 2 − 2 z
π 2 × 0.02 5
= 1013250 2 − 3752871163.3 z
P = 1013250 2 − 3752871163.3 z
dX
= H (1 − X A ) 2 P 2
dz
X
1
∫0 (1 − X A ) 2 dx = HP dz
2

X
= HP 2 Z
1− X
X = HP 2 Z − XHP 2 Z
X + XHP 2 Z = HP 2 Z
( )
X 1 + HP 2 Z = HP 2 Z
2
HP Z
X =
1 + HP 2 Z
Ak π × 0.02 × 0.02 × 0.0001
H= 2 2 = = 1.2 × 10 −14
PO ν O 1013250 × 1013250 × 0.005 × 0.005 × 4

124 REE2601/1
 1050000

1000000

950000

900000
Pressure (Pa)

850000

800000

750000

700000

650000

600000
0 20 40 z (m) 60 80 100

0.5
0.45
0.4
0.35
Conversion

0.3
0.25
0.2
0.15
0.1
0.05
0
0 20 40 60 80 100 120
z (m)

Solution:
From conversion vs distance graph, distance is 72 m. Pressure at 72 m is 860 000 Pa. The
pressure drop is
1013250 − 860000 = 153250𝑃𝑃𝑃𝑃

125 REE2601/1
REFERENCES
Fogler, HS. (2011). Essentials of Chemical Reaction Engineering. Prentice Hall
International series in the physical and chemical engineering sciences. Pearson.
International Edition, ISBN: 978-0-13-211936-8.

126 REE2601/1