Advanced Process Engineering

Advanced Process Engineering
For Graduate and Undergraduate Students…
1st Edition
Dr. Nadeem Feroze

Engr. Anees Ahmad
University of Engineering and Technology (UET) Lahore
ENGINEERING
CHEMICAL
Department of Chemical Engineering

University of Engineering and Technology Lahore, Pakistan
Advanced Process Engineering
For Graduate and Undergraduate Students…
FIRST EDITION
Dr. Nadeem Feroze

Ex-Dean of Chemical, Polymer, & Metallurgical Engineering
Engr. Anees Ahmad

Research Associate (Chemical and Process Engineering), Microsoft .NET Developer
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Contents
Contents .............................................................................................................................................................................. 3
About the authors............................................................................................................................................................. 7
Preface ................................................................................................................................................................................. 8
Nomenclature .................................................................................................................................................................... 9
Chapter-1: Introduction ................................................................................................................................................. 13
1.0 Introduction to Chemical Engineering (CE) ............................................................................................... 13
1.0.1 Process Engineering ................................................................................................................................ 14
1.0.2 Energy Engineering ................................................................................................................................. 14
1.0.3 Biochemical Engineering ........................................................................................................................ 14
Chapter-2: Process Engineering ................................................................................................................................. 15
2.0 Introduction to Process Engineering (PE) ................................................................................................... 15
2.1 Core Areas........................................................................................................................................................... 16
2.1.1 Mathematics .............................................................................................................................................. 16
2.1.2 Thermodynamics ...................................................................................................................................... 16
2.1.3 Reaction Engineering .............................................................................................................................. 16
2.1.4 Transport Phenomena ............................................................................................................................ 16
2.2 Specialization Areas .......................................................................................................................................... 17
2.2.1 Process Synthesis ..................................................................................................................................... 17
2.2.2 Process Intensification ............................................................................................................................. 17
2.2.3 Process Optimization .............................................................................................................................. 17
2.2.4 Process Control......................................................................................................................................... 17
2.2.5 Process Safety ........................................................................................................................................... 18
2.3 Introduction to Process Systems Engineering (PSE) ................................................................................ 18
2.3.1 Process Modelling and Simulation ...................................................................................................... 18
2.4 Tree Diagram...................................................................................................................................................... 19
Chapter-3: Mathematics ............................................................................................................................................... 21
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3.0 Introduction ........................................................................................................................................................ 21
Chapter-4: Thermodynamics .......................................................................................................................................22
4.0 Introduction ........................................................................................................................................................22
Chapter-5: Reaction Engineering ...............................................................................................................................23
5.0 Introduction ........................................................................................................................................................23
5.1 Generalized View of Chemical Reactor Design ........................................................................................23
5.2 General Mole Balance Equation (G.M.B.E.) ................................................................................................25
5.3 Application of G.M.B.E to Industrial Reactors ............................................................................................29
5.3.1 Mole Balance for Batch Reactor (BR) ..................................................................................................29
5.3.2 Mole Balance for Continuous Stirred Tank Reactor (CSTR) .........................................................30
5.3.3 Mole Balance for Plug Flow Reactor (PFR) ........................................................................................ 31
5.3.4 Mole Balance for Packed Bed Reactor (PBR)....................................................................................34
5.4 Reaction Coordinates and their Applications ............................................................................................36
5.4.1 Reaction Conversion ...............................................................................................................................37
5.4.2 Mole Balances in terms of Conversion ...............................................................................................37
5.4.3 Reaction Concentration ..........................................................................................................................42
5.4.4 Reaction Stoichiometry ...........................................................................................................................42
5.4.5 Reaction Phase..........................................................................................................................................45
5.4.6 Reaction Types ..........................................................................................................................................53
5.4.7 Reaction Rates...........................................................................................................................................55
5.4.8 Reaction Rate Law....................................................................................................................................57
5.4.9 Reaction Rate Constant ..........................................................................................................................62
5.4.10 Reaction Equilibrium Constant .............................................................................................................63
5.4.11 Reaction Extent ......................................................................................................................................... 71
5.4.12 Reaction Selectivity and Yield ...............................................................................................................76
5.4.13 Space Time and Space Velocity ........................................................................................................... 77
5.5 Reactor Pressure Drop .....................................................................................................................................78
5.5.1 Pressure Drop in PFR ..............................................................................................................................79
5.5.2 Pressure Drop in PBR ..............................................................................................................................84
5.6 General Energy Balance Equation (G.E.B.E) ...............................................................................................92
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5.6.1 The Accumulation Term .........................................................................................................................94
5.6.2 The Inlet and Outlet Energy Flow Terms ...........................................................................................96
5.6.3 The Work Term .........................................................................................................................................98
5.6.4 The Enthalpy Term ...................................................................................................................................99
5.7 Application of G.E.B.E to Industrial Reactors ........................................................................................... 102
5.7.1 Energy Balance for Batch Reactor (BR) ............................................................................................ 102
5.7.2 Energy Balance for Continuous Stirred Tank Reactor (CSTR) .....................................................115
5.7.3 Energy Balance for Plug Flow Reactor (PFR) ...................................................................................119
5.7.4 Energy Balance for Packed Bed Reactor (PBR) .............................................................................. 132
Chapter-6: Transport Phenomena ........................................................................................................................... 136
6.0 Introduction ...................................................................................................................................................... 136
Chapter-7: Process Synthesis..................................................................................................................................... 138
7.0 Introduction ...................................................................................................................................................... 138
7.1 Process Terminologies ................................................................................................................................... 139
7.2 Process Design ..................................................................................................................................................141
7.2.1 Step-1: Collection of Information ........................................................................................................141
7.2.2 Step-2: Experimentation....................................................................................................................... 142
7.2.3 Step-3: Preliminary Process Synthesis .............................................................................................. 142
7.2.4 Step-4: Other Process Design Tasks ................................................................................................. 163
7.2.5 Step-5: Decision of Preliminary Flowsheet ...................................................................................... 163
7.2.6 Step-6: Perform Process Simulation ................................................................................................. 177
7.3 Plant Design .......................................................................................................................................................181
Chapter-8: Process Intensification ............................................................................................................................ 182
8.0 Introduction ...................................................................................................................................................... 182
Chapter-9: Process Optimization ............................................................................................................................. 183
9.0 Introduction ...................................................................................................................................................... 183
Chapter-10: Process Control ...................................................................................................................................... 184
10.0 Introduction ...................................................................................................................................................... 184
Chapter-11: Process Safety.......................................................................................................................................... 185
11.0 Introduction ...................................................................................................................................................... 185
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Chapter-12: Process Modelling and Simulation ................................................................................................... 187
12.0 Introduction ...................................................................................................................................................... 187
Appendices ..................................................................................................................................................................... 188
Appendix-A:.................................................................................................................................................................... 189
Appendix-B: .................................................................................................................................................................... 190
Appendix-C:.....................................................................................................................................................................191
Appendix-D: ................................................................................................................................................................... 192
Appendix-E: .................................................................................................................................................................... 193
Appendix-F: .................................................................................................................................................................... 194
References ....................................................................................................................................................................... 197
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About the authors
Dr. Engr. Nadeem Feroze

Ex-Dean of Chemical, Metallurgical, and Polymer Engineering
University of Engineering and Technology (UET) Lahore, Pakistan
Dr. Nadeem Feroze was a dean of faculty and a reputable Professor in the Department of Chemical Engineering, University
of Engineering and Technology (UET) Lahore. He did his Ph.D. in Chemical Engineering from the University of Manchester,
Institute of Science and Technology (UMIST), Manchester, UK in 1997. And he did his M.S. in Chemical Engineering from
UET Lahore in 1990. Moreover, his B.S. in Chemical Engineering was also from UET Lahore (1981).
Engr. Anees Ahmad

Research Associate (Chemical and Process Engineering), Microsoft .NET Developer
University of Engineering and Technology (UET) Lahore, Pakistan
Engr. Anees Ahmad was a Research Associate in the Department of Chemical Engineering, UET Lahore. He did his M.S. in
Chemical Engineering with specialization in Process Engineering from UET Lahore in 2018. And he did his B.S. in Chemical
Engineering from COMSATS Lahore, Pakistan in 2015. Moreover, his areas of specialization are Process Synthesis, Process
Optimization, Process Control, Process Safety, and Process Modelling and Simulation. In addition to the specialization areas
he has excellent expertise in the core areas of chemical engineering like Thermodynamics, Reaction Engineering, and
Transport Phenomena.
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Preface
As everyone knows there are many books present on Chemical and Process Engineering in the
world. But this book is mainly intended for the supply of all the basic and advanced concepts
of chemical and process engineering. This book covers four main core areas of chemical and
process engineering like Mathematics, Thermodynamics, Reaction Engineering, and Transport
Phenomena in a very comprehensive way. These four areas will help students of graduate and
undergraduate level to understand the concepts in a minimum possible time but in a very
comprehensive way. The material presented here is basically a collection of information
extracted from different books of international standards. This book also covers Process
Synthesis, Process Intensification, Process Optimization, Process Control, Process Safety, and
Process Modelling and Simulation. These six areas correspond to the specialization of process
engineering and process systems engineering at postgraduate level.
Chapter 1 will introduce the introductory material. While Chapter 2 will focus on the description
of core and specialization areas of chemical and process engineering. Chapter 3 is intended
for the collection of mathematical techniques and their applications to solve problems which
can arise in chemical and process engineering. Chapter 4 will introduce the fundamentals and
advanced concepts of phase equilibrium, chemical equilibrium, and thermodynamic analysis
of chemical processes. It will also help students in the selection of operating conditions of a
chemical processing unit in addition to the exploration of restrictions imposed on the process
due to equilibrium. Chapter 5 deals with the fundamental and advanced topics related to
chemical reaction engineering for the rate-based analysis and design of chemical reactors.
Chapter 6 will develop mathematical relationships for the microscopic conservation of
momentum, energy, and mass by different possible mechanisms. Chapter 7 will give us the
shortcut and rigorous procedures for computer-aided process synthesis in addition to standard
methods of chemical equipment design (Reactors, Separators, Exchangers etc.). Chapter 8
deals with advanced techniques of conserving energy and material with the help of changes in
the plant design and plant configuration by using process intensification. Chapter 9 is focused
on the optimization of the design and operating conditions of processing units. Chapter 10 and
Chapter 11 will provide detailed methods and understanding of process control and process
safety respectively. Moreover, Chapter 12 will introduce the mathematical modelling of physical
and chemical processes. Commercial process simulator used to solve process models will also
be discussed in detail in Chapter 12.
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Nomenclature
Symbols (Applicable for all Chapters):
Symbol Description Unit
Generalized Symbols
m Mass kg
n Mole kgmol
M Molar Mass kg/kgmol
t Time s
T Temperature K
P Pressure Pa
x x-Coordinate m
y y-Coordinate m
z z-Coordinate (Axial Coordinate) m
r Radial Coordinate m
θ Tangential Coordinate Radian
φ Spherical Coordinate Radian
R Radius m
d Diameter m
A Area m2
V Volume m3
v Velocity m/s
g Gravitational Acceleration m/s2
h Height m
ρ Mass Density kg/m3
C Molar Density kgmol/m3
ო Mass Flowrate kg/s
F Molar Flowrate kgmol/s
υ Volumetric Flowrate m3/s
ϑ Mass Concentration kg/m3
c Molar Concentration kgmol/m3
ω Mass Fraction Unitless
x Mole Fraction Unitless
Thermodynamic Symbols
R Ideal Gas Constant J/kgmol⋅K
Z Compressibility Factor Unitless
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E Total Energy J
K.E. Kinetic Energy J
P.E. Potential Energy J
Ek Molar Kinetic Energy J/kgmol
Ep Molar Potential Energy J/kgmol
Q Heat J
W Work J
U t
Total Internal Energy J
H t
Total Enthalpy J
S t
Total Entropy J/K
At Total Helmholtz Free Energy J
G t
Total Gibbs Free Energy J
U Molar Internal Energy J/kgmol
H Molar Enthalpy J/kgmol
S Molar Entropy J/kgmol⋅K
A Molar Helmholtz Free Energy J/kgmol
G Molar Gibbs Free Energy J/kgmol
Hf Molar Enthalpy of Formation J/kgmol
Sf Molar Entropy of Formation J/kgmol⋅K
Gf Molar Gibbs Free Energy of Formation J/kgmol
Hrxn Molar Enthalpy of Reaction J/kgmol
Srxn Molar Entropy of Reaction J/kgmol⋅K
Grxn Molar Gibbs Free Energy of Reaction J/kgmol
Hfu Molar Enthalpy of Fusion J/kgmol
Hsf Molar Enthalpy of Solidification J/kgmol
Hvap Molar Enthalpy of Vaporization J/kgmol
Hcond Molar Enthalpy of Condensation J/kgmol
Hsub Molar Enthalpy of Sublimation J/kgmol
Hdsub Molar Enthalpy of De-Sublimation J/kgmol
Tm Melting Point K
Tb Boiling Point K
Tt Phase Transition Temperature K
Cv Molar Heat Capacity at Constant Volume J/kgmol⋅K
Cp Molar Heat Capacity at Constant Pressure J/kgmol⋅K
Fp Fluid Phase (Fp = 0 for Liquids) (Fp = 1 for Gases) Unitless
f Fugacity Pa
Reaction Engineering Symbols

ν Stoichiometric Number / Change in Total Moles Unitless
ε Extent of Reaction kgmol or kgmol/s
X Conversion Unitless
SD/U Instantaneous Selectivity Unitless
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S̅ D/U Overall Selectivity Unitless
YD Instantaneous Yield Unitless
Y̅ D Overall Yield Unitless
r Rate of Reaction [Homogeneous System] kgmol/m3⋅s
rPrime Rate of Reaction [Heterogeneous System] kgmol/kg⋅s
k Reaction Rate Constant Dynamic
A Arrhenius Constant / Frequency Factor Dynamic
Ea Activation Energy J/kgmol
K True Chemical Equilibrium Constant Unitless
KC Chemical Equilibrium Constant [Concentration based] Dynamic
KP Chemical Equilibrium Constant [Pressure based] Dynamic
Ka Catalyst Adsorption Constant Dynamic
ST Space Time s
SV Space Velocity 1/s
ϕ Porosity / Void Fraction Unitless
Transport Phenomena Symbols

μ Viscosity Pa⋅s
F Fanning Friction Factor Unitless
Q̇ Heat Transfer Rate J/s
K.E.Rate Kinetic Energy Rate J/s
P.E.Rate Potential Energy Rate J/s
Uh Overall Heat Transfer Coefficient J/s⋅m2⋅K
As Heat Transfer Surface Area m2
Ta Temperature of Heat Transfer Fluid K
Re Reynolds Number Unitless
ϕp Pipe Roughness Unitless
hp Height of Protuberances m
ɑv Specific Surface Area 1/m
σ Collision Diameter Å
Ωμ Collision Integral for Viscosity Unitless
∁αβ Empirical Correction Factor for Viscosity Unitless
ϐ Characteristic Energy J
κ Boltzmann’s Constant J/K
Subscripts
ref Value at Reference State
0 Initial or Inlet Quantity
h Material Stream “h”
i Chemical Species “i”
j Chemical Reaction “j”
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s Solid Phase
l Liquid Phase
g Gas Phase
T Total Quantity
e Equilibrium Condition
r Reactor Condition
p Particle Condition
c Critical Property / Catalyst Particle Condition
rxn Chemical Reaction
Superscripts
o Value at Standard State (At Tref = 298.15 K and Pref = 1 atm)
Notes
~ Tilde on a symbol denotes a property value per unit mole

^ Circumflex on a symbol denotes a property in solution
· Dot on a symbol denotes a property per unit time
∆ Delta denotes a change in the variable
Note: There are some chapter specific symbols which are explained where they are declared.
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Chapter-1
Introduction
1.0 Introduction to Chemical Engineering (CE)

Chemical engineering is a branch of engineering that uses principles of chemistry, physics,
mathematics, biology, and economics to efficiently convert raw materials into useful products.
Areas of Chemical Engineering Main Branches of Chemical

• Plant Design Engineering[1]
• Plant Operation • Process Engineering
• Plant Analysis • Energy Engineering
• Plant Troubleshooting • Biochemical Engineering
Chemical
Engineering
Figure 1.1: Branches of Chemical Engineering*
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1.0.1 Process Engineering
It is the branch of chemical engineering which deals with the creation of new processes in
addition to conducting their control, optimization, intensification, and safety studies with the
help of specialized computer simulation software packages and theoretical techniques.
1.0.2 Energy Engineering

In this branch of chemical engineering, generation of energy by the combustion of coal,
petroleum, or natural gas is studied. It also deals with the energy conservation and auditing of
chemical processes and their environment impact assessment.
1.0.3 Biochemical Engineering

Biochemical engineering is the branch of chemical engineering which deals with the analysis,
troubleshooting, and design of biochemical reactors and separators along with the
development of biofuels and biorefineries. It also deals with the safe biochemical treatment
and disposal of industrial wastes.
Footnotes:
* There are other branches of chemical engineering like polymer engineering, nuclear chemical engineering,
electrochemical engineering etc., But here only the Process Engineering will be discussed.
14
Chapter-2
Process Engineering
2.0 Introduction to Process Engineering (PE)

Process engineering is further subdivided into four core areas and five specialization areas.
Each core area builds a base for every specialization area, while each specialization area covers
detailed aspects of the chemical processes.
Core Areas of Process Engineering[1]
• Mathematics → Maps to the course of Chemical Engineering Mathematics

• Thermodynamics → Maps to the course of Chemical Engineering Thermodynamics
• Reaction Engineering → Maps to the course of Chemical Reaction Engineering
• Transport Phenomena → Maps to the course of Transport Processes
Specialization Areas of Process Engineering[1]
• Process Synthesis → Maps to the course of Computer-Aided Process Synthesis

• Process Intensification → Maps to the course of Process Intensification
• Process Optimization → Maps to the course of Optimization of Chemical Processes
• Process Control → Maps to the course of Advanced Process Control
• Process Safety → Maps to the course of Advanced Process Safety
Branches of Process Engineering
• Process Systems Engineering
Specialization Areas
Process Synthesis, Process Intensification, Process Optimization, Process Control, Process Safety
Core Areas
Mathematics, Thermodynamics, Reaction Engineering, and Transport Phenomena
Process Engineering
Figure 2.1: Building blocks of Process Engineering
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2.1 Core Areas
Description of each core area is presented below.
2.1.1 Mathematics
Mathematics is the base of every engineering discipline. Subject of mathematics is used to
develop and solve the mathematical modelling equations of the different physical and chemical
phenomena occurring in the processing equipment. Study of mathematics with respect to
engineering perspective includes Arithmetic, Algebra, Trigonometry, Matrices and
Determinants, Sequence and Series, Vectors, Tensors, Basic Calculus, Differential Calculus,
Integral Calculus, Vector Calculus, Tensor Calculus, Ordinary Differential Equations, Partial
Differential Equations, Integral Equations, Integral Transforms, Analytical Geometry, and
Numerical Analysis.
2.1.2 Thermodynamics
Thermodynamics uses the mathematics as a tool to quantify physical and chemical equilibrium
processes. First law of thermodynamics (i.e. statement of the law of conservation of energy)
provides us a strong foundation for the mathematical modelling of physical and chemical
processes involving many types of energy changes [e.g. Heat (Q), Work (W), Internal Energy
(Ut), and Enthalpy (Ht)]. Second law of thermodynamics (i.e. related to the Entropy (St)
generation of universe) gives us the quantitative relationships to demonstrate the possibility of
physical existence of a theoretical chemical process. Third law of thermodynamics is related to
the absolute value of entropy change of a crystalline solid.
2.1.3 Reaction Engineering

Chemical reaction engineering is used for the mathematical modelling of chemical reactors. It
is also used to analyze, design, and troubleshoot different types of chemical reactors e.g. Batch
Reactor (BR), Continuous Stirred Tank Reactor (CSTR), Plug Flow Reactor (PFR), Packed Bed
Reactor (PBR), and Fluidized Bed Reactor (FBR). Field of Catalysis is also discussed under
chemical reaction engineering.
2.1.4 Transport Phenomena

It is the branch of physics which is utilized for the differential and integral mathematical
modelling of physical and chemical processes which involves the transfer of momentum,
energy, and mass. Newton’s law of viscosity, Fourier’s law of heat conduction, and Fick’s first
law of diffusion governs molecular mechanisms of momentum, energy, and mass transport,
respectively. Complete momentum transfer involves molecular and convective transport
16
mechanisms. And complete energy transfer involves molecular, convective, and radiative
transport mechanisms. Moreover, the complete transfer of mass follows molecular and
convective mechanisms.
2.2 Specialization Areas

Description of each specialization area is presented below.
2.2.1 Process Synthesis

Process synthesis is also known as process design or process creation. In this area a completely
new process is invented from the idea of product conception. This area utilizes many theoretical
techniques in combination with computer simulation software to invent a feasible process in
an iterative manner. Several process heuristics are employed in this phase of process creation
to arrive at a feasible process design. Block flow diagrams (BFD’s) and Process flow diagrams
(PFD’s) are created in the result of process synthesis.
2.2.2 Process Intensification

In the area of process intensification several different alternative unit operations are tested for
the replacement of already installed unit operation to control and minimize the utilization of
energy and work. It is also used to modify the configuration of equipment design for the most
economical operation. It also involves the use of micro equipment and rotational equipment
for building the most economical process.
2.2.3 Process Optimization

Process optimization utilizes many different mathematical and numerical techniques for the
determination of process design and operating conditions under some constraints in such a
way as to minimize the cost and to maximize the profit. It also involves the structural
optimization of chemical processes.
2.2.4 Process Control

In the area of process control many different process control configurations are implemented
on the process to maintain the values of process output variables at their specified steady state
values under dynamically changing process input variables. It also involves the design of
controllers. It is used to make a process automatically controlled by an analog controller or by
a digital computer. Piping and instrumentation diagrams (P&ID’s) are developed in the result
of successful process control.
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2.2.5 Process Safety
Area of process safety gives us many different techniques like Hazard and Operability Study
(HAZOP), Fault Tree Analysis (FTA), Event Tree Analysis (ETA), Bow and Tie Analysis (BTA) etc.
These techniques are used to conduct the process safety analysis of a chemical process using
their P&ID’s. It is also used for the environmental impact assessment of chemical processes as
well as for the process safety management (PSM).
2.3 Introduction to Process Systems Engineering (PSE)

Process Systems Engineering (PSE) is an interdisciplinary field, focusing on the design and
operation of complex production systems. More specifically, it focuses on the development
and application of modelling and computational methods to simulate, design, control and
optimize complex processes. These are studied through the mathematical description of the
underlying physiochemical and biochemical phenomena. [2]
Areas of Process Systems Engineering
• Process Modelling and Simulation
2.3.1 Process Modelling and Simulation

Process modelling is used to express the unit operations and unit processes into the
mathematical modelling equations like Algebraic Equations (AEs), Ordinary Differential
Equations (ODEs), Partial Differential Equations (PDEs), Differential and Algebraic Equations
(DAEs), Integral Equations (IE), and Integro-Differential Equations (IDEs). Simulation is the
process of finding the analytical or numerical solution of the mathematical model equations
using theoretical or computer techniques. Solutions of the mathematical model equations help
us to find the unknown physical and chemical properties of the chemical species involved in
the process. These results also help us to find the unknown process variables which can be
used in the phases of process synthesis, process intensification, process optimization, process
control, and process safety.
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2.4 Tree Diagram
The following diagram can be used to conceptualize the whole theory:
• Process Synthesis
• Plant Design
• Process Intensification
• Plant Operation
• Process Optimization Chemical Engineering • Plant Analysis
• Process Control
• Plant Troubleshooting
• Process Safety
Process Engineering Energy Engineering Biochemical Engineering
Process Systems
• Process Modelling and Simulation
Engineering
Figure 2.2: Area and branch and diagram
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Section-I
Core Areas of Process Engineering
Reaction Transport
Mathematics Thermodynamics
Engineering Phenomena
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Chapter-3
Mathematics
Chemical Engineering Mathematics
3.0 Introduction
Coming soon.
21
Chapter-4
Thermodynamics
Chemical Engineering Thermodynamics
4.0 Introduction
Coming soon.
22
Chapter-5
Reaction Engineering
Chemical Reaction Engineering
5.0 Introduction
Reaction engineering is one of the core parts of chemical and process engineering. It is used
to understand chemical phenomena occurring within the chemical reactors. It is also used in
the following scenarios as well: [3]
• To study the effects of Catalysts on Reaction Rate

• In the development of Chemical Reaction Mechanisms
• In the development of Chemical Reaction Kinetics
• In the development of Mole and Energy Balances of Chemical Reactors
• To design the Chemical Reactors
• To find the performance of Chemical Reactors
5.1 Generalized View of Chemical Reactor Design

Chemical reactor design scenario is governed by five different factors:
• Thermodynamic Operation Consideration (Isothermal, Adiabatic, or Non-Isothermal)

• Fluid Dynamics Consideration (Without Pressure Drop, or With Pressure Drop)
• Reaction Engineering Consideration (Single Reaction, or Multiple Reactions)
• Fluid Phase Consideration (Liquid Phase, Gas Phase, Two Phase, or Three Phase)
• Operating Mode Consideration (Batch, Steady State Continuous, or Unsteady State
Continuous)
Possible combinations of these factors dictate a specific reactor design method for each case.
If we exclude two phase, and three phase reactor design; then 72 different reactor design
scenarios arise with different reactor design equations. Each scenario can be visualized easily
with the help of Figure 5.1 as shown below: [3]
23
Batch
Liquid Phase Steady State
Single Continuous
Chemical Unsteady State
Reaction Batch
Gas Phase Steady State
Continuous
Without Unsteady State
Pressure Drop
Batch
Multiple Continuous
Isothermal
Operation Reactions Batch
OR Gas Phase Steady State
Adiabatic Continuous
Operation
Reactor
OR Batch
Non-
Isothermal Single Continuous
Operation Chemical Unsteady State
Reaction Batch
Continuous
With Unsteady State
Pressure Drop
Batch
Multiple Continuous
Reactions Batch
Continuous
Unsteady State
Figure 5.1: Possible Reactor Design Scenarios
Why each unique scenario dictates a different set of mathematical model equations?
ANSWER:
With respect to Thermodynamic Operation Consideration:
• If thermodynamic operation is isothermal, then there is no need to include the energy

balance equation in the mathematical model of the reactor for design and analysis
purposes.
24
• If thermodynamic operation is adiabatic then there is a need to include the energy
balance equation for the reactor itself.
• If thermodynamic operation is non-isothermal, then there is a need to include the
energy balance equation for the reactor itself as well as for the heating or cooling utility.
With respect to Fluid Dynamics Consideration:
• If there is no or negligible pressure drop then there is no need to include the pressure
drop equation.
• If there is a pressure drop then there is a need to include the pressure drop equation.
With respect to Reaction Engineering Consideration:
• If there is a single chemical reaction occurring in the reactor then only component mole
balance equation for limiting reactant is needed to design the reactor.
• If there are multiple chemical reactions occurring in the reactor then component mole
balance equations for all present components (reactive + inert) are needed to design
the reactor.
With respect to Fluid Phase Consideration:
• If there is a liquid phase chemical reaction occurring in the reactor then equation for
the liquid density = f (Temperature, Pressure, Composition) is needed.
• If there is a gas phase chemical reaction occurring in the reactor then equation of state
is needed which gives us the gas density = f (Temperature, Pressure, Composition).
With respect to Operating Mode Consideration:
• If the operating mode is batch then unsteady state mole balance equation is needed.
• If the operating mode is continuous then unsteady state and/or steady state mole
balance is needed.
5.2 General Mole Balance Equation (G.M.B.E.)

To perform a mole balance on any system, the system boundaries must first be specified. The
volume enclosed by these boundaries is referred to as the system volume. We shall perform a
mole balance on species “i” in a system volume V, where species “i” represents the particular
chemical species of interest, such as water or NaOH. [3]
25
Fi0 Fi
Gi
System Volume (V)
Figure 5.2: Mole balance on species “i” in a system of volume V
A mole balance on species “i” for a time duration of ∆t, yields the following equation:
[In] - [Out] + [Generation] - [Consumption] = [Accumulation] (Eq. 5.2.1)
[In] - [Out] ± [Generation and/or Consumption] = [Accumulation]
Generation
and/or consumption Accumulation
Moles Moles
of i
of i into of i out of of i by chemical
[the system] - [the system ] ± = within
reaction within the system
(kgmol) (kgmol) the system
[ (kgmol) ]
[ (kgmol) ]
Fi0 ∆t - Fi ∆t ± gi ∆t = ni |t+∆t -ni |t
ni |t+∆t -ni |t
Fi0 - Fi ± gi =
∆t
ni |t+∆t -ni |t
lim (Fi0 - Fi ± gi ) = lim
∆t→0 ∆t→0 ∆t
Right side of this equation becomes the definition of the derivative.
dni
Fi0 - Fi ± gi =
dt
If we embed (±) sign into the value of (Gi=±gi) term then,
dni
Fi0 - Fi + Gi = (Eq. 5.2.2)
dt
In this equation, Fi0 and Fi represents molar flowrates of species i at inlet and outlet, respectively.
And ni represents the number of moles of species i in the system at any instant of time. If all
the system variables (e.g., temperature, catalytic activity, and concentration of the chemical
species) are spatially uniform throughout the system volume, the rate of generation of species
i, Gi, is just the product of the reaction volume, V, and the rate of reaction of species i, ri.
G i = ri V
26
Where, ri represents the rate of reaction of species i which is the number of moles of i (e.g.,
chlorine) reacting (disappearing -ve) and/or producing (appearing +ve) per unit time per unit
volume (kgmol/m3⋅s).
Now suppose that the rate of reaction of species i for the reaction varies with position in the
system volume. That is, it has a value ri1 at location 1, which is surrounded by a small volume,
delta V1 within which the rate is uniform; similarly, the reaction rate has a value ri2 at location
2 and an associated volume, delta V2, and so on (Figure 5.3).
ri1
ri2
Figure 5.3: Dividing up the system volume, V
Then the rates of generation for each individual small volume will be:
∆Gi1 =ri1 ∆V1
∆Gi2 =ri2 ∆V2
∆Gi3 =ri3 ∆V3
If the total system volume is divided into n sub-volumes, then for the nth sub-volume:
∆Gi,n =ri,n ∆Vn
Hence, the total rate of generation will be the sum of individual rates of generation:
n
Gi =∆Gi1 +∆Gi2 +∆Gi3 …+∆Gi,n = ∑ ∆Gik

k=1
n
Gi =ri1 ∆V1 +ri2 ∆V2 +ri3 ∆V3 …+ri,n ∆Vn = ∑ rik ∆Vi
k=1
If number of sub-volumes approaches infinity then a point value can be calculated by:
27
n
lim Gi = lim ∑ rik ∆Vi

n→∞ n→∞
k=1
Using definition of integral:

V
Gi = ∫ ri dV (Eq. 5.2.3)
0
Here,
V
Gi =±Value of Gi= ∫ (± Value of ri )dV
0
So, sign convention (+ve for species i formation) and (-ve for species i disappearance) is
included into the value of rate of reaction (i.e. Rate Law ri =+ve or -ve).
By putting Eq. 5.2.3 in 5.2.2:

V
dni
= Fi0 - Fi + ∫ ri dV (Eq. 5.2.4)
dt 0
Eq. 5.2.4 is the GENERAL MOLE BALANCE EQUATION for species i, if the reactor has only
single inlet and single outlet. For Multi-Stream Reactor (having multiple inlets and multiple
outlets) the flows must be summed over all inlet and outlet streams:
Nin Nout V
dni
= ∑ Fi0,h - ∑ Fi,h + ∫ ri dV (Eq. 5.2.4b)
dt 0
h=1 h=1
Here,
Nin = Total number of inlets of the reactor

Nout = Total number of outlets of the reactor
From this general mole balance equation, we can develop the design equations for the various
types of industrial reactors: batch, semi-batch, and continuous flow. Upon evaluation of these
equations, we can determine the time (batch) or reactor volume (continuous flow) necessary
to convert a specified amount of the reactants into products.
28
5.3 Application of G.M.B.E to Industrial Reactors
Most common reactor types are:
• Batch Reactor (BR) [Batch Operation]

• Continuous Stirred Tank Reactor (CSTR) [Continuous Operation]
• Plug Flow Reactor (PFR) [Continuous Operation]
• Packed Bed Reactor (PBR) [Continuous Operation]
5.3.1 Mole Balance for Batch Reactor (BR)

A batch reactor is used for small-scale operation, for testing new processes that have not been
fully developed, for the manufacture of expensive products, and for processes that are difficult
to convert to continuous operations. The reactor can be charged (i.e., filled) through the holes
at the top (see Figure 5.4). The batch reactor has the advantage of high conversions that can
be obtained by leaving the reactant in the reactor for long periods of time, but it also has the
disadvantages of high labor costs per batch, the variability of products from batch to batch,
and the difficulty of large-scale production. [3]
Figure 5.4: Batch Reactor (BR)
A batch reactor has neither inflow nor outflow of reactants or products while the reaction is
being carried out: Fi0 = Fi = 0. Then according to Eq. 5.2.4:
V
dni
=Fi0 - Fi + ∫ ri dV
dt 0
V
dni
=0 - 0+ ∫ ri dV
dt 0
V
dni
= ∫ ri dV
dt 0
29
If the reaction mixture is perfectly mixed (as shown in Figure 5.4) so that there is no variation
in the rate of reaction throughout the reactor volume, we can take r i out of the integral,
integrate, and write the mole balance in the form:
V
dni
=r ∫ dV =ri (V-0)
dt i 0
dni
= ri V (Eq. 5.3.1)
dt
This is the specific mole balance equation for Batch Reactor (BR). Batch reactor always operates
at unsteady state.
5.3.2 Mole Balance for Continuous Stirred Tank Reactor (CSTR)

A type of reactor commonly used in industrial processing is the stirred tank operated
continuously (Figure 5.5). It is referred to as the continuous-stirred tank reactor (CSTR) or vat,
or back mix reactor, and is primarily used for liquid-phase reactions. It is normally operated at
steady state and is assumed to be perfectly mixed; consequently, there is no position
dependence of the temperature, concentration, or reaction rate inside the CSTR. That is, every
variable is the same at every point inside the reactor. Because the temperature and
concentration are identical everywhere within the reaction vessel, they are the same at the exit
point as they are elsewhere in the tank. Thus, the temperature and concentration in the exit
stream are modeled as being the same as those inside the reactor. In systems where mixing is
highly nonideal, the well-mixed model is inadequate, and we must resort to other modeling
techniques, such as residence time distributions, to obtain meaningful results. [3]
Figure 5.5: Continuous Stirred Tank Reactor (CSTR)
30
Then according to Eq. 5.2.4:
V
dni
=Fi0 - Fi + ∫ ri dV
dt 0
Due to perfect mixing, we can take ri out of the integral, integrate, and write the mole balance
in the form:
V
dni
=Fi0 - Fi +ri ∫ dV
dt 0
dni
=F - F +r (V-0)
dt i0 i i
dni
=F - F +r V (Eq. 5.3.2)
dt i0 i i
This is the specific mole balance equation for Unsteady State Operation of Continuous Stirred
Tank Reactor (CSTR).
For Steady State Operation (ni does not change with time):
dni
=0
dt
Hence,
Fi0 - Fi +ri V=0 (Eq. 5.3.3)
5.3.3 Mole Balance for Plug Flow Reactor (PFR)

In addition to the BR and CSTR, another type of reactor commonly used in industry is the
tubular reactor or plug flow reactor. It consists of a cylindrical pipe and is normally operated at
steady state, as is the CSTR. Tubular reactors are used most often for gas-phase reactions.
Schematic and a photograph of industrial tubular reactors are shown in Figure 5.6.
In the tubular reactor, the reactants are continually consumed as they flow down the length of
the reactor. In modeling the tubular reactor, we assume that the concentration varies
continuously in the axial direction through the reactor. Consequently, the reaction rate, which
is a function of concentration for all but zero-order reactions, will also vary axially. [3]
31
Figure 5.6: Bundle of Industrial PFRs
For the purposes of the material presented here, we consider systems in which the flow field
may be modeled by that of a plug-flow profile (e.g., uniform velocity as in turbulent flow), as
shown in Figure 5.7. That is, there is no radial variation in reaction rate, and the reactor is
referred to as a Plug Flow Reactor (PFR).
Figure 5.7: Plug Flow Reactor (PFR)

V
dni
=F - F + ∫ r dV
dt i0 i 0 i
In PFR there is not perfect mixing, so, the values of Fi, ci, ni and ri will also vary with axial direction
(i.e. x or more formally with V). Hence, we consider a volume element of volume (dV) and
length (dx) which have an area of cross section (A) equal to that of PFR (as shown in Figure
5.8). So, with increase in the value of “dx” value of (dV=Adx) will also increases. Hence, we must
differentiate Eq. 5.2.4 with respect to V to get point value changes in the axial direction as well.
For Unsteady State Operation:
Fi =Fi (V,t) and ni =ni (V,t) and ri =ri (V,t)
32
Figure 5.8: PFR differential volume element
So, Eq. 5.2.4 will be converted to Partial Differential Equation (PDE) instead of an Ordinary
Differential Equation (ODE).
V
∂ni
=Fi0 - Fi + ∫ ri ∂V
∂t 0
Partially differentiate this equation w.r.t V:

V
∂ ∂ni ∂
( ) = (Fi0 - Fi + ∫ ri ∂V)
∂V ∂t ∂V 0
∂ ci ∂V ∂Fi ∂ V implies that ∂ni

( ) = (0 - + ∫ r ∂V) ⇐ ci =
∂V ∂t ∂V ∂V 0 i ∂V
∂ci ∂Fi
=- +r (Eq. 5.3.4)
∂t ∂V i
For Steady State Operation of PFR (ci =Molar Concentration (kgmol/m3) ≠ ci(t) and Fi = f(V)
alone), So PDE will be converted back to an ODE:
dFi
0=- +r
dV i
dFi
= ri (Eq. 5.3.5)
dV
33
5.3.4 Mole Balance for Packed Bed Reactor (PBR)
Packed Bed Reactor (PBR) is also known as a Fixed Bed Reactor (FBR) or Industrial Catalytic
Reactor (ICR).
The principal difference between reactor design calculations involving homogeneous reactions
and those involving fluid-solid heterogeneous reactions is that for the latter, the reaction takes
place on the surface of the catalyst. [3]
The greater the mass of a given catalyst, the greater the reactive surface area. Consequently,
the reaction rate is based on mass of solid catalyst, W, rather than on reactor volume, V. For a
fluid–solid heterogeneous system:
ni,reacting
ri, Prime =
t⋅W
Where ri, Prime represents the rate of reaction of species i which is the number of moles of i (e.g.,
chlorine) reacting (disappearing -ve) and/or producing (appearing +ve) per unit time per unit
weight of catalyst (kgmol/kg⋅s).
There is a relationship between Homogeneous Reaction Rate (r i) and the Heterogeneous

Reaction Rate (ri, Prime):
W
ri =ρb ×ri, Prime and ρb = (Eq. 5.3.6a and 5.3.6b)
Vtotal bed
Here, ρb represents the Bulk Density of Catalyst (kg/m3). The ρb (mass of catalyst per unit
volume of total bed) is just the product of the density of the solid catalyst particles ρc and the
fraction of solids (1-ϕ):
ρb =ρc ×(1-ϕ) (Eq. 5.3.7)
mcatalyst particles Vvoid Vsolid particles
ρc = and ϕ= and 1-ϕ= (Eq. 5.3.8a, b, c)
Vcatalyst particles Vtotal bed Vtotal bed
Where ϕ represents the Porosity (or Void Fraction) (Unitless) and V represents respective
volumes (m3).
So, the catalyst weight can be calculated practically from:

W=(1-ϕ)×V×ρc (Eq. 5.3.9)
The reactor volume that contains the catalyst is of secondary significance. Figure 5.9 shows a
schematic of an industrial catalytic reactor (PBR) with vertical tubes packed with solid catalyst.
34
Figure 5.9: Packed Bed Reactor (PBR)
In the three idealized types of reactors just discussed (the perfectly mixed batch reactor, the
plug-flow or tubular reactor [PFR], and the perfectly mixed continuous-stirred tank reactor
[CSTR]), mole balances were developed based on reactor volume. The derivation of the mole
balance for a packed-bed catalytic reactor (PBR) will be carried out in a manner analogous to
the development of the PFR mole balance. To accomplish this derivation, we simply replace
the volume coordinate in Equation 5.2.4 with the catalyst mass (i.e., weight) coordinate W. And
homogeneous rate of reaction will be replaced with heterogeneous rate of reaction.

W
dni
=Fi0 - Fi + ∫ ri, Prime dW (Eq. 5.3.10)
dt 0
In PBR there is not perfect mixing, so, the values of F i, ci, ni and ri, Prime will also vary with axial
direction (i.e. x or more formally with W). Hence, we consider a weight element of weight (dW)
(as shown in Figure 5.10). Hence, we must differentiate Eq. 5.3.10 with respect to W to get point
value changes in the axial direction as well. For Unsteady State Operation:
Fi =Fi (W,t) and ni =ni (W,t) and ri =ri (W,t)
35
Fi0 Fi
Fi (W) Fi (W+∆W)
Figure 5.10: Catalytic Reactor Weight Element
So, Eq. 5.3.10 will be converted to Partial Differential Equation (PDE) instead of an Ordinary
Differential Equation (ODE).
W
∂ni
=Fi0 - Fi + ∫ ri, Prime ∂W
∂t 0
Partially differentiate this equation w.r.t W:

W
∂ ∂ni ∂ implies that ∂ni
( )= (Fi0 - Fi + ∫ ri, Prime ∂W) ⇐ ci =
∂W ∂t ∂W 0 ∂V
∂ ci ∂V ∂Fi ∂ W implies that

( ) = (0 - + ∫ ri, Prime ∂W) ⇐ ∂W=ρc (1-ϕ)∂V
ρc (1-ϕ)∂V ∂t ∂W ∂W 0
1 ∂ci ∂Fi
=- +r (Eq. 5.3.11)
ρc (1-ϕ) ∂t ∂W i, Prime
For Steady State Operation of PBR (ci ≠ ci(t) and Fi = f(W) alone), So PDE will be converted
back to an ODE:
dFi
0=- +r
dW i, Prime
dFi
= ri, Prime (Eq. 5.3.12)
dW
5.4 Reaction Coordinates and their Applications

In Section 5.3 steady state and unsteady state (i.e. dynamic or transient) mole balances are
derived in terms of molar flowrates and moles, these are useful for chemical reactor design in
which multiple chemical reactions take place simultaneously. For reactors in which single
chemical reaction takes place it is more convenient to write them in terms of conversion instead
36
of moles or molar flowrates. For liquid phase reactions it is more convenient to write them in
terms of concentration. [3]
5.4.1 Reaction Conversion

In defining conversion, we choose one of the reactants as the basis of calculation and then
relate the other species involved in the reaction to this basis. In virtually all instances we must
choose the limiting reactant as the basis of calculation. We will develop the relationships by
considering the general reaction: [3]
aA + bB → cC + dD (Eq. 5.4.1)
Capital A, B, C, and D represent chemical species. While small a, b, c, and d represent

stoichiometric coefficients.
Here, A=Limiting Reactant (the reactant that will be completely consumed first after the
reactants have been mixed) so we divide the whole equation by “a”:
b c d
A+ B→ C+ D (Eq. 5.4.2)
a a a
Quantification of how far a reaction proceeds to the right is given by Conversion (XA) [Unitless].
Conversion of A is defined as:
Moles of "A" Reacted nA, Reacted nA0 − nA FA0 − FA cA0 − cA
XA = = = = = (Eq. 5.4.3)
Moles of "A" Fed nA, Fed nA0 FA0 cA0
By rearranging Eq. 5.4.3 nA, FA, and cA can be written in terms of conversion of “A”.
nA =nA0 (1-XA ) (Eq. 5.4.4)
FA =FA0 (1-XA ) (Eq. 5.4.5)
cA =cA0 (1-XA ) (Eq. 5.4.6)
These equations will be used to convert mole balances to other useful forms in addition to
other applications.
5.4.2 Mole Balances in terms of Conversion

Previously developed mole balances can now be written in terms of conversion instead of nA
and FA. These new forms of mole balances are especially useful in reactor design in which a
single chemical reaction occurs. For the case of multiple reactions, the original forms in terms
of nA and FA are useful. Conversion as a reaction performance indicator is useful only in those
reactors in which single chemical reaction takes place, because, in such a case conversion of
limiting reactant indicates that how much reactant is converted to the desired product only.
37
While in the case of multiple reactions the limiting reactant may consume in more than one
reaction, e.g. one reaction will give us desired product and the others will give undesired
products. So, in the case of multiple reactions, conversion indicates the amount of reactant
converted to both desired and undesired products, so it is not useful in this case. In other
words, for example, we have achieved an 80% conversion of limiting reactant in the case of
multiple reactions, then it is not necessary that this much reactant is converted to the desired
product only, because it may also consume in other side reactions to form large amounts of
undesired product. So, conversion as a reaction performance indicator is useful only in single
reaction scenarios, while for the case of multiple reactions other reaction performance
indicators will be defined such as Reaction Yield and Reaction Selectivity. [3]
For Batch Reactors [Unsteady State] (Recall Eq. 5.3.1):

dni
=r V (Eq. 5.3.1)
dt i
For species “A” it will become:
dnA
=rA V
dt
Use Eq. 5.4.4 to convert this equation to conversion form:
d
[n (1-XA )]=rA V
dt A0
Because initial number of moles nA0 present in the reactor is a constant quantity hence,
d
nA0 (1-XA )=rA V
dt
dXA
nA0 (0- ) =rA V
dt
dXA
-nA0 =rA V
dt
dXA -rA V
= (Eq. 5.4.7)
dt nA0, system
For CSTR [Unsteady State] (Recall Eq. 5.3.2):

dni
=F - F +r V (Eq. 5.3.2)
dt i0 i i
38
dnA
=FA0 - FA +rA V
dt
Use Eq. 5.4.4 and 5.4.5 to convert this equation to conversion form:
d
[n (1-XA )]=FA0 - FA0 (1-XA )+rA V
dt A0
Because initial number of moles nA0 present in the reactor and inlet molar flowrate FA0 are
constant hence,
d
nA0 (1-XA )=FA0 XA +rA V
dt
dXA
nA0 (0- ) =FA0 XA +rA V
dt
dXA
-nA0 =FA0 XA +rA V
dt
dXA
-nA0 -F X =r V
dt A0 A A
dXA
nA0, system +FA0 XA =-rA V (Eq. 5.4.8)
dt
For CSTR [Steady State] (Recall Eq. 5.3.3):
Fi0 - Fi +ri V=0 (Eq. 5.3.3)

FA0 - FA +rA V=0

FA0 - FA0 (1-XA )+rA V=0
Because inlet molar flowrate FA0 is constant hence,

FA0 XA =-rA V (Eq. 5.4.9)
For PFR [Unsteady State] (Recall Eq. 5.3.4):

∂ci ∂Fi
+ = ri (Eq. 5.3.4)
∂t ∂V
∂cA ∂FA
+ = rA
∂t ∂V
39
∂ ∂
[cA0, system (1-XA )]+ FA0 (1-XA ) = rA
∂t ∂V
Because initial concentration cA0, system of reaction mixture inside the reactor and inlet molar
flowrate FA0 are constant hence,
∂ ∂
cA0, system [ (1-XA )] +FA0 (1-XA ) = rA
∂t ∂V
∂XA ∂XA
cA0, system (0- ) +FA0 (0- ) = rA
∂t ∂V
∂XA ∂XA
-cA0, system -FA0 = rA
∂t ∂V
∂XA ∂XA
cA0, system +FA0 = -rA (Eq. 5.4.10)
∂t ∂V
For PFR [Steady State] (Recall Eq. 5.3.5):

dFi
= ri (Eq. 5.3.5)
dV
dFA
= rA
dV
d
F (1-XA ) = rA
dV A0
d
FA0 (1-XA ) = rA
dV
dXA
FA0 (0- ) = rA
dV
dXA
-FA0 = rA
dV
dXA -rA
= (Eq. 5.4.11)
dV FA0
40
For PBR [Unsteady State] (Recall Eq. 5.3.11):
1 ∂ci ∂Fi
+ = ri, Prime (Eq. 5.3.11)
ρc (1-ϕ) ∂t ∂W

1 ∂cA ∂FA
+ = rA, Prime
ρc (1-ϕ) ∂t ∂W
1 ∂ ∂
[cA0, system (1-XA )]+ F (1-XA ) = rA, Prime
ρc (1-ϕ) ∂t ∂W A0
Because initial concentration cA0, system of reaction mixture inside the reactor and inlet molar
flowrate FA0 are constant hence,
cA0, system ∂ ∂
[ (1-XA )] +FA0 (1-XA ) = rA, Prime
ρc (1-ϕ) ∂t ∂W
cA0, system ∂XA ∂XA
(0- ) +FA0 (0- ) = rA, Prime
ρc (1-ϕ) ∂t ∂W
- -FA0 = rA, Prime
ρc (1-ϕ) ∂t ∂W
+FA0 = -rA, Prime (Eq. 5.4.12)
ρc (1-ϕ) ∂t ∂W
For PBR [Steady State] (Recall Eq. 5.3.12):

dFi
= ri, Prime (Eq. 5.3.12)
dW
dFA
= rA, Prime
dW
d
F (1-XA ) = rA, Prime
dW A0
d
FA0 (1-XA ) = rA, Prime
dW
41
dXA
FA0 (0- ) = rA, Prime
dW
dXA
-FA0 = rA, Prime
dW
dXA -rA, Prime
= (Eq. 5.4.13)
dW FA0
5.4.3 Reaction Concentration

Definition of molar concentration [“ci” (kgmol/m3)] in terms of Volume [m3] is given by:
ni dni
ci = = or ni = ci V (Eq. 5.4.14a and 5.4.14b)
V dV
While its definition in terms of total volumetric flowrate (υ) [m3/s] is given by:
Fi dFi
ci = = or Fi = ci υ (Eq. 5.4.15a and 5.4.15b)
υ dυ
Eq. 5.4.14 (a and b) and 5.4.15 (a and b) are useful for further study while preparing
stoichiometric tables for batch and continuous reactors in addition to other applications. [3]
5.4.4 Reaction Stoichiometry
In this topic we will develop relationships for:
1. ni = f(XA)
2. Fi = f(XA)
For Batch Systems:

Recall Eq. 5.4.2:
b c d
A+ B→ C+ D (Eq. 5.4.2)
a a a
Let us suppose that above chemical reaction is occurring in the batch reactor (Figure 5.11) so:
42
nA0
nB0
nC0
nD0
nI0
nA
nB
nC
nD
nI
Figure 5.11: Batch System
Table 5.1 is showing the initial, reacting, and final values of various quantities of moles:
Table 5.1: Stoichiometric Table for a Batch System
Chemical Species Initial Moles Reacted Moles Remaining Moles
A nA0 -nA0 XA nA = nA0 -nA0 XA

b b
B nB0 - nA0 XA nB = nB0 - nA0 XA
a a
c c
C nC0 + nA0 XA nC = nC0 + nA0 XA
a a
d d
D nD0 + nA0 XA nD = nD0 + nA0 XA
a a
I (Inerts) nI0 0 nI = nI0
d c b d c b
Totals nT0 ( + - -1) nA0 XA nT = nT0 + ( + - -1) nA0 XA
a a a a a a
The stoichiometric coefficients in parentheses (d/a + c/a - b/a - 1) represent the change in the
total number of moles per mole of A reacted. Because this term occurs so often in our
calculations, so it is given the symbol ν: [3]
43
d c b
ν= + - -1 (Eq. 5.4.16)
a a a
Here a new quantity will be declared which is known as θi:

ni0 Fi0 ci0
θi = = = (Eq. 5.4.17)
nA0 FA0 cA0
Hence,
nA = nA0 (1-XA ) = nA0 (θA -XA ) (Eq. 5.4.18)
nB0 b b
nB = nA0 ( - XA ) = nA0 (θB - XA ) (Eq. 5.4.19)
nA0 a a
nC0 c c
nC = nA0 ( + XA ) = nA0 (θC + XA ) (Eq. 5.4.20)
nA0 a a
nD0 d d
nD = nA0 ( + XA ) = nA0 (θD + XA ) (Eq. 5.4.21)
nA0 a a
nI = nA0 θI (Eq. 5.4.22)
nT =nT0 +ν(nA0 XA ) (Eq. 5.4.23)
For Continuous Systems:
Recall Eq. 5.4.2:

b c d
A+ B→ C+ D (Eq. 5.4.2)
a a a
Let us suppose that above chemical reaction is occurring in the continuous reactor (Figure 5.12)
so:
FA0 FA
FB0 b c d FB
FC0 A+ B→ C+ D FC
a a a
FD0 FD
FI0 FI
Figure 5.12: Continuous System
Table 5.2 is showing the initial, reacting, and final values of various quantities of molar flowrates:
44
Table 5.2: Stoichiometric Table for a Continuous System
Chemical Species Initial Moles Reacted Moles Remaining Moles
A FA0 -FA0 XA FA = FA0 -FA0 XA

b b
B FB0 - FA0 XA FB = FB0 - FA0 XA
a a
c c
C FC0 + FA0 XA FC = FC0 + FA0 XA
a a
d d
D FD0 + FA0 XA FD = FD0 + FA0 XA
a a
I (Inerts) FI0 0 FI = FI0
d c b d c b
Totals FT0 ( + - -1) FA0 XA FT = FT0 + ( + - -1) FA0 XA
a a a a a a
Hence,
FA = FA0 (1-XA ) = FA0 (θA -XA ) (Eq. 5.4.24)
FB0 b b
FB = FA0 ( - XA ) = FA0 (θB - XA ) (Eq. 5.4.25)
FA0 a a
FC0 c c
FC = FA0 ( + XA ) = FA0 (θC + XA ) (Eq. 5.4.26)
FA0 a a
FD0 d d
FD = FA0 ( + XA ) = FA0 (θD + XA ) (Eq. 5.4.27)
FA0 a a
FI = FA0 θI (Eq. 5.4.28)
FT =FT0 +ν(FA0 XA ) (Eq. 5.4.29)
Eq. 5.4.18-5.4.23 and Eq. 5.4.24-5.4.29 in combination with Eq. 5.4.14-5.4.15 will be used to
write concentration ci = f(XA) for liquid and gas phase systems. ci = f(XA) is needed to convert
the reaction rate law into conversion terms as -rA = f(XA). [3]
5.4.5 Reaction Phase

Chemical reactions can occur in:
• Liquid Phase (or Aqueous Phase)

e.g. HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
45
• Gas Phase
e.g. H2(g) + Cl2(g) → 2HCl(g)
• Two Phase (Solid-Liquid, Solid-Gas, Gas-Liquid)
e.g. 3NO2(g) + H2O(l) → 2HNO3(aq) + NO(g)
• Three Phase (Solid-Liquid-Gas)
e.g. 2NH4Cl(s) + Ca(OH)2(s) → 2NH3(g) + CaCl2(s) + 2H2O(l)
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
For the sake of convenience and for fundamental understanding we will consider only Liquid
Phase and Gas Phase Reactions. Because liquid and gas phase Density (ρ) [kg/m3] calculation
methods are different so there are differences in the model equations of the reactors.
According to thermodynamics, value of density depends on Temperature (T) [K], Pressure (P)
[Pa], and Concentration (ci) [kgmol/m3] of the fluid. [4]
ρ = f(T,P,ci )
Any mathematical thermodynamic equation which is used to relate these variables together
for any fluid is called an Equation of State (EOS).
Liquid Phase Reactions
Because no Standard Equations of State (EOS) exist for liquid phase property calculations so,
at fixed values of T, P and ci, the Liquid Phase Density (ρL) can be calculated using:
mL
ρL = (Eq. 5.4.30)
VL
Where mL and VL represent the mass of liquid (kg) and volume of liquid (m3) respectively. The
same procedure is repeated for different values of T, P and ci to obtain:
ρL = f(T,P,ci )
According to fluid mechanics, liquids can be considered nearly incompressible in nature so,
their density, volume, and volumetric flowrate remains nearly constant (independent of T, P,
and ci), hence (For Liquids):
ρL = ρ0 = Constant (Eq. 5.4.31)
V = V0 = Constant (Eq. 5.4.32)

υ = υ0 = Constant (Eq. 5.4.33)
These results will be utilized in combination with Eq. 5.4.14 and 5.4.15 to convert mole balance
equations into concentration terms for liquid phase reactions as well as to write ci = f(XA) and
-rA = f(XA) for those reactors in which only single chemical reaction is occurring. [3]
46
ci = f(XA) for Liquid Phase Batch Systems (Use Eq. 5.4.14, 5.4.18-5.4.23, and 5.4.32):
nA nA0 (θA -XA )
cA = = = cA0 (θA -XA ) (Eq. 5.4.34)
V V0
b
nB nA0 (θB - a XA ) b
cB = = = cA0 (θB - XA ) (Eq. 5.3.35)
V V0 a
c
nC nA0 (θC + a XA ) c
cC = = = cA0 (θC + XA ) (Eq. 5.4.36)
V V0 a
d
nD nA0 (θD + a XA ) d
cD = = = cA0 (θD + XA ) (Eq. 5.4.37)
V V0 a
nI nA0 θI
cI = = = cA0 θI (Eq. 5.4.38)
V V0
cT nT0 +ν(nA0 XA ) nT0 ν(nA0 XA )
cT = = = + = cT0 +cA0 νXA (Eq. 5.4.39)
V V0 V0 V0
ci = f(XA) for Liquid Phase Continuous Systems (Use Eq. 5.4.15, 5.4.24-5.4.29, and 5.4.33):
FA FA0 (θA -XA )
cA = = = cA0 (θA -XA ) (Eq. 5.4.40)
υ υ0
b
FB FA0 (θB - a XA ) b
cB = = = cA0 (θB - XA ) (Eq. 5.4.41)
υ υ0 a
c
FC FA0 (θC + a XA ) c
cC = = = cA0 (θC + XA ) (Eq. 5.4.42)
υ υ0 a
d
FD FA0 (θD + a XA ) d
cD = = = cA0 (θD + XA ) (Eq. 5.4.43)
υ υ0 a
FI FA0 θI
cI = = = cA0 θI (Eq. 5.4.44)
υ υ0
FT FT0 +ν(FA0 XA ) FT0 ν(FA0 XA )
cT = = = + = cT0 +cA0 νXA (Eq. 5.4.45)
υ υ0 υ0 υ0
Eq. 5.4.34-5.4.45 can be used to convert -rA in terms of XA for liquid phase batch and
continuous reactors.
47
Gas Phase Reactions
There exist a lot of Standard Equations of State (EOS) for gas phase property calculations but,
the important one is the Real Gas Law: [4]
For Batch Systems:

PT V = ZnT RT (Eq. 5.4.46)
Divide Eq. 5.4.46 with time (t) [s]:

V nT
PT = Z RT
t t
PT υ = ZFT RT (Eq. 5.4.47)
PT = Absolute Total Pressure of the Gas [N/m2]

V = Volume of the Gas [m3]
υ = Total Volumetric Flowrate of the Gas [m3/s]
Z = Compressibility Factor [Unitless] [Z = 1 for ideal gases]
nT = Total Moles of the Gas [kgmol]
FT = Total Molar Flowrate of the Gas [kgmol/s]
R = Ideal Gas Constant = 8314 J/kgmol.K
T = Absolute Temperature of Gas on Kelvin Scale [K]
Eq. 5.4.46 can be written in terms of density after rearrangement:

mT
PT V = Z RT
M
Where mT [kg] and M [kg/kgmol] represent Total Mass of the Gas and Molecular Weight of the
Gas respectively:
mT
PT M = Z RT
V
PT M = ZρG RT
The Gas Phase Density (ρG) can be calculated using:

PT M
ρG = (Eq. 5.4.48)
ZRT
Derivation of the Equations for Variable Volume and Variable Volumetric Flowrate of the Gas:
Recall Eq. 5.4.47:
48
PT υ = ZFT RT
Upon rearrangement:
FT PT
=
υ ZRT
Writing in terms of Total Molar Concentration (cT) [kgmol/m3]:
FT PT
cT = = (Eq. 5.4.49)
υ ZRT
This equation gives us cT at any point in the reactor. While for the reactor entrance conditions
this equation can be written as:
FT0 PT0
cT0 = = (Eq. 5.4.50)
υ0 Z0 RT0
Taking ratio of Eq. 5.4.49 to Eq. 5.4.50:

FT PT
υ = ZRT
FT0 PT0
υ0 Z0 RT0
FT υ0 PT Z0 RT0
× = ×
υ FT0 ZRT PT0
υ0 FT PT T0 Z0
× = × ×
υ FT0 PT0 T Z
Assume negligible changes in the compressibility factor:

Z ≅ Z0
υ0 FT PT T0
× = ×
υ FT0 PT0 T
υ FT PT0 T
= × ×
υ0 FT0 PT T0
FT PT0 T
υ =υ0 × × ×
FT0 PT T0
Replace PT with P:
FT P0 T
υ =υ0 ( ) ( ) ( )
FT0 P T0
Its Batch System Equivalent can be written as:
49
nT P0 T
V =V0 ( ) ( ) ( )
nT0 P T0
According to fluid mechanics, gas is a compressible fluid in nature so, its density, volume, and
volumetric flowrate are variables, hence (For Gases): [3]
PT M
ρG = = Variable (Eq. 5.4.51)
ZRT
nT P0 T
V =V0 ( ) ( ) ( ) = Variable (Eq. 5.4.52)
nT0 P T0
FT P0 T
υ = υ0 ( ) ( ) ( ) = Variable (Eq. 5.4.53)
FT0 P T0
Because Eq. 5.4.51-5.4.53 are expressed in terms of Moles and Molar Flowrates so, these are
useful in reactor design in which multiple reactions are occurring.
For Batch Systems:
The total moles are just the sum of the moles of each of the species in the system and is:
n
nT = nA +nB +nC +nD +nI +… = ∑ ni (Eq. 5.4.54)

i=1
And the total initial moles are just the sum of the initial moles of each of the species and is:
n
nT0 = nA0 +nB0 +nC0 +nD0 +nI0 +… = ∑ ni0 (Eq. 5.4.55)

i=1
The total molar flowrate is just the sum of the molar flowrates of each of the species in the
system and is:
n
FT = FA +FB +FC +FD +FI +… = ∑ Fi (Eq. 5.4.56)

i=1
And the total molar flowrate at reactor entrance is just the sum of the molar flowrates of each
of the species at reactor entrance and is:
n
FT0 = FA0 +FB0 +FC0 +FD0 +FI0 +… = ∑ Fi0 (Eq. 5.4.57)

i=1
50
For the case of single reaction systems, Eq 5.4.52 and 5.4.53 needs to be converted into
conversion form hence:
Recall Eq. 5.4.29:

FT =FT0 +ν(FA0 XA )
Divide by FT0:
FT FA0
=1+ X ν (Eq. 5.4.58)
FT0 FT0 A
Definition of Mole Fraction (xi) [Unitless]:

Fi Fi0
xi = and xi0 = (Eq. 5.4.59)
FT FT0
For Species “A”:

FA0
xA0 =
FT0
Put it in Eq. 5.4.58:

FT
=1+xA0 XA ν (Eq. 5.4.60)
FT0
Define a new factor ϵ:

ϵ=xA0 ν (Eq. 5.4.61)
So, Eq. 5.4.60 will become:

FT
=1+ϵXA (Eq. 5.4.62)
FT0
Its batch equivalent is:

nT
=1+ϵXA (Eq. 5.4.63)
nT0
Put Eq. 5.4.62 into Eq. 5.4.53, and Put Eq. 5.4.63 into Eq. 5.4.52:
P0 T
V =V0 (1+ϵXA ) ( ) ( ) = Variable (Eq. 5.4.64)
P T0
P0 T
υ = υ0 (1+ϵXA ) ( ) ( ) = Variable (Eq. 5.4.65)
P T0
51
[3]
These results are useful for reactor design in which single chemical reaction is occurring.
ci = f(XA) for Gas Phase Batch Systems (Use Eq. 5.4.14, 5.4.18-5.4.23, and 5.4.64):
nA nA0 (θA -XA ) (θA -XA ) P T0
cA = = = cA0 ( )( ) (Eq. 5.4.66)
V P0 T (1+ϵXA ) P0 T
V0 (1+ϵXA ) ( ) ( )
P T0
b b
nB nA0 (θB - a XA ) (θB - XA ) P T
a 0
cB = = = cA0 ( )( ) (Eq. 5.4.67)
V P T (1+ϵXA ) P0 T
V0 (1+ϵXA ) ( 0 ) ( )
P T0
c c
nC nA0 (θC + a XA ) (θC + a XA ) P T0
cC = = = cA0 ( )( ) (Eq. 5.4.68)
V0 (1+ϵXA ) ( 0 ) ( )
P T0
d d
nD nA0 (θD + a XA ) (θD + XA ) P T
a 0
cD = = = cA0 ( )( ) (Eq. 5.4.69)
V P0 T (1+ϵXA ) P0 T
V0 (1+ϵXA ) ( ) ( )
P T0
nI nA0 θI θI P T0
cI = = = cA0 ( )( ) (Eq. 5.4.70)
V0 (1+ϵXA ) ( 0 ) ( )
P T0
nT nT0 +ν(nA0 XA ) [nT0 +ν(nA0 XA )] P T0
cT = = = ( )( )
V P0 T V (1+ϵXA ) P0 T
V0 (1+ϵXA ) ( ) ( ) 0
P T0
nT0 ν(nA0 XA ) 1 P T0
=[ + ]( )( )( )
V0 V0 1+ϵXA P0 T
cT0 +ν(cA0 XA ) P T0
cT = ( )( ) (Eq. 5.4.71)
(1+ϵXA ) P0 T
ci = f(XA) for Gas Phase Continuous Systems (Use Eq. 5.4.15, 5.4.24-5.4.29, and 5.4.65):
FA FA0 (θA -XA ) (θA -XA ) P T0
cA = = = cA0 ( )( ) (Eq. 5.4.72)
υ P0 T (1+ϵXA ) P0 T
υ0 (1+ϵX )
A ( P ) (T )
0
b b
FB FA0 (θB - a XA ) (θB - XA ) P T
a 0
cB = = = cA0 ( )( ) (Eq. 5.4.73)
υ P T (1+ϵXA ) P0 T
υ0 (1+ϵXA ) ( 0 ) ( )
P T0
52
c c
FC FA0 (θC + a XA ) (θC + a XA ) P T0
cC = = = cA0 ( )( ) (Eq. 5.4.74)
υ P0 T (1+ϵXA ) P0 T
υ0 (1+ϵXA ) ( ) ( )
P T0
d d
FD FA0 (θD + a XA ) (θD + XA ) P T
a 0
cD = = = cA0 ( )( ) (Eq. 5.4.75)
υ0 (1+ϵXA ) ( 0 ) ( )
P T0
FI FA0 θI θI P T0
cI = = = cA0 ( )( ) (Eq. 5.4.76)
υ0 (1+ϵXA ) ( 0 ) ( )
P T0
FT FT0 +ν(FA0 XA ) [FT0 +ν(FA0 XA )] P T0
cT = = = ( )( )
υ P T υ0 (1+ϵXA ) P0 T
υ0 (1+ϵXA ) ( 0 ) ( )
P T0
FT0 ν(FA0 XA ) 1 P T0
=[ + ]( )( )( )
υ0 υ0 1+ϵXA P0 T
cT0 +ν(cA0 XA ) P T0
cT = ( )( ) (Eq. 5.4.77)
(1+ϵXA ) P0 T
Eq. 5.4.66-5.4.77 can be used to convert -rA in terms of XA for gas phase batch and continuous
reactors.
5.4.6 Reaction Types

Based on different factors, reactions can be divided into following main types:
Based on the Number of Phases:
• Homogeneous Reactions (i.e. The reaction that involves only one phase)
• Heterogeneous Reactions (i.e. The reaction that involves more than one phases)
Based on the Direction of Reaction:
• Irreversible Reaction (i.e. The reaction that proceeds only in one direction)
An irreversible reaction behaves as if no equilibrium condition exists. Strictly speaking,
no chemical reaction is completely (100%) irreversible. However, for many reactions, the
equilibrium point lies so far to the product side that these reactions are treated as
irreversible reactions.
• Reversible Reaction (i.e. The reaction that proceeds in forward and/or reverse direction)
53
Based on Molecularity of the Reaction:
The molecularity of a reaction is the number of atoms, ions, or molecules involved (or colliding)
in a reaction step.
• Unimolecular Reactions (i.e. The reaction that involves one atom or molecule colliding
in any one reaction step)
• Bimolecular Reactions (i.e. The reaction that involves two atoms or molecules colliding
in any one reaction step)
• Termolecular Reactions (i.e. The reaction that involves three atoms or molecules
colliding in any one reaction step)
Based on the Number of Reactions:
• Single Reaction (i.e. only one reaction occurs)

• Multiple Reactions (i.e. more than one reaction occur simultaneously) [3]
✓ Series Reactions (or Consecutive Reactions)
These are reactions where the reactant forms an intermediate product, which
reacts further to form another product:
k1 k2
A →B →C
✓ Parallel Reactions (or Competing Reactions)
These are reactions where the reactant is consumed by two different reaction
pathways to form different products:
𝐵
𝐴
𝐶
✓ Reversible Reactions (or Opposite Reactions)
These are reactions which are driving in opposite directions. Reactants are
consumed to form products and products are consuming simultaneously to
generate same reactants. When they approach chemical equilibrium (the state
at which forward and reverse reaction rates becomes equal) then net rates of all
species become zero and production is ceased.
A+B↔C+D
✓ Independent Reactions
These are reactions that occur at the same time but neither the products nor
the reactants react with themselves or one another:
A→B+C
D→E+F
54
✓ Complex Reactions
These are multiple reactions that involve combinations of series, parallel, and
independent reactions, such as:
A+B→C+D
A+C→E
E→G
5.4.7 Reaction Rates

Rate of Reaction can be divided based on the number of phases as given below:
• Homogeneous Rate of Reaction (rA)

The number of moles of species “A” reacting (producing or consuming) per unit time
per unit volume of reaction mixture.
nA, Producing
+rA =
t∙V
nA,Consuming
-rA =
t∙V
• Heterogeneous Rate of Reaction (rA, Prime)

The number of moles of species “A” reacting (producing or consuming) per unit time
per unit weight of catalyst.
nA, Producing
+rA, Prime =
t∙W
nA,Consuming
-rA, Prime =
t∙W
NOTE: If the number of moles of the species “A” are producing then +ve sign is used with
reaction rate and if they are consuming then -ve sign will be used.
Because values of nA, Producing and nA, Consuming cannot be measured directly so, rate is expressed
in terms of Rate Constant (k), Equilibrium Constants (Kc or Kp), Catalyst Adsorption Constant
(Ka), Concentration of species involved in the reaction (ci) or Partial Pressure of species i (Pi)
and other factors as:
-rA or -rA, Prime = f(k,KC or KP ,Ka ,ci or Pi )
Where k, KC, KP, and Ka have dynamic units depending upon different reaction kinetics. A
mathematical equation which relates reaction rate (-rA or -rA, Prime) with these factors for a
particular chemical reaction is known as Reaction Rate Law for that reaction. And reaction rate
law determination requires practical data in addition to theoretical knowledge. Reaction rate
law is always in the form of an Algebraic Equation only. [3]
55
Other types of the reaction rate are:
• Relative Rates of Reaction

It tells us how fast one species is consuming or producing relative to the other species
in the given reaction. The relative rates of reaction of the various species involved in a
reaction can be obtained from the ratio of the stoichiometric coefficients. Recall Eq.
5.4.1:
aA + bB → cC + dD (Eq. 5.4.1)
For this reaction, relative rates of reaction can be written as:
-rA -rB rC rD
= = = (Eq. 5.4.78)
a b c d
• Net Rates of Reaction
It is useful only for the case of multiple reactions. And so, it is the sum of the rate of
reactions of species “i” in all the reactions in which “i” is either a reactant or a product
in the system.
n
ri = ∑ ri,j =ri,1 +ri,2 +ri,3 +ri,4 +…+ri,n (Eq. 5.4.79)

j=1
Here,
i = A chemical species involved in the reaction on reactant or product side
j = A number representing any specific chemical reaction
n = Total number of chemical reactions
In Eq. 5.4.79 sign convention should only be used in the values of (ri,j).
For example, if the following multiple reactions are occurring in the reactor:
R-1 a1A + b1B → c1C + d1D
R-2 a2A + c2C → e2E
R-3 a3A + e3E → f3F + g3G
Individual Reaction Rates:
These are represented by rate laws which are determined experimentally or present in
the literature and are different for different reactions. Let us use these dummy non-
elementary rate laws (which will be discussed later) for R-1, R-2, and R-3 respectively:
-rA,1 =kA,1 cA cB (Eq. 5.4.80)
-rC,2 =kC,2 cA cC (Eq. 5.4.81)
-rA,3 =kA,3 cA cE (Eq. 5.4.82)
Relative Reaction Rates:
Relative rates of reaction for each individual reaction can be written as:
56
-rA,1 -rB,1 rC,1 rD,1
= = = (Eq. 5.4.83)
a1 b1 c1 d1
-rA,2 -rC,2 rE,2
= = (Eq. 5.4.84)
a2 c2 e2
-rA,3 -rE,3 rF,3 rG,3
= = = (Eq. 5.4.85)
a3 e3 f3 g3
Net Reaction Rates:

Net rates of reaction for all the species involved can be written as (Combining individual,
relative, and net rate equations):
3
a2 a2
rA = ∑ rA,j =rA,1 +rA,2 +rA,3 =rA,1 + r +r = − kA,1 cA cB − kC,2 cA cC − kA,3 cA cE (Eq. 5.4.86)
c2 C,2 A,3 c2
j=1
3
b1 b1
rB = ∑ rB,j =rB,1 +rB,2 +rB,3 =rB,1 +0+0=rB,1 = r = − kA,1 cA cB (Eq. 5.4.87)
a1 A,1 a1
j=1
3
c1 c1
rC = ∑ rC,j =rC,1 +rC,2 +rC,3 =rC,1 +rC,2+0=rC,1 +rC,2 = − r +r = k c c − kC,2 cA cC (Eq. 5.4.88)
a1 A,1 C,2 a1 A,1 A B
j=1
3
d1 d1
rD = ∑ rD,j =rD,1 +rD,2 +rD,3 =rD,1 +0+0=rD,1 = − rA,1 = kA,1 cA cB (Eq. 5.4.89)
a1 a1
j=1
3
e2 e3 e2 e3
rE = ∑ rE,j =rE,1 +rE,2 +rE,3 =0+rE,2 +rE,3 =rE,2 +rE,3 = − r + r = k c c − k c c (Eq. 5.4.90)
c2 C,2 a3 A,3 c2 C,2 A C a3 A,3 A E
j=1
3
f3 f3
rF = ∑ rF,j =rF,1 +rF,2 +rF,3 =0+0+rF,3 =rF,3 = − r = k c c (Eq. 5.4.91)
a3 A,3 a3 A,3 A E
j=1
3
g3 g3
rG = ∑ rG,j =rG,1 +rG,2 +rG,3 =0+0+rG,3 =rG,3 = − rA,3 = kA,3 cA cE (Eq. 5.4.92)
a3 a3
j=1
These net reaction rates will be used in combination with mole balances for reactor
design with multiple reactions. [3]
5.4.8 Reaction Rate Law

The mathematical form of the reaction rate law can be a simple or difficult algebraic expression.
And it can follow:
• Power Law Kinetic Model

According to power law kinetic model, rate can be expressed as:
−rA = [kA (T)][f(cA ,cB ,cC ,cD …)]
Or more specifically as:
n
α α α α α α α α
-rA =kA ∏ ci i =kA (c1 1 ∙ c2 2 ∙ c3 3 … ∙ cn n )=kA (cAαA ∙ cB B ∙ cCC … ∙ cn n ) (Eq. 5.4.93)
i=1
Where,
57
kA = kA(T) = Reaction Rate Constant with respect to species A [dynamic units]
i = A chemical species
n = Total number of species contributing in rate determination
(For Irreversible Reactions n = Total number of species on reactant side)
(For Reversible Reactions n = Total number of species on reactant and product both sides)
ci = Concentration of species i (kgmol/m3)
αi = Order of reaction with respect to species i (Unitless)
Rate constant kA, like the reaction rate, –rA, always refers to a particular species in the
reaction and normally should be subscripted with respect to that species. A relationship
among rate constants referring to different species can be derived as:
Recall Eq. 5.4.1 and Eq. 5.4.78: [3]
aA + bB → cC + dD (Eq. 5.17)
-rA -rB rC rD
= = = (Eq. 5.4.78)
a b c d
Substitute corresponding non-elementary rate laws:
kA cA cB kB cA cB kC cA cB kD cA cB
= = =
a b c d
kA kB kC kD
= = = (Eq. 5.4.94)
a b c d
However, for reactions in which the stoichiometric coefficient is 1 for all species involved
in the reaction, then we shall delete the subscript on the reaction rate constant.
CASE-A: For Irreversible Reactions:
Recall Eq. 5.4.1:
aA + bB → cC + dD (Eq. 5.4.1)
Specifically, for this irreversible reaction power law kinetic model can be written as:
β
-rA = kA cαA cB
The order of a reaction refers to the powers to which the concentrations are raised in
the kinetic rate law (order of reaction can only be determined practically).
Where,
α = Reaction Order w.r.t Species A [Unitless]
β = Reaction Order w.r.t Species B [Unitless]
η = α + β = Overall Order of Reaction [Unitless]
Elementary Kinetics
The rate law in which orders of reaction are equal to the corresponding stochiometric
coefficients appearing in the reaction.
α=a
β=b
58
Nonelementary Kinetics
The rate law in which orders of reaction are not equal to the corresponding
stochiometric coefficients appearing in the reaction. [3]
α≠a
β≠b
CASE-B: For Reversible Reactions:
Recall Eq. 5.4.1 and write it as reversible reaction (R-O):
aA + bB ↔ cC + dD (Eq. 5.4.95)
In order to develop power law kinetics for it, this reversible reaction must be written as
two separate irreversible reactions occurring simultaneously as: [3]
Forward Reaction R-f:
aA + bB → cC + dD (Eq. 5.4.1)
Rate constant for this forward reaction is kf. And power law kinetic model for this forward
reaction can be written as (Individual Reaction Rate):
α α
-rA,f = kA,f cA1 cB 2 (Eq. 5.4.96)
Reverse Reaction R-r:
cC + dD → aA + bB (Eq. 5.4.97)
Rate constant for this reverse reaction is kr. And power law kinetic model for this reverse
reaction can be written as (Individual Reaction Rate):
α α
-rC,r = kC,r cC3 cD4 (Eq. 5.4.98)
(Relative Reaction Rates for R-r)
-rC,r -rD,r rA,r rB,r
= = =
c d a b
-rC,r rA,r kC,r kA,r
= and =
c a c a
-a a α3 α4 α3 α4
rA,r = rC,r = kC,r cC cD =kA,r cC cD (Eq. 5.4.99)
c c
(Net Reaction Rate for Overall Reversible Reaction R-O)
rA = rA,1 +rA,2 = rA,f +rA,r
Use Eq. 5.4.96 and 5.4.99 to write:
α α α α
rA =-kA,f cA1 cB 2 +kA,r cC3 cD4
α α α α
-rA =kA,f cA1 cB 2 -kA,r cC3 cD4
α α kA,r α3 α4
-rA =kA,f (cA1 cB 2 - c c ) (Eq. 5.4.100)
kA,f C D
Now write down relative rate constant equation for (R-f) and (R-r):
kA,f kB,f kC,f kD,f
= = = (Eq. 5.4.101)
a b c d
kA,r kB,r kC,r kD,r
= = = (Eq. 5.4.102)
a b c d
Take ratio of Eq. 5.3.101 to Eq. 5.4.102:
59
kA,f kB,f kC,f kD,f
a = b = c = d
kA,r kB,r kC,r kD,r
a b c d
kA,f kB,f kC,f kD,f
= = =
kA,r kB,r kC,r kD,r
These ratios represent a new quantity called Chemical Equilibrium Constant (KC) [have
dynamic units]:
kA,f kB,f kC,f kD,f
KC = = = = (Eq. 5.4.103)
kA,r kB,r kC,r kD,r
Put Eq. 5.4.103 into E. 5.4.100:
α3 α4
α1 α2 cC cD
-rA =kA,f (cA cB - ) (Eq. 5.4.104)
KC
Equation 5.4.104 gives us net rate of consumption of species A in R-O.
In a reaction when the rate of forward and reverse reaction becomes equal then that
state is known as a state of Chemical Equilibrium. [3]
rf = rr
At this state net rate of production or consumption of all the species becomes zero:
-rA = -rB = rC = rD = 0
Now evaluate Eq. 5.4.104 at equilibrium:
α α
α α cCe3 cDe4
0=kA,f (cAe1 cBe2 - )
KC
α3 α4
α1 α2 cCe cDe
cAe cBe - =0
KC
α3 α4
α1 α2 cCe cDe
cAe cBe =
KC
α α
cCe3 cDe4
KC = α α (Eq. 5.4.105)
cAe1 cBe2
If reaction (R-O) is an elementary reaction then (α1 = a, α2 = b, α3 = c, α4 = d):

ccCe cdDe
KC =
caAe cbBe
All rate laws for reversible reactions must reduce to the thermodynamic relationship
relating the reacting species concentrations at equilibrium with K C.
60
Sometimes rate law can also be expressed in terms of partial pressures instead of
concentrations. In such cases, partial pressure of species i (Pi) (N/m2) can be written in
terms of concentration of species i (ci) (kgmol/m3) by the use Ideal Gas Law as:
Pi = ci RT (Eq. 5.4.106)
• Langmuir-Hinshelwood-Hougen-Watson (LHHW) Kinetic Model
This is especially used for catalytic reactions. It is a difficult kinetic expression.
Generalized LHHW Kinetics Model is presented below: [3]
Reaction Rate Constant × Driving Force Expression
-rA = (Eq. 5.4.107)
Adsorption Expression
For example:
CO2 + 3H2 ↔ CH3 OH + H2 O
4413.76⁄ ) PCH3 OH ×PH2 O
1.07×10-13 ×e( T (Kf1 ×PCO2 ×PH2 -Kb1 × )
P2H2
rCH3 OH = 3
PH2 O
(1+K1 × ( ⁄P ) +K2 P0.5
H2 +K P
3 H2 O )
H2
Other Examples: [3]
A. First-Order Rate Laws

C2 H6 → C2 H4 + H2 -rC2 H6 = kcC2 H6
C6 H5 N2 Cl → C6 H5 Cl + N2 -rC6 H5 N2 Cl = kcC6 H5 N2 Cl
H2 SO4
CH2 OCH2 + H2 O → (CH2 OH)2 -rCH2 OCH2 = kcCH2 OCH2
CH3 COCH3 → CH2 CO + CH4 -rCH3 COCH3 = kcCH3 COCH3

ciC4 H10
nC4 H10 ↔ iC4 H10 -rnC4 H10 = k [cnC4 H10 − ]
KC
B. Second-Order Rate Laws

C6 H4 NO2 Cl + 2NH3 → C6 H4 NO2 NH2 + NH4 Cl -rC6 H4 NO2 Cl = kcC6 H4 NO2 Cl cNH3
CNBr + CH3 NH2 → CH3 Br + NCNH2 -rCNBr = kcCNBr cCH3 NH2
CH3 COOC2 H5 + C4 H9 OH ↔ CH3 COOC4 H9 + C2 H5 OH
cCH3 COOC4 H9 cC2 H5 OH
-rCH3 COOC2 H5 = k [cCH3 COOC2 H5 cC4 H9 OH − ]
KC
61
C. Nonelementary Rate Laws
cat 3⁄
CH3 CHO → CH4 + CO -rCH3 CHO = kcCH2 CHO
3
PC6 H6 PC3 H6
k [PC6 H5 CH(CH3 )2 - ]
C6 H5 CH(CH3 )2 → C6 H6 + C3 H6 KP
-rC6 H5 CH(CH3 )2 , Prime =
1 + KC6 H6 PC6 H6 + KC3 H6 PC3 H6
D. Enzymatic Reactions
+H2 O kcNH2 CONH2

NH2 CONH2 + Urease → 2NH3 + CO2 + Urease -r NH CONH =
2 2
KM + cNH2 CONH2
E. Biomass Reactions
kcSubstrate cCells
Substrate + Cells → More Cells + Product -rSubstrate =
KS + cSubstrate
5.4.9 Reaction Rate Constant

It is dependent on temperature. For isothermal operation it remains constant while for adiabatic
and non-isothermal operation its value is a strong function of temperature. It varies with
temperature exponentially. Its temperature dependence is given by Arrhenius Law. The
reaction rate constant ki is not truly a constant; it is merely independent of the concentrations
of the species involved in the reaction. The quantity k i is referred to as either the specific
reaction rate or the rate constant. It is almost always strongly dependent on temperature. It
also depends on whether a catalyst is present, and in gas-phase reactions, it may be a function
of total pressure. In liquid systems it can also be a function of other parameters, such as ionic
strength and choice of solvent. These other variables normally exhibit much less effect on it
than does temperature, except for supercritical solvents, such as supercritical water.
Consequently, for the purposes of the material presented here, it will be assumed that k i
depends only on temperature. This assumption is valid in most laboratory and industrial
reactions, and seems to work quite well. [3]
The Arrhenius Law states that:

-Ea
ki = ki (T) = Ae RT (Eq. 5.4.108)
Where,
ki = Reaction Rate Constant w.r.t species i [dynamic units]

T = Absolute Temperature of Reaction on Kelvin Scale (K)
A = Arrhenius Constant (or Frequency Factor) [dynamic units]
62
Ea = Activation Energy of Reaction (J/kgmol) (It is the minimum amount of energy
required to make effective collision among reactant molecules to form product).
It does not depend on temperature. [Constant Quantity]
R = Ideal Gas Constant = 8314 J/kgmol.K
One final comment on the Arrhenius equation, Equation 5.4.108. It can be put in a most useful
form by finding the reaction rate constant at a temperature T0; that is,
-Ea
ki (T0 ) = AeRT0
And at a temperature T:
-Ea
ki (T) = Ae RT
And taking the ratio to obtain:

-Ea
ki (T) Ae RT
=
ki (T0 ) -Ea
AeRT0
ki (T) -Ea Ea
= e RT ×eRT0
ki (T0 )
ki (T) Ea E
− a
= eRT0 RT
ki (T0 )
ki (T) Ea 1 1
( − )
= e R T0 T
ki (T0 )
Ea 1 1
( − )
ki = ki (T) = ki (T0 ) e R T0 T
Ea 1 1
ki = ki (T) = ki (T0 ) exp [ ( − )] (Eq. 5.4.109)
R T0 T
Here, T0 is any temperature at which value of ki(T0) is available. This equation says that if we
know the reaction rate constant ki(T0) at a temperature, T0, and we know the activation energy,
Ea, then we can find the reaction rate constant ki(T) at any other temperature, T, for that
reaction.
5.4.10 Reaction Equilibrium Constant

Chemical reactions tend to move towards a dynamic equilibrium in which both reactants and
products are present but have no further tendency to undergo net change. In some cases, the
concentration of products in the equilibrium mixture is so much greater than that of the
63
unchanged reactants that for all practical purposes the reaction is ‘complete’ (Irreversible
Reaction). However, in many important cases the equilibrium mixture has significant
concentrations of both reactants and products (Reversible Reaction). At constant temperature
and pressure, a mixture of reactants tends to undergo reaction until the Gibbs energy of the
mixture has reached a minimum: that condition corresponds to a state of chemical equilibrium.
The equilibrium is dynamic in the sense that the forward and reverse reactions continue, but
at matching rates. [5]
Every irreversible reaction of the world is not completely irreversible in nature. In other words,
some degree of reversibility is also present in irreversible reactions as well, hence irreversible
reactions are a special case of reversible reactions. So, irreversible reactions also possess a state
of dynamic equilibrium but that lies farther away on the product side.
Recall Eq. 5.4.95 (Let us suppose, it is elementary): [3]
aA + bB ↔ cC + dD
At Equilibrium:
-rA,forward = rA,reverse
-rA,f = rA,r
For Liquid Phase Reaction For Gas Phase Reaction

kA,f caA cbB = kA,r ccC cdD kA,f PaA PbB = kA,r PcC PdD
kA,f ccC cdD kA,f PcC PdD
= a b = a b
kA,r cA cB kA,r PA PB
This ratio is called chemical equilibrium This ratio is called chemical equilibrium
constant (concentration based): constant (partial pressure based):
kA,f ccC cdD kA,f PcC PdD
KC = = a b (Eq. 5.4.110) KP = = a b (Eq. 5.4.111)
kA,r cA cB kA,r PA PB
Hence in general for the following reaction:

|ν1 |A1 +|ν2 |A2 +…→|ν3 |A3 +|ν4 |A4 +… (Eq. 5.4.112)
Here, νi represents a stoichiometric number (Unitless, +ve for Product, -ve for Reactant): [4]
For Liquid Phase Reaction

n
KC = ∏(ci )νi (Eq. 5.4.113)

i=1
64
Assumptions
• Incompressible Liquid
• Ideal Solution
Where, ci represents concentration of species i. For liquid phase reactions, concentration-based

equilibrium constant is used.
For Gas Phase Reaction

n
KP = ∏(Pi )νi (Eq. 5.4.114)

i=1
Assumptions
• Ideal Gas
• Ideal Solution
Where, Pi represents partial pressure of species i. For gas phase reactions, partial pressure-
based equilibrium constant is used.
Relation between KP and KC for Gas Phase Reactions
This development is for gas phase reactions only because liquid phase reactions cannot be
expressed in terms of partial pressures hence, there are no meanings of Kp for them. [3], [4]
Recall Eq. 5.4.106:

Pi = ci RT
So, Eq. 5.4.114 will lead to:

n
KP = ∏(ci RT)νi =(c1 RT)ν1 ∙(c2 RT)ν2 ∙(c3 RT)ν3 ∙…∙(cn RT)νn
i=1
= [(c1 )ν1 ∙(c2 )ν2 ∙…∙(cn )νn ][(RT)ν1 +ν2 +…+νn ] (Eq. 5.4.115)
Recall Eq. 5.4.16:

d c b
ν= + - -1
a a a
This equation gives us the change in the total number of moles for the following reaction:
b c d
A+ B→ C+ D
a a a
Here we know:
νA = -1, νB = -b/a, νC = c/a, νD = d/a
65
So,
d c b
ν= + - -1 = νD +νC +νB +νA = ν4 +ν3 +ν2 +ν1 = ν1 +ν2 +ν3 +ν4
a a a
For generalized reaction of Eq. 5.4.112:
n
ν = ν1 +ν2 +ν3 +…+νn = ∑ νi (Eq. 5.4.116)

i=1
So,
KP = [(c1 )ν1 ∙(c2 )ν2 ∙…∙(cn )νn ](RT)ν
n
KP = [∏(ci )νi ] ×(RT)ν

i=1
KP = KC (RT)ν (Eq. 5.4.117)
Significance of the Magnitudes of Chemical Equilibrium Constants
Case-A: (If KC or Kp is extremely large): Then only forward reaction is important and such type
of reversible reaction can be treated as irreversible reaction.
Case-B: (If KC or Kp > 1): Reaction is driving in forward direction with more speed than in reverse
direction.
Case-C: (If KC or Kp = 1): Then reaction is at equilibrium.
Case-D: (If KC or Kp < 1): Reaction is driving in reverse direction with more speed than in forward
direction.
Case-E: (If KC or Kp is extremely small): Then only reverse reaction will be considered while
ignoring the forward reaction.
Temperature Dependence of Chemical Equilibrium Constants (K, Kc, Kp)
A dimensionless chemical equilibrium constant based on fugacity is defined for Non-Ideal

Liquid and Gas Mixtures, which is represented by simply K in thermodynamics. K p and Kc are
its special cases for ideal solutions of ideal gases and incompressible liquids, respectively. The
fundamental treatment of the dependence of equilibrium constant on temperature will be
based on K. [4]
According to thermodynamics:
66
n νi
f̂i
−∆Grxn
K = ∏ ( o ) = exp ( ) (Eq. 5.4.118)
fi RT
i=1
n
∆Grxn = ∑ νi Gi = ∆Hrxn − T∆Srxn (Eq. 5.4.119)

i=1
n T
o
∆Hrxn = ∑ νi Hi = ∆Hrxn + ∫ ∆Cp dT (Eq. 5.4.120)
i=1 Tref
n T
o dT
∆Srxn = ∑ νi Si = ∆Srxn + ∫ ∆Cp (Eq. 5.4.121)
Tref T
i=1
n
∆Horxn = ∑ νi Hofi (Eq. 5.4.122)

i=1
n
∆Gorxn = ∑ νi Gofi (Eq. 5.4.123)

i=1
∆Horxn − ∆Gorxn
∆Sorxn = (Eq. 5.4.124)
Tref
n
∆Cp = ∑ νi CPi (Eq. 5.4.125)

i=1
CPi = R×(A+BT+CT2 +DT−2 ) (Eq. 5.4.126)
Combine Eq. 5.4.118-5.4.121, and 5.4.124 to yield:

K = f(T) and KP = f(T) and KC = f(T)
−∆Grxn 1
K = exp ( ) = exp [ (T∆Srxn − ∆Hrxn )]
RT RT
T T
1 dT
K = exp [ (T (∆Sorxn + ∫ ∆Cp ) − (∆Horxn + ∫ ∆Cp dT))]
RT Tref T Tref
T T
1 o dT o
K = exp [ (T∆Srxn +T ∫ ∆Cp − ∆Hrxn − ∫ ∆Cp dT)]
RT Tref T Tref
1 ∆Horxn − ∆Gorxn T
dT T
K = exp [ (T ( ) +T ∫ ∆Cp − ∆Horxn − ∫ ∆Cp dT)]
RT Tref Tref T Tref
1 1 T
dT ∆Horxn 1 T
K = exp [ ( (∆Horxn − ∆Gorxn )+ ∫ ∆Cp − − ∫ ∆Cp dT)]
R Tref Tref T T T Tref
∆Horxn − ∆Gorxn ∆Horxn 1 T 1 T dT

K(T) = exp ( − − ∫ ∆Cp dT + ∫ ∆Cp ) (Eq. 5.4.127)
RTref RT RT Tref R Tref T
67
Eq. 5.4.127 is used to calculate K = K(T) for any value of T. It gives us rigorous method of
calculation for True Chemical Equilibrium Constant (K). To relate K(T) with K(T0), where T0 is any
other temperature at which value of K(T0) is available to us, we write Eq. 5.4.127 for T=T0:
∆Horxn − ∆Gorxn ∆Horxn 1 T0
1 T0 dT
K(T0 ) = exp ( − − ∫ ∆Cp dT + ∫ ∆Cp ) (Eq. 5.4.128)
RTref RT0 RT0 Tref R Tref T
Take ratio of Eq. 5.4.127 to Eq. 5.4.128:
K(T) exp ( − − ∫T ∆Cp dT + ∫T ∆Cp )
RTref RT RT ref R ref T
= o o o
K(T0 ) ∆H − ∆Grxn ∆Hrxn 1 T0 1 T dT
exp ( rxn − − ∆C dT + ∫T 0 ∆Cp )
RTref RT0 RT0 ∫Tref p R ref T
K(T) = K(T0 )exp [( − − ∫ ∆Cp dT + ∫ ∆Cp )
1 T0 dT
−( − − ∫ ∆Cp dT + ∫ ∆Cp )]

K(T) = K(T0 )exp [ − − ∫ ∆Cp dT + ∫ ∆Cp
1 T0 dT
− + + ∫ ∆Cp dT − ∫ ∆Cp ]
∆Horxn 1 T 1 T dT ∆Horxn 1 T0
1 T0 dT
K(T) = K(T0 )exp [− − ∫ ∆Cp dT + ∫ ∆Cp + + ∫ ∆Cp dT − ∫ ∆Cp ]
RT RT Tref R Tref T RT0 RT0 Tref R Tref T
∆Horxn ∆Horxn 1 T0
1 T 1 T dT 1 T0 dT
K(T) = K(T0 )exp [ − + ∫ ∆Cp dT − ∫ ∆Cp dT + ∫ ∆Cp − ∫ ∆Cp ]
RT0 RT RT0 Tref RT Tref R Tref T R Tref T
∆Horxn 1 1 1 T0
1 T 1 T0 dT 1 T dT
K(T) = K(T0 )exp [ ( − )+ ∫ ∆Cp dT − ∫ ∆Cp dT − ∫ ∆Cp + ∫ ∆Cp ] (Eq. 5.4.129)
R T0 T RT0 Tref RT Tref R Tref T R Tref T
By using Eq. 5.4.129, if we know K(T0) then we can find K(T) at any other temperature T.
For those systems in which ∆Cp = 0, the Eq. 5.4.129 reduces to:
∆Horxn 1 1
K(T) = K(T0 )exp [ ( − )] (Eq. 5.4.130)
R T0 T
This temperature dependence can also be calculated by the integration of vant Hoff’s equation
for ∆Cp = 0 (Means for ∆Hrxn = ∆Horxn = constant).
d lnK ∆Hrxn
= (Eq. 5.4.131)
dT RT2
68
Relationships among K, KC, and KP can be developed using Eq. 5.4.118 by thermodynamics for
the liquid phase assumptions (Incompressible Liquid, Ideal Solution) and for the gas phase
assumptions (Ideal Gas, Ideal Solution). Their development is discussed in Chapter 4 while only
results are presented here. [4]
KC
K= (For Liquid Phase Reactions) (Eq. 5.4.132)
̃ )ν
(1/V
KP
K= (For Gas Phase Reactions) (Eq. 5.4.133)
(Pref )ν
Eq. 5.4.129-5.4.131 can also be expressed in terms of KC and KP for the cases of ideal solutions
(Let exponential term in Eq. 5.4.129 = E1 and exponential term in Eq. 5.4.130 = E2):
K(T) = K(T0 )exp(E1 ) and K(T) = K(T0 )exp(E2 ) (Eq. 5.4.134)
For Liquid Phase Reactions:
Use Eq. 5.4.132 for Liquid Phase in combination with Eq. 5.4.134 (Incompressible Liquid and
Ideal Solution → Molar Volume = Constant):
KC (T) KC (T0 ) KC (T) KC (T0 )

ν = ν exp(E1 ) and ν = exp(E2 )
̃)
(1/V ̃)
(1/V ̃)
(1/V ̃ )ν
(1/V
KC (T) = KC (T0 )exp(E1 ) and KC (T) = KC (T0 )exp(E2 )
And for vant Hoff’s Equation:
KC
lnK = ln( ̃ ν
ν ) = lnKC − ln(1/V) = lnKC +νlnV
̃
̃)
(1/V
d ∆H
̃)= rxn
(lnKC +νlnV
dT RT2
d lnKC d ∆H
̃)= rxn
+ (νlnV
dT dT RT2
For Incompressible Liquids (Molar Volume = Constant) so,
d lnKC ∆Hrxn
+0 =
dT RT2
69
d lnKC ∆Hrxn
=
dT RT2
For Gas Phase Reactions:
Use Eq. 5.4.133 for Gas Phase in combination with Eq. 5.4.134 (Ideal Gas and Ideal Solution):
KP (T) KP (T0 ) KP (T) KP (T0 )

= exp(E 1 ) and = exp(E2 )
(Pref )ν (Pref )ν (Pref )ν (Pref )ν
KP (T) = KP (T0 )exp(E1 ) and KP (T) = KP (T0 )exp(E2 )
And for vant Hoff’s Equation:
KP
lnK = ln( ) = lnKP − ln(Pref )ν = lnKP − νlnPref
(Pref )ν
d ∆Hrxn
(lnKP − νlnPref )=
dT RT2
d lnKP d ∆Hrxn
− (νlnPref )=
dT dT RT2
Because Pref = Constant (1 atm) so,
d lnKP ∆Hrxn
+0 =
dT RT2
d lnKP ∆Hrxn
=
dT RT2
So, [4]
For Liquid Phase Reactions:
∆Horxn 1 1 1 T0
1 T 1 T0 dT 1 T dT
KC (T) = KC (T0 )exp [ ( − )+ ∫ ∆Cp dT − ∫ ∆Cp dT − ∫ ∆Cp + ∫ ∆Cp ] (Eq. 5.4.135)
∆Horxn 1 1
KC (T) = KC (T0 )exp [ ( − )] (Eq. 5.4.136)
R T0 T
d lnKC ∆Hrxn
= (Eq. 5.4.137)
dT RT2
70
For Gas Phase Reactions:
∆Horxn 1 1 1 T0
1 T 1 T0 dT 1 T dT
KP (T) = KP (T0 )exp [ ( − )+ ∫ ∆Cp dT − ∫ ∆Cp dT − ∫ ∆Cp + ∫ ∆Cp ] (Eq. 5.4.138)
∆Horxn 1 1
KP (T) = KP (T0 )exp [ ( − )] (Eq. 5.4.139)
R T0 T
d lnKP ∆Hrxn
= (Eq. 5.4.140)
dT RT2
For endothermic reactions, the equilibrium constant, KC or KP, increases with increasing
temperature; while for exothermic reactions, KC or KP decreases with increasing temperature.
Here,
K=K(T) = True Chemical Equilibrium Constant (Unitless)
KC=KC(T)= Chemical Equilibrium Constant (Concentration Based) (Dynamic Units)
KP=Kp(T) = Chemical Equilibrium Constant (Partial Pressure Based) (Dynamic Units)
i = Chemical Species
n = Total No. of Species in the Chemical Reaction
̂f = Fugacity of Species “i” in the Solution (Pa)
i
o
fi = Fugacity of Pure Species “i” at Standard State (Pa)
νi = Stoichiometric No. (Unitless)
R = Ideal Gas Constant (8314 J/kgmol.K)
T = Absolute Temperature (K)
T0 = Absolute Temperature (K) at which property values are known
Tref = Reference Temperature (298.15 K)
Pref = Reference Pressure (1 atm)
V
̃ = Molar Volume of Reaction Mixture (m3/kgmol)
ν = Change in the Total No. of Moles in the Reaction (Unitless)
Cpi = Molar Heat Capacity of Species “i” (J/kgmol of i.K)
∆Cp = Molar Heat Capacity Change of Reaction (J/kgmol.K)
∆Horxn = Molar Enthalpy Change of Reaction at Reference Temperature (Tref) (J/kgmol)
∆Sorxn = Molar Entropy Change of Reaction at Reference Temperature (Tref) (J/kgmol.K)
∆Gorxn = Molar Gibbs Free Energy Change of Reaction at Reference Temperature (Tref) (J/kgmol)
∆Hrxn = Molar Enthalpy Change of Reaction at any Temperature (T) (J/kgmol)
∆Srxn = Molar Entropy Change of Reaction at any Temperature (T) (J/kgmol.K)
∆Grxn = Molar Gibbs Free Energy Change of Reaction at any Temperature (T) (J/kgmol)
Hofi = Molar Enthalpy of Formation for Species “i” at Temperature (Tref) (J/kgmol of i)
Gofi = Molar Gibbs Free Energy of Formation for Species “i” at Temperature (Tref) (J/kgmol of i)
5.4.11 Reaction Extent

For Single Reaction Stoichiometry: [4]
Recall the general chemical reaction of Eq. 5.4.112:

|ν1 |A1 +|ν2 |A2 +…→|ν3 |A3 +|ν4 |A4 +… (Eq. 5.4.112)
71
Where, |νi| represents a stoichiometric coefficient and Ai represents a chemical formula while
νi itself is called a stoichiometric number which is a:
• Unitless Quantity
• +ve for Product
• -ve for Reactant
The stoichiometric number for a species that does not participate in the reaction, that is, an
inert species, is zero. As the reaction represented by Eq. 5.4.112 progresses, the changes in the
number of moles of species “i” present are in direct proportion to the corresponding
stoichiometric number. Applied to a differential amount of species, this principle provides the
equations:
dni ∝ νi
dni = constant × νi = Cνi
dni
=C
νi
dn1 dn2
= C and = C so on…
ν1 ν2
So, the list continues to include all species.

dn1 dn2 dn3 dni
= = =…=
ν1 ν2 ν3 νi
All terms being equal, they can be identified collectively by a single quantity representing an
extent of reaction. Thus dε, a single variable representing the extent to which the reaction has
proceeded, is defined by the equation:
dn1 dn2 dn3 dni
= = =…= = dε (Eq. 5.4.141)
ν1 ν2 ν3 νi
The general relation connecting the differential change in moles dni with dε is therefore:
dni
dε = and dni = νi dε (Eq. 5.4.142a and b)
νi
This new variable ε, is called the extent of reaction or simply the reaction coordinate, which
characterizes the extent or degree to which a reaction has taken place. Only changes in ε with
respect to changes in the moles of species are defined by Eq. 5.4.142b. The definition of ε itself
depends for a specific application on setting it equal to zero for the initial state of the system
72
prior to reaction. Thus, integration of Eq. 5.4.142b from an initial unreacted state where ε = 0
and ni = ni0 to a state reached after an arbitrary amount of reaction gives:
ni ε
∫ dni = νi ∫ dε
ni0 0
(ni -ni0 ) = νi ε
For Batch Systems:

ni -ni0
ε= or ni = ni0 +νi ε (Eq. 5.4.143)
νi
So, ε possess the units of moles for batch systems i.e. kgmol. Summation over all species yields:
n n n
∑ ni = ∑ ni0 + ∑ νi ε
i=1 i=1 i=1
n
nT = nT0 +ε ∑ νi
i=1
nT = nT0 +εν (Eq. 5.4.144)
Relation of Reaction Extent with Reaction Conversion for Single Reaction Scenario:
Write Eq. 5.4.143 for Species “A” (Limiting Reactant):

nA -nA0
ε=
νA
-νA ε = nA0 -nA (Eq. 5.4.145)
Recall Eq. 5.4.2 and Eq. 5.4.4:

b c d
A+ B→ C+ D (Eq. 5.4.2)
a a a
nA =nA0 (1-XA ) (Eq. 5.4.4)
For this generic reaction:

νA = -1

-(-1)ε = nA0 -nA
ε = nA0 -nA
Put Eq. 5.4.4 in it:
73
ε = nA0 -nA0 (1-XA )
ε = nA0 (1-1+XA )
ε = nA0 XA (Eq. 5.4.146)
For Continuous Systems (By Analogous Treatment):

Fi = Fi0 +νi ε (Eq. 5.4.147)
FT = FT0 +εν (Eq. 5.4.148)
ε = FA0 XA (Eq. 5.4.149)
So, ε possess the units of molar flowrate for flow systems i.e. kgmol/s.
For Multireaction Stoichiometry: [4]
For following generic multiple reactions (R-1 to R-n):
R-1 |ν1,1 |A1 +|ν2,1 |A2 +…→|ν3,1 |A3 +|ν4,1 |A4 +…

R-2 |ν1,2 |B1 +|ν2,2 |B2 +…→|ν3,2 |B3 +|ν4,2 |B4 +…
So on… (The last reaction can be written as):
R-n |ν1,n |N1 +|ν2,n |N2 +…→|ν3,n |N3 +|ν4,n |N4 +…
Where, |νi,j| represents a stoichiometric coefficient of ith species in jth reaction. and Ai, Bi, … Ni
represents chemical formulas while νi,j itself is called a stoichiometric number of species ”i” in
reaction “j”. When two or more reactions proceed simultaneously, a second subscript, here
indicated by j, serves as the reaction index. A separate reaction coordinate ε j then applies to
each reaction. The stoichiometric numbers are doubly subscripted to identify their association
with both a species and a reaction. Then, Extent of Reaction for Multireaction Stoichiometry
can be defined as:
dni,j = νi,j dεj (Eq. 5.4.150)
Summation over all reactions yield:

m m
∑ dni,j = ∑ νi,j dεj

j=1 j=1
m m
d( ∑ ni,j ) = ∑ νi,j dεj

j=1 j=1
m
dni = ∑ νi,j dεj (Eq. 5.4.151)

j=1
74
Because the number of moles of a species n i may change because of several reactions, the
general equation analogous to Eq. 5.4.142b includes a sum. Here, variable εj, is called the extent
of reaction “j”. Integrate Eq. 5.4.151 from an initial unreacted state where εj = 0 and ni = ni0 to
a state reached after an arbitrary amount of reaction gives:
ni εj m
∫ dni = ∫ ∑ νi,j dεj
ni0 0 j=1
ni m εj
∫ dni = ∑ (νi,j ∫ dεj )
ni0 j=1 0
m
(ni -ni0 ) = ∑ νi,j εj

j=1
For Batch Systems:
m
ni = ni0 + ∑ νi,j εj (Eq. 5.4.152)

j=1
Summation over all species yield:

n n n m
∑ ni = ∑ ni0 + ∑ ∑ νi,j εj
i=1 i=1 i=1 j=1
n m
nT = nT0 + ∑ ∑ νi,j εj
i=1 j=1
m n
nT = nT0 + ∑ ( ∑ νi,j )εj

j=1 i=1
m
nT = nT0 + ∑ (νj )εj

j=1
The definition of a total stoichiometric number ν is:
n
ν = ∑ νi (Eq. 5.4.153)
i=1
This is for a single reaction. And it has its multireaction counterpart here in the definition:
n
νj = ∑ νi,j (Eq. 5.4.154)

i=1
75
m
nT = nT0 + ∑ νj εj (Eq. 5.4.155)

j=1
m
Fi = Fi0 + ∑ νi,j εj (Eq. 5.4.156)

j=1
m
FT = FT0 + ∑ νj εj (Eq. 5.4.157)

j=1
In this topic “n” as an upper limit of sigma summation indicates total no. of species. While “m”
as upper limit of sigma summation denotes total no. of reactions.
5.4.12 Reaction Selectivity and Yield

Here, in the case of Multiple Reactions the reactants that are consumed in the formation of a
desired product (D), and the formation of an undesired product (U), are of particular interest.
[3]
For example:
In Series Reaction Sequence:
kD kU
A → D→U
In Parallel Reaction Sequence:
kD
A→D
kU
A→U
• Reaction Selectivity
Now we want to minimize the formation of (U) and maximize the formation of (D). And
for this purpose, we define a new term known as reaction selectivity. “Selectivity tells us
how one product is favored over another when we have multiple reactions.” We can
quantify the formation of (D) with respect to (U) by defining the selectivity of the system.
[3]
Instantaneous Selectivity
The instantaneous selectivity of (D) with respect to (U) is the ratio of the rate of formation
of (D) to the rate of formation of (U).
rD Rate of formation of D
SD/U = = (Eq. 5.4.158)
rU Rate of formation of U
Overall Selectivity
Another definition of selectivity used in the literature is given in terms of moles or molar
flow rates:
For Batch Reactors:
76
nD Moles of D present at the end of reaction time
S̅ D/U = = (Eq. 5.4.159)
nU Moles of U present at the end of reaction time
For Continuous Reactors:
FD Molar Flowrate of D at reactor exit
S̅D/U = = (Eq. 5.4.160)
FU Molar Flowrate of U at reactor exit
• Reaction Yield
Now we want to quantify the production of a specific product with respect to the
consumption of limiting reactant. For this purpose, we define a new term known as
reaction yield. “Yield tells us how much desired product is produced with respect to
limiting reactant consumed.” [3]
Instantaneous Selectivity
The yield at a point can be defined as the ratio of the reaction rate of a given product
to the reaction rate of the limiting reactant A.
rD Rate of formation of D
YD = = (Eq. 5.4.161)
−rA Rate of consumption of A
Overall Selectivity
Another definition of yield used in the literature is given in terms of moles or molar flow
rates:
For Batch Reactors:
nD Moles of D present at the end of reaction time
Y̅ D = = (Eq. 5.4.162)
nA0 − nA Moles of A reacted
For Continuous Reactors:

FD Molar Flowrate of D at reactor exit
Y̅ D = = (Eq. 5.4.163)
FA0 − FA "A" reacted on the basis of reactor exit conditions
There often is a conflict between selectivity and conversion. Because according to selectivity
you want to make as much as possible of your desired product (D) and at the same time
minimize the undesired product (U). However, according to conversion, the greater the
conversion you achieve, not only do you make more (D), but you also form more (U). [3]
5.4.13 Space Time and Space Velocity

Another quantity known as Space Time is often used in the favor of reactor volume. The Space
Time (ST) having units of (s), is obtained by dividing the reactor volume (V) (m3) by the
volumetric flow rate entering the reactor (υ0) (m3/s):
77
V
ST = (Eq. 5.4.164)
υ0
The Space Velocity (SV) (1/s), is the reciprocal of space time (ST) defined as: [3]
υ0 1
SV = = (Eq. 5.4.165)
V ST
5.5 Reactor Pressure Drop

For liquid phase chemical reactions (ρL = Constant) which employs that (υ = υ0 = Constant)
hence, pressure term does not appear in the reaction rate law. So, pressure drop does not
impact reaction rate for liquid phase reactions and so in this case pressure drop calculation can
be ignored. On the other hand, for gas phase chemical reactions (ρG = Variable) which
employs that (υ = υ0 x (FT/FT0) x (P0/P) x (T/T0) = Variable) hence, pressure term does appear
in the reaction rate law. So, pressure drop impacts the reaction rate significantly for gas phase
reactions and so in this case pressure drop calculation cannot be ignored. This concept is
illustrated in Figure 5.13. [3]
Moreover, pressure drop is only a functionality of continuous systems. So, in Batch Reactors
(BR) there is no concept of pressure drop. In flow systems CSTR, PFR, and PBR lies. For CSTR’s
pressure drop modelling is not an easy task due to mixing and container-based reactor. And
usually gas phase reactions are not carried out in CSTRs except for gas bubbling through liquid
phase in case of Gas-Liquid reactions. So, pressure drop consideration for CSTRs can be
ignored or a practical procedure can be employed for the modelling of pressure drop in them.
[3]
.
In conclusion, only pressure drop of gas phase reactions occurring in PFR and PBR will be
considered in this text. In these scenarios, pressure drop affects the reaction rate significantly
and so, reactor size changes.
78
ρL = Density = Constant
Liquid Phase No Need to Incorporate Effects
Reaction Phase
of Pressure Drop
ρG = Density = Variable
Gas Phase There is a Need to Incorporate
Effects of Pressure Drop
Figure 5.13: Consideration of Pressure Drop with respect to Reaction Phase
5.5.1 Pressure Drop in PFR

Normally, the pressure drop for gases flowing through pipes without packing can be neglected.
But if you want to consider the pressure drop along the length of the pipe due to skin friction
then it can be calculated by using: [3]
Figure 5.14: Plug Flow Reactor (PFR)
dP 16ρυ dυ 2fυ
=− ( + ) (Eq. 5.5.1)
dz π2 dr dz dr
4
P = Pressure (Pa)
z = Axial coordinate (m)
ρ = Density of gas (kg/m3)
υ = Volumetric flowrate of gas (m3/s)
dr = Inner diameter of reactor (m)
f = Fanning friction factor (Unitless)
• Volumetric Flowrate of Gas (υ)
Volumetric flowrate of gas depends on: [3]
υ = υ(T,P,ci) = ?
Recall Eq. 5.4.53:
79
FT P0 T
υ = υ0 ( ) ( ) ( ) (Eq. 5.4.53)
FT0 P T0
Where FT is the total molar flow rate of gas at any point within the reactor, which is
indirect representation of concentration of all species.
• Density of Gas (ρ)
Density of gas depends on: [3]
ρ = ρ(T,P,ci) = ?
Because the reactor (either PFR or PBR) is operated at steady state, the mass flow rate
at any point down the reactor, ო (kg/s), is equal to the entering mass flow rate, ო0 (kg/s)
(i.e., Equation of Continuity):
ო = ო0 or ρυ = ρ0 υ0
ρ0 υ0
ρ=
υ
Put Eq. 5.4.53 in it:
ρ0 υ0 ρ0
ρ= =
F P T F P T
υ0 ( T ) ( 0 ) ( ) ( T ) ( 0 ) ( )
FT0 P T0 FT0 P T0
FT0 P T0
ρ = ρ0 ( ) ( ) ( ) (Eq. 5.5.2)
FT P0 T
• Fanning friction factor (f)
The Fanning friction factor is a function of the Reynolds Number (Re) and Pipe
Roughness (ϕp): [3]
f = f(Re,ϕp) = ?
Where, Reynolds number (Re) (Unitless) for pipe flow can be defined as: [6]
4ρυ
Re = (Eq. 5.5.3)
πdr μ
Put Eq. 5.4.53 and Eq. 5.5.2 in Eq. 5.5.3:
F P T F P T
4ρ0 ( T0 ) ( ) ( 0 ) υ0 ( T ) ( 0 ) ( ) 4ρ υ
FT P0 T FT0 P T0 0
Re = = 0
πdr μ πdr μ
For a gas mixture flowing through a PFR, the viscosity of gas (μ) (Pa.s) is only a function
of gas temperature and composition (as will be shown in the next article). For the sake
of convenience, in the calculation of Reynolds number for compressible flow, it is usually
assumed that this variance in viscosity is weak. So, it is assumed that the viscosity of gas
mixture at any point along the length of reactor is approximately same as its value at
the reactor inlet, hence (μ = μ0). Therefore,
80
4ρ0 υ0
Re = (Eq. 5.5.4)
πdr μ0
While, pipe roughness (ϕp) (Unitless) is given by: [6]

hp Height of protuberances (m)
ϕp = = (Eq. 5.5.5)
dr Inner Diameter of Reactor (m)
Height of protuberances (hp) (m) is the average distance between the bumps and
hollows on the inside surface of the pipe. That is:
D1 +D2 +D3 +D4 +…+DN
hp = (Eq. 5.5.6)
N
Where, N = Total number of patches into which a considered area is divided (Unitless)
e.g. in the Figure 5.15 (N = 5).
Figure 5.15: Height of protuberances (hp)
Now, we will consider five cases, to express fanning friction factor as a function of
Reynolds number and pipe roughness.
f = f(Re,ϕp) = ?
So, Fanning friction factor for the case of laminar or turbulent flow can now be
calculated using any one of the following suitable cases: [6]
Case-1: Hagen-Poiseuille Equation:
Explicit Equation
16
f= (Eq. 5.5.7)
Re
81
Laminar flow
For { Re<2100 stable
Re>2100 usually unstable
Case-2: Blasius Equation:
Explicit Equation
0.0791
f= (Eq. 5.5.8)
Re1/4
Turbulent flow in smooth pipes
For {
2.1×103 <Re<105
Case-3: Prandtl Equation:
Implicit Equation
1
= 1.737 ln (Re√f) − 0.4 (Eq. 5.5.9)
√f
For {
2.3×103 <Re<4×106
Case-4: Barenblatt Equation:
Explicit Equation
-4 ln Re
3 3+2 ln Re
(ln Re)2 e2 8√3(ln Re)+60
f = 2[ ( )] (Eq. 5.5.10)
3 24(ln Re)2 +54(ln Re)+27
2ln(Re)2
For {
3.07×103 <Re<3.23×106
Case-5: Haaland Equation:
Explicit Equation
-2
10/9
6.9 ϕp
f = [-1.563 ln ( + ( ) )] (Eq. 5.5.11)
Re 3.7
Turbulent flow in rough pipes

For { 4×104 <Re<108
0<ϕp <0.05
Now, we are going to calculate the pressure drop through a Plug Flow Reactor (PFR). Recall
Eq. 5.5.1: [3]
dP 16ρυ dυ 2fυ
=− ( + ) (Eq. 5.5.1)
dz π2 dr dz dr
4
Put Eq. 5.4.53 and Eq. 5.5.2 in Eq. 5.5.1:
82
FT P0 T
υ = υ0 ( ) ( ) ( ) (Eq. 5.4.53)
FT0 P T0
FT0 P T0
ρ = ρ0 ( ) ( ) ( ) (Eq. 5.5.2)
FT P0 T
F P T F P T F P T F P T
dP 16ρ0 ( T0 ) ( ) ( 0 ) υ0 ( T ) ( 0 ) ( ) d [υ0 ( T ) ( 0 ) ( )] 2fυ0 ( T ) ( 0 ) ( )
FT P0 T FT0 P T0 FT0 P T0 FT0 P T0
=− [ + ]
dz 4
π2 d r dz dr
dP 16ρ0 υ0 d FT P0 T 2fυ0 FT P0 T
=− [υ0 [( ) ( ) ( )] + ( ) ( ) ( )]
dz 4
π2 dr dz FT0 P T0 dr FT0 P T0
dP 16ρ0 υ20 d FT P0 T 2f FT P0 T
=− [ [( ) ( ) ( )] + ( ) ( ) ( )] (Eq. 5.5.12)
dz π dr dz FT0 P T0
2 4 dr FT0 P T0
It is more convenient to convert Eq. 5.5.12 in terms of reactor volume (V) instead of reactor length (z)
by using:
V = Ar z
By taking differential of both sides:

dV = Ar dz
Or,
π 2
dV = d dz
4 r
Upon rearrangement:
4dV
dz = 2
πdr
=− [( ) ( ) ( )] + ( ) ( ) ( )
4dV 4
π2 dr 4dV FT0 P T0 dr FT0 P T0
2 2
πdr [ πdr ]
2 2
πdr dP 16ρ0 υ20 πdr d FT P0 T 2f FT P0 T
=− [( ) [( ) ( ) ( )] + ( ) ( ) ( )]
4 dV 4
π2 dr 4 dV FT0 P T0 dr FT0 P T0
=− [ [( ) ( ) ( )] + ( ) ( ) ( )] (Eq. 5.5.13)
dV π2 dr dV FT0 P T0
4
πdr FT0 P T0
3
83
Let,
16ρ0 υ20
αPFR = 4
(Eq. 5.5.14)
π2 dr
So,
dP d FT P0 T 8f FT P0 T
= − αPFR [ [( ) ( ) ( )] + 3 ( ) ( ) ( )] (Eq. 5.5.15)
dV dV FT0 P T0 πd FT0 P T0
r
Here, Fanning friction factor can be calculated using any equation from Eq. 5.5.7-5.5.11
depending upon flow regime and pipe roughness. Usually in the industrial systems, the flow is
turbulent and pipe is rough so Eq. 5.5.11 will be the best choice. Here, αPFR possess the units of
(kg/m.s2). And Equation 5.5.15 is useful for the case of multiple reactions. For single reaction
scenario, Eq. 5.4.62 will be substituted in Eq. 5.5.15 to convert it in terms of conversion as: [3]
FT
= 1+ϵXA
FT0
dP d P0 T 8f P0 T
= − αPFR [ [(1+ϵXA ) ( ) ( )] + 3 (1+ϵXA ) ( ) ( )] (Eq. 5.5.16)
dV dV P T0 πd P T0
r
5.5.2 Pressure Drop in PBR

Most gas-phase reactions are catalyzed by passing the reactant through a packed bed of
catalyst particles. The equation used most often to calculate pressure drop in a packed bed is
the Ergun Equation. [3],[6]
Figure 5.16: Packed Bed Reactor (PBR)
Term 1 Term 2
dP 4υ 1 − ϕ ⏞ 150(1 − ϕ)μ 7ρυ
⏞
= − 2 ( 3 ) + (Eq. 5.5.17)
dz πdr dp ϕ dp 2
πdr
[ ]
Term 1 is dominant for laminar flow, and Term 2 is dominant for turbulent flow.
P = Pressure (Pa)
z = Axial coordinate (m)
υ = Volumetric flowrate of gas (m3/s)
dr = Inner diameter of reactor (m)
84
dp = Mean diameter of catalyst particle in the bed (m)
ϕ = Void fraction (or porosity) of catalyst bed (Unitless)
μ = Viscosity of gas (Pa.s)
ρ = Density of gas (kg/m3)
• Mean Diameter of Catalyst Particle (dp):

Catalyst particles are available in a variety of shapes. Therefore, the generic relation for
the mean diameter of particle having any shape is (dp): [6]
6
dp = (Eq. 5.5.18)
ɑv
Where ɑv represents “specific surface area” (1/m):
Surface area of particle Sp
ɑv = = (Eq. 5.5.19)
Volume of particle Vp
a. For Particles having Uniform Spherical Shape throughout the bed:

The diameter of spherical catalyst particles can be uniform throughout the packed
bed in which case, dp represents diameter of any individual catalyst particle.
4 3
6 6Vp 6 (3 πRp ) 2Rp
3
dp = = = = 2 =2Rp
ɑv Sp 4πR2p Rp
dp = 2Rp (Eq. 5.5.20)
Here “Rp” denotes the radius of spherical catalyst particle (m).

b. For Particles having Variable Spherical Shape throughout the bed:
However, if packed bed of catalyst is made up of solid particles of different sizes (a
rare case) then dp will be the arithmetic mean diameter of catalyst particles.
4 3
6 6Vp 6 (3 πRp,mean ) 2Rp,mean
3
dp = = = = =2Rp,mean
ɑv Sp 4πR2p,mean R2p,mean
n
Rp1 +Rp2 +Rp3 +…+Rpn 2
dp = 2Rp,mean =2 ( ) = ∑ Rpk
n n
k=1
n
2Rp1 +2Rp2 +2Rp3 +…+2Rpn dp1 +dp2 +dp3 +…+dpn 1
dp = = = ∑ dpk (Eq. 5.5.21)
n n n
k=1
Here,
Rp,mean = Arithmetic mean radius of catalyst particles (m)
Rpk = Radius of kth individual catalyst particle (m)
85
dp = Arithmetic mean diameter of catalyst particles (m)
dpk = Diameter of kth individual catalyst particle (m)
n = No. of sample particles having different diameter
• Void Fraction of Catalyst Bed (ϕ)
While void fraction or porosity of catalyst bed is defined already by Eq. 5.3.8b:
Vvoid
ϕ= (Eq. 5.3.8b)
Vtotal bed
• Volumetric Flowrate of Gas (υ)
Volumetric flowrate of gas depends on:
υ = υ(T,P,ci) = ?
Recall Eq. 5.4.53:
FT P0 T
υ = υ0 ( ) ( ) ( ) (Eq. 5.4.53)
FT0 P T0
Where FT is the total molar flow rate of gas at any point within the reactor, which is
indirect representation of concentration of all species.
• Density of Gas (ρ)
Density of gas depends on:
ρ = ρ(T,P,ci) = ?
Recall Eq. 5.5.2:
FT0 P T0
ρ = ρ0 ( ) ( ) ( ) (Eq. 5.5.2)
FT P0 T
• Viscosity of Gas (μ)
The viscosity of non-polar real gases at low density conditions (High Temperature and
Low Pressure) increases with temperature, and is independent of the pressure. [6]
Therefore:
For a Pure Gas: μi = μi(T) = ?
For Mixture of Gases: μ = μ(T,ci) = ?
Case 1: Viscosity of Pure Gas (μi):
For the above stated assumptions, the viscosity of a pure gas μi as a function of
temperature can be empirically expressed in terms of Lennard-Jones parameters (σi
and Ωμ,i) as: [6]
√Mi T
μi = kμ (Eq. 5.5.22)
σ2i Ωμ,i
In which,
86
1/2 2
-6 kgmol ∙ Å ∙ Pa ∙ s
kμ = 2.6693×10 1/2
(Eq. 5.5.23)
kg ∙ K1/2
Moreover, one can use the following empirical equations to predict the values of
Lenard-Jones parameters from the critical properties of the gas (where the critical
properties are given in Table F.1 of Appendix-F):
1/3
Tc,i Å ∙ Pa1/3
σi = Cμ ( ) and Cμ = 113.7528 (Eq. 5.5.24 a and b)
Pc,i K1/3
1.11716 0.52487 2.16178
Ωμ,i = + + (Eq. 5.5.25)
T 0.14874 1.00416T 3.16606T
exp ( ) exp ( )
( )
Tc,i Tc,i Tc,i
Alternatively, the values of Mi, σi, ϐi/κ, Tc,i, Pc,i and, V

̃c,i can be found in Table F.1 of
Appendix-F for various substances. In the tabulated approach, ϐi/κ will be used to
calculate κT/ϐi (the dimensional temperature) and then values of Ω μ,i as a function of
dimensional temperature can be found in Table F.2 of Appendix-F.
Equations 5.5.22 through 5.5.25 can be combined for the case of non-polar real gases
at low density conditions, to give μi = μi(T) for pure gases.
-1
4/3
Pc,i 1.11716 0.52487 2.16178
μi = Ck √Mi T ( ) × + + (Eq. 5.5.26)
Tc,i T 0.14874 1.00416T 3.16606T
exp ( ) exp ( )
( )
[ Tc,i Tc,i Tc,i ]
1/2
kgmol ∙K2/3 ∙Pa∙s
Ck = 2.06288×10-10 × 1/2
(Eq. 5.5.27)
kg ∙K1/2 ∙Pa2/3
Where,
μi = Viscosity of pure species “i” (Pa.s)
Mi = Molar mass of species “i” (kg/kgmol)
σi = Collision diameter of species “i” (Å) (1Å = 10-10m)
Ωμ,i = Collision integral of viscosity for species “i” (Unitless)
T = Absolute temperature (K)
Tc,i = Critical temperature of species “i” (K)
Pc,i = Critical pressure of species “i” (Pa)
V
̃c,i = Critical molar volume of species “i” (m3/kgmol)
ϐi = Characteristic energy of species “i”(J)
kμ = Constant (kgmol1/2.Å2.Pa.s)/(kg1/2.K1/2)
Cμ = Constant (Å.Pa1/3)/(K1/3)
Ck = Constant (kgmol1/2.K2/3.Pa.s)/(kg1/2.K1/2.Pa2/3)
87
κ = Boltzmann’s constant (1.38066 x 10-23 J/K)
Case 2: Viscosity of Gas Mixture (μ):
To calculate the viscosity of a multicomponent gas mixture the following semiempirical
formula (μ=μ(T,ci))can be used: [6]
N
xα μα x1 μ1 x2 μ2 xN μN
μ=∑ = + +…+ (Eq. 5.5.28)
∑N
β=1 xβ ∁αβ ∑N
β=1 xβ ∁1β ∑N
β=1 xβ ∁2β ∑N
β=1 xβ ∁Nβ
α=1
In fully expanded form it is:

x1 μ 1 x2 μ 2 xN μ N
μ= + +…+ (Eq. 5.5.29)
x1 ∁11 +x2 ∁12 +…+xN ∁1N x1 ∁21 +x2 ∁22 +…+xN ∁2N x1 ∁N1 +x2 ∁N2 +…+xN ∁NN
In which the unitless quantities ∁αβ (Empirical and Dimensionally Consistent Expressions)
are:
-1/2 1/2 1/4 2
1 Mα μ Mβ
∁αβ = (1+ ) [1+ ( α ) ( ) ] (Eq. 5.5.30)
√8 Mβ μβ Mα
The dependence of gas mixture viscosity on composition is extremely nonlinear for

some mixtures, particularly of light and heavy gases. In summary, Eq. 5.5.26, 5.5.28, and
5.5.30 are useful formulas for computing viscosities of non-polar gases and gas mixtures
at low density from the values of temperature. These formulas will not give reliable
results for gases consisting of polar (e.g. H2O, NH3, CHOH, NOCl) or highly elongated
molecules because of the angle dependent force fields that exist between such
molecules. Moreover, these formulas give more accurate results if these are used in
combination with Table F.1 and Table F.2 in Appendix-F, instead of using empirical
correlations for Lenard Jones (intermolecular force) parameters.
Many additional empiricisms are available for estimating viscosities of gases and gas
mixtures. A standard reference is that of Reid, Prausnitz, and Pooling.
Here,
μ = Viscosity of gas mixture (Pa.s)
μi = Viscosity of pure species “i" at System T and P (Pa.s)
xi = Mole fraction of species “i” (Unitless)
∁αβ = Empirical correction factor for viscosity (Unitless)
α = Species “i" in the mixture
β = Species “i" in the mixture
N = No. of species in the gas mixture
88
Now, we are going to calculate the pressure drop through a Packed Bed Reactor (PBR). Recall
Eq. 5.5.17:
dP 4υ 1 − ϕ 150(1 − ϕ)μ 7ρυ
= − 2 ( 3 )[ + 2] (Eq. 5.5.17)
dz πdr dp ϕ dp πdr
Put Eq. 5.4.53 and Eq. 5.5.2 in Eq. 5.5.17:
FT P0 T
υ = υ0 ( ) ( ) ( ) (Eq. 5.4.53)
FT0 P T0
FT0 P T0
ρ = ρ0 ( ) ( ) ( ) (Eq. 5.5.2)
FT P0 T
So,
F P T F P T F P T
dP 4υ0 ( T ) ( 0 ) ( ) 1 − ϕ 150(1 − ϕ)μ 7ρ0 ( T0 ) ( ) ( 0 ) υ0 ( T ) ( 0 ) ( )
FT0 P T0 FT P0 T FT0 P T0
= − ( 3 )[ + ]
dz 2
πdr dp ϕ dp πdr
2
F P T
dP 4υ0 ( T ) ( 0 ) ( ) 1 − ϕ 150(1 − ϕ)μ 7ρ υ
FT0 P T0 0
= − ( 3 )[ + 02 ]
dz 2
πdr dp ϕ dp πdr
dP 4υ0 1 − ϕ 150(1 − ϕ)μ 7ρ0 υ0 FT P0 T
= − 2 ( 3 )[ + ]( )( )( ) (Eq. 5.5.31)
dz πdr dp ϕ dp πdr
2 FT0 P T0
For PBR it is convenient to convert Eq. 5.5.31 in terms of Catalyst Weight instead of Reactor
Length (z). So, Recall Eq. 5.3.9:
W = (1-ϕ)Vρc = (1-ϕ)Ar zρc
Taking the differential of both sides:
dW = (1-ϕ)Ar ρc dz
dW
dz =
(1-ϕ)Ar ρc
dW
dz = π
(1-ϕ) d2r ρc
4
4dW
dz =
(1-ϕ)πd2r ρc
dP 4υ0 1 − ϕ 150(1 − ϕ)μ 7ρ0 υ0 FT P0 T
= − 2 ( 3 )[ + ]( )( )( )
4dW πdr dp ϕ dp πdr
2 FT0 P T0
2
(1-ϕ)πdr ρc
(1-ϕ)πd2r ρc dP 4υ0 1 − ϕ 150(1 − ϕ)μ 7ρ0 υ0 FT P0 T
= − 2 ( 3 )[ + ]( )( )( )
4 dW πdr dp ϕ dp πdr
2 FT0 P T0
89
dP 16υ0 150(1 − ϕ)μ 7ρ0 υ0 FT P0 T
= − [ + ]( )( )( ) (Eq. 5.5.32)
dW 4
π2 dr dp ρc ϕ
3 dp πdr
2 FT0 P T0
Now we consider two different cases:

• CASE-A: The case in which Viscosity of Gas Mixture (μ) does not vary so much and it
can be considered constant throughout the catalyst bed (μ = μ0 = Constant) [3]
Put μ = μ0 (Viscosity of gas mixture at reactor inlet) = Constant in Eq. 5.5.32:
dP 16υ0 150(1 − ϕ)μ0 7ρ0 υ0 FT P0 T
= − [ + ]( )( )( ) (Eq. 5.5.33)
dW 4
π2 dr dp ρ ϕ
3 dp πdr
2 FT0 P T0
c
Let,
16υ0 150(1 − ϕ)μ0 7ρ0 υ0
αPBR = [+ ] (Eq. 5.5.34)
4
π2 dr dp ρc ϕ dp 3
πdr
2
Then Eq. 5.5.33 will leads to:

dP FT P0 T
= − αPBR ( ) ( ) ( ) (Eq. 5.5.35)
dW FT0 P T0
This equation gives us pressure drop in the packed bed in terms of inlet process
variables, inlet fluid properties, reactor diameter, and properties of the catalyst bed. This
equation will be used in case of multiple reactions in PBR with pressure drop. Here, αPBR
possess the units of (Pa/kg). For the case of single reaction, it is more convenient to
express it in terms of conversion, by using Eq. 5.4.62 as follows:
FT
= 1+ϵXA
FT0
dP P0 T
= − αPBR (1+ϵXA ) ( ) ( ) (Eq. 5.5.36)
dW P T0
• CASE-B: The case in which Viscosity of Gas Mixture (μ) vary significantly and it cannot
be considered constant throughout the catalyst bed (μ = Variable), then, Recall Eq.
5.5.28 and Eq.5.5.30 and combine them:
N
xα μα
μ=∑ (Eq. 5.5.28)
∑N x ∁
α=1 β=1 β αβ
-1/2 1/2 1/4 2
1 Mα μα Mβ
∁αβ = (1+ ) [1+ ( ) ( ) ] (Eq. 5.5.30)
√8 Mβ μβ Mα
N
xα μ α
μ=∑ 2
1/2
α=1 x M -1/2 μ Mβ 1/4
∑Nβ=1 ( β (1+ α ) [1+ ( α ) ( ) ])
√8 Mβ μβ Mα
The mole fractions can also be expressed in terms of molar flowrates as:
90
Fα Fβ
xα = and xβ =
FT FT
So,
N
F α μα N
F α μα
FT FT
μ =∑ 2
or μ = ∑ 2
1/2 1/4 1/2
α=1 Fβ M -1/2 μ Mβ α=1 1 N F M -1/2 μ Mβ 1/4
∑Nβ=1 ( (1+ α ) [1+ ( α ) ( ) ] ) ∑β=1 ( β (1+ α ) [1+ ( α ) ( ) ] )
FT √8 Mβ μβ Mα FT √8 Mβ μβ Mα
N
Fα μα
μ =∑ 2
(Eq. 5.5.37)
-1/2 1/2 1/4
α=1 Fβ Mα μ Mβ
∑N
β=1 ( (1+ ) [1+ ( μα ) ( ) ] )
√8 Mβ β Mα
The Eq. 5.5.37 gives us a relationship for point to point variation of gas mixture viscosity
with respect to Temperature and Composition, where (we recall Eq. 5.5.26-5.5.27,
5.5.32),
-1
4/3
Pc,α 1.11716 0.52487 2.16178
μα = Ck √Mα T ( ) × + + (Eq. 5.5.38a)
Tc,α T 0.14874 exp (1.00416T) exp (3.16606T)
( )
[ Tc,α Tc,α Tc,α ]
-1
4/3
Pc,β 1.11716 0.52487 2.16178
μβ = Ck √Mβ T ( ) × + + (Eq. 5.5.38b)
Tc,β T 0.14874 1.00416T 3.16606T
exp ( ) exp ( )
( )
[ Tc,β Tc,β Tc,β ]
1/2
-10 kgmol ∙K2/3 ∙Pa∙s
Ck = 2.06288×10 × 1/2
(Eq. 5.5.38c)
kg ∙K1/2 ∙Pa2/3
dP 16υ0 150(1 − ϕ)μ 7ρ0 υ0 FT P0 T
= − [ + ]( )( )( ) (Eq. 5.5.32)
dW 4
π2 dr dp ρc ϕ
3 dp πdr
2 FT0 P T0
In the case of multiple gas phase reactions, occurring in PBR, with variable viscosity, Eq.
5.5.32, 5.5.37, and 5.5.38a, b, c will be solved simultaneously in combination with
differential mole balances (for each species) for reactor design.
For the case of single gas phase reaction, occurring in PBR, with variable gas viscosity
we Combine Eq. 5.5.32 and Eq.5.4.62 to yield Eq.5.5.39:
dP 16υ0 150(1 − ϕ)μ 7ρ0 υ0 P0 T
= − [ + ] (1+ϵXA ) ( ) ( ) (Eq. 5.5.39)
dW 4
π2 dr dp ρc ϕ
3 dp πdr
2 P T0
And now we write Equations 5.4.24-28 in generalized form as:

Fi = FA0 (θi +νi XA ) (Eq. 5.5.40a)
For i = α, β Eq. 5.5.40a can be written as:
91
Fα = FA0 (θα +να XA ) (Eq. 5.5.40b)
Fβ = FA0 (θβ +νβ XA ) (Eq. 5.5.40c)
And now combine Eq. 5.5.37 with Eq. 5.5.40b and c:
N
(θα +να XA )μα
μ =∑ 2
(Eq. 5.5.41)
-1/2 1/2 1/4
α=1 (θβ +νβ XA ) M μ Mβ
∑N
β=1 ( (1+ α ) [1+ ( μα ) ( ) ] )
√8 Mβ β Mα
Hence, in the case of single gas phase reaction in PBR, with variable viscosity, Eq. 5.5.39,
5.5.41, 5.4.17, and 5.5.38a, b, c will be solved simultaneously in combination with
differential mole balance and rate law (in terms of conversion) for reactor design. [3]
5.6 General Energy Balance Equation (G.E.B.E)

We shall carry out an energy balance on the open system as shown in Figure 5.17. For an open
system some of the energy exchange is brought about by the flow of mass across the system
boundaries. [3]
Q̇
Fi0 Fi
System
Hi0 Hi
Ẇ s
Figure 5.17: System under consideration for general energy balance
The total energy balance for a time duration of ∆t, yields the following equation:
[Accumulation] = [In] - [Out] (Eq. 5.6.1)
Note that, we are implementing energy balance on the total energy basis. As we know that,
the total energy generation and consumption is always zero so here it is not included.
Accumulation Energy added Energy removed
Heat Added Work done
of energy
to the system to the system from the system by the system on
within = + - + [ ]
by mass flow from surrounding by mass flow the surrounding
the system
([ (J) ] [ (J) ]) ([ (J) ] (J) )
[ (J) ]
92
Accumulation Energy added Energy removed Heat Added Work done
of energy
to the system from the system to the system by the system on
within = - + -[ ]
by mass flow by mass flow from surrounding the surrounding
the system
[ (J) ] [ (J) ] [ (J) ] (J)
[ (J) ]
The unsteady state energy balance for an open system that has n species, each entering and
leaving the system at its respective molar flow rate Fi (moles of i per sec) and with its respective
energy Ei (joules per mole of i) for a duration of ∆t, is:
n n
Esystem | - Esystem | = (∑ Fi0 Ei0 - ∑ Fi Ei ) ∆t + Q̇ ∆t - Ẇ ∆t

t+∆t t
i=1 i=1
Division by ∆t yields:
n n
Esystem | - Esystem |
t+∆t t
= ∑ Fi0 Ei0 - ∑ Fi Ei + Q̇ - Ẇ
∆t
i=1 i=1
Taking limit ∆t approaches zero:

n n
Esystem | - Esystem |
t+∆t t
lim = lim (∑ Fi0 Ei0 - ∑ Fi Ei + Q̇ - Ẇ )
∆t→0 ∆t ∆t→0
i=1 i=1
Left side of this equation becomes the definition of the derivative:

n n
dEsystem
= ∑ Fi0 Ei0 - ∑ Fi Ei + Q̇ - Ẇ (Eq. 5.6.2)
dt
i=1 i=1
Eq. 5.6.2 is the GENERAL ENERGY BALANCE EQUATION for the total system if the reactor has
only single inlet and single outlet. For Multi-Stream Reactor (having multiple inlets and multiple
outlets) the energies must be summed over all inlet and outlet streams as well:
Min Nin, h Mout Nout, h
dEsystem
= ∑ ∑ Fi0, h Ei0, h - ∑ ∑ Fi, h Ei, h + Q̇ - Ẇ (Eq. 5.6.3)
dt
h=1 i=1 h=1 i=1
Summation with index “h” is on streams, while summation with index “i” is on species.
Keep in mind that from the startup of the discussion we are considering only reactors with
single inlet and single outlet if any stream mixing is needed then it will be considered upstream
of the reactor, conversely stream splitting will only be considered downstream of the reactor.
It is needed; otherwise the reactor balances will be so complex that they are not easily
considered, not easily conceptualized, and not easily programmed in computer for their
solution to design reactors. By proceeding further with adiabatic and non-isothermal reactor
93
design you will grasp that the consideration of even single inlet and single outlet reactor stream
will also present many design and solution challenges for us. So, always design reactor such
that there must be premixed reactant inlet stream with single mixture product outlet stream.
And also keep in mind that handmade solution of non-isothermal and adiabatic reactor design
can only be carried out with lot of assumptions which can hold well in the real world but more
accurate and more rigorous results can only be obtained by computer solution of the model
equations under consideration with the help of Polymath, MATLAB, or COMSOL. If you do not
want to develop and solve these equations (not to re-invent the wheel) then prefer to solve
reaction engineering problems with ASPEN Plus and ASPEN Plus Dynamics which has built in
pre developed equations in its GUI, you have to put only values of the parameters and it is
ready for solution. Because I am going to deliver fundamental and advanced concepts of
reactor design that is why it is necessary to make those equations and to solve those equations
then we can learn that what is happening behind the scenes in Aspen Simulator.
Up to this point the developed G.E.B.E Eq. 5.6.2 is not in a form which is most suitable for
reactor design. To make it more suitable for non-isothermal and adiabatic reactor operation
we simplify it term by term.
5.6.1 The Accumulation Term

We shall first concentrate on evaluating the change in the total energy of the system w.r.t. time,
dEsystem /dt. The total energy of the system is the sum of the products of specific energies, Ei
(e.g., J/kgmol i), of the various species in the system volume and the number of moles, ni
(kgmol i), of that species: [3]
n
Esystem = ∑ ni Ei = n1 E1 +n2 E2 +…+nn En (Eq. 5.6.4)

i=1
For example, if our system consists of five species (A, B, C, D, I) then:

Esystem = nA EA +nB EB +nC EC +nD ED +nI EI
Molar energy of species “i” can be expressed as:

Ei = Molar Internal Energy of Species i + Molar Kinetic Energy of Species i + Molar Potential Energy of Species i
Ei = Ui + Ek,i + Ep,i
1
Ei = Ui + M v2 + Mi gh (Eq. 5.6.5)
2 i
Here,
Ui = Molar internal energy of species “i” (J/mol)
Ek,i = Molar bulk kinetic energy of species “i” (J/mol)
94
Ep,i = Molar bulk potential energy of species “i” (J/mol)
v = Average bulk velocity of fluid (m/s)
g = Gravitational acceleration = 9.8 m/s2
h = Height of fluid (m)
Put Eq. 5.6.5 in Eq. 5.6.4:

n n n
1 1
Esystem = ∑ ni Ei = ∑ ni (Ui + Mi v2 + Mi gh) = ∑ (ni Ui + ni Mi v2 + ni Mi gh)
2 2
i=1 i=1 i=1
n n n
1 mi mi 1
Esystem = ∑ (ni Ui + ni v2 + ni gh) = ∑ (ni Ui + mi v2 + mi gh) = ∑(ni Ui + K.E.i + P.E.i )
2 ni ni 2
i=1 i=1 i=1
Differentiate this equation with respect to time:

n n n n
dEsystem d d d d
= ∑(ni Ui + K.E.i + P.E.i ) = ∑ (ni Ui ) + ∑ (K.E.i ) + ∑ (P.E.i )
dt dt dt dt dt
i=1 i=1 i=1 i=1
In chemical engineering processing systems, the changes in kinetic and potential energy are
very small than the changes in internal energy. So, kinetic energy and potential energy changes
can be neglected:
n n n
dEsystem d d d
= ∑ (ni Ui ) + ∑ (K.E.i ) + ∑ (P.E.i )
dt dt dt dt
i=1 i=1 i=1
n
dEsystem d
= ∑ (ni Ui )
dt dt
i=1
If we make use of the definition of molar enthalpy (H = U + PV

̃) to express internal energy in
terms of enthalpy (U = H - PṼ) then:
n n n n n
dEsystem d d d d
= ∑ [ni (Hi - PV
̃i )] = ∑ [ni Hi - Pni V
̃i ] = [∑ ni Hi - P ∑ ni V
̃i ] = [(∑ ni Hi ) - PV]
dt dt dt dt dt
i=1 i=1 i=1 i=1 i=1
n n n n
dEsystem d d d d d dHi dni d
= [(∑ ni Hi ) - PV] = [ ∑(ni Hi ) - (PV)] = [∑ (ni Hi ) - (PV)] = [∑ (ni +Hi ) - (PV)]
dt dt dt dt dt dt dt dt dt
i=1 i=1 i=1 i=1
n n
dEsystem dHi dni d
= [∑ ni + ∑ Hi - (PV)] (Eq. 5.6.6)
dt dt dt dt
i=1 i=1
As we know that liquids are nearly incompressible so that their volume and pressure change
w.r.t. time is zero hence derivative of PV term w.r.t. time for liquid systems is zero. But for
95
gaseous systems it can be significant and can be calculated using (PV = ZnTRT). And if the gas
can be considered ideal then (Z = 1) so that (PV = nTRT).
For liquids (Incompressible fluids):

n n
dEsystem dHi dni
= [∑ ni + ∑ Hi ] (Eq. 5.6.7a)
dt dt dt
i=1 i=1
For ideal gases (Compressible fluids):
Put (PV = nTRT),

n n n n
dEsystem dHi dni d dHi dni dT dnT
= [∑ ni + ∑ Hi - R (nT T)] = [∑ ni + ∑ Hi - R (nT +T )]
dt dt dt dt dt dt dt dt
i=1 i=1 i=1 i=1
And we know that:

n
nT = ∑ ni (Eq. 5.6.8)
i=1
n n n n
dEsystem dHi dni dT dni
= [∑ ni + ∑ Hi - R ( ∑ ni +T ∑ )] (Eq. 5.6.7b)
dt dt dt dt dt
i=1 i=1 i=1 i=1
5.6.2 The Inlet and Outlet Energy Flow Terms

Now we are going to consider the inlet and outlet energy flow terms of Eq. 5.6.2: [3]
n n
dEsystem
= ∑ Fi0 Ei0 - ∑ Fi Ei + Q̇ - Ẇ (Eq. 5.6.2)
dt
i=1 i=1
Recall Eq. 5.6.5 and consider it for reactor outlet:

1
Ei = Ui + Mi v2 + Mi gh (Eq. 5.6.5a)
2
Now write down Eq. 5.6.5 for reactor inlet:
1
Ei0 = Ui0 + M v 2 + Mi gh0 (Eq. 5.6.5b)
2 i 0
Put Eq. 5.6.5a and Eq. 5.6.5b in Eq. 5.6.2,
n n
dEsystem 1 1
= ∑ Fi0 (Ui0 + Mi v0 2 + Mi gh0 ) - ∑ Fi (Ui + Mi v2 + Mi gh) + Q̇ - Ẇ
dt 2 2
i=1 i=1
96
n n n
dEsystem 1 1
= ∑(Fi0 Ui0 - Fi Ui ) + ∑ ( Fi0 Mi v0 2 - Fi Mi v2 ) + ∑(Fi0 Mi gh0 - Fi Mi gh) + Q̇ - Ẇ
dt 2 2
i=1 i=1 i=1
n n n
dEsystem 1 1
= ∑(Fi0 Ui0 - Fi Ui ) + ∑ ( ოi0 v0 2 - ოi v2 ) + ∑(ოi0 gh0 - ოi gh) + Q̇ - Ẇ
dt 2 2
i=1 i=1 i=1
Where, ო = Mass flowrate (kg/s),

n n n
dEsystem 1 1
= ∑(Fi0 Ui0 - Fi Ui ) - ∑ ( ოi v2 - ოi0 v0 2 ) - ∑(ოi gh - ოi0 gh0 ) + Q̇ - Ẇ
dt 2 2
i=1 i=1 i=1
n n n
dEsystem
= ∑(Fi0 Ui0 - Fi Ui ) - ∑(K.Erate, out - K.Erate, in ) - ∑(P.Erate, out - P.Erate, in ) + Q̇ - Ẇ
dt
i=1 i=1 i=1
n n n
dEsystem
= ∑(Fi0 Ui0 - Fi Ui ) - ∑(∆K.Erate ) - ∑(∆P.Erate ) + Q̇ - Ẇ
dt
i=1 i=1 i=1
n n n
dEsystem
= ∑ Fi0 Ui0 - ∑ Fi Ui - ∑(∆K.Erate +∆P.Erate ) + Q̇ - Ẇ
dt
i=1 i=1 i=1
In virtually all chemical processing systems, the change in kinetic energy rate (delta K.Erate) and
potential energy rate (delta P.Erate) is very small in magnitude as compared to the change in
internal energy rate so it can be neglected.
n n n
dEsystem
= ∑ Fi0 Ui0 - ∑ Fi Ui - ∑(∆K.Erate +∆P.Erate ) + Q̇ - Ẇ
dt
i=1 i=1 i=1
n n
dEsystem
= ∑ Fi0 Ui0 - ∑ Fi Ui + Q̇ - Ẇ (Eq. 5.6.9)
dt
i=1 i=1
For Liquids (Incompressible fluids):
Put Eq. 5.6.7a in Eq. 5.6.9:

n n n n
dHi dni
[∑ ni + ∑ Hi ] = ∑ Fi0 Ui0 - ∑ Fi Ui + Q̇ - Ẇ (Eq. 5.6.10a)
dt dt
i=1 i=1 system i=1 i=1
For Gases (Compressible fluids):
Put Eq. 5.6.7b in Eq. 5.6.9:
97
n n n n n n
dHi dni dT dni
[∑ ni + ∑ Hi - R ( ∑ ni +T ∑ )] = ∑ Fi0 Ui0 - ∑ Fi Ui + Q̇ - Ẇ (Eq. 5.6.10b)
dt dt dt dt
i=1 i=1 i=1 i=1 system i=1 i=1
We know that if we keep considering the G.E.B.Es. 5.6.10a (For Liquids) and 5.6.10b (For Gases)
separately then it will complicate the onward development. So, to keep it simple we introduce
a new dimensionless factor (Fp) which is short notation for Fluid Phase such that:
For Liquids: Fp = 0
For Gases: Fp = 1
Hence,
n n n n n n
dHi dni dT dni
[∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = ∑ Fi0 Ui0 - ∑ Fi Ui + Q̇ - Ẇ (Eq. 5.6.11)
dt dt dt dt
When user encounters the liquid phase reaction then (F p = 0) which automatically reduces the
Eq. 5.6.11 to Eq. 5.6.10a. While the reverse will reduce the Eq. 5.6.11 to Eq. 5.6.10b for gas phase
reactions.
5.6.3 The Work Term

It is customary to separate the work rate, Ẇ , into net rate of flow work Ẇ flow and rate of shaft
work Ẇ s . The shaft work could be produced from such things as a stirrer in a CSTR or a turbine
in a PFR. Flow work is work that is necessary to get the mass into and out of the system.
Ẇ = Ẇ flow + Ẇ s (Eq. 5.6.12)
Because from the beginning of the development of energy balance we have considered the
work term in outlet so when the work is done by the system on surrounding it will be considered
(+ve) and when work is done on the system by the surrounding it will be (-ve). i.e. stirrer work
(-ve), turbine work (+ve). According to thermodynamics the molar flow work for species “i”
(Wflow, i) (J/kgmol of i) is:
Wflow, i = PV
̃i
So, the net rate of flow work Ẇ flow (J/s) for our system will be:
n n
Ẇ flow = - ∑ Fi0 P0 V
̃i0 + ∑ Fi PV
̃i
i=1 i=1
98
n n
Ẇ = - ∑ Fi0 P0 V
̃i0 + ∑ Fi PV
̃i + Ẇ s (Eq. 5.6.13)
i=1 i=1
Now we will further simplify Eq. 5.6.11 by introducing Eq. 5.6.13 in it:
n n n n n n n n
dHi dni dT dni
[∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = ∑ Fi0 Ui0 - ∑ Fi Ui + Q̇ - [- ∑ Fi0 P0 V
̃i0 + ∑ Fi PV
̃i + Ẇ s ]
dt dt dt dt
i=1 i=1 i=1 i=1 system i=1 i=1 i=1 i=1
n n n n n n n n
dHi dni dT dni
[∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = ∑ Fi0 Ui0 - ∑ Fi Ui + Q̇ + ∑ Fi0 P0 V
̃i0 - ∑ Fi PV
̃i - Ẇ s
dt dt dt dt
i=1 i=1 i=1 i=1 system i=1 i=1 i=1 i=1
n n n n n n
dHi dni dT dni
[∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = ∑ Fi0 (Ui0 +P0 V
̃i0 ) - ∑ Fi (Ui +PV
̃i ) + Q̇ - Ẇ s
dt dt dt dt
As we know from thermodynamics that: H = U + PV

̃ , So,
n n n n n n
dHi dni dT dni
[∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = ∑ Fi0 Hi0 - ∑ Fi Hi + Q̇ - Ẇ s (Eq. 5.6.14)
dt dt dt dt
Eq. 5.6.14 is the G.E.B.E which is valid for liquid as well as gas phase reactions. It is also valid for
those reactors in which phase transformation occurs. It is the starting point of reactor specific
energy balance development. It is also applicable for non-reactive processes.
Note that, we have considered the heat transfer rate term as an input in G.E.B.E so the right
convention is that heat added to the system is taken as (+ve) while the heat removed from the
system is taken as (-ve) while the reverse is true for work. [3]
5.6.4 The Enthalpy Term

The formula for calculation of enthalpy change from the reference state to the present state is
different depending on the phase of species at reference state as well as on the present state.
From thermodynamics treatment we know that Hi = Hi(T, P). It is proved from thermodynamics
that for ideal gas Hi = Hi(T) only. While for real gases Hi = Hi(T, P) but the contribution of
pressure in enthalpy is much smaller than temperature so pressure dependence of enthalpy
for real gases can also be ignored. For liquids, Hi is a weak function of pressure so the effect of
pressure on enthalpy can also be neglected. Hence, we will consider H i = Hi(T) only.
Table 5.3 presents the differential and integral forms of formulas for enthalpy calculation of
non-sublime reactive substances. If the substance is not taking part in the chemical reaction,
then omit its standard heat of formation from the integral form of enthalpy calculation formula.
[7]
99
∆Hfu at Tm ∆Hvap at T
b
fusion (fu) vaporization (vap)
→ →
Solid Liquid Gas
← ←
solidfication (sf) condensation (cond)
∆Hsf at Tm = − ∆Hfu at Tm ∆Hcond at T = −∆Hvap at T
b b
Table 5.3: For Non-Sublime Substances
Enthalpy Formula Enthalpy Formula Reference Present

No.
(Integral Form) (Differential Form) State State
T
1. Hi = Hofi + ∫ Cps dT dHi = Cps dT s s
Tref
T
2. Hi = Hofi + ∫ Cpl dT dHi = Cpl dT l l
Tref
T
3. Hi = Hofi + ∫ Cpg dT dHi = Cpg dT g g
Tref
Tm T
4. Hi = Hofi + ∫ Cps dT +∆Hfu at Tm + ∫ Cpl dT dHi = (Cps +Cpl )dT s l
Tref Tm
Tm T
5. Hi = Hofi + ∫ Cpl dT +∆Hsf at Tm + ∫ Cps dT dHi = (Cps +Cpl )dT l s
Tref Tm
Tb T
6. Hi = Hofi + ∫ Cpl dT +∆Hvap at Tb + ∫ Cpg dT dHi = (Cpl +Cpg )dT l g
Tref Tb
Tb T
7. Hi = Hofi + ∫ Cpg dT +∆Hcond at Tb + ∫ Cpl dT dHi = (Cpl +Cpg )dT g l
Tref Tb
Tm Tb T
8. Hi = Hofi + ∫ Cps dT +∆Hfu at Tm + ∫ Cpl dT +∆Hvap at Tb + ∫ Cpg dT dHi = (Cps +Cpl +Cpg )dT s g
Tref Tm Tb
Tb Tm T
9. Hi = Hofi + ∫ Cpg dT +∆Hcond at Tb + ∫ Cpl dT +∆Hsf at Tm + ∫ Cps dT dHi = (Cps +Cpl +Cpg )dT g s
Tref Tb Tm
While Table 5.4 presents the differential and integral forms of formulas for enthalpy calculation
of sublime reactive substances. If the substance is not taking part in the chemical reaction, then
omit its standard heat of formation from the integral form of enthalpy calculation formula. [7]
∆Hsub at Tt
sublimation (sub)
→
Solid Gas
←de-sublimation (dsub)
∆Hdsub at Tt = − ∆Hsub at Tt
100
Table 5.4: For Sublime Substances
Enthalpy Formula Enthalpy Formula Reference Present

No.
(Integral Form) (Differential Form) State State
Tt T
1. Hi = Hofi + ∫ Cps dT +∆Hsub at Tt + ∫ Cpg dT dHi = (Cps +Cpg )dT s g
Tref Tt
Tt T
2. Hi = Hofi + ∫ Cpg dT +∆Hdsub at Tt + ∫ Cps dT dHi = (Cps +Cpg )dT g s
Tref Tt
Where,
Tref = Reference Temperature (K) = 298.15 K
T = Present Temperature (K)
Tm = Melting Point (K)
Tb = Boiling Point (K)
Tt = Phase Transition Temperature (K)
H = Molar Enthalpy of Formation at Present Temperature
Hofi = Molar Enthalpy of Formation at Reference Temperature (J/kgmol)
∆Hfu at Tm = Molar Enthalpy of Fusion at Melting Point (J/kgmol)
∆Hsf at Tm = Molar Enthalpy of Solidification at Melting Point (J/kgmol)
∆Hvap at Tb = Molar Enthalpy of Vaporization at Boiling Point (J/kgmol)
∆Hcond at Tb = Molar Enthalpy of Condensation at Boiling Point (J/kgmol)

∆Hsub at Tt = Molar Enthalpy of Sublimation at Phase Transition Temperature (J/kgmol)
∆Hdsub at Tt = Molar Enthalpy of De-Sublimation at Phase Transition Temperature (J/kgmol)
Cps = Molar Heat Capacity of Solid (J/kgmol.K)
Cpl = Molar Heat Capacity of Liquid (J/kgmol.K)
Cpg = Molar Heat Capacity of Gas (J/kgmol.K)
Reference State: Tref = 298.15 K (25 oC) | Pref = 101325 Pa (1 atm)
101
5.7 Application of G.E.B.E to Industrial Reactors
Now we will reduce or enhance the G.E.B.E (Eq. 5.6.14) for each specific reactor type:
• Batch Reactor (BR)

• Continuous Stirred Tank Reactor (CSTR)
• Plug Flow Reactor (PFR)
• Packed Bed Reactor (PBR)
5.7.1 Energy Balance for Batch Reactor (BR)

In order to develop specific energy balance for Batch Reactor (BR) we will apply G.E.B.E (Eq.
5.6.14) to BR, So, recall Eq. 5.6.14:
n n n n n n
dHi dni dT dni
dt dt dt dt
Eq. 5.6.14 is directly valid for those reactors in which the reaction variables (ci, T etc.) are spatially
uniform due to perfect mixing e.g. BR or CSTR. [3]
As we know that, for Batch Reactor (BR) there is not any inflow and outflow during the reactor
operation hence for BR’s (Fi0 = 0 and Fi = 0), so, Eq. 5.6.14 will reduce to:
n n n n n n
dHi dni dT dni
[∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = ∑ Fi0 Hi0 - ∑ Fi Hi + Q̇ - Ẇ s
dt dt dt dt
n n n n
dHi dni dT dni
[∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = Q̇ - Ẇ s (Eq. 5.7.1)
dt dt dt dt
i=1 i=1 i=1 i=1 system
Now we must combine the batch reactor energy balance with its corresponding mole balance.
For this purpose, we recall mole balance equation of batch reactor i.e. Eq. 5.3.1,
dni
= ri V (Eq. 5.3.1)
dt
Recall Eq. 5.4.1 and Eq. 5.4.78:
aA + bB → cC + dD (Eq. 5.4.1)
rA rB rC rD
= = = (Eq. 5.4.78)
-a -b c d
Now we generalize Eq. 5.4.1 based on limiting reactant:
102
b c d
A+ B →… νi i …→ C + D
a a a
Now we generalize Eq. 5.4.78 for species “i”:
rA ri
=
-1 νi
ri = νi (-rA ) (Eq. 5.7.2)
Where νi is the stoichiometric coefficient for species “i” based on limiting reactant. Now put Eq.
5.7.2 in Eq. 5.3.1:
dni
= νi (-rA V) (Eq. 5.7.3)
dt
Eq. 5.7.3 is the most generalized form of mole balance equation for batch reactor.
Put Eq. 5.7.3 in Eq. 5.7.1:

n n n n
dHi dT
[∑ ni + ∑ Hi νi (-rA V) - FP R (T ∑ νi (-rA V)+ ∑ ni )] = Q̇ - Ẇ s
dt dt
n n n n
dHi dT
[∑ ni +(-rA V) ∑ νi Hi - FP R (T(-rA V) ∑ νi + ∑ ni )] = Q̇ - Ẇ s (Eq. 5.7.4)
dt dt
Recall Eq. 5.4.120:

n
∆Hrxn = ∑ νi Hi
i=1
Recall Eq. 5.4.116:

n
ν = ∑ νi
i=1
Put Eq. 5.4.120 and Eq. 5.4.116 in Eq. 5.7.4:

n n
dHi dT
[∑ ni +(∆Hrxn )(-rA V)- FP R (T(-rA V)ν+ ∑ ni )] = Q̇ - Ẇ s
dt dt
i=1 i=1 system
n n
dHi dT
[∑ ni +(∆Hrxn )(-rA V) - νFP RT(-rA V) - FP R ∑ ni ] = Q̇ - Ẇ s
dt dt
i=1 i=1 system
103
n n
dHi dT
[∑ ni - FP R ∑ ni ] +(∆Hrxn )(-rA V) - νFP RT(-rA V) = Q̇ - Ẇ s
dt dt
i=1 i=1 system
n n
dHi dT
[∑ ni - FP R ∑ ni ] = Q̇ - Ẇ s +(-∆Hrxn )(-rA V) + νFP RT(-rA V)
dt dt
i=1 i=1 system
n n
dHi dT
[∑ ni - FP R ∑ ni ] = Q̇ - Ẇ s +[(-∆Hrxn ) + νFP RT](-rA V) (Eq. 5.7.5)
dt dt
i=1 i=1 system
Eq. 5.7.5 is the most generalized form of energy balance for batch reactor and this is valid for
liquid as well as gas phase reactions in BR. It is also valid for those batch reactors in which
phase transformation occurs.
BR Energy Balance Eq. 5.7.5 and BR Mole Balance (Eq. 5.7.3) will be combined with selective
equations of enthalpy calculation which are presented in Table 5.3 and Table 5.4 as well as with
proper substitution of Q̇ to solve adiabatic or non-isothermal reaction engineering problems
with phase transformations included.
Now we will further restrict our discussion to those reactors in which there is not any phase
transformation present. For the case of no phase change involved, the enthalpy of gas, liquid,
or solid can be calculated using the differential form of Eq. 1, 2 or 3 of Table 5.3. And this can
be generalized as:
dHi = Cpi dT (Eq. 5.7.6)
Put Eq. 5.7.6 in Eq. 5.7.5:

n n
dT dT
[∑ ni Cpi - FP R ∑ ni ] = Q̇ - Ẇ s +[(-∆Hrxn ) + νFP RT](-rA V)
dt dt
i=1 i=1 system
n n
dT
[∑ ni Cpi - FP R ∑ ni ] = Q̇ - Ẇ s + [(-∆Hrxn ) + νFP RT](-rA V)
dt
i=1 i=1 system
n
dT
[∑ ni (Cpi - FP R)] = Q̇ - Ẇ s + [(-∆Hrxn ) + νFP RT](-rA V)
dt
i=1 system
dT Q̇ - Ẇ s + [(-∆Hrxn ) + νFP RT](-rA V)

= (Eq. 5.7.7)
dt [∑ni=1 ni (Cpi - FP R)]
system
104
In Eq. 5.7.7, ∆Hrxn represents heat of reaction at temperature T. We can express ∆Hrxn in terms
of ∆Horxn which is standard heat of reaction at temperature Tref. For this purpose, we will use
Kirchhoff’s Equation (Eq. 5.4.120):
T
o
∆Hrxn = ∆Hrxn + ∫ ∆Cp dT (Eq. 5.4.120)
Tref
Recall Eq. 5.4.122,

n
∆Horxn = ∑ νi Hofi
i=1
Recall Eq. 5.4.125:

n
∆Cp = ∑ νi CPi
i=1

T n
o
∆Hrxn = ∆Hrxn + ∫ ∑ νi CPi dT
Tref i=1
n T
o
∆Hrxn = ∆Hrxn + ∑ ∫ νi CPi dT
i=1 Tref
Hence,
n T
o
∆Hrxn = ∆Hrxn + ∑ (νi ∫ CPi dT) (Eq. 5.7.8a)
i=1 Tref
Here, it is necessary to note that Eq. 5.7.8a is not specific to batch reactor, it is also valid for
CSTR, PFR, and PBR. Moreover, Eq. 5.7.8a is valid for Single Reaction Scenario. If multiple
reactions are occurring, then its counterpart Eq. 5.7.8b will be used instead. Eq. 5.7.8b will be
introduced later. In Eq. 5.7.8a heats of reaction are based on limiting reactant “A”. [3]
For the case of Single Chemical Reaction
Recall Eq. 5.7.7,

Term-1
dT Q̇ - Ẇ s + ⏞
[(-∆Hrxn ) + νFP RT](-rA ) V
= (Eq. 5.7.7)
system
105
Here,
Q̇ rxn, V = [(-∆Hrxn ) + νFP RT](-rA ) (Eq. 5.7.9a)
Q̇ rxn, V is rate of heat generation or consumption per unit volume due to single chemical
reaction.
Now we generalize Eq. 5.4.18 through Eq. 5.4.22 as follows:

ni = nA0 (θi + νi XA ) (Eq. 5.7.10)
If there is only one chemical reaction is occurring in the system, then it is more convenient to
write Eq. 5.7.7 in terms of conversion using Eq. 5.7.10 as follows.
Batch Reactor (BR) Energy Balance for Single Chemical Reaction
At Unsteady State (dT/dt ≠ 0):

= (Eq. 5.7.11a)
dt [nA0 ∑ni=1(Cpi - FP R)(θi + νi XA )]
system
For the case of Multiple Chemical Reactions
Reconsider Eq. 5.7.7:

= (Eq. 5.7.7)
system
Term-1 Term-2
⏞ )(-∆H ) + ⏞
Q̇ - Ẇ s + [(-r (-rA )(ν) FP RT] V
A rxn
dT
=
system
Let,
Term-1 Term-2
Q̇ rxn, V ⏞ )(-∆H ) + ⏞
= [(-r (-rA )(ν) FP RT] (Eq. 5.7.12)
A rxn
So that,
dT Q̇ - Ẇ s + Q̇ rxn, V V
= n (Eq. 5.7.13)
dt [∑i=1 ni (Cpi - FP R)]
system
Only Term-1 and Term-2 in this equation are the reaction dependent terms. When we have
multiple reactions occurring, we must account for, and sum up, all the heats of reaction in the
106
reactor for each and every reaction. If “n” multiple reactions are occurring in the reactor then
the heat generated or consumed due to each reaction can be summed up to give us net rate
of heat generated or consumed per unit volume,
n
Term-1 = ∑(-rij )(-∆Hrxn, ij ) (Eq. 5.7.14)

j=1
Note that we have two subscripts now, on the heat of reaction. The heat of reaction for reaction
“j” must be referenced to the same species “i” in the rate, r ij, by which ∆Hrxn, ij is multiplied,
which is,
Moles of species i reacted in reaction j Joules "released or consumed" in reaction j
[ × ]
Volume × Time Moles of species i reacted in reaction j
Similarly, Term-2 can be summed up over all the reactions to give,

n
Term-2 = ∑(-rij )(νj ) (Eq. 5.7.15)

j=1
Now we generalize Eq. 5.7.12 for multiple reactions as follows,

n n
Q̇ rxn, V = [∑(-rij )(-∆Hrxn, ij ) + ∑(-rij )(νj ) FP RT]

j=1 j=1
Q̇ rxn, V = ∑[(-∆Hrxn, ij ) + νj FP RT](-rij ) (Eq. 5.7.9b)

j=1
Substitute Eq. 5.7.9b in Eq. 5.7.13 for multiple reactions as follows:
Batch Reactor (BR) Energy Balance for Multiple Chemical Reactions

n
dT Q̇ - Ẇ s + ∑j=1[(-∆Hrxn, ij ) + νj FP RT] (-rij V)
= (Eq. 5.7.11b)
system
Now we further generalize Eq. 5.7.8a:

n T
o
∆Hrxn, ij = ∆Hrxn, ij + ∑ (νij ∫ CPi dT) (Eq. 5.7.8b)
i=1 Tref
107
Here, it is also necessary to note that Eq. 5.7.8b is not specific to batch reactor, it is also valid
for CSTR, PFR, and PBR. Moreover, Eq. 5.7.8b is valid for Multi Reaction Scenario. In Eq. 5.7.8b
heats of reaction are based on species “i”.
Now it is the time to derive formulas for the Heat Transfer Rate Term (Q̇ ). As we know that
there is no need to consider energy balance for isothermal reactor design so, here we will only
consider adiabatic and non-isothermal reactor operations for heat transfer consideration. [3]
CASE-1: Adiabatic Operation
For adiabatic reactor operation there is no heat transfer across the system boundaries hence,
the heat transfer rate is zero.
Q̇ = 0 (Eq. 5.7.16)
CASE-2: Non-Isothermal Operation
For non-isothermal reactor operation there is heat transfer across the system boundaries for
heating or cooling of reaction mixture depending on endothermic or exothermic reaction type.
The heat transfer rate for the case of Jacketed BR as well as for Jacketed CSTR can be expressed
in terms of Overall Heat Transfer Coefficient (Uh) [J/(s.m2.K)], Heat Transfer Surface Area (As)
[m2], Heat Transfer Fluid Temperature (Ta) [K], and Reactor Temperature (T) [K] as follows,
For Endothermic Reactions (Heat added to the system):
Q̇ = +Q̇ added = Uh As (Ta - T)
For Exothermic Reactions (Heat removed from the system):
Q̇ = -Q̇ removed = -Uh As (T - Ta ) = Uh As (Ta - T)
From this fact we have generalized that whether the reaction is endothermic or exothermic the
heat transfer rate term evaluates to:
Q̇ = Uh As (Ta - T) (Eq. 5.7.17)
In this equation temperature (Ta) is variable temperature and can only be determined by
making a differential energy balance on jacket to develop differential equation in terms of Ta.
Because differential energy balance on jacket will not be an easy task due to complex flow
patterns within the jacket, hence we will consider integral energy balance instead. So that Eq.
5.7.17 cannot be used in combination with reactor energy balance. Hence, we must develop
an alternative equation for the incorporation of heat transfer rate into the reactor energy
balance. For this purpose, an integral energy balance on the jacket will be considered to
calculate overall changes involved. The jacket side flows in batch reactor and CSTR are similar
108
so that we will develop formulas for CSTR which are also applicable for batch reactor. For this
purpose, let us consider the following CSTR as or system of interest,
Figure 5.18: CSTR with heat effects
The heat transfer fluid enters the jacket at Temperature (T a1) and leaves the jacket at
Temperature (Ta2) and its molar flowrate is (Fa ). The volume of jacket side fluid is negligible as
compared to volume of reaction mixture so, jacket side dynamics can be ignored hence, steady
state mole balance for jacket leads to,
Fa, in - Fa, out = 0
Fa, in = Fa, out = Fa
For endothermic reaction, the steady state energy balance for jacket is:
Fa Ha, in - Fa Ha, out - Q̇ removed from jacket = 0
Q̇ removed from jacket = Fa (Ha1 - Ha2 )
Q̇ = +Q̇ added to reactor = +Q̇ removed from jacket = Fa (Ha1 - Ha2 )
Q̇ = Fa (Ha1 - Ha2 )
For exothermic reaction, the steady state energy balance for jacket is:
Fa Ha, in - Fa Ha, out + Q̇ added to jacket = 0
Q̇ added to jacket = Fa (Ha2 - Ha1 )
Q̇ = -Q̇ removed from reactor = -Q̇ added to jacket = -Fa (Ha2 - Ha1 ) = Fa (Ha1 - Ha2 )
Q̇ = Fa (Ha1 - Ha2 )
Therefore, equation of heat transfer rate Q̇ for reactor is same for endothermic and exothermic
reaction. That is:
Q̇ = Fa (Ha1 - Ha2 ) (Eq. 5.7.18)
109
Eq. 5.7.18 is in the form of thermodynamic variables. Another alternative overall equation in
the form of transport variables can also be developed as follows,
For endothermic reaction (Ta1 > Ta2 > T):
The overall rate of heat transfer from the exchanger to the reactor fluid at Temperature (T) can
be expressed as,
∆T1 - ∆T2 (Ta1 - T) - (Ta2 - T) Uh As (Ta1 - Ta2)

Q̇ = +Q̇ added = Uh As ∆TLMTD = Uh As ( ) = Uh As ( ) =
∆T1 Ta1 - T ln[(T - Ta1 )⁄(T - Ta2)]
ln ( ) ln ( )
∆T2 Ta2 - T
For exothermic reaction (Ta1 < Ta2 < T):
While the overall rate of heat transfer from the reactor to the exchanger can be expressed as:
∆T1 - ∆T2 (T - Ta1 ) - (T - Ta2 ) -Uh As (Ta2 - Ta1 ) Uh As (Ta1 - Ta2 )

Q̇ = -Q̇ removed = -Uh As ∆TLMTD = -Uh As ( ) = -Uh As ( )= =
∆T1 T - Ta1 ln[(T - T )⁄(T - Ta2 )] ln[(T - Ta1 )⁄(T - Ta2 )]
ln ( ) ln ( ) a1
∆T2 T - Ta2
Where, ∆TLMTD is the Logarithmic Mean Temperature Difference (K) for the jacket.
Therefore, this equation of heat transfer rate Q̇ for reactor is also same for endothermic and
exothermic reaction. That is: [3]
Uh As (Ta1 - Ta2 )
Q̇ = (Eq. 5.7.19)
ln[(T - Ta1 )⁄(T - Ta2 )]
If the reaction is endothermic then we must add heat to the reaction mixture. So that heat
transfer fluid will be a heating medium e.g. (Condensing saturated steam, superheated steam,
hot oil etc.)
• CASE-1: If the heating medium is condensing saturated steam, then Eq. 5.7.18 can be
reduced to Eq. 5.7.20a and Eq. 5.7.20b after incorporating the corresponding formula
of enthalpy calculation from Table 5.3:
Q̇ = Fa (Ha1 - Ha2 )
Tb Ta1 Ta2
Q̇ = Fa [(∫ Cpl dT +∆Hvap at Tb + ∫ Cpg dT) - (∫ Cpl dT )]
Tref Tb Tref
For saturated steam Ta1 = Tb = Boiling Point,

Tb Tb Ta2
Q̇ = Fa [(∫ Cpl dT +∆Hvap at Tb + ∫ Cpg dT) - (∫ Cpl dT )]
Tref Tb Tref
110
Tb Ta2
Q̇ = Fa [(∫ Cpl dT +∆Hvap at Tb ) - (∫ Cpl dT )]
Tref Tref
Tb Ta2
Q̇ = Fa (∫ Cpl dT - ∫ Cpl dT + ∆Hvap at Tb )
Tref Tref
Tb Tref
Q̇ = Fa (∫ Cpl dT + ∫ Cpl dT + ∆Hvap at Tb )
Tref Ta2
Tref Tb
Q̇ = Fa (∫ Cpl dT + ∫ Cpl dT + ∆Hvap at Tb )
Ta2 Tref
Now the integrals can be combined mathematically,

Tb
Q̇ = Fa (∫ Cpl dT + ∆Hvap at Tb ) (Eq. 5.7.20a)
Ta2
If Cpl = constant at mean value, then,
Q̇ = Fa [Cpl (Tb - Ta2 ) + ∆Hvap at Tb ] (Eq. 5.7.20b)
• CASE-2: If the heating medium is superheated steam, then Eq. 5.7.18 can be reduced to
Eq. 5.7.21a and Eq. 5.7.21b after incorporating the corresponding formula of enthalpy
calculation from Table 5.3:
Q̇ = Fa (Ha1 - Ha2 )
Tb Ta1 Tb Ta2
Q̇ = Fa [(∫ Cpl dT +∆Hvap at Tb + ∫ Cpg dT ) - (∫ Cpl dT +∆Hvap at Tb + ∫ Cpg dT )]
Tref Tb Tref Tb
Ta1 Ta2
Q̇ = Fa (∫ Cpg dT - ∫ Cpg dT)
Tb Tb
Ta1 Tb
Q̇ = Fa (∫ Cpg dT + ∫ Cpg dT)
Tb Ta2
Tb Ta1
Q̇ = Fa (∫ Cpg dT + ∫ Cpg dT)
Ta2 Tb
Ta1
Q̇ = Fa ∫ Cpg dT (Eq. 5.7.21a)
Ta2
If Cpg = constant at mean value, then,
111
Q̇ = Fa Cpg (Ta1 - Ta2 ) (Eq. 5.7.21b)
• CASE-3: If the heating medium is hot oil, then Eq. 5.7.18 can be reduced to Eq. 5.7.22a
and Eq. 5.7.22b after incorporating the corresponding formula of enthalpy calculation
from Table 5.3:
Ta1 Ta2
Q̇ = Fa (∫ Cpl dT - ∫ Cpl dT)
Tref Tref
Ta1 Tref
Q̇ = Fa (∫ Cpl dT + ∫ Cpl dT)
Tref Ta2
Tref Ta1
Ta2 Tref
Ta1
Q̇ = Fa ∫ Cpl dT (Eq. 5.7.22a)
Ta2
Q̇ = Fa Cpl (Ta1 - Ta2 ) (Eq. 5.7.22b)
If the reaction is exothermic then we must remove heat from the reaction mixture. So that heat
transfer fluid will be a cooling medium e.g. (Cooling water, refrigerant etc.)
• CASE-4: If the cooling medium is cooling water, then Eq. 5.7.18 can be reduced to Eq.
5.7.23a and Eq. 5.7.23b after incorporating the corresponding formula of enthalpy
calculation from Table 5.3:
Q̇ = Fa (Ha1 - Ha2 )
Ta1 Ta2
Q̇ = Fa (∫ Cpl dT - ∫ Cpl dT)
Tref Tref
Ta1 Tref
Tref Ta2
Tref Ta1
Ta2 Tref
Ta1
Q̇ = Fa ∫ Cpl dT (Eq. 5.7.23a)
Ta2
112
Q̇ = Fa Cpl (Ta1 - Ta2 ) (Eq. 5.7.23b)
• CASE-5: If the cooling medium is refrigerant (liquid at inlet and vapors at outlet), then
Eq. 5.7.18 can be reduced to Eq. 5.7.24a and Eq. 5.7.24b after incorporating the
corresponding formula of enthalpy calculation from Table 5.3:
Q̇ = Fa (Ha1 - Ha2 )
Tb Ta1 Ta2
Q̇ = Fa [(∫ Cpg dT + ∆Hcond at Tb + ∫ Cpl dT ) - (∫ Cpg dT )]
Tref Tb Tref
Tb Ta2 Ta1
Q̇ = Fa (∫ Cpg dT - ∫ Cpg dT + ∆Hcond at Tb + ∫ Cpl dT )
Tref Tref Tb
Tb Tref Ta1
Q̇ = Fa (∫ Cpg dT + ∫ Cpg dT + ∆Hcond at Tb + ∫ Cpl dT )
Tref Ta2 Tb
Tref Tb Ta1
Q̇ = Fa (∫ Cpg dT + ∫ Cpg dT + ∆Hcond at Tb + ∫ Cpl dT )
Ta2 Tref Tb
Tb Ta1
Q̇ = Fa (∫ Cpg dT + ∆Hcond at Tb + ∫ Cpl dT )
Ta2 Tb
Tb Ta2
Q̇ = Fa (- ∫ Cpl dT - ∆Hvap at Tb - ∫ Cpg dT)
Ta1 Tb
Tb Ta2
Q̇ = -Fa (∫ Cpl dT + ∆Hvap at Tb + ∫ Cpg dT) (Eq. 5.7.24a)
Ta1 Tb
If Cpl and Cpg = constant at mean value, then,
Q̇ = -Fa [Cpl (Tb - Ta1 ) + ∆Hvap at Tb + Cpg (Ta2 - Tb )] (Eq. 5.7.24b)
Mathematical Analysis:
For Case-1: If we combine Eq. 5.7.20b with Eq. 5.7.19 to express Ta2 explicitly then, it is
not possible; because the resulting equation is implicit and causes complex
mathematical problems.
Uh As (Tb - Ta2 )
= Fa [Cpl (Tb - Ta2 ) + ∆Hvap at Tb ]
ln[(T - Tb )⁄(T - Ta2 )]
For Case-5: If we combine Eq. 5.7.24b with Eq. 5.7.19 to express Ta2 explicitly then it is
also not possible because the resulting equation is also implicit and causes complex
mathematical problems.
113
Uh As (Ta1 - Ta2 )
= -Fa [Cpl (Tb - Ta1 ) + ∆Hvap at Tb + Cpg (Ta2 - Tb )]
ln[(T - Ta1 )⁄(T - Ta2 )]
Reason: The problems in case 1 and case 5 arise due to phase change of heating or
cooling fluid. So, for the sake of simplicity for non-isothermal batch and CSTR reactor
design we will consider only those heating or cooling mediums which do not involve
phase transformation during heat transfer operation. For those heat transfer fluids
which do not involve phase change operations Eq. 5.7.21b (of case-2), Eq. 5.7.22b (of
case-3), Eq. 5.7.23b (of case-4) can be generalized to:
Q̇ = Fa Cpa (Ta1 - Ta2 ) (Eq. 5.7.25)
Recall Eq. 5.7.19,

Uh As (Ta1 - Ta2 )
Q̇ =
ln[(T - Ta1 )⁄(T - Ta2 )]

Uh As (Ta1 - Ta2 )
= Fa Cpa (Ta1 - Ta2 )
ln[(T - Ta1 )⁄(T - Ta2 )]
U h As
= ln[(T - Ta1 )⁄(T - Ta2 )]
Fa Cpa
U h As
exp [ ] = (T - Ta1 )⁄(T - Ta2 )
Fa Cpa
U h As
(T - Ta2 ) = (T - Ta1 )⁄exp [ ]
Fa Cpa
-Uh As
T - Ta2 = (T - Ta1 )exp [ ]
Fa Cpa
-Uh As
Ta2 = T - (T - Ta1 )exp [ ]
Fa Cpa
Put it in Eq. 5.7.25,
-Uh As
Q̇ = Fa Cpa (Ta1 - (T - (T - Ta1 )exp [ ]))
Fa Cpa
-Uh As
Q̇ = Fa Cpa ((Ta1 - T) - (Ta1 - T)exp [ ])
Fa Cpa
114
-Uh As
Q̇ = Fa Cpa (Ta1 - T) (1 - exp [ ]) (Eq. 5.7.26)
Fa Cpa
So, only Eq. 5.7.26 is useful one and alternative to Eq. 5.7.17 because in this equation jacket
fluid outlet temperature (Ta2) is not present. But this is valid for the case of only those heat
transfer fluids which do not involve phase change during heat transfer operation in the jacket
of BR or CSTR. Moreover, constant mean heat capacity of heat transfer fluid (C pa) is used while
deriving it. For Non-Isothermal Operation of Batch Reactor Eq. 5.7.26 will be used to substitute
for Q̇ , in BR energy balance.
Note: Because batch reactors can only be operated at unsteady state so that the steady state
equivalents of all the batch reactor energy balances are not feasible.
5.7.2 Energy Balance for Continuous Stirred Tank Reactor (CSTR)

In order to develop specific energy balance for Continuous Stirred Tank Reactor (CSTR) we will
apply G.E.B.E (Eq. 5.6.14) to CSTR, So, recall Eq. 5.6.14: [3]
n n n n n n
dHi dni dT dni
dt dt dt dt
uniform due to perfect mixing e.g. BR or CSTR.
Now we must combine the CSTR energy balance with its corresponding mole balance.
For this purpose, we recall mole balance equation of CSTR i.e. Eq. 5.3.2,
dni
= Fi0 - Fi + ri V (Eq. 5.3.2)
dt
Recall Eq. 5.7.2,
ri = νi (-rA ) (Eq. 5.7.2)
Put Eq. 5.7.2 in Eq. 5.3.2,

dni
= Fi0 - Fi +νi (-rA V) (Eq. 5.7.27)
dt
Eq. 5.7.27 is the most generalized form of mole balance equation for CSTR. Now put Eq. 5.7.27
in Eq. 5.6.14,
n n n n n n
dHi dT
[∑ ni + ∑ Hi (Fi0 - Fi +νi (-rA V)) - FP R ( ∑ ni +T ∑(Fi0 - Fi +νi (-rA V)))] = ∑ Fi0 Hi0 - ∑ Fi Hi + Q̇ - Ẇ s
dt dt
115
n n n n n n n n n n
dHi dT
[∑ ni + ∑ Fi0 Hi - ∑ Fi Hi +(-rA V) ∑ νi Hi - FP R ( ∑ ni +T ∑ Fi0 -T ∑ Fi +T(-rAV) ∑ νi )] = ∑ Fi0 Hi0 - ∑ Fi Hi + Q̇ - Ẇ s (Eq. 5.7.28)
dt dt
i=1 i=1 i=1 i=1 i=1 i=1 i=1 i=1 system i=1 i=1
Recall Eq. 5.4.120:

n
i=1
Recall Eq. 5.4.116:

n
ν = ∑ νi
i=1
Put Eq. 5.4.120 and Eq. 5.4.116 in Eq. 5.7.28:

n n n n n n n n
dHi dT
[∑ ni + ∑ Fi0 Hi - ∑ Fi Hi +(-rA V)∆Hrxn - FP R ( ∑ ni +T ∑ Fi0 -T ∑ Fi +T(-rA V)ν)] = ∑ Fi0 Hi0 - ∑ Fi Hi + Q̇ - Ẇ s
dt dt
i=1 i=1 i=1 i=1 i=1 i=1 system i=1 i=1
n n n n n n n n
dHi dT
[∑ ni - FP R ( ∑ ni +T ∑ Fi0 -T ∑ Fi +T(-rA V)ν)] + ∑ Fi0 Hi - ∑ Fi Hi +(-rA V)∆Hrxn = ∑ Fi0 Hi0 - ∑ Fi Hi + Q̇ - Ẇ s
dt dt
i=1 i=1 i=1 i=1 system i=1 i=1 i=1 i=1
n n n n n n n n
dHi dT
[∑ ni - FP R ( ∑ ni +T ∑ Fi0 -T ∑ Fi +T(-rA V)ν)] = ∑ Fi0 Hi0 - ∑ Fi0 Hi - ∑ Fi Hi + ∑ Fi Hi + Q̇ - Ẇ s +(-∆Hrxn )(-rA V)
dt dt
i=1 i=1 i=1 i=1 system i=1 i=1 i=1 i=1
n n n n n n
dHi dT
[∑ ni - FP R (νT(-rA V)+ ∑ ni +T ∑ Fi0 -T ∑ Fi )] = ∑ Fi0 Hi0 - ∑ Fi0 Hi + Q̇ - Ẇ s + (-∆Hrxn )(-rA V)
dt dt
n n n n n
dHi dT
[∑ ni - FP R (νT(-rA V)+ ∑ ni + T (∑ Fi0 - ∑ Fi ))] = ∑ Fi0 (Hi0 - Hi ) +(-∆Hrxn )(-rA V) + Q̇ - Ẇ s
dt dt
i=1 i=1 i=1 i=1 i=1
system
n n n n n
dHi dT
[∑ ni -νFP RT(-rA V) - FP R ∑ ni - FP RT (∑ Fi0 - ∑ Fi )] = ∑ Fi0 (Hi0 - Hi ) +(-∆Hrxn )(-rA V) + Q̇ - Ẇ s
dt dt
i=1 i=1 i=1 i=1 system i=1
n n n n n
dHi dT
[∑ ni - FP R ∑ ni ] -νFP RT(-rA V) - FP RT (∑ Fi0 - ∑ Fi ) = ∑ Fi0 (Hi0 - Hi ) +(-∆Hrxn )(-rA V) + Q̇ - Ẇ s
dt dt
i=1 i=1 system i=1 i=1 i=1
n n n n n
dHi dT
[∑ ni - FP R ∑ ni ] = ∑ Fi0 (Hi0 - Hi ) + FP RT (∑ Fi0 - ∑ Fi ) +(-∆Hrxn )(-rA V) + νFP RT(-rA V) + Q̇ - Ẇ s
dt dt
n n n n n
dHi dT
[∑ ni - FP R ∑ ni ] = Q̇ - Ẇ s + ∑ Fi0 (Hi0 - Hi ) + FP RT (∑ Fi0 - ∑ Fi ) + [(-∆Hrxn )+ νFP RT](-rA V) (Eq. 5.7.29)
dt dt
116
Eq. 5.7.29 is the most generalized form of energy balance for CSTR and this is valid for
liquid as well as gas phase reactions in CSTR. It is also valid for those CSTRs in which
phase transformation occurs.
CSTR Energy Balances (Eq. 5.7.29) and CSTR Mole Balance (Eq. 5.7.27) will be combined with
selective equations of enthalpy calculation which are presented in Table 5.3 and Table 5.4 as
well as with proper substitution of Q̇ to solve adiabatic or non-isothermal reaction engineering
problems with phase transformations included.
be generalized as Eq. 5.7.6, so now recall Eq. 5.7.6,
dHi = Cpi dT (Eq. 5.7.6)
Put Eq. 5.7.6 in Eq. 5.7.29,

n n n n n
dT dT
[∑ ni Cpi - FP R ∑ ni ] = Q̇ - Ẇ s + ∑ Fi0 (Hi0 - Hi ) + FP RT (∑ Fi0 - ∑ Fi ) + [(-∆Hrxn )+ νFP RT](-rA V)
dt dt
n n n n n
dT
[∑ ni Cpi - FP R ∑ ni ] = Q̇ - Ẇ s - ∑ Fi0 (Hi - Hi0 ) + FP RT (∑ Fi0 - ∑ Fi ) + [(-∆Hrxn )+ νFP RT](-rA V)
dt
dT Q̇ - Ẇ s - ∑ni=1 Fi0 (Hi - Hi0 ) + FP RT(∑ni=1 Fi0 - ∑ni=1 Fi )+ [(-∆Hrxn )+ νFP RT](-rA V)
= (Eq. 5.7.30)
dt [∑ni=1 ni Cpi - FP R ∑ni=1 ni ]
system
Integrate Eq. 5.7.6 between reactor inlet and outlet as follows,

Hi T
∫ dHi = ∫ Cpi dT
Hi0 Ti0
T
(Hi - Hi0 ) = ∫ Cpi dT (Eq. 5.7.31)
Ti0
Put Eq. 5.7.31 in Eq. 5.7.30,

T
dT Q̇ - Ẇ s - ∑ni=1 Fi0 ∫T Cpi dT + FP RT(∑ni=1 Fi0 - ∑ni=1 Fi ) + [(-∆Hrxn )+ νFP RT](-rA V)
= i0
(Eq. 5.7.32)
system
117
First, we generalize Eq. 5.4.24 through Eq. 5.4.28 as follows:

Fi = FA0 (θi + νi XA ) (Eq. 5.7.33)
Now recall Eq. 5.7.10,

ni = nA0 (θi + νi XA ) (Eq. 5.7.10)
write Eq. 5.7.32 in terms of conversion using Eq. 5.7.33 and Eq. 5.7.10.
Continuous Stirred Tank Reactor (CSTR) Energy Balance for Single Chemical Reaction

T
dT Q̇ - Ẇ s - ∑ni=1 Fi0 ∫T Cpi dT + FP RT(∑ni=1 Fi0 - FA0 ∑ni=1(θi + νi XA )) + [(-∆Hrxn )+ νFP RT](-rA V)
i0
= (Eq. 5.7.34a)
dt [nA0 ∑ni=1(Cpi - FP R)(θi + νi XA )]
system
At Steady State (dT/dt = 0):

n n n
T
Q̇ - Ẇ s - ∑ Fi0 ∫ Cpi dT + FP RT (∑ Fi0 - FA0 ∑(θi + νi XA )) + [(-∆Hrxn )+ νFP RT](-rA V) = 0 (Eq. 5.7.35a)
i=1 Ti0 i=1 i=1
Recall 5.7.32,
Term-1
T
dT Q̇ - Ẇ s - ∑ni=1 Fi0 ∫T Cpi dT + FP RT(∑ni=1 Fi0 - ∑ni=1 Fi ) +⏞
[(-∆Hrxn )+ νFP RT](-rA ) V
= i0
system
Now we use the same analogy which is used while developing Eq. 5.7.11b, and directly replace
Term-1 in the above equation with Eq. 5.7.9b to give Eq. 5.7.34b,
n

j=1
Continuous Stirred Tank Reactor (CSTR) Energy Balance for Multiple Chemical Reactions

T
dT Q̇ - Ẇ s - ∑ni=1 Fi0 ∫T Cpi dT + FP RT(∑ni=1 Fi0 - ∑ni=1 Fi ) + ∑nj=1[(-∆Hrxn, ij ) + νj FP RT](-rij V)
= i0
(Eq. 5.7.34b)
system
118
At Steady State (dT/dt = 0):
n T n n n
Q̇ - Ẇ s - ∑ Fi0 ∫ Cpi dT + FP RT (∑ Fi0 - ∑ Fi ) + ∑[(-∆Hrxn, ij ) + νj FP RT](-rij V) = 0 (Eq. 5.7.35b)

i=1 Ti0 i=1 i=1 j=1
the heat transfer rate is zero according to Eq. 5.7.16.
Q̇ = 0 (Eq. 5.7.16)
The heat transfer rate for the case of Jacketed CSTR can be expressed in terms of Overall Heat
Transfer Coefficient (Uh) [J/(s.m2.K)], Heat Transfer Surface Area (As) [m2], Heat Transfer Fluid
Molar Flowrate (Fa) [kgmol/s], Heat Transfer Fluid Mean Heat Capacity (Cpa) [J/kgmol.K], Heat
Transfer Fluid Inlet Temperature (Ta1) [K], and Reactor Temperature (T) [K] according to Eq.
5.7.26 as follows, [3]
-Uh As
Q̇ = Fa Cpa (Ta1 - T) (1 - exp [ ]) (Eq. 5.7.26)
Fa Cpa
5.7.3 Energy Balance for Plug Flow Reactor (PFR)

In order to develop specific energy balance for Plug Flow Reactor (PFR) we will apply G.E.B.E
(Eq. 5.6.14) to PFR, So, recall Eq. 5.6.14:
n n n n n n
dHi dni dT dni
[∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = Q̇ - Ẇ s + ∑ Fi0 Hi0 - ∑ Fi Hi (Eq. 5.6.14)
dt dt dt dt
uniform due to perfect mixing e.g. BR or CSTR. But keep in mind that in PFR and PBR the
reaction variables are not spatially uniform and change with volume as well. i.e.
ni = ni(V,t) | Fi = Fi(V,t) | Hi = Hi(T,t) | Hi = Hi(V,t) | T = T(V,t) Eq. 5.7.36
Hence, Eq. 5.6.14 is not a suitable form of G.E.B.E for PFR and PBR. Now we will enhance this
equation to make it suitable for PFR and PBR. If we consider Eq. 5.7.36 then Eq. 5.6.14 will be
converted to Partial Differential Equation (PDE) instead of an Ordinary Differential Equation
(ODE) for PFR and PBR. [3], [6]
119
n n n n n n
∂Hi ∂ni ∂T ∂ni
∂t ∂t ∂t ∂t
Now, partially differentiate Eq. 5.7.37 with respect to volume to get point value changes in
space.
n n n n n n
∂ ∂Hi ∂ni ∂T ∂ni ∂
[∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = [Q̇ - Ẇ s + ∑ Fi0 Hi0 - ∑ Fi Hi ]
∂V ∂t ∂t ∂t ∂t ∂V
n n n n n n
∂ ∂Hi ∂ ∂ni ∂ ∂T ∂ni ∂Q̇ ∂Ẇ s ∂ ∂
[ ∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = [ - + ∑ Fi0 Hi0 - ∑ Fi Hi ]
∂V ∂t ∂V ∂t ∂V ∂t ∂t ∂V ∂V ∂V ∂V
We know that,
Fi0 ≠ Fi0(V) | Fi0 = Fi0(t) | Hi0 = f(Ti0) | T i0 ≠ T i0(V) | T i0 = T i0(t) Eq. 5.7.38
So, the product (Fi0Hi0) is the function of time only which is constant with respect to V. So, its
partial derivative w.r.t V will be zero. Moreover, in practice it is extremely rare case that a PFR
or PBR have a turbine in it. Because turbine blades can deteriorate due to reaction mixture if it
is corrosive. And the presence of stirring mechanism in PFR and PBR is not allowed otherwise
there will be no spatial variations and in this way the difference between PFR and CSTR will be
eliminated. So, the shaft work term will also be zero.
n n n n n n
∂ ∂Hi ∂ ∂ni ∂ ∂T ∂ni ∂Q̇ ∂Ẇ s ∂ ∂
[ ∑ ni + ∑ Hi - FP R ( ∑ ni +T ∑ )] = [ - + ∑ Fi0 Hi0 - ∑ Fi Hi ]
∂V ∂t ∂V ∂t ∂V ∂t ∂t ∂V ∂V ∂V ∂V
Hence,
n n n n n
∂ ∂Hi ∂ ∂ni ∂ ∂T ∂ni ∂Q̇ ∂
[∑ (ni ) + ∑ (Hi ) - FP R ( ∑ ni +T ∑ )] = [ - ∑ (Fi Hi )]
∂V ∂t ∂V ∂t ∂V ∂t ∂t ∂V ∂V
i=1 i=1 i=1 i=1 system i=1
n n
∂ ∂Hi n ∂ ∂T n n
∑ (ni ) ∂ ∂ni ( ∑ ni ) ∂ ∂ni ∂Q̇ ∂
∂V ∂t + ∑ (Hi ) - FP R [∂V ∂t + (T ∑ )] = [ - ∑ (Fi Hi )]
⏟i=1 ∂V ∂t ⏟ i=1 ∂V ∂t ∂V ∂V
i=1 i=1 i=1
[ Term-1 Term-2 ]system
∂2 T
Term-1 and Term-2 in the above equation will generate ∂V∂t , and this mixed rate of change of
∂T ∂T
temperature is smaller than the ∂V and which are primarily responsible for major changes in
∂t
∂2 T
temperature. Moreover, the presence of second order perturbances of temperature ∂V∂t in this
equation will also complicate the solution procedure of this PDE significantly. So, to keep the
120
scenario simplified we will ignore Term-1 and Term-2 as did most of the authors e.g. H. Scott
Fogler. When we compare the solution generated by ignoring these two terms of PDE with
practical situations then we can see that these two terms can be safely ignored as they do not
contribute to significant temperature changes.
Hence,
n n
∂ ∂Hi n ∂ ∂T n n
∑ (ni ) ∂ ∂ni ( ∑ ni ) ∂ ∂ni ∂Q̇ ∂
∂V ∂t + ∑ (Hi ) - FP R [∂V ∂t + (T ∑ )] = [ - ∑ (Fi Hi )]
⏟i=1 ∂V ∂t ⏟ i=1 ∂V ∂t ∂V ∂V
i=1 i=1 i=1
[ Term-1 Term-2 ]system
n n n
∂ ∂ni ∂ ∂ni ∂Q̇ ∂
[∑ (Hi ) - FP R [ (T ∑ )]] = [ - ∑ (Fi Hi )]
∂V ∂t ∂V ∂t ∂V ∂V
i=1 i=1 i=1
system
n n n n
∂ ∂ni ∂ni ∂Hi ∂ ∂ni ∂ni ∂T ∂Q̇ ∂Hi ∂Fi
[∑ (Hi ( ) + ) - FP R (T (∑ ) + (∑ ) )] = - ∑ (Fi +Hi )
∂V ∂t ∂t ∂V ∂V ∂t ∂t ∂V ∂V ∂V ∂V
i=1 i=1 i=1 system i=1
n n n n
∂ ∂ni ∂ni ∂Hi ∂ ∂ni ∂T ∂ni ∂Q̇ ∂Hi ∂Fi
[∑ (Hi ( ) + ) - FP R (T ∑ ( ) + (∑ ))] = - ∑ (Fi +Hi ) (Eq. 5.7.39)
∂t ∂V ∂V ∂t ∂t ∂V ∂t ∂V ∂V ∂V ∂V
i=1 i=1 i=1 i=1
system
Recall Eq. 5.4.14a, and write it in terms of partial derivative instead of ordinary derivative by the
consideration of Eq. 5.7.36,
Differential form:
∂ni
ci = (Eq. 5.7.40)
∂V
Integral form:
ni
ci = (Eq. 5.4.14a)
V
Put Eq. 5.7.40 in Eq. 5.7.39,
n n n n
∂ ∂Hi ∂ ∂T ∂Q̇ ∂Hi ∂Fi
[∑ (Hi (ci )+ci ) - FP R (T ∑ (ci ) + (∑ ci ))] = - ∑ (Fi +Hi )
∂t ∂t ∂t ∂t ∂V ∂V ∂V
i=1 i=1 i=1 i=1
system
n n n n
∂ci ∂Hi ∂ci ∂T ∂Q̇ ∂Hi ∂Fi
[∑ (Hi +ci ) - FP R (T ∑ + ∑ ci )] = - ∑ (Fi +Hi ) (Eq. 5.7.41)
∂t ∂t ∂t ∂t ∂V ∂V ∂V
Eq. 5.7.41 is the form of G.E.B.E which is valid for PFR and PBR.
121
Now we must combine the PFR energy balance with its corresponding mole balance. For this
purpose, we recall mole balance equation of PFR i.e. Eq. 5.3.4,
∂ci ∂Fi
=- + ri (Eq. 5.3.4)
∂t ∂V
Recall Eq. 5.7.2,
ri = νi (-rA ) (Eq. 5.7.2)
Put Eq. 5.7.2 in Eq. 5.3.4,

∂ci ∂Fi
=- + νi (-rA ) (Eq. 5.7.42)
∂t ∂V
Eq. 5.7.42 is the most generalized form of mole balance equation for PFR. Now put Eq. 5.7.42
in Eq. 5.7.41,
n n n n
∂Fi ∂Hi ∂Fi ∂T ∂Q̇ ∂Hi ∂Fi
[∑ (Hi (- + νi (-rA )) +ci ) - FP R (T ∑ (- + νi (-rA )) + ∑ ci )] = - ∑ (Fi +Hi )
∂V ∂t ∂V ∂t ∂V ∂V ∂V
n n n n n n
[∑ (-Hi + νi Hi (-rA )+ci ) - FP R (-T ∑ +T ∑ νi (-rA ) + ∑ ci )] = - ∑ Fi - ∑ Hi
∂V ∂t ∂V ∂t ∂V ∂V ∂V
n n n n n n n n
[- ∑ Hi +(-rA ) ∑ νi Hi + ∑ ci +FP RT ∑ -F RT ∑ νi (-rA ) -FP R ∑ ci ] = - ∑ Fi - ∑ Hi (Eq. 5.7.43)
∂V ∂t ∂V P ∂t ∂V ∂V ∂V
i=1 i=1 i=1 i=1 i=1 i=1 system i=1 i=1
Recall Eq. 5.4.120:

n
i=1
Recall Eq. 5.4.116:

n
ν = ∑ νi
i=1
Put Eq. 5.4.120 and Eq. 5.4.116 in Eq. 5.7.43:

n n n n n n
[- ∑ Hi +(-rA )(∆Hrxn )+ ∑ ci +FP RT ∑ -FP RTν(-rA )-FP R ∑ ci ] = - ∑ Fi - ∑ Hi
∂V ∂t ∂V ∂t ∂V ∂V ∂V
n n n n n n
∂Hi ∂Fi ∂T ∂Fi ∂Q̇ ∂Hi ∂Fi
[∑ ci +FP RT ∑ -FP R ∑ ci ] - ∑ Hi +(-rA )(∆Hrxn ) - νFP RT(-rA ) = - ∑ Fi - ∑ Hi
∂t ∂V ∂t ∂V ∂V ∂V ∂V
i=1 i=1 i=1 system i=1 i=1 i=1
122
n n n n n n
∂Hi ∂Fi ∂T ∂Q̇ ∂Hi ∂Fi ∂Fi
[∑ ci +FP RT ∑ -F R ∑ ci ] = - ∑ Fi - ∑ Hi + ∑ Hi +(-rA )(-∆Hrxn ) + νFP RT(-rA )
∂t ∂V P ∂t ∂V ∂V ∂V ∂V
i=1 i=1 i=1 system i=1 i=1 i=1
n n n n
∂Hi ∂T ∂Fi ∂Q̇ ∂Hi
[∑ ci -FP R ∑ ci ] +FP RT ∑ = - ∑ Fi +[(-∆Hrxn ) + νFP RT](-rA )
∂t ∂t ∂V ∂V ∂V
Hence,
n n n n
∂Hi ∂T ∂Q̇ ∂Hi ∂Fi
[∑ ci -FP R ∑ ci ] = - ∑ Fi - FP RT ∑ +[(-∆Hrxn ) + νFP RT](-rA ) (Eq. 5.7.44)
∂t ∂t ∂V ∂V ∂V
Eq. 5.7.44 is the most generalized form of energy balance for PFR and PBR and this is valid for
liquid as well as gas phase reactions in PFR and PBR. It is also valid for those PFRs and PBRs in
which phase transformation occurs.
PFR Energy Balance (Eq. 5.7.44) and PFR Mole Balance (Eq. 5.7.42) will be combined with
selective equations of enthalpy calculation which are presented in Table 5.3 and Table 5.4 as
∂Q̇
well as with proper substitution of ∂V
to solve adiabatic and non-isothermal reaction
engineering problems with phase transformations included.
be generalized as Eq. 5.7.6, so now we recall Eq. 5.7.6 in partial differential form by considering
Eq. 5.7.36, [3]
∂Hi = Cpi ∂T (Eq. 5.7.45)
Put Eq. 5.7.45 in Eq. 5.7.44,

n n n n
∂T ∂T ∂Q̇ ∂T ∂Fi
[∑ ci Cpi -FP R ∑ ci ] = - ∑ Fi Cpi - FP RT ∑ +[(-∆Hrxn ) + νFP RT](-rA )
∂t ∂t ∂V ∂V ∂V
n n n n
∂T ∂Q̇ ∂T ∂Fi
[∑ ci Cpi -FP R ∑ ci ] = - ∑ Fi Cpi - FP RT ∑ +[(-∆Hrxn ) + νFP RT](-rA )
∂t ∂V ∂V ∂V
∂Q̇ ∂T ∂F
∂T - ∑ni=1 Fi Cpi - FP RT ∑ni=1 i +[(-∆Hrxn ) + νFP RT](-rA )
= ∂V ∂V ∂V
∂t [∑i=1 ci Cpi - FP R ∑ni=1 ci ]
n
system
123
Finally,
∂Q̇ ∂T ∂F
∂T - ∑ni=1 Fi Cpi - FP RT ∑ni=1 i +[(-∆Hrxn ) + νFP RT](-rA )
= ∂V ∂V ∂V (Eq. 5.7.46)
∂t n
[∑i=1 ci (Cpi - FP R)]
system
Recall Eq. 5.7.33,

Fi = FA0 (θi + νi XA ) (Eq. 5.7.33)
Now, recall Eq. 5.4.116,

n
ν = ∑ νi (Eq. 5.4.116)
i=1
write Eq. 5.7.46 in terms of conversion using Eq. 5.7.33, and Eq. 5.4.116.
Plug Flow Reactor (PFR) Energy Balance for Single Chemical Reaction
At Unsteady State (ꝺT/ꝺt ≠ 0):
∂Q̇ ∂T ∂X
∂T - FA0 ∑ni=1 Cpi (θi + νi XA ) - νFP RTFA0 A +[(-∆Hrxn ) + νFP RT](-rA )
= ∂V ∂V ∂V (Eq. 5.7.47a)
∂t [∑ni=1 ci (Cpi - FP R)]
system
At Steady State (ꝺT/ꝺt = 0):
dQ̇ dX
dT - νFP RTFA0 A +[(-∆Hrxn ) + νFP RT](-rA )
= dV dV (Eq. 5.7.48a)
dV FA0 ∑ni=1 Cpi (θi + νi XA )
In Eq. 5.7.47a, formula for the evaluation of concentration of species “i” within the system (ci =
f(XA)) is different for liquid and gas phase.
For Liquid Phase Concentration
We generalize Eq. 5.4.40 through Eq. 5.4.44 for liquid phase concentration (ci = f(XA)) as
follows:
ci = cA0 (θi + νi XA ) (Eq. 5.7.49a)
124
For Gas Phase Concentration
We generalize Eq. 5.4.72 through Eq. 5.4.76 for gas phase concentration (ci = f(XA)) as follows:
(θi + νi XA ) P T0
ci = cA0 ( )( ) (Eq. 5.7.49b)
(1 + ϵXA ) P0 T
Recall 5.7.46,
Term-1
∂Q̇ ∂T ∂F
∂T - ∑ni=1 Fi Cpi - FP RT ∑ni=1 i + ⏞ [(-∆Hrxn )+ νFP RT](-rA )
= ∂V ∂V ∂V (Eq. 5.7.46)
system
Now we use the same analogy which is used while developing Eq. 5.7.11b, and directly replace
Term-1 in the above equation with Eq. 5.7.9b to give Eq. 5.7.47b,
n

j=1
Plug Flow Reactor (PFR) Energy Balance for Multiple Chemical Reactions
At Unsteady State (ꝺT/ꝺt ≠ 0):
∂Q̇ ∂T ∂F
∂T -(∑ni=1 Fi Cpi ) - FP RT ∑ni=1 i + ∑nj=1[(-∆Hrxn, ij ) + νj FP RT](-rij )
= ∂V ∂V ∂V (Eq. 5.7.47b)
∂t n
system
At Steady State (ꝺT/ꝺt = 0):
dQ̇ dF
dT - FP RT ∑ni=1 i + ∑nj=1[(-∆Hrxn, ij ) + νj FP RT](-rij )
= dV dV (Eq. 5.7.48b)
dV ∑ni=1 Fi Cpi
∂Q̇ dQ̇
Now it is the time to derive formulas for the Heat Transfer Rate Term ( ∂V or dV
). As we know
that there is no need to consider energy balance for isothermal reactor design so, here we will
only consider adiabatic and non-isothermal reactor operations for heat transfer consideration.
Q̇ = 0 (Eq. 5.7.16)
125
So that, for Unsteady State Operation,
∂Q̇
=0 (Eq. 5.7.50)
∂V
And for, Steady State Operation,
dQ̇
=0 (Eq. 5.7.51)
dV
The heat transfer rate for the case of double pipe PFR and PBR (Figure 5.19) can be expressed
in terms of Overall Heat Transfer Coefficient (Uh) [J/(s.m2.K)], Heat Transfer Surface Area (As)
[m2], Heat Transfer Fluid Temperature (Ta) [K], and Reactor Temperature (T) [K] as follows,
For endothermic reaction,
Q̇ = +Q̇ added = Uh As (Ta - T)
For exothermic reaction,
Q̇ = -Q̇ removed = -Uh As (T - Ta ) = Uh As (Ta - T)
From this fact we have generalized that whether the reaction is endothermic or exothermic the
heat transfer rate term evaluates to:
Q̇ = Uh As (Ta - T) (Eq. 5.7.52a)
Figure 5.19: Double pipe PFR with heat exchange
For the case of a differential element of double pipe PFR and PBR having length dL, Eq. 5.7.52a
can be written as,
∂Q̇ = Uh (Ta - T)∂As (Eq. 5.7.52b)
126
Now we define a new term known as specific surface area (ɑv ) (i.e. heat transfer surface area
per unit volume of reactor) is:
As πDL 4
ɑv = = = (Eq. 5.7.53a)
V 2
πD L D
4
In differential form Eq. 5.7.53a can be written as:
∂As
ɑv = (Eq. 5.7.53b)
∂V
From Eq. 5.7.53b,
∂As = ɑv ∂V
Put it in Eq. 5.7.52b,
∂Q̇ = Uh ɑv (Ta - T)∂V
For Unsteady State Operation, [3]
∂Q̇
= Uh ɑv (Ta - T) (Eq. 5.7.54a)
∂V
Equivalently, for Steady State Operation, PDE will be converted back to ODE due to elimination
of time dependence of variables,
dQ̇
= Uh ɑv (Ta - T) (Eq. 5.7.54b)
dV
If we use Eq. 5.7.54 a or b in the PFR energy balance to replace the heat transfer rate term
then, a problem will arise which is due to Heat Transfer Fluid Temperature (T a) at any point
along the length of reactor. So, first let us consider two different cases concerning temperature
(Ta):
1. Ta = Constant
If we increase the molar flow (Fa) of heat transfer fluid so much that Ta can be considered
constant, then Eq. 5.7.54 (a or b) is directly applicable with constant value of Ta.
2. Ta = Variable
If molar flow (Fa) of heat transfer fluid is limited, then the temperature (T a) of heat
transfer fluid cannot be considered constant. In this case temperature (Ta) varies along
the length of reactor. So that, temperature (Ta) can be expressed in the form of
differential equation by making an energy balance on the heat transfer fluid. Then this
127
differential equation can be solved simultaneously with PFR energy balance to model
non-isothermal PFR with variable heat transfer fluid temperature (T a). Because energy
balance involves some terms of mole balance as well, hence first we make a mole
balance on heat transfer fluid as follows, For mole balance, Recall Eq. 5.2.4 (G.M.B.E.),
V
dni
= Fi0 - Fi + ∫ ri dV (Eq. 5.2.4)
dt 0
Apply this equation on heat transfer fluid in the annulus (i.e. single species “a” i.e. H2O,
Steam, Oil, or Refrigerant etc.),
V
dna
= Fa0 - Fa + ∫ ra dV
dt 0
Because in the annulus there is no chemical reaction of heat transfer fluid so that rate
of formation of “a” is zero (ra = 0). So,
V
dna
= Fa0 - Fa + ∫ ra dV
dt 0
dna
= Fa0 - Fa
dt
For annulus side, na = na(V,t), hence ODE will change to PDE,
∂na
= Fa0 - Fa
∂t
Partially differentiate it w.r.t to V to get point value changes in volume,
∂ ∂na ∂
= (F - F )
∂V ∂t ∂V a0 a
Because Fa0 = Fa0(t) and Fa = Fa(t) so their derivatives w.r.t V are zero, Hence,
2
∂ na ∂Fa0 ∂Fa
= -
∂V∂t ∂V ∂V
2
∂ na
=0 (Eq. 5.7.55)
∂V∂t
Note that Fa ≠ Fa(V) because there is no chemical reaction in the annulus.
For energy balance, Recall Eq. 5.6.14 (G.E.B.E.),

n n n n n n
dHi dni dT dni
dt dt dt dt
128
Apply this equation on heat transfer fluid in the annulus (i.e. single species “a” i.e. H2O,
Steam, Oil, or Refrigerant etc.) with zero shaft work,
dHa dna dTa dna
[na +Ha - FP R ( na +Ta )] = Q̇ annulus + Fa0 Ha0 - Fa Ha
dt dt dt dt system
For annulus side, Ha = Ha(V,t) | na = na(V,t) | Ta = Ta(V,t), hence ODE will change to PDE,
∂Ha ∂na ∂Ta ∂na
[na +Ha - FP R ( na +Ta )] = Q̇ annulus + Fa0 Ha0 - Fa Ha
∂t ∂t ∂t ∂t system
Partially differentiate it w.r.t to V to get point value changes in volume,

∂ ∂Ha ∂na ∂Ta ∂na ∂
[na +Ha - FP R ( na +Ta )] = (Q̇ + Fa0 Ha0 - Fa Ha )
∂V ∂t ∂t ∂t ∂t system ∂V annulus
∂ ∂Ha ∂ ∂na ∂ ∂Ta ∂ ∂na ∂Q̇ annulus ∂ ∂

[ (n ) + (Ha ) - FP R (na ) - FP R (Ta )] = + (F H ) - (F H )
∂V a ∂t
⏟ ∂V ∂t ⏟ ∂V ∂t ∂V ∂t ∂V ⏟ a0 a0
∂V ∂V a a
Term-1 Term-2 system Term-3
Because Fa0 = Fa0(t) | Ha0 = Ha0(Ta0) | Ta0 = Ta0(t) Hence, Fa0Ha0 = f(t), so that its derivative
w.r.t. V is zero. Moreover Term-1 and Term-2 will generate second order mixed
perturbances in Ta and those are negligible as compared to other terms so that,
∂ ∂Ha ∂ ∂na ∂ ∂Ta ∂ ∂na ∂Q̇ annulus ∂ ∂

[ (n ) + (Ha ) - FP R (na ) - FP R (Ta )] = + (F H ) - (F H )
∂V a ∂t
⏟ ∂V ∂t ⏟ ∂V ∂t ∂V ∂t ∂V ⏟ a0 a0
∂V ∂V a a
Term-1 Term-2 system Term-3
∂2 na ∂na ∂Ha ∂2 na ∂na ∂Ta ∂Q̇ annulus ∂Ha ∂Fa

[(Ha + ) - FP R (Ta + )] = - (Fa +Ha ) (Eq. 5.7.56)
∂V∂t ∂t ∂V ∂V∂t ∂t ∂V system ∂V ∂V ∂V
Put Eq. 5.7.55 in Eq. 5.7.56,
∂na ∂Ha ∂na ∂Ta ∂Q̇ annulus ∂Ha ∂Fa

[( ) - FP R ( )] = - (Fa +Ha )
∂t ∂V ∂t ∂V system ∂V ∂V ∂V
Moreover, note that Fa ≠ Fa(V) and Fa = Fa(t) because there is no chemical reaction in
the annulus. Hence its derivative w.r.t to V is zero. So,
∂na ∂Ha ∂na ∂Ta ∂Q̇ annulus ∂Ha ∂Fa

[( ) - FP R ( )] = - (Fa +Ha )
∂V ∂t ∂V ∂t system ∂V ∂V ∂V
∂na ∂Ha ∂Ta ∂Q̇ annulus ∂Ha

[ - FP R ] = - Fa (Eq. 5.7.57)
∂V ∂t ∂t system ∂V ∂V
Recall Eq. 5.7.40 and write it for species “a”,
129
∂na
ca = (Eq. 5.7.58)
∂V
So, Eq. 5.7.55 will be converted to,
∂ca
=0 (Eq. 5.7.55N)
∂t
Because heat transfer fluid is pure fluid (not a mixture) so that its molar concentration
(ca) will represent its molar density [kgmol/m3] and that is a constant quantity. For the
case of no phase change of heat transfer fluid, recall Eq. 5.7.45, and write it for anulus
fluid,
∂Ha = Cpa ∂Ta (Eq. 5.7.59)
And note that heat transfer rate is as follows,
Q̇ annulus = -Q̇
∂Q̇ annulus ∂Q̇

=- (Eq. 5.7.60)
∂V ∂V
Recall Eq. 5.7.54a,
∂Q̇
= Uh ɑv (Ta - T) (Eq. 5.7.54a)
∂V
Put Eq. 5.7.54a in Eq. 5.7.60,
∂Q̇ annulus
= -Uh ɑv (Ta - T)
∂V
∂Q̇ annulus
= Uh ɑv (T - Ta ) (Eq. 5.7.61)
∂V
Now put Eq. 5.7.58, Eq. 5.7.59, and Eq. 5.7.61 in Eq. 5.7.57,
Cpa ∂Ta ∂Ta Cpa ∂Ta
ca [ - FP R ] = Uh ɑv (T - Ta ) - Fa
∂t ∂t system ∂V
∂Ta ∂Ta
[ca (Cpa - FP R)] = Uh ɑv (T - Ta ) - Fa Cpa (Eq. 5.7.62a)
∂t system ⏟ ∂V
Outflow Term
130
For Co-Current Flow
If the heat transfer fluid and the reaction mixture are flowing in the same direction, then
this mode of fluid flow is called co-current flow. And all the development related to the
mole balance and energy balance of heat transfer fluid in the annulus up to this point
is valid for the co-current flow. So, the Eq. 5.7.62a is valid for co-current flow. Hence, [3]
At Unsteady State Ta = Ta(V,t),

∂T
∂Ta Uh ɑv (T - Ta ) - Fa Cpa a
= ∂V (Eq. 5.7.63a)
∂t [ca (Cpa - FP R)]
system
At Steady State Ta = Ta(V),

dTa Uh ɑv (T - Ta )
= (Eq. 5.7.64a)
dV Fa Cpa
For Counter Current Flow
If the heat transfer fluid and the reaction mixture are flowing in the opposite direction,
then this mode of fluid flow is called counter-current flow. All the development related
to the mole balance and energy balance of heat transfer fluid in the annulus up to this
point is valid for the co-current flow. But we can convert it to counter current flow
without re-establishing the whole picture. For counter current flow, inlet of the annulus
becomes its outlet and outlet becomes inlet. So, the outflow term in the Eq. 5.7.62a will
become the inflow term by switching -ve sign to +ve sign. Hence,
∂Ta ∂Ta
[ca (Cpa - FP R)] = Uh ɑv (T - Ta ) + Fa Cpa (Eq. 5.7.62b)
∂t system ⏟ ∂V
Inflow Term
At Unsteady State Ta = Ta(V,t),

∂T
∂Ta Uh ɑv (T - Ta ) + Fa Cpa a
= ∂V (Eq. 5.7.63b)
system
At Steady State Ta = Ta(V),

dTa Uh ɑv (Ta - T)
= (Eq. 5.7.64b)
dV Fa Cpa
131
5.7.4 Energy Balance for Packed Bed Reactor (PBR)
In order to develop specific energy balance for Packed Bed Reactor (PBR) we will recall Eq.
5.3.7 and Eq. 5.3.6a.
ρb = ρc (1 - ϕ) (Eq. 5.3.7)
(-ri ) = ρb (-ri, Prime ) (Eq. 5.3.6a)
Put Eq. 5.3.7 in Eq. 5.3.6a, and write it for multiple reactions as well,
(-ri ) = ρc (1 - ϕ)(-ri, Prime ) (Eq. 5.7.65a)
(-rij ) = ρc (1 - ϕ)(-rij, Prime ) (Eq. 5.7.65b)
Now, we recall Eq. 5.3.9,

W = ρc (1-ϕ)V (Eq. 5.3.9)
In differential form it can be written as:

∂W = ρc (1-ϕ)∂V
∂W
∂V = (Eq. 5.7.66)
ρc (1-ϕ)
Every energy balance equation which is developed for PFR is also valid for PBR. But for PBR it
customary to express equations in terms of catalyst weight (W) instead of Reactor Volume (V).
For this purpose, we can use Eq. 5.7.65 (a or b) and Eq. 5.7.66. Demonstration of approach can
be conceptualized as follows, [3]
Recall Eq. 5.7.47a,
∂Q̇ ∂T ∂X
∂T - FA0 ∑ni=1 Cpi (θi + νi XA ) - νFP RTFA0 A +[(-∆Hrxn ) + νFP RT](-rA )
= ∂V ∂V ∂V (Eq. 5.7.47a)
∂t n
system
Put Eq. 5.7.65a and Eq. 5.7.66 in it,

∂Q̇ ∂T ∂XA
- FA0 ∑ni=1 Cpi (θi + νi XA ) - νFP RTFA0 +[(-∆Hrxn ) + νFP RT]ρc (1 - ϕ)(-rA, Prime )
∂W ∂W ∂W
∂T ρc (1-ϕ) ρc (1-ϕ) ρc (1-ϕ)
=
system
∂Q̇ ∂T n ∂X
∂T ρc (1-ϕ) - ρc (1-ϕ)FA0 ∑ C (θ + νi XA ) - ρc (1-ϕ)νFP RTFA0 A +[(-∆Hrxn ) + νFP RT]ρc (1 - ϕ)(-rA, Prime )
= ∂W ∂W i=1 pi i ∂W
system
132
∂Q̇ ∂T n ∂X
ρc (1-ϕ) [ -F ∑ C (θ + νi XA ) - νFP RTFA0 A +[(-∆Hrxn ) + νFP RT](-rA, Prime )]
∂T ∂W A0 ∂W i=1 pi i ∂W
=
system
∂Q̇ ∂T n ∂X
1 ∂T - FA0 ∑i=1 Cpi (θi + νi XA ) - νFP RTFA0 A +[(-∆Hrxn ) + νFP RT](-rA, Prime )
= ∂W ∂W ∂W (Eq. 5.7.67a)
ρc (1-ϕ) ∂t [∑ni=1 ci (Cpi - FP R)]
system
By following this analogy, we can directly convert PFR Equations to PBR Equations.
Packed Bed Reactor (PBR) Energy Balance for Single Chemical Reaction
At Unsteady State (ꝺT/ꝺt ≠ 0) [Analog of Eq. 5.7.47a]:

∂Q̇ ∂T n ∂X
1 ∂T - FA0 ∑i=1 Cpi (θi + νi XA ) - νFP RTFA0 A +[(-∆Hrxn ) + νFP RT](-rA, Prime )
= ∂W ∂W ∂W (Eq. 5.7.67a)
ρc (1-ϕ) ∂t n
system
At Steady State (ꝺT/ꝺt = 0) [Analog of Eq. 5.7.48a]:

dQ̇ dX
dT - νFP RTFA0 A +[(-∆Hrxn ) + νFP RT](-rA, Prime )
= dW dW (Eq. 5.7.68a)
dW FA0 ∑ni=1 Cpi (θi + νi XA )
Packed Bed Reactor (PBR) Energy Balance for Multiple Chemical Reactions
At Unsteady State (ꝺT/ꝺt ≠ 0) [Analog of Eq. 5.7.47b]:

∂Q̇ ∂T ∂F
1 ∂T -(∑ni=1 Fi Cpi ) - FP RT ∑ni=1 i + ∑nj=1[(-∆Hrxn, ij ) + νj FP RT](-rij, Prime )
= ∂W ∂W ∂W (Eq. 5.7.67b)
ρc (1-ϕ) ∂t [∑ni=1 ci (Cpi - FP R)]
system
At Steady State (ꝺT/ꝺt = 0) [Analog of Eq. 5.7.48b]:

dQ̇ dF
dT - FP RT ∑ni=1 i + ∑nj=1[(-∆Hrxn, ij ) + νj FP RT](-rij, Prime )
= dW dW (Eq. 5.7.68b)
dW ∑ni=1 Fi Cpi
PBR Mole Balance [Analog of Eq. 5.7.42]:

1 ∂ci ∂Fi
=- + νi (-rA, Prime ) (Eq. 5.7.69)
ρc (1-ϕ) ∂t ∂W
133
Q̇ = 0 (Eq. 5.7.16)
So that, for Unsteady State Operation,
∂Q̇
=0 (Eq. 5.7.70)
∂W
And for, Steady State Operation,
dQ̇
=0 (Eq. 5.7.71)
dW
The heat transfer rate for the case of double pipe PBR (recall Figure 5.19) can be expressed in
terms of Overall Heat Transfer Coefficient (Uh) [J/(s.m2.K)], Specific Surface Area of Reactor (ɑv )
[1/m], Heat Transfer Fluid Temperature (Ta) [K], and Reactor Temperature (T) [K] according to
Eq. 5.7.54 (a or b) as follows,
∂Q̇
= Uh ɑv (Ta - T) (Eq. 5.7.54a)
∂V
dQ̇
= Uh ɑv (Ta - T) (Eq. 5.7.54b)
dV
Their analogs for PBR are,
For Unsteady State Operation [Analog of Eq. 5.7.54a],
∂Q̇ Uh ɑv (Ta - T)
= (Eq. 5.7.72a)
∂W ρc (1-ϕ)
Equivalently, for Steady State Operation, PDE will be converted back to ODE due to elimination
of time dependence of variables, [Analog of Eq. 5.7.54b]
dQ̇ Uh ɑv (Ta - T)
= (Eq. 5.7.72b)
dW ρc (1-ϕ)
134
If the Heat Transfer Fluid Temperature (Ta) can be considered constant, then its constant value
can be directly used in Eq. 5.7.72 (a and b). And if it is variable then,
For Co-Current Flow
At Unsteady State [Analog of Eq. 5.7.63a],

∂T
∂Ta Uh ɑv (T - Ta ) - ρc (1-ϕ)Fa Cpa a
= ∂W (Eq. 5.7.73a)
system
At Steady State [Analog of Eq. 5.7.64a],

dTa Uh ɑv (T - Ta )
= (Eq. 5.7.74a)
dW ρc (1-ϕ)Fa Cpa
For Counter Current Flow
At Unsteady State [Analog of Eq. 5.7.63b],

∂T
∂Ta Uh ɑv (T - Ta ) + ρc (1-ϕ)Fa Cpa a
= ∂W (Eq. 5.7.73b)
system
At Steady State [Analog of Eq. 5.7.42],

dTa Uh ɑv (Ta - T)
= (Eq. 5.7.74b)
dW ρc (1-ϕ)Fa Cpa
135
Chapter-6
Transport Phenomena
Transport Processes
6.0 Introduction
Coming soon.
136
Section-II
Specialization Areas of Process Engineering
Process Process Process

Process Control Process Safety
Synthesis Intensification Optimization
137
Chapter-7
Process Synthesis
Computer-Aided Process Synthesis
7.0 Introduction
Process synthesis is composed of the following main fields:
• Product Design → It deals with (What to make?)

• Process Design → It deals with (How to make?)
• Plant Design → It deals with (How to find equipment dimensions?)
In this chapter only process design and plant design will be discussed. Product design is beyond
the scope of this discussion.
Product Design
(Finalize Desired
Product)
Process Design Plant Design

(Develop Process (Find Equipment
Flowsheet) Sizes)
Figure 7.1: Fields of process synthesis
138
7.1 Process Terminologies
Following are the main terms which are frequently used in the subject of process synthesis:
1. Raw Material: 21. Disturbance:

Chemicals which are required to produce desired An input process variable whose value is fluctuating
chemicals using a chemical process. over time is called disturbance.
2. Desired Product: 22. Set point:

Desired chemicals produced by transforming the raw Desired value of an output process variable assigned
materials physically and chemically in a chemical by the user to the controller in order to eliminate the
process. effect of disturbance and to keep the value of same
output process variable at desired levels.
3. Undesired Product:
Unwanted chemicals produced during the production 23. Manipulated Process Variable:
of desired chemicals. They are also known as by- A variable whose value can be manipulated by a
products or side-products. controller using final control element or manually by a
person.
4. Intermediate Product:
A chemical product which is not desired but needs to 24. Sensor:
be further processed to produce a desired product. A device which is used to measure the value of a
process variable.
5. Unit Operation:
Equipment used for the physical transformation of raw 25. Controller:
materials or intermediate products. An electronic circuit which has intelligence and uses
the output signal of a sensor and compares it with the
6. Unit Process: given setpoint and then changes the value of a
Equipment used for the chemical transformation of manipulated process variable in order to keep the
raw materials or intermediate products. value of an output process variable at desired level.
7. Chemical Processing Unit: 26. Final Control Element:
A unit operation or unit process in generic words. A device which is used by the controller to change the
8. Chemical Process: value of a manipulated process variable. It can be a
A logically assembled sequence of the processing control valve, variable speed pump, variable speed
units which is used to convert raw materials into compressor, or a relay switch.
desired, undesired, and intermediate products. 27. Process Instrument:
9. Flow diagram or Flowsheet: A sensor, a controller, or a final control element in
A pictorial representation of the chemical process. generic words is known as a process instrument.
10. Equipment Symbol: 28. Control Signal (Electronic):

A symbol made of the basic engineering shapes which A black dashed line with arrowhead at its end is called
can be used as an alternative to the processing unit to an electronic control signal. It is used to connect
make flow diagrams. process instruments together.
11. Process Stream or Material Stream:

A solid line with arrowhead at its end is called process 29. Control Signal (Pneumatic):
stream. It is used to connect equipment symbols A black dashed line with double cuts on it and with an
together in a flow diagram. It is used as an alternative arrowhead at its end is a pneumatic control signal.
to pipes and ducts.
139
12. Input Process Stream: 30. Block Flow Diagram (BFD):
A process stream which is introduced into the process. A diagram which reflects the whole chemical process
pictorially by the use of blocks in place of the set of
13. Output Process Stream: processing units.
A process stream which is drawn out of the process.
31. Process Flow Diagram (PFD):
14. Energy Stream (Heat, Work): A diagram which reflects the whole chemical process
A colored (red for heat and blue for work) dashed line pictorially by the use of equipment symbols in place
with arrowhead at its end is called energy stream. It is of processing units.
used to show energy transfer between system and its
surrounding. 32. Piping and Instrumentation Diagram
(P&ID):
A diagram which reflects the whole chemical process
and its associated control systems pictorially using
15. Thermodynamic Variables: equipment symbols and controllers in place of
Variables appeared in thermodynamic equations are processing units.
called thermodynamic variables. Constant Volume 33. Mass Separating Agent:
Heat Capacity (CV), Constant Pressure Heat Capacity A chemical which assists the separation of a chemical
(Cp), Internal Energy (Ut), Enthalpy (Ht), Entropy (St), mixture into its individual components. e.g. Solvent for
Heat (Q), Work (W) etc. Gas Absorption, An Adsorbent, Chemical agent for
16. Kinetic Variables: azeotropic or extractive distillation, etc.
Variables appeared in reaction engineering equations 34. Energy Separating Agent:
are called kinetic variables. Activation Energy (Ea), Any form of energy which is used for the separation
Frequency Factor (A), Rate Constant (k), Order of of chemical mixture into its individual components.
Reaction (n), Reaction Rate (-rA), Equilibrium Constant E.g. Heat, Work etc.
(Kc) etc.
35. Material Safety Data Sheet (MSDS):
17. Transport Variables: MSDS is a sheet holding chemical safety data (health
Variables appeared in transport rate equations are hazard data, flammability hazard data, reactivity
called transport variables. Viscosity (µ), Thermal hazard data, and radioactivity hazard data) about any
Conductivity (k), Mass Diffusivity (ƊAB), Heat Transfer chemical substance under consideration. MSDS can
Coefficient (h), Mass Transfer Coefficient (kc) etc. be found at:
18. Process Variables: URL: https://chemicalsafety.com/sds-search/
Variables which are used to represent the state of a
chemical species (Temperature, Pressure, Flowrate, 35. Material of Construction (MOC):
and Composition). Any material of which processing units are made is
called its material of construction (MOC).
19. Input Process Variables:
Process variables associated with the input process
streams.
20. Output Process Variables:

Process variables associated with the output process
streams.
140
7.2 Process Design
Various processing units are used to carry out chemical reactions and to separate products
and byproducts from each other and from unreacted raw materials. The logical assembly of
these processing units into a process flowsheet is known as process design. The steps involved
in process design algorithm are described below with Example 7.1 [8]:
7.2.1 Step-1: Collection of Information

Following information must be collected before proceeding further:
• Importance and Applications of the Product to be Manufactured

(Book Source: Kirk-Othmer Encyclopedia of Chemical Technology)
(Internet Source: Wikipedia, URL: https://en.wikipedia.org/wiki/Main_Page)
• Market Competitors of the Product

(Internet Source-1: Google Search Engine, URL: https://www.google.com)
(Internet Source-2: Bing Search Engine, URL: https://www.bing.com)
• Physical and Chemical Properties of all the chemical species involved in the Process*
(Book Source: Perry’s Chemical Engineers’ Handbook)
(Database Source: Database of Aspen Plus Process Simulator)
(Internet Source: National Institute of Standards and Technology (NIST) Database,
URL: https://webbook.nist.gov/chemistry/)
• Environmental and Safety Data of all the chemical species involved in the Process
(Book Source: Perry’s Chemical Engineers’ Handbook)
(Internet Source-1: MSDS, URL: https://chemicalsafety.com/sds-search/)
(Internet Source-2: Environmental Protection Agency (EPA), URL: https://comptox.epa.gov/dashboard)
(Internet Source-3: Toxic Release Inventory (TRI),
URL: https://enviro.epa.gov/triexplorer/tri_release.chemical)
(Internet Source-4: Ratings of the National Fire Protection Association (NFPA),
URL: https://www.newenv.com/resources/nfpa_chemicals/)
• Chemical Prices of all the chemical species involved in the Process**

(Manufacturer Source: Directly contact with chemical manufacturers)
(Internet Source: ICIS Chemical Business, URL: https://www.icis.com/explore/)
• Utility Prices (Steam, Cooling Water, and Electricity)

(Government Source: Directly contact with local government organizations)
Such type of data is used in Step-3 of process design algorithm.
Footnotes:
* All the chemical species involved in the process means (Raw materials, desired products, undesired products,
intermediates etc.).
** This data is related to supply and demand so, it fluctuates periodically, hence; it is difficult to predict.
141
7.2.2 Step-2: Experimentation
In most cases, when a process looks promising, an experimental program is initiated. The
objectives of experimentation include the following:
• Determination of Reaction Mechanisms

• Finding Reaction Kinetics (Reaction Rate Laws)
• Look for a suitable Catalyst (If possible)
• Research on the Catalyst Life Testing
• Determination of the parameter values and equilibrium diagrams for separation
operations
• Look for suitable Mass Separating Agents
The results of experimentation can be presented in three different ways:
1. Graphical Results
2. Numerical Results (Tabulated results)
3. Mathematical Equation based Results (Regressed data)
The results of experiments also assist in Step-3 of the process design algorithm.
7.2.3 Step-3: Preliminary Process Synthesis

Having gathered information and carried out experiments, a process design team is prepared
to create an initial process flowsheet to convert the potential raw materials into chemical
products.
Raw Materials Desired Product

Process Flowsheet?
Figure 7.2: Objective of process design
• Chemical States (For raw materials, products, and byproducts specifications)

“A set of the values of following process variables is known as a chemical state.”
✓ Temperature
✓ Pressure
✓ Flowrate (Mass, Molar, and Volumetric flowrate) [Overall & Component based]
✓ Composition (Mass and Molar concentration of chemical species)
✓ Phase (Solid, Liquid, and Gas)
✓ Form, if solid phase (Particle size distribution and particle shape)
142
• Processing Units
✓ For Chemical Reaction Operations
[Batch Reactor (BR), Continuous Stirred Tank Reactor (CSTR), Plug Flow Reactor (PFR), Packed
Bed Reactor (PBR), and Fluidized Bed Reactor (FBR)]
✓ For Chemical Separation Operations

[Sieve Separators, Filtration Equipment, Magnetic Separators, Hydro-cyclone Separator, Cyclone
Separator, Electrostatic Precipitator, Flash Separator, Distillation Columns, Absorption Columns,
Stripping Columns, Liquid-Liquid-Extraction Equipment, Solid Extractors, Leaching Equipment,
Crystallizers, Adsorption Columns, and Membrane Separators]
✓ For Phase Separation Operation

[Two Phase Separators and Three Phase Separators]
✓ For Temperature Change Operations

[Heat Exchangers and Cooling Towers]
✓ For Pressure Change Operations

[Pressure Reduction Valves, Pumps, Fans, Blowers, Compressors, Gas Turbines]
✓ For Phase Change Operations

[Evaporators and Condensers]
✓ For Mixing and Splitting Operations

[Mixing Valves, Stream Splitters, and Mixing Vessels]
✓ For Particulate Operations

Size Reduction Equipment: (Crushers and Grinders)
Size Enlargement Equipment: (Agglomerators)
Solid Transportation Equipment: (Conveyors)
• Process Synthesis Sub Steps [8]

“Given the states of the raw-material and product streams, process synthesis involves the
selection of processing units to convert the raw materials into products. In other words, each
operation can be viewed as having a role in eliminating one or more of the property differences
between the raw materials and the desired products. As each operation is inserted into a
flowsheet, the effluent streams from the new operation are closer to those of the required
products.”
✓ Sub Step I: Eliminate Differences in Molecular Types

(Using Chemical Reaction Operations)
✓ Sub Step II: Distribute the Chemicals by matching Sources and Sinks (e.g.
Recycle, Bypass, and Purge Streams)
(Using Mixing and Splitting Operations)
✓ Sub Step III: Eliminate Differences in Composition

(Using Chemical Separation Operations)
143
✓ Sub Step IV: Eliminate Differences in Temperature, Pressure, and Phase
(Using Temperature, Pressure, and Phase Change Operations)
✓ Sub Step V: Task Integration (The selection of Processing Units) [BFD → PFD]
(Using Processing Units in Place of Blocks)
Rather than discuss these steps in general, it is preferable to examine how they are applied for
synthesis of a process e.g. for vinyl-chloride production. [8]
• Processing Modes
✓ Continuous Processing is used for large scale chemical production e.g. for
Commodity Chemical Production
✓ Batch Processing is used for small scale chemical production e.g. for Specialty
Chemical Production
✓ Semi-continuous Processing is used for hybrid chemical production.
Example 7.1: Process Synthesis for Vinyl Chloride Manufacturing

Step-1: Collection of Information:
Consider the need to manufacture vinyl chloride,
a monomer intermediate for the production of polyvinyl chloride,
an important polymer (usually referred to just as vinyl) that is widely used for rigid plastic
piping, fittings, and similar products. Over the years, large commercial plants have been
built, some of which produce over 1 billion lb ∕ yr. Hence, polyvinyl chloride and the
monomer from which it is derived are referred to commonly as commodity chemicals that
are produced continuously, rather than in batch, virtually everywhere. Historically, vinyl
chloride was discovered in 1835 in the laboratory of the French chemist Regnault, and the
first practical method for polymerizing vinyl chloride was developed in 1917 by the German
chemists Klatte and Rollett. Vinyl chloride is an extremely toxic substance and, therefore,
industrial plants that manufacture it or process it must be designed carefully to satisfy
government health and safety regulations.
An opportunity has arisen to satisfy a new demand, on the order of 800 million pounds per
144
year, for vinyl-chloride monomer in a petrochemical complex on the Gulf Coast of the
United States, given that an existing plant owned by the company produces 1 billion lb ∕ yr
of this commodity chemical. At this point, a design team has been formulated, and it has
begun to consider four potential alternatives, including:
• Alternative-1:
A competitor’s vinyl-chloride plant, which produces 2 billion lb ∕ yr of vinyl chloride
and is located about 100 miles away, might be expanded to produce the required
amount, which would be shipped by truck or rail in tank car quantities. In this case,
the design team projects the purchase price and designs storage facilities. This might
be the simplest solution to provide the monomer required to expand the local PVC
plant.
• Alternative-2:
Chlorine from the electrolysis of NaCl solution could be processed and shipped by
pipeline from a nearby plant. Then, chlorine could be reacted with in-house ethylene
to produce the monomer and HCl as a byproduct.
• Alternative-3:
Because the existing company petrochemical complex produces HCl as a byproduct
in many processes (e.g., in chloroform and carbon tetrachloride manufacture) at a
depressed price because large quantities are produced, HCl is normally available at
low prices. Reactions of HCl with acetylene, or ethylene and oxygen, could produce
1,2-dichloroethane, an intermediate that can be cracked to produce vinyl chloride.
• Alternative-4:
Design an electrolysis plant to produce chlorine. One possibility is to electrolyze the
HCl, available from within the petrochemical complex, to obtain H2 and Cl2. Then,
chlorine could be reacted according to alternative 2. Elsewhere in the petrochemical
complex, hydrogen could be reacted with nitrogen to form ammonia or with CO to
produce methanol.
These are typical of the alternatives that might be selected from a large number of ideas
that serve as a base on which to begin the process design. For this example, it’s sufficient
to consider only the production of the monomer with a focus on alternatives 2 and 3.
Data from chemistry laboratories focus on several promising chemical reactions involving
the chemicals in Table 7.1. Thermophysical property data (e.g., normal boiling points, vapor
pressures, heat capacities, latent heats of vaporization, heats of formation, and liquid
densities) for these (and many other similar chemicals) are available in extensive databases
(of the process simulators; like Aspen Plus) and, when not available, can be estimated fairly
145
reliably. The data of toxicity, safety, and purchase price can be found using MSDS and
internet.
Table 7.1: Objective of process design
Chemical Molecular Weight Chemical Formula

Acetylene 26.04 C2H2
Chlorine 70.91 Cl2
1,2-Dichloroethane 98.96 C2H4Cl2
Ethylene 28.05 C2H4
Hydrogen Chloride 36.46 HCl
Vinyl Chloride 62.50 C2H3Cl
Step-2: Experimentation:
In this case approximately all data is known so, experiments are not needed.
Step-3: Preliminary Process Synthesis:
Following the Process Synthesis Sub Steps (I–V), a process flowsheet to manufacture vinyl
chloride is synthesized in this example. Note that some assistance was provided by two
patents (Benedict, 1960; B. F. Goodrich Co., 1963). Often, similar patents, located by design
teams when gathering information, provide considerable help during process synthesis.
Sub Step I: Eliminate Differences in Molecular Types
For the manufacture of vinyl chloride, data from the chemistry laboratory focus on several
promising chemical reactions involving the chemicals shown in Table 7.1. Note that since
vinyl chloride has been a commodity chemical for many years, these chemicals and the
reactions involving them are well known. For newer substances, the design team often
begins to carry out process synthesis as the data are emerging from the laboratory. The
challenge, in these cases, is to guide the chemists away from those reaction paths that lead
to processes that are costly to build and operate, and to arrive at designs as quickly as
possible, in time to capture the market before a competitive process or chemical is
developed by another company. Returning to the manufacture of vinyl chloride, the
principal reaction pathways are as follows.
1. Direct Chlorination of Ethylene:

C2H4 + Cl2 → C2H3Cl + HCl (Eq. 7.1)
This reaction appears to be an attractive solution to design alternative 2. It occurs

spontaneously at a few hundred degrees Celsius, but unfortunately does not give a
146
high yield of vinyl chloride without simultaneously producing large amounts of
byproducts such as dichloroethylene. Another disadvantage is that one of the two
atoms of expensive chlorine is consumed to produce the byproduct hydrogen
chloride, which may not be sold easily.
2. Hydrochlorination of Acetylene:
C2H2 + HCl → C2H3Cl (Eq. 7.2)
This exothermic reaction is a potential solution for the concept denoted as
alternative 3. It provides a good conversion (98%) of acetylene to vinyl chloride at
150 ∘C in the presence of mercuric chloride (HgCl2) catalyst impregnated in activated
carbon at atmospheric pressure. These are fairly moderate reaction conditions, and
hence, this reaction deserves further study.
3. Thermal Cracking of Dichloroethane from Chlorination of Ethylene:
C2H4 + Cl2 → C2H4Cl2 (Eq. 7.3)
C2H4Cl2 → C2H3Cl + HCl (Eq. 7.4)
______________________________________________________
C2H4 + Cl2 → C2H3Cl + HCl (Eq. 7.1) [Overall]
The sum of reactions (7.3) and (7.4) is equal to reaction (7.1). This two-step reaction
path has the advantage that the conversion of ethylene to 1,2-dichloroethane in
exothermic reaction (7.3) is about 98% at 90 ∘C and 1 atm with a Friedel–Crafts
catalyst such as ferric chloride (FeCl3). Then, the dichloroethane intermediate is
converted to vinyl chloride by thermal cracking according to the endothermic
reaction (7.4), which occurs spontaneously at 500 ∘C and has conversions as high as
65%. The overall reaction presumes that the unreacted dichloroethane is recovered
entirely from the vinyl chloride and hydrogen chloride and recycled. This reaction
path has the advantage that it does not produce dichloroethylene in significant
quantities, but it shares the disadvantage with reaction path 1 of producing HCl. It
deserves further examination as a solution to design alternative 2.
4. Thermal Cracking of Dichloroethane from Oxychlorination of Ethylene:
C2H4 + 2HCl + ½ O2 → C2H4Cl2 + H2O (Eq. 7.5)
C2H4Cl2 → C2H3Cl + HCl (Eq. 7.4)

_____________________________________________________________________
C2H4 + HCl + ½ O2 → C2H3Cl + H2O (Eq. 7.6) [Overall]
In reaction (7.5), which oxy-chlorinates ethylene to produce 1,2-dichloroethane, HCl

is the source of chlorine. This highly exothermic reaction achieves a 95% conversion
of ethylene to dichloroethane at 250 ∘C in the presence of cupric chloride (CuCl2)
147
catalyst, and is an excellent candidate when the cost of HCl is low. As in reaction
path 3, the dichloroethane is cracked to vinyl chloride in a pyrolysis step. This
reaction path should be considered also as a solution for design alternative 3.
5. Balanced Process for Chlorination of Ethylene:
C2H4 + Cl2 → C2H4Cl2 (Eq. 7.3)
C2H4 + 2HCl + ½ O2 → C2H4Cl2 + H2O (Eq. 7.5)
2C2H4Cl2 → 2C2H3Cl + 2HCl (Eq. 7.4)

_____________________________________________________________________
2C2H4 + Cl2 + ½ O2 → 2C2H3Cl + H2O (Eq. 7.7) [Overall]
This reaction path combines paths 3 and 4. It has the advantage of converting both
atoms of the chlorine molecule to vinyl chloride. All of the HCl produced in the
pyrolysis reaction is consumed in the oxychlorination reaction. Indeed, it is a fine
candidate for the solution of design alternative 2.
Economic Analysis:
Given this information, it seems clear that the design team would reject reaction path 1 on
the basis of its low selectivity with respect to the competing reactions (not shown) that
produce undesirable byproducts. This leaves the other reaction paths as potentially
attractive to be screened on the basis of the chemical prices. Although it is too early to
estimate the cost of the equipment and its operation before the remaining process
operations are in place, the design team normally computes the economic potential for each
reaction path and uses it as a vehicle for screening out those that cannot be profitable.
Economic Potential (EP) = Sales Revenue – Cost of Raw Materials (Eq. A)

(Excluding Capital and Operating Costs)
To illustrate this process for the production of vinyl chloride, Table 7.2 provides a
representative set of prices for the principal chemicals, obtained from a source such as the
Table 7.2: Assumed Cost of Chemicals Purchased or Sold in Bulk Quantities
Chemical Cost (cents/lb)

Ethylene 30
Acetylene 80
Chlorine 18
Vinyl Chloride 35
Hydrogen Chloride 25
Water 0
Oxygen (Air) 0
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ICIS Business Americas (formerly the Chemical Marketing Reporter), as discussed earlier.
The economic potential is computed by first converting to a mass basis, as illustrated for
reaction path 3:
Table 7.3: Economic potential pre-requisites for reaction path 3
Chemical Reaction C2H4 + Cl2 → C2H3Cl + HCl

Quantity C2H4 Cl2 C2H3Cl HCl
Mole (lbmol) 1 1 1 1
Molecular Weight (lb/lbmol) 28.05 70.91 62.50 36.46
Mass (lb) 28.05 70.91 62.50 36.46
Mass Ratio (lb/lb of vinyl chloride) 0.449 1.134 1 0.583
Cost (cents/lb) 30 18 35 25
Then, the economic potential is:
Economic Potential (EP) = [35(1) + 25(0.583)] − [ 30(0.449) + 18(1.134)]
= 15.69 cents ∕ lb of vinyl chloride
Similar estimates are made for the overall reaction in each of the reaction paths, it being
assumed that complete conversion can be achieved without any side reactions (not shown),
with the results shown in Table 7.4.
Even without the capital costs (for construction of the plant, purchase of land, etc.) and the
operating costs (for labor, steam, electricity, etc.), the economic potential for reaction path
2 is negative, whereas the economic potentials for the other reaction paths are positive.
This is principally because acetylene is very expensive relative to ethylene. The fairly high
price of HCl also contributes to the inevitable conclusion that vinyl chloride cannot be
produced profitably using this reaction path.
Table 7.4: Economic Potential for Production of Vinyl Chloride (Based on Chemical Prices in Table 7.2)
Economic Potential
Reaction Path Overall Reaction
(cents/lb of vinyl chloride)
2 C2H2 + HCl → C2H3Cl -16.00
3 C2H4 + Cl2 → C2H3Cl + HCl 15.69
4 C2H4 + HCl + 1/2 O2 → C2H3Cl + H2O 6.96
5 2C2H4 + Cl2 + 1/2 O2 → 2C2H3Cl + H2O 11.32
It should be noted that the price of HCl is often very sensitive to its availability in a
petrochemical complex. In some situations, it may be available in large quantities as a
byproduct from another process at very low cost.
149
At a much lower price, reaction path 2 would have a positive economic potential, but would
not be worthy of further consideration when compared with the three reaction paths
involving ethylene. Turning to these paths, all have sufficiently positive economic potentials,
and hence are worthy of further consideration. It is noted that the price of HCl strongly
influences the economic potentials of reaction paths 3 and 4, with the economic potential
of reaction path 5 midway between the two. Before proceeding with the synthesis, the
design team would be advised to examine how the economic potentials vary with the price
of HCl.
Figure 7.3 shows the first step toward creating a process flowsheet for reaction path 3. Each
reaction operation is positioned with arrows representing its feed and product chemicals.
The sources and sinks are not shown because they depend on the distribution of chemicals,
the next step in process synthesis. The flow rates of the external sources and sinks are
computed assuming that the ethylene and chlorine sources are converted completely to
the vinyl chloride and hydrogen chloride sinks. Here, a key decision is necessary to set the
scale of the process, that is, the production rate at capacity. In this case, a capacity of
100,000 lb ∕ hr (∼800 million lb ∕ yr, assuming operation 330 days annually and an operating
factor of 0.904) is dictated by the opportunity presented above. Given this flow rate for the
product (principal sink for the process), the flow rates of the HCl sink and the raw-material
sources can be computed by assuming that the raw materials are converted to the products
according to the overall reaction. Any unreacted raw materials are separated from the
reaction products and recycled. Material balance is shown in Table 7.5 and so the results of
Figure 7.3 are obtained, where each flow rate in lbmol ∕ hr is 1,600.
Table 7.5: Overall mass balance
Chemical Reaction C2H4 + Cl2 → C2H3Cl + HCl

Quantity C2H4 Cl2 C2H3Cl HCl
Mole (lbmol) 1 1 1 1
Molecular Weight (lb/lbmol) 28.05 70.91 62.50 36.46
Mass (lb) 28.05 70.91 62.50 36.46
Mass Ratio (lb/lb of vinyl chloride) 0.449 1.134 1 0.583
Material Balance (lb) 44,900 113,400 100,000 58,300
Similar flowsheets, containing the reaction operations for reaction paths 4 and 5, would be
prepared to complete Step 1 of the synthesis. These are represented in the synthesis tree
in Figure 7.8, which will be discussed after all of the synthesis steps have been completed.
Note that their flowsheets are not included here due to space limitations. As the next steps
in the synthesis are completed for reaction path 3, keep in mind that they would be carried
out for the other reaction paths as well. Note, also, that only the most promising flowsheets
150
are developed in detail, usually by an expanded design team or, in some cases, by a
competitive design team.
Figure 7.3: Reaction operations for the thermal cracking of dichloroethane from the chlorination of ethylene
(reaction path 3)
Sub Step II: Distribute the chemicals by matching sources and sinks (e.g. Recycle, Bypass,
and Purge Streams)
In Sub Step II, where possible, the sources and sinks for each of the chemical species in
Figure 7.3 are matched so that the total mass flow into a reactor equals the total mass flow
out. This often entails the introduction of mixing operations to eliminate differences in flow
rates when a single sink is supplied by two or more sources. In other cases, a single source
is divided among several sinks. To achieve the distribution of chemicals in Figure 7.4, the
ethylene and chlorine sources are matched with their sinks into the chlorination reactor.
Figure 7.4: Flowsheet showing a distribution of chemicals for thermal cracking of dichloroethane from
chlorination of ethylene (reaction path 3)
151
It is assumed that ethylene and chlorine enter the reactor in the stoichiometric ratio of 1:1
as in (Eq. 7.3). Because the raw materials are in this ratio, no differences exist between the
flow rates of the sources and sinks, and hence, no mixers are needed. Flow rates of 113,400
lb ∕ hr of chlorine and 44,900 lb ∕ hr of ethylene produce 158,300 lb ∕ hr of dichloroethane.
When it is desired to have an excess of one chemical in relation to the other so as to
completely consume the other chemical, which may be toxic or very expensive (e.g., Cl2),
the other raw material (e.g., C2H4) is mixed with recycle and fed to the reactor in excess.
For example, if the reactor effluent contains unreacted C2H4, it is separated from the
dichloroethane product and recycled to the reaction operation. Note that the recycle is the
source of the excess chemical, and the flow rate of the external source of C2H4 for a given
production rate of dichloroethane is unaffected. This alternative distribution of chemicals
can be explored further. Returning to the distribution of chemicals in Figure 7.4, note that,
at reactor conditions of 90 ∘C and 1.5 atm, experimental data indicate that 98% of the
ethylene is converted to dichloroethane, with the remainder converted to unwanted
byproducts such as trichloroethane. This loss of yield of main product and small fraction of
byproduct is neglected at this stage in the synthesis.
Next, the dichloroethane source from the chlorination operation is sent to its sink in the
pyrolysis operation, which operates at 500 ∘C. Here only 60% of the dichloroethane is
converted to vinyl chloride with a byproduct of HCl, according to reaction (7.4). This
conversion is within the 65% conversion claimed in the patent. To satisfy the overall material
balance, 158,300 lb ∕ hr of dichloroethane must produce 100,000 lb ∕ hr of vinyl chloride and
58,300 lb ∕ hr of HCl. But a 60% conversion produces only 60,000 lb ∕ hr of vinyl chloride.
Material balance for the calculation of recycle flowrate (R):
System: Mixing Point
FC2H4Cl2, Mix-IN + R = FC2H4Cl2, Pyrolysis-IN
FC2H4Cl2, Pyrolysis-IN = 158300 lb / hr + R (Eq. I)
System: Pyrolizer
X C2H4Cl2 = (FC2H4Cl2, Pyrolysis-IN – FC2H4Cl2, Pyrolysis-OUT) / FC2H4Cl2, Pyrolysis-IN
0.6 × FC2H4Cl2, Pyrolysis-IN = FC2H4Cl2, Pyrolysis-IN – FC2H4Cl2, Pyrolysis-OUT
FC2H4Cl2, Pyrolysis-OUT = FC2H4Cl2, Pyrolysis-IN – (0.6 × FC2H4Cl2, Pyrolysis-IN)
FC2H4Cl2, Pyrolysis-OUT = [1 – 0.6] × FC2H4Cl2, Pyrolysis-IN (Eq. II)
Put Eq. I in Eq. II: FC2H4Cl2, Pyrolysis-OUT = [1 – 0.6] × (158300 lb / hr + R)
152
FC2H4Cl2, Pyrolysis-OUT = 0.4 × (158300 lb / hr + R)
FC2H4Cl2, Pyrolysis-OUT = 63320 lb / hr + (0.4 × R) (Eq. III)
System: Splitting Point
FC2H4Cl2, Pyrolysis-OUT = R (Eq. IV)
Solve Eq. III and Eq. IV simultaneously:
R = 63320 lb / hr + (0.4 × R)
R – (0.4 × R) = 63320 lb / hr
(1 – 0.4) × R = 63320 lb / hr
0.6 × R = 63320 lb / hr
R = (63320/0.6) lb / hr
R = (63320/0.6) lb / hr
R = 105,533 lb / hr (~ 105,500 lb / hr)
Its source is a recycle stream (unreacted dichloroethane), so a mixing operation is inserted

to combine the two sources, to give a total of 263,800 lb ∕ hr. The effluent stream from the
pyrolysis operation is the source for the vinyl-chloride product, the HCl byproduct, and the
dichloroethane recycle. To enable these chemicals to be supplied to their sinks, one or
more separation operations are needed and are addressed in the next synthesis step.
Figure 7.4 also shows the heats of reaction for the two reaction steps. These are computed
at the temperatures and pressures of the reaction operations from heats of formation and
heat capacities as a function of temperature. There are many sources of these data,
especially the process simulators. When a simulator, such as ASPEN PLUS, is used, it is
convenient to define each of the reaction operations and to perform an energy balance at
reactor conditions. The simulators report the rate at which heat must be transferred to or
from the reactor to achieve exit conditions from given inlet conditions or, if operated
adiabatically, the exit conditions for no heat transfer. For reaction path 3, the chlorination
operation provides a large source of energy, 150 million Btu ∕ hr, but at a low temperature,
90 ∘C, whereas the pyrolysis operation requires much less energy, 52 million Btu ∕ hr, at an
elevated temperature, 500 ∘C. Since this heat source cannot be used to provide the energy
for pyrolysis, other uses for this energy should be sought as the synthesis proceeds. These
and other sources as well as sinks for energy are considered during task integration in Sub
Step V.
153
As for the pressure levels in the reaction operations, 1.5 atm is selected for the chlorination
reaction to prevent the leakage of air into the reactor to be installed in the task-integration
step. At atmospheric pressure, air might leak into the reactor and build up in sufficiently
large concentrations to exceed the flammability limit. For the pyrolysis operation, 26 atm is
recommended by the B. F. Goodrich patent (1963) without any justification. Since the
reaction is irreversible, the elevated pressure does not adversely affect the conversion. Most
likely, the patent recommends this pressure to increase the rate of reaction and, thus,
reduce the size of the pyrolysis furnace, although the tube walls must be thick and many
precautions are necessary for operation at elevated pressures. The pressure level is also an
important consideration in selecting the separation operations, as will be discussed in the
next synthesis step.
Referring to Figure 7.8, at the “Distributions of Chemicals” level, two branches have been
added to the synthesis tree to represent the two distributions in connection with reaction
path 3. Each of these branches represents a different partially completed flowsheet. Other
distributions arise in connection with reaction paths 4 and 5. These are represented using
dashed lines in the synthesis tree.
Sub Step III: Eliminate differences in Compositions
As mentioned earlier, for each distribution of chemicals, the needs for separation become
obvious. In Figure 7.4, for example, it is clear that the pure effluent from the chlorination
reaction operation needs no separation, but the effluent from the pyrolysis operation is a
mixture that needs to be separated into nearly pure species. Here, the source of the three
species in the effluent is at a composition far different from the compositions of the three
sinks: vinyl-chloride product, HCl byproduct, and the dichloroethane for recycle. To
eliminate these composition differences, one or more separation operations are needed.
One possibility is shown in Figure 7.5, in which two distillation towers in series are inserted
into the flowsheet. Distillation is possible because of the large volatility differences among
the three species. This can be seen by examining the boiling points in Table 7.6, which can
be obtained from vapor pressure data in the preliminary database, or from a process
simulator. In the first column, HCl is separated from the two organic chemicals. In the
second column, vinyl chloride is separated from dichloroethane. At 1 atm, the boiling point
of HCl is very low, −84.8 ∘C, and hence if HCl were recovered at 1 atm as the distillate of
the first tower, very costly refrigeration would be necessary to condense the reflux stream.
At 26 atm (the pyrolysis reaction pressure), HCl boils at 0 ∘C, and much less costly
refrigeration could be used. The B.F. Goodrich patent recommends operation at 12 atm
without any justification.
154
Figure 7.5: Flowsheet including the separation operations for the vinyl-chloride process
At this pressure, HCl boils at –26.2 ∘C and the bottoms product, comprised of vinyl chloride
and dichloroethane with trace quantities of HCl, has a bubble point of 93 ∘C, which can be
calculated by a process simulator. The bottoms product at this reduced temperature and
pressure is farther away from the critical points of vinyl chloride–dichloroethane mixtures at
the bottom of the distillation column.
Table 7.6: Boiling Points and Critical Constants
Normal Boiling Point Boiling Point (∘C) Critical Constants

Chemical
(1 atm, ∘C) 4.8 atm 12 atm 26 atm Tc (∘C) Pc (atm)
HCl -84.8 -51.7 -26.2 0 51.4 82.1
C2H3Cl -13.8 33.1 70.5 110 159 56
C2H4Cl2 83.7 146 193 242 250 50
It is likely, therefore, that B. F. Goodrich selected this lower pressure to avoid operation in
the critical region where the vapor and liquid phases approach each other and are much
more difficult to disengage (i.e., have small flooding velocities and require very large
diameters and tray spacings). Furthermore, low-pressure steam is adequate for the reboiler.
When this distillation tower is inserted into the flowsheet, the conditions of its feed stream,
or sink, need to be identified. If the feed is a saturated liquid, the temperature is 6 ∘C at 12
atm, with a mild refrigerant required for cooling. A preferable feed temperature would be
35 ∘C or higher, which could be achieved by completing the cooling and partial
condensation of the pyrolysis reactor effluent with cooling water, but the introduction of –
155
vapor into the column would increase the refrigeration load of the condenser at −26.2 ∘C.
Upon making this specification, key differences (temperature, pressure, and phase) appear
between the effluent from the pyrolysis operation and the feed to the distillation column.
These are eliminated in the next synthesis step by inserting temperature and pressure
change operations, with each temperature specification leading to a somewhat different
flowsheet.
After the first distillation operation is inserted into the flowsheet, the second follows
naturally. The bottoms from the HCl-removal tower is separated into nearly pure species in
the second tower, which is specified at 4.8 atm, as recommended by the B. F. Goodrich
patent. Under these conditions, the distillate (nearly pure vinyl chloride) boils at 33 ∘C and
can be condensed with inexpensive cooling water, which is available at 25 ∘C. The bottoms
product boils at 146 ∘C, and hence, the vapor boil-up can be generated with medium-
pressure steam, which is widely available in petrochemical complexes.
Alternative separation operations can be inserted into Figure 7.4. When distillation is used,
it is also possible to recover the least volatile species, dichloroethane, from the first column,
and separate HCl from vinyl chloride in the second column. Yet another possibility is to use
a single column with a side stream that is concentrated in the vinyl-chloride product.
Absorption with water, at atmospheric pressure, can be used to remove HCl. The resulting
vapor stream, containing vinyl chloride and dichloroethane, could be dried by adsorption
and separated using distillation. With so many alternatives possible, the process designer
needs time or help to select the most promising separation operations.
Furthermore, as before, the synthesis tree in Figure 7.8 is augmented. In this case, the new
branches represent the different flowsheets for the alternative separation operations.
Clearly, as each step of the synthesis is completed, the tree represents many more possible
flowsheets.
Sub Step IV: Eliminate Differences in Temperature, Pressure, and Phase
When the reaction and separation operations are positioned, the states of their feed and
product streams are selected. This is accomplished usually by adjusting the temperature
and pressure levels to achieve the desired reaction conversions and separation factors.
Subsequently, after the flowsheets have been created, these are often adjusted toward the
economic optimum, often using the optimizers in the process simulators. In this synthesis
step, however, the states are assumed to be fixed and operations are inserted to eliminate
the temperature, pressure, and phase differences between the feed sources, the product
sinks, and the reaction and separation operations.
156
Figure 7.6 shows one possible flowsheet. It can be seen that liquid dichloroethane from the
recycle mixer at 90 ∘C and 1.5 atm undergoes the following operations:
1. Its pressure is increased to 26 atm.

2. Its temperature is raised to the boiling point, which is 242 ∘C at 26 atm.
3. Dichloroethane liquid is vaporized at 242 ∘C.
4. Its temperature is raised to the pyrolysis temperature, 500 ∘C.
Note that an alternative flowsheet would place operations 1 and 2 after operation 3.
However, this is very uneconomical, as the cost of compressing a vapor is far greater than
the cost of pumping a liquid because the molar volume of a vapor is so much greater than
that of a liquid (typically, a factor of 100 times greater). It is just one of many design heuristics
or rules of thumb.
Figure 7.6: Flowsheet with temperature-, pressure-, and phase-change operations in the vinyl-chloride process
In addition, the hot vapor effluent from the pyrolysis operation (at 500 ∘C and 26 atm) is
operated upon as follows:
1. Its temperature is lowered to its dew point, 170 ∘C at 26 atm.
2. The vapor mixture is condensed to a liquid at its bubble point, 6 ∘C at 12 atm, by
lowering the pressure and cooling and removing the latent heat of condensation.
Finally, the dichloroethane recycle stream is cooled to 90 ∘C to avoid vaporization when
mixed with the reactor effluent at 1.5 atm.
157
When positioning these operations, calculations to determine their heat duties and power
loads are often carried out using process simulators. Branches to represent the two new
flowsheets are added to the synthesis tree in Figure 7.8 after this synthesis step has been
completed.
Sub Step V: Task Integration (Conversion of BFD to PFD)
At the completion of Sub Step IV, each of the candidate flowsheets has a complete set of
operations that eliminates the differences between the raw materials and the products. Still,
with the exception of the distillation operations, specific equipment items are not shown.
“The selection of the processing units is known as task integration.”
To assist in this selection, the reader is referred to Chemical Process Equipment (Walas,
1988).
Figure 7.7 shows one example of task integration for the vinyl-chloride process. At this stage
in process synthesis, it is common to combine processing operations, leaving many
possibilities to be considered when the flowsheet is sufficiently promising to undertake the
preparation of a base-case design. As you examine this flowsheet, with the descriptions of
the process units that follow, see if you can suggest improvements.
Figure 7.7: Flowsheet showing task integration for the vinyl-chloride process
158
1. Chlorination reactor and condenser. The direct chlorination operation in Figure 7.6
is replaced by a cylindrical reaction vessel, containing a rectifying section, and a
condenser. A pool of liquid dichloroethane, with ferric chloride catalyst dissolved,
fills the bottom of the vessel at 90 ∘C and 1.5 atm. Ethylene is obtained commonly
from large cylindrical vessels, where it is stored as a gas at an elevated pressure and
room temperature, typically 1,000 psia and 70 ∘F. Chlorine, which is stored
commonly in the liquid phase, typically at 150 psia and 70 ∘F, is evaporated carefully
to remove the viscous liquid (taffy) that contaminates most chlorine produced by
electrolysis. Chlorine and ethylene in the vapor phase bubble through the liquid and
release the heat of reaction as dichloroethane is produced. This heat causes the
dichloroethane to vaporize and rise up the rectifying section into the condenser,
where it is condensed with cooling water. Note that heat is needed to drive the
reboiler in the first distillation column at 93 ∘C, but the heat of reaction cannot be
used for this purpose unless the temperature levels are adjusted. How can this be
accomplished? Most of the condensate is mixed with the effluent from the recycle
cooler to be processed in the pyrolysis loop. However, a portion is refluxed to the
rectifying section of the column, which has several trays, to recover any of the less
volatile species (e.g., trichloroethane) that may have vaporized. These heavies
accumulate at the bottom of the liquid pool and are removed periodically as
impurities.
2. Pump. Since the pressure-change operation involves a liquid, it is accomplished by
a pump, which requires only 66 Bhp, assuming an 80% efficiency. The enthalpy
change in the pump is very small and the temperature does not change by more
than 1 ∘C.
3. Evaporator. This unit, in the form of a large kettle, with a tube bundle inserted across
the bottom, performs the temperature- and phase-change operations. Saturated
steam that passes through the tubes condenses as the dichloroethane liquid is
heated to its boiling point and vaporized. The large vapor space is provided to
enable liquid droplets, entrained in the vapor, to coalesce and drop back into the
liquid pool, that is, to disengage from the vapor that proceeds to the pyrolysis
furnace.
4. Pyrolysis. This unit also performs two operations: It preheats the vapor to its reaction
temperature, 500 ∘C, and it carries out the pyrolysis reaction. The unit is constructed
of refractory brick, with natural gas-fired heaters, and a large bundle of Nickel,
Monel, or Inconel tubes, within which the reaction occurs. The tube bundle enters
the coolest part of the furnace, the so-called economizer at the top, where the
preheating occurs.
159
5. Spray quench tank and cooler. The quench tank is designed to rapidly quench the
pyrolysis effluent to avoid carbon deposition in a heat exchanger. Cold liquid
(principally dichloroethane) is showered over the hot gases, cooling them to their
dew point, 170 ∘C. As the gases cool, heat is transferred to the liquid and removed
in the adjacent cooler. The warm liquid from the pool at the base of the quench
vessel is circulated to the cooler, where it is contacted with cooling water. Any
carbon that deposits in the quench vessel settles to the bottom and is bled off
periodically. Unfortunately, this carbon deposition, as well as the corrosive HCl, is
anticipated to prevent the use of the hot effluent gases in the tubes of the
evaporator, which would have to be serviced often to remove carbon and replace
corroded tubes. Note that coke formation in the pyrolysis products is discussed by
Borsa et al. (2001). Consequently, large amounts of heat are transferred to cooling
water, and the fuel requirements for the process are high. The design team is likely
to measure the rate of carbon deposition and, if it is not very high, may decide to
implement a design with a feed/product heat exchanger.
6. Condenser. To produce a saturated liquid at 6 ∘C, the phase-change operation is
carried out by a condenser that transfers heat to a mild refrigerant. Then the
pressure is lowered to 12 atm across a valve.
7. Recycle cooler. To prevent vapor from entering the pump when the recycle stream
is mixed with effluent from the direct chlorination reactor, the recycle stream is
cooled to 90 ∘C (below the boiling point of dichloroethane at 1.5 atm) using cooling
water.
This completes the task integration in Figure 7.7. Can you suggest ways to reduce the need
for fuel and hot utilities such as steam?
Synthesis Tree
Throughout the synthesis of the vinyl-chloride process, branches have been added to the
synthesis tree in Figure 7.8 to represent the alternative flowsheets being considered. The
bold branches trace the development of just one flowsheet as it evolves in Figures 7.3–7.7.
Clearly, there are many alternative flowsheets, and the challenge in process synthesis is to
find ways to eliminate whole sections of the tree without doing much analysis. By eliminating
reaction paths 1 and 2, as much as 40% of the tree is eliminated in the first synthesis step.
Similar screening techniques are applied by the design team in every step.
To satisfy the objective of generating the most promising flowsheets, care must be taken
to include sufficient analysis in each synthesis step to check that each step does not lead to
a less profitable flowsheet or exclude the most profitable flowsheet prematurely. For this –
160
reason, it is common practice in industry to mix these synthesis steps with analysis using the
simulators.
Figure 7.8: Inverted synthesis tree for the production of vinyl chloride
Heuristics
It is important to keep in mind that, when carrying out the steps in preliminary process
synthesis, the resulting synthesis tree is closely related to any heuristics or rules of thumb
used by the design team. In the vinyl-chloride example, emphasis was placed on the
synthesis steps, not on the use of heuristics by the design team. An exception is the heuristic
that it is cheaper to pump a liquid than compress a gas. See also Conceptual Design of
Chemical Processes (Douglas, 1988) and Walas (1988), where many heuristics are presented.
161
Checking the Key Assumptions in Process Synthesis
After several promising flowsheets are synthesized, often the key assumptions are revisited
before proceeding to the next steps in process design. Returning to Figure 7.7, one
promising flowsheet for the vinyl-chloride process, a key limitation is that the cold C 2H4Cl2
stream is not heated by the pyrolysis products because the rate of carbon deposition in
such a feed/product heat exchanger is anticipated to be high, and would cause the heat
exchanger to foul with carbon. Instead, large quantities of heating utility (steam) are needed
to vaporize the C2H4Cl2 stream, and large quantities of cooling water utility are needed to
cool the hot pyrolysis products. Before adopting this design, which uses excessive amounts
of steam and cooling water, it becomes important to learn more about the rate of carbon
deposition. Perhaps the rate is sufficiently low to allow the installation of a feed/product
heat exchanger in which the carbon buildup is sufficiently low to require infrequent
maintenance for carbon removal. Even at higher rates, to remove carbon deposits
periodically, two heat exchangers could be installed in parallel, one of which would be
operated while the other is being cleaned. This would provide substantial savings in steam
and cooling-water utilities.
To check this and other assumptions, it is often desirable to construct a pilot plant that can
produce quantities of product suitable for testing and evaluation by potential customers.
Very few processes that include reaction steps are constructed without some form of pilot-
plant testing prior to doing detailed design calculations. This is an expensive, time-
consuming step that needs to be anticipated and planned for by the design team as early
as possible, so as to avoid excessive delays. Also, for the vinyl-chloride process, kinetic data
are needed for both the chlorination and pyrolysis reactors, as well as to determine the rate
of carbon deposition. In all three cases, it is unlikely that adequate data can be located in
the open literature. Consequently, unless sufficient data exist in company files or were taken
in the laboratory and judged to be adequate, pilot-plant testing is needed. Generally, pilot-
plant tests are conducted by a development team working closely with the design team.
Also, process simulators are often used during process synthesis, but this topic is entirely
devoted to a later chapter.
162
7.2.4 Step-4: Other Process Design Tasks
• Overall Mass Balances of the Process
(Approximated; As shown in Example 7.1)
• Selection of Process Stream Conditions

(In Example 7.1 these are carried out by technical knowledge and by process simulators)
• Detailed Mass and Energy Balances

(Component mass balances and overall energy balances can be best performed by ASPEN PLUS)
• Equipment Sizing and Costing

(Article 7.3 will present detailed methods of important unit operation sizing)
• Economic Evaluation
(In Example 7.1 Method of ECONOMIC POTENTIALS was discussed; More detailed calculation can be
performed by hand as well as by process simulators)
• Heat and Mass Integration

(E.g. For heat integration Technique of Pinch Analysis can also be performed by hand as well as by
process simulators)
• Environment Impact Assessment, Sustainability Analysis, and Safety Analysis

(HAZOP Analysis, Fault Tree Analysis, Event Tree Analysis, and etc. are used for this purpose)
• Process Controllability Assessment

(Steady State Simulation by ASPEN PLUS followed by Dynamic Simulation using ASPEN PLUS DYNAMICS
is the best method for controllability assessment, all these topics will be discussed later)
• Process Optimization
(It will also be discussed later in the chapter of process optimization by mathematical techniques and by
process simulators)
7.2.5 Step-5: Decision of Preliminary Flowsheet

• Flow Diagrams
✓ Block Flow Diagram (BFD)
Definition: “A diagram which reflects the whole chemical process pictorially by the use of blocks
in place of processing units.”
OR
“The block flow diagram represents the main processing sections in terms of functional blocks.
Note that the diagram also indicates the overall material balances and the conditions at each
stage, where appropriate.”
Usage: It is used for the basic understanding of material and energy flows in early process design
stages where alternative processes are usually under consideration.
Software for BFD Preparation: Microsoft Visio Professional
Example: Figure 7.9 represents BFD for Example 7.1:
163
Figure 7.9: Block flow diagram for the vinyl-chloride process
✓ Process Flow Diagram (PFD)

Definition: “A diagram which reflects the whole chemical process pictorially by the use of
equipment symbols in place of processing units.”
Usage: It is used for the detailed understanding of material and energy flows as well as for
equipment design.
Software for PFD Preparation: Microsoft Visio Professional, Edraw Max
Example: Figure 7.10 represents PFD for Example 7.1:
Figure 7.10: Process flow diagram for the vinyl-chloride process
✓ Piping and Instrumentation Diagram (P&ID)

Definition: “A diagram which reflects the whole chemical process and its associated control
systems pictorially by the use of equipment symbols and controllers in place of processing units.”
Usage: It is used for the process control system design and for process safety analysis.
Software for P&ID Preparation: Microsoft Visio Professional, Edraw Max
Example: Figure 7.11 represents a typical P&ID for heat exchanger control system:
164
Figure 7.11: Piping and Instrumentation Diagram (P&ID)
• Flow Diagram Elements

✓ Processing Units
Unit Operations (e.g. Distillation, Absorption, Adsorption etc.) and Unit
Processes (Batch Reactors, CSTR’s etc.) collectively known as processing units.
Icons used to represent processing units in PFD’s and P&ID’s are known as
Graphical Symbols. Standard Graphical Symbols for PFD’s and P&ID’s are
presented by American Society for Mechanical Engineers (ASME) and must be
followed while preparing these diagrams. Figure 7.12 represents a partial list of
these symbols. While Table 7.7 presents a complete list of symbols according to
ASME Standards 1961. More recent lists of graphical symbols according to
Microsoft Visio 2019 standards are presented in Fig. 7.13 through 7.20. Moreover,
Table 7.8 presents Graphical Symbols of PSE gPROMS Model Builder
(Commercial Process Simulator).
165
UNIT LABELING CONVENTION
Note that each unit is labeled according to the convention:
U-XYY
Where;
U = The Unit Type (Single Letter)
E.g. (V for vessel, E for exchanger, R for reactor, T for tower, P for pump
C for compressor etc.)
X = The Process Area where the unit is installed (Single Digit)
YY = The Unit Itself (Two-Digit Number)
For Example;
E-100 represents a heat exchanger number 00 which is installed in plant area 1.
Figure 7.12: Icons in process flow diagrams [8]
Complete list of standard graphical symbols is given by ASME as shown below [9]:
166
Table 7.7: ASME Standard Graphical Symbols for Processing Units
Category Graphical Symbols

Processing Lines
Feed Stock Product Connecting Lines
Crossover Line
Gate Valve Globe Valve Plug Valve

Valves
Check Valve
Process Quantities
Liquid Flowrate Mass Flowrate Gas Flowrate
Pressure Temperature
Furnaces and Boilers
“A” Frame Box Type Radiant Type (Single Coil)
Vertical Boiler Fired or Waste Heat
Water Cooled Exchanger Water Cooled Condenser Shell and Tube Exchanger
Heat Transfer Equipment
Box Cooler (Single Coil) Cooling Tower Reboiler (Kettle Type)
Reboiler (Thermo Siphon) Super Heater or Reheater Barometric Condenser
167
Compressors
Pumps and
Centrifugal Reciprocating Rotary
Proportioning Blower or Fan (Centrifugal)

Drives
Motor Engine Turbine
Steam Piston
Pressure Vessels, Columns, and
Horizontal Drums Vertical Drums Jacketed Vessel (Partial)

Reactors
Columns (Towers) Reactor (Catalytic) Reactor (Nuclear)

Dryers
Batch Trays Spray Desiccant
Continuous Tunnel Rotary Drum Dryer (Kiln)

Equipment
Handling
Material
Air Lift Belt or Shaker Bucket or Flight Conveyor
168
Screw Conveyor Roller Conveyor Feeder and Hooper
Rotary Feeder
Size Reduction Equipment
Ball Mill Grinder Roller Crusher
Screener
Blowing Egg Extractor Mixer

Processing Equipment
Settler Autoclave Kettle (Jacketed)
Rotary Film Dryer (Flaker) Jet Mixer Injector, Ejector Thickener

Separators
Centrifuge Cyclone Electrostatic Precipitator
Filter Press Drum Settler Open Settling Tank
169
Rotary Vacuum Filter
Storage Vessels
Atmospheric Tank (Cone Roof) Floating Roof Tank Gas Holder
Bulk Storage (Non-

Pressurized Storage (Sphere) Bulk Storage Vessel Pressurized)
List of graphical symbols for processing units and other process accessories according to
Microsoft Visio 2019 is given below:
Figure 7.13: Equipment - General
Figure 7.14: Equipment - Heat Exchangers
170
Figure 7.15: Equipment - Pumps
Figure 7.16: Equipment - Vessels
Figure 7.17: Process Instruments
171
Figure 7.18: Pipelines
Figure 7.19: Process Annotations
Figure 7.20: Valves and Fittings
List of graphical symbols for processing units and other process accessories according to
Process Systems Enterprise gPROMS Model Builder is given below:
172
Table 7.8: Graphical Symbols of PSE gPROMS Model Builder
Category Graphical Symbols
Source and Sink Simple Pipe Recycle Breaker
Simple Valve Non-Return Valve Junction

General
Dead End Momentum Holdup Liquid Valve
Gas Valve Actuator Pipe
Tank
Fluid Transportation
Simple Pump Centrifugal Pump Centrifugal Compressor
Liquid Header Gas Header

Heat Transfer
Heat Exchanger Pipe Heater Tubular Pipe Heater
Tubular Heater Tubular Heat Exchanger

Separation
Flash Drum Column Section Distillation Column
173
Equilibrium Reactor Kinetic Reactor Equilibrium CSTR
Reaction
Kinetic CSTR Tubular Reactor

Instrumentation
Measurement Device Flow Measurement Signal Delay
Ratio Calculator PID Controller
✓ Stream Information (Refer to Figure 7.10)

❖ Directed arcs that represent the streams with flow direction are
numbered for reference wherever possible.
❖ When streamlines cross each other an arc is made, with the vertical line
broken.
❖ Each stream is labeled on the PFD by a numbered diamond.
❖ The feed and product streams are identified by name.
❖ Mass flow rates, temperatures, pressures, and compositions may appear
on the PFD directly, but more often are placed in the stream table
instead, for clarity.
❖ The Stream Table has a column for each stream and can appear at the
bottom of the PFD or as a separate table. Here, because of formatting
limitations in this text, the stream table for the vinyl-chloride process is
presented separately in Table 7.9.
❖ At least the following entries are presented for each stream in Stream
Table:
➢ Label
➢ Temperature
➢ Pressure
➢ Vapor Fraction
174
➢ Total Mass Flowrate
➢ Total Molar Flowrate
➢ Component Molar Flowrates
❖ In addition, stream properties such as the enthalpy, density, heat
capacity, viscosity, and entropy may also be displayed.
❖ Stream tables are often completed using a process simulator.
Table 7.9: Stream Table for the Vinyl-Chloride Process in Figure 7.10
Stream Number 1 2 3 4 5 6 7 8
Temperature (oC) 25 25 90 90 91.3 242 500 170
Pressure (atm) 1.5 1.5 1.5 1.5 26 26 26 26
Vapor Fraction 1.0 1.0 0.0 0.0 0.0 1.0 1.0 1.0
Mass Flow (lb/hr) 44900 113400 158300 263800 263800 263800 263800 263800
Molar Flow (lbmol/hr) 1600 1600 1600 2667 2667 2667 4267 4267
Component Molar Flow (lbmol/hr):
Ethylene 1600 0 0 0 0 0 0 0
Chlorine 0 1600 0 0 0 0 0 0
1,2-Dichloroethane 0 0 1600 2667 2667 2667 1067 1067
Vinyl Chloride 0 0 0 0 0 0 1600 1600
Hydrogen Chloride 0 0 0 0 0 0 1600 1600
Stream Number 9 10 11 12 13 14 15 16
Temperature (oC) 6 6.5 -26.4 94.6 57.7 32.2 145.6 90
Pressure (atm) 26 12 12 12 4.8 4.8 4.8 4.8
Vapor Fraction 0.0 0.0 1.0 0.0 0.23 1.0 0.0 0.0
Mass Flow (lb/hr) 263800 263800 58300 205500 205500 100000 105500 105500
Molar Flow (lbmol/hr) 4267 4267 1600 2667 2667 1600 1067 1067
Component Molar Flow (lbmol/hr):
Ethylene 0 0 0 0 0 0 0 0
Chlorine 0 0 0 0 0 0 0 0
1,2-Dichloroethane 1067 1067 0 1067 1067 0 1067 1067
Vinyl Chloride 1600 1600 0 1600 1600 1600 0 0
Hydrogen Chloride 1600 1600 1600 0 0 0 0 0
✓ Utilities
As shown in Figure 7.10, various utility streams are utilized for heating or cooling
the process streams. Each utility is selected according to the temperature level
of the required utility. A list of heating and cooling utilities, with temperature
ranges, and the abbreviations commonly used on PFDs is presented in Table
7.10.
175
Table 7.10: Heating and Cooling Utilities-Identifiers and Temperature Ranges
Identifier Utility Typical Operating Range
Hot Utilities – In increasing Cost per BTU

lps Low-pressure steam, 15 to 30 psig 250 to 275 ∘F
mps Medium-pressure steam, 100 to 150 psig 325 to 366 ∘F
hps High-pressure steam, 400 to 600 psig 448 to 488 ∘F
fo Fuel oils
fg Fuel gas Process waste stream
po Petroleum oils Below 600 ∘F
dt Dowtherms Below 750 ∘F
Cold Utilities – In increasing Cost per BTU
bfw Boiler feed water Used to raise process steam
ac Air cooling Supply at 85 to 95 ∘F - Temperature approach 4 ∘F
rw River water Supply at 80 to 90 ∘F (from cooling tower), return at 110
∘F
cw Cooling water Supply at 80 to 90 ∘F (from cooling tower), return at 115

to 125 ∘F
cw Chilled water 45 to 90 ∘F
rb Refrigerated brine 0 to 50 ∘F
pr Propane refrigerant –40 to 20 ∘F
✓ Equipment Summary Table

❖ This provides information for each equipment item in the PFD, with the
kind of information typically provided for each type of unit shown in Table
7.11.
Table 7.11: Equipment Summary Specifications
Equipment Type Required Specifications

Reactors and Vessels Height; diameter; orientation; pressure; temperature; materials of construction (MOC)
Columns Height; diameter; orientation; pressure; temperature; number of trays and type of trays;
height and type of packing; MOC
Pumps Driver type; flow; suction and discharge pressures; temperature; shaft power; MOC
Compressors Driver type; inlet flow; suction and discharge pressures; temperature; shaft power; MOC
Heat Exchangers Type; area; duty; number of shell and tube passes; for both shell and tubes: operating
temperature; pressure; pressure drop; and MOC
Fired Heaters Type; tube pressure and temperature; duty; radiant; and convective heat transfer area;
MOC
❖ Note that the materials of construction (MOC), and operating

temperature and pressure, are required for all units. Consult Perry’s
176
Chemical Engineers Handbook 8th Ed. Section-25 for the selection of
materials of construction.
In summary, the Block Flow Diagram (BFD) is the base of any chemical process
conceptualized, while the Process Flow Diagram (PFD) is the most definitive
process design document, encapsulating much of the design information. As
such, it is used and updated throughout the process design. However, it lacks
many details required to begin the construction engineering work for the plant.
Many of these details are transmitted in a Piping and Instrumentation Diagram
(P&ID). Typical examples of real industrial BFD, PFD, and P&ID are shown in
Figure 7.21 through 7.23:
7.2.6 Step-6: Perform Process Simulation

• Commercial Process Simulators (For Details Consult Chapter-12)
✓ Aspen Plus ®
https://www.aspentech.com/en/products/engineering/aspen-plus
✓ Aspen HYSYS ®
https://www.aspentech.com/en/products/engineering/aspen-hysys
✓ UniSim ® Design Suite

https://www.honeywellprocess.com/en-US/online_campaigns/unisim-design/Pages/index.html
✓ PRO/II ® Process Engineering

https://sw.aveva.com/engineer-procure-construct/process-engineering-and-simulation/pro-ii-
process-engineering
✓ PSE gPROMS Model Builder ®

https://www.psenterprise.com/products/gproms/modelbuilder
✓ COMSOL Multiphysics ®
https://www.comsol.com/products
177
Figure 7.21: Block flow diagram of the revamp of a 30,000 Bbl/day refinery with supplementary light stocks [10]
178
Figure 7.22: Piping and instrumentation diagram for the manufacture of benzene by dealkylation of toluene [10]
179
Figure 7.23: P&ID for the reaction section of dealkylation of benzene plant [10]
180
7.3 Plant Design
In plant design part of process synthesis, equipment dimensions are calculated by shortcut as
well as by rigorous methods of design.
181
Chapter-8
Process Intensification
Process Intensification
8.0 Introduction
Coming soon.
182
Chapter-9
Process Optimization
Optimization of Chemical Processes
9.0 Introduction
Coming soon.
183
Chapter-10
Process Control
Advanced Process Control
10.0 Introduction
Coming soon.
184
Chapter-11
Process Safety
Advanced Process Safety
11.0 Introduction
Coming soon.
185
Section-III
Specialization in Process Systems Engineering
Process Modelling
and Simulation
186
Chapter-12
Process Modelling and Simulation
Mathematical Modelling of Chemical Processes
12.0 Introduction
Coming soon.
187
Appendices
List of Appendices:
Appendix-A: Scientific and Mathematical Constants
Appendix-B: Conversion Factors
Appendix-C: Mathematical Formulas
Appendix-D: Thermodynamics Data
Appendix-E: Reaction Kinetics Data
Appendix-F: Transport Processes Data
Appendix-G: Process Synthesis Data
Appendix-H: Process Intensification Data
Appendix-I: Process Optimization Data
Appendix-J: Process Control Data
Appendix-K: Process Safety Data
Appendix-K: Process Modelling and Simulation Data
188
Appendix-A:
Scientific and Mathematical Constants
Table-1: ….
Table-2: ….
189
Appendix-B:
Conversion Factors
Table-1: …
Table-2: …
190
Appendix-C:
Mathematical Formulas
Table-1: ….
Table-2: ….
191
Appendix-D:
Thermodynamics Data
Table-1: ….
Table-2: ….
192
Appendix-E:
Reaction Kinetics Data
Table-1: ….
Table-2: ….
193
Appendix-F:
Transport Processes Data
Table-F.1: Intermolecular force parameters and critical properties

Table-F.2: Functions for prediction of transport properties of gases at low densities
Table-F.1: Intermolecular force parameters and critical properties
Lennard-Jones parameters Critical properties

Molecular Pc,i V
̃c,i
Weight (Mi) σi ϐi/κ Tc,i
Substance (Pa) (m /kgmol)
3
(kg/kgmol) (Å) (K) (K)

x 101325 x 10-3
Light elements:
H2 2.02 2.915 38.0 33.3 12.8 65.0
He 4.00 2.576 10.2 5.3 2.3 57.8
Noble gases:
Ne 20.18 2.789 35.7 44.5 26.9 41.7
Ar 39.95 3.432 122.4 150.7 48.0 75.2
Kr 83.80 3.675 170.0 209.4 54.3 92.2
Xe 131.30 4.009 234.7 289.8 58.0 118.8
Simple polyatomic gases:
Air 28.97 3.617 97.0 132.0 36.4 86.6
N2 28.01 3.667 99.8 126.2 33.5 90.1
O2 32.00 3.433 113.0 154.4 49.7 74.4
CO 28.01 3.590 110.0 132.9 34.5 93.1
CO2 44.01 3.996 190.0 304.2 72.8 94.1
NO 30.01 3.470 119.0 180.0 64.0 57.0
N2O 44.01 3.879 220.0 309.7 71.7 96.3
SO2 64.06 4.026 363.0 430.7 77.8 122.0
F2 38.00 3.653 112.0 - - -
Cl2 70.91 4.115 357.0 417.0 76.1 124.0
Br2 159.82 4.268 520.0 584.0 102.0 144.0
I2 253.81 4.982 550.0 800.0 - -
Hydrocarbons:
CH4 16.04 3.780 154.0 191.1 45.8 98.7
CH≡CH 26.04 4.114 212.0 308.7 61.6 112.9
CH2=CH2 28.05 4.228 216.0 282.4 50.0 124.0
C2H6 30.07 4.388 232.0 305.4 48.2 14.0
CH3C≡CH 40.06 4.742 261.0 394.8 - -
CH3CH=CH2 42.08 4.766 275.0 365.0 45.5 181.0
C3H8 44.10 4.934 273.0 369.8 41.9 200.0
194
n-C4H10 58.12 5.604 304.0 425.2 37.5 255.0
i-C4H10 58.12 5.393 295.0 408.1 36.0 263.0
n-C5H12 72.15 5.850 326.0 469.5 33.2 311.0
i-C5H12 72.15 5.812 327.0 460.4 33.7 306.0
C(CH3)4 72.15 5.759 312.0 433.8 31.6 303.0
n-C6H14 86.18 6.264 342.0 507.3 29.7 370.0
n-C7H16 100.20 6.663 352.0 540.1 27.0 432.0
n-C8H18 114.23 7.035 361.0 568.7 24.5 492.0
n-C9H20 128.26 7.463 351.0 594.6 22.6 548.0
Cyclohexane 84.16 6.143 313.0 553.0 40.0 308.0
Benzene 78.11 5.443 387.0 562.6 48.6 260.0
Other organic compounds:
CH3Cl 50.49 4.151 355.0 416.3 65.9 143.0
CH2Cl2 84.93 4.748 398.0 510.0 60.0 -
CHCl3 119.38 5.389 340.0 536.6 54.0 240.0
CCl4 153.82 5.947 323.0 556.4 45.0 276.0
C 2N2 52.04 4.361 349.0 400.0 59.0 -
COS 60.07 4.130 336.0 378.0 61.0 -
CS2 76.14 4.483 467.0 552.0 78.0 170.0
CCl2F2 120.92 5.116 280.0 384.7 39.6 218.0
Table-F.2: Functions for prediction of transport properties of gases at low densities
κT/ϐi Ωμ,i κT/ϐi Ωμ,i

(Unitless) (Unitless) (Unitless) (Unitless)
0.30 2.8400 2.70 1.0691
0.35 2.6760 2.80 1.0583
0.40 2.5310 2.90 1.0482
0.45 2.4010 3.00 1.0388
0.50 2.2840 3.10 1.0300
0.55 2.1780 3.20 1.0217
0.60 2.0840 3.30 1.0139
0.65 1.9990 3.40 1.0066
0.70 1.9220 3.50 0.9996
0.75 1.8530 3.60 0.9931
0.80 1.7900 3.70 0.9868
0.85 1.7340 3.80 0.9809
0.90 1.6820 3.90 0.9753
0.95 1.6360 4.00 0.9699
1.00 1.5930 4.10 0.9647
1.05 1.5540 4.20 0.9598
1.10 1.5180 4.30 0.9551
1.15 1.4850 4.40 0.9506
1.20 1.4550 4.50 0.9462
1.25 1.4270 4.60 0.9420
1.30 1.4010 4.70 0.9380
1.35 1.3770 4.80 0.9341
195
1.40 1.3550 4.90 0.9304
1.45 1.3340 5.00 0.9268
1.50 1.3150 6.00 0.8962
1.55 1.2970 7.00 0.8727
1.60 1.2800 8.00 0.8538
1.65 1.2640 9.00 0.8380
1.70 1.2490 10.00 0.8244
1.75 1.2350 12.00 0.8018
1.80 1.2220 14.00 0.7836
1.85 1.2090 16.00 0.7683
1.90 1.1980 18.00 0.7552
1.95 1.1860 20.00 0.7436
2.00 1.1760 25.00 0.7198
2.10 1.1560 30.00 0.7010
2.20 1.1380 35.00 0.6854
2.30 1.1220 40.00 0.6723
2.40 1.1070 50.00 0.6510
2.50 1.0933 75.00 0.6140
2.60 1.0807 100.00 0.5887
196
References
1. UET, Chemical Engineering Postgraduate Curriculum. 2016.

2. Cambridge. Process Systems Engineering (PSE): An overview. 1995; Available from:
https://www.ceb.cam.ac.uk/research/groups/rg-pse.
3. Fogler, H.S., Elements of Chemical Reaction Engineering. 5th. ed. 2016: Prentice Hall.
4. Smith, J.M., Introduction to Chemical Engineering Thermodynamics. 8th ed. 2017.
5. Atkins, P., Physical Chemistry. 11th ed. 2018.
6. Bird, R.B., Transport Phenomena. 2nd. ed. 2002: John Wiley & Sons, Inc.
7. Himmelblau, D.M., Basic Principles and Calculations in Chemical Engineering. 7th ed. 2004: Prentice Hall
International Series.
8. Seider, W.D., Product and Process Design Principles. 2017.
9. ASME, Graphical Symbols for Process Flow Diagrams. 1961.
10. Walas, S.M., Chemical Process Equipment. 3rd. ed. 2012.
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Advanced Process Engineering

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Advanced Process Engineering

For Graduate and Undergraduate Students…

Dr. Nadeem Feroze

University of Engineering and Technology (UET) Lahore

Department of Chemical Engineering

Dr. Nadeem Feroze

Engr. Anees Ahmad

Dr. Engr. Nadeem Feroze

Engr. Anees Ahmad

Symbols (Applicable for all Chapters):

Symbol Description Unit

Reaction Engineering Symbols

Transport Phenomena Symbols

~ Tilde on a symbol denotes a property value per unit mole

1.0 Introduction to Chemical Engineering (CE)

Areas of Chemical Engineering Main Branches of Chemical

Figure 1.1: Branches of Chemical Engineering*

1.0.2 Energy Engineering

1.0.3 Biochemical Engineering

2.0 Introduction to Process Engineering (PE)

Core Areas of Process Engineering[1]

• Mathematics → Maps to the course of Chemical Engineering Mathematics

Specialization Areas of Process Engineering[1]

• Process Synthesis → Maps to the course of Computer-Aided Process Synthesis

Branches of Process Engineering

• Process Systems Engineering

2.1.3 Reaction Engineering

2.1.4 Transport Phenomena

2.2 Specialization Areas

2.2.1 Process Synthesis

2.2.2 Process Intensification

2.2.3 Process Optimization

2.2.4 Process Control

2.3 Introduction to Process Systems Engineering (PSE)

Areas of Process Systems Engineering

• Process Modelling and Simulation

2.3.1 Process Modelling and Simulation

Process Engineering Energy Engineering Biochemical Engineering

Figure 2.2: Area and branch and diagram

• To study the effects of Catalysts on Reaction Rate

5.1 Generalized View of Chemical Reactor Design

• Thermodynamic Operation Consideration (Isothermal, Adiabatic, or Non-Isothermal)

Figure 5.1: Possible Reactor Design Scenarios

With respect to Thermodynamic Operation Consideration:

• If thermodynamic operation is isothermal, then there is no need to include the energy

With respect to Fluid Dynamics Consideration:

With respect to Reaction Engineering Consideration:

With respect to Fluid Phase Consideration:

With respect to Operating Mode Consideration:

5.2 General Mole Balance Equation (G.M.B.E.)

System Volume (V)

Figure 5.2: Mole balance on species “i” in a system of volume V

Figure 5.3: Dividing up the system volume, V

Gi =∆Gi1 +∆Gi2 +∆Gi3 …+∆Gi,n = ∑ ∆Gik

lim Gi = lim ∑ rik ∆Vi

Using definition of integral:

By putting Eq. 5.2.3 in 5.2.2:

Nin = Total number of inlets of the reactor

• Batch Reactor (BR) [Batch Operation]

5.3.1 Mole Balance for Batch Reactor (BR)

Figure 5.4: Batch Reactor (BR)

5.3.2 Mole Balance for Continuous Stirred Tank Reactor (CSTR)

Figure 5.5: Continuous Stirred Tank Reactor (CSTR)