Chemical

Process
Calculations
D.C. Sikdar
Chemical Process Calculations

D.C. SIKDAR
Associate Professor
Department of Chemical Engineering
Dayananda Sagar College of Engineering
Bangalore

Delhi-110092
2013
CHEMICAL PROCESS CALCULATIONS
D.C. Sikdar

© 2013 by PHI Learning Private Limited, Delhi. All rights reserved. No part of this book may be
reproduced in any form, by mimeograph or any other means, without permission in writing from
the publisher.

ISBN-978-81-203-4782-3

The export rights of this book are vested solely with the publisher.

Published by Asoke K. Ghosh, PHI Learning Private Limited, Rimjhim House, 111, Patparganj
Industrial Estate, Delhi-110092 and Printed by Raj Press, Delhi-110012.
 To
My wife BULU, son ATANU
and Parents
for their Love, Understanding and Support
 Contents

Foreword........................................................................................................................................ix
Preface............................................................................................................................................xi
Acknowledgements....................................................................................................................... xiii
List of Symbols.............................................................................................................................. xv

1.  Units and Dimensions......................................................................................................1–30

1.1 Introduction...................................................................................................................1
1.2 Fundamental and Derived Units...................................................................................1
1.2.1  Fundamental Quantities....................................................................................2
1.2.2  Derived Quantities............................................................................................2
1.3 System of Units............................................................................................................2
1.4 Conversion of Units......................................................................................................3
1.5 Dimensional Consistency of Equations.......................................................................8
1.6 Dimensional Equations.................................................................................................9
1.7 Dimensionless Group and Constant.............................................................................9
1.8 Dimensionless Equation..............................................................................................10
1.9 Dimensional Analysis.................................................................................................11
1.9.1  Rayleigh’s Method..........................................................................................12
1.9.2 Buckingham’s r-method................................................................................12
1.10 Conversion of Equation..............................................................................................16
1.11 Graphical Method of Integration................................................................................19
1.12 Least Square Method..................................................................................................20
1.13 Curve Fitting...............................................................................................................21
1.14 Regression...................................................................................................................22
Exercises.................................................................................................................................23

2. Basic Chemical Calculations......................................................................................31–112

2.1 Introduction.................................................................................................................31
2.2 Concept of Atom........................................................................................................32
2.3 Moles and Mole Fraction...........................................................................................33
2.4 Method of Expressing the Composition of Mixtures...............................................34
2.5 Equivalent Weight.......................................................................................................40
v
 vi Contents

2.6 Concept of Normality, Molarity and Molality..........................................................43

2.6.1 Normality........................................................................................................43
2.6.2 Molarity...........................................................................................................43
2.6.3 Molality...........................................................................................................43
2.7 Concept of PPM (Parts Per Million).........................................................................51
2.8 Application of Different Types of Graph..................................................................52
2.8.1 Ordinary Graph...............................................................................................52
2.8.2 Semi-log Graph..............................................................................................53
2.8.3 Log-Log Graph...............................................................................................54
2.8.4 Triangular Graph............................................................................................55
2.9 Gases............................................................................................................................56
2.9.1 Ideal Gas Law................................................................................................57
2.10 Dalton’s Law...............................................................................................................58
2.10.1 Partial Pressure...............................................................................................58
2.11 Amagat’s Law.............................................................................................................59
2.11.1 Pure Component Volume...............................................................................59
2.12 Gaseous Mixtures........................................................................................................59
2.13 Relationship between Partial Pressure, Mole Fraction of Component
Gas to Total Pressure.................................................................................................59
2.14 Average Molecular Weight of Gas Mixture..............................................................61
2.15 Density of Gas Mixture..............................................................................................61
2.16 Non-ideal Behaviour of Gases...................................................................................62
2.17 Gas–Liquid System.....................................................................................................65
2.17.1 Raoult’s Law..................................................................................................65
2.17.2 Henry’s Law...................................................................................................66
2.18 Vapour Pressure..........................................................................................................66
2.18.1 Saturated Vapour Pressure.............................................................................66
2.18.2 Unsaturated Vapour Pressure.........................................................................67
2.18.3 Boiling Point...................................................................................................67
2.18.4 Normal Boiling Point.....................................................................................67
2.18.5 Effect of Temperature on Vapour Pressure..................................................67
2.19 Vapour Pressure of Immiscible Liquid Mixture.......................................................78
2.19.1 Hansbrand Chart.............................................................................................78
2.20 Cox Chart....................................................................................................................78
2.21 Non-volatile Solution..................................................................................................80
2.22 Relative Vapour Pressure...........................................................................................80
2.23 Humidity......................................................................................................................81
2.23.1 Saturated Humidity.........................................................................................82
2.23.2 Percentage of Humidity.................................................................................82
2.23.3 Relative Humidity..........................................................................................83
2.23.4 Humid Volume...............................................................................................83
2.23.5 Humid Heat....................................................................................................83
2.23.6 Dew Point (D.P.)............................................................................................83
 Contents vii

2.23.7 Dry Bulb Temperature...................................................................................83

2.23.8 Wet Bulb Temperature...................................................................................83
2.24 Humidity Chart...........................................................................................................84
2.24.1 Humidity vs Temperature Curve...................................................................84
2.24.2 Humidity vs Humid Heat Line......................................................................84
2.24.3 Specific Volume vs Temperature Line.........................................................85
2.24.4 Adiabatic Cooling Lines................................................................................85
2.24.5 Application of Humidity Chart......................................................................86
2.25 Humidification.............................................................................................................88
2.26 Dehumidification.........................................................................................................89
2.26.1 Mechanism of Dehumidification...................................................................89
2.26.2 Approaches to Dehumidification...................................................................91
Exercises...............................................................................................................................100

3. Material Balance without Chemical Reactions.....................................................113–168

3.1 Introduction...............................................................................................................113
3.2 Classification of Material Balance without Chemical Reaction.............................113
3.3 Guidelines for Material Balance without Chemical Reactions..............................114
3.4 Various Important Operations Carried Out in Industry..........................................114
3.4.1 Distillation.....................................................................................................115
3.4.2 Absorption.....................................................................................................119
3.4.3 Extraction......................................................................................................125
3.4.4 Crystallization...............................................................................................128
3.4.5 Drying...........................................................................................................135
3.4.6 Mixing...........................................................................................................139
3.4.7 Evaporation...................................................................................................144
3.5 Bypass Operation......................................................................................................148
3.6 Recycle Operation.....................................................................................................152
3.7 Purging Operation.....................................................................................................155
Exercises...............................................................................................................................156

4. Material Balance with Chemical Reactions...........................................................169–234

4.1 Introduction...............................................................................................................169
4.2 Principle of Stoichiometry........................................................................................169
4.2.1  Stoichiometric Coefficient............................................................................170
4.2.2  Stoichiometric Ratio.....................................................................................170
4.2.3  Stoichiometric Proportion.............................................................................170
4.3 Limiting Reactants....................................................................................................171
4.4 Excess Reactant.........................................................................................................171
4.4.1  Percentage of Excess Reactants...................................................................171
4.5 Inerts..........................................................................................................................172
4.6 Percentage Conversion..............................................................................................173
4.7 Percentage Yield.......................................................................................................173
 viii Contents

4.8 Selectivity..................................................................................................................174
4.9 Material Balance with Single Chemical Reaction..................................................174
4.10 Material Balance with Multiple Chemical Reaction...............................................175
4.11 Bypass Operation......................................................................................................175
4.12 Recycle Operation.....................................................................................................176
4.13 Purging Operation.....................................................................................................176
Exercises...............................................................................................................................223
5.  Combustion of Fuels ...................................................................................................235–279
5.1 Introduction...............................................................................................................235
5.1.1  Solid Fuels.....................................................................................................235
5.1.2  Liquid Fuels..................................................................................................235
5.1.3  Gaseous Fuels...............................................................................................236
5.2 Calorific Value of Fuels...........................................................................................237
5.3 Analysis of Fuel........................................................................................................238
5.3.1  Ultimate Analysis..........................................................................................238
5.3.2  Proximate Analysis.......................................................................................238
Exercises...............................................................................................................................272
6. Energy Balances.........................................................................................................280–330
6.1 Introduction...............................................................................................................280
6.1.1  Internal Energy..............................................................................................280
6.1.2  Kinetic Energy..............................................................................................280
6.1.3  Potential Energy............................................................................................281
6.2 General Steady State Energy Balance Equation.....................................................281
6.3 Thermophysics...........................................................................................................282
6.4 Thermochemistry.......................................................................................................282
6.5 Heat Capacity............................................................................................................283
6.5.1  Heat Capacity at Constant Pressure.............................................................283
6.5.2  Heat Capacity at Constant Volume.............................................................286
6.6 Enthalpy.....................................................................................................................286
6.6.1  Heat of Formation.........................................................................................287
6.6.2  Heat of Reaction...........................................................................................287
6.6.3  Heat of Combustion......................................................................................288
6.7 Heat of Solution........................................................................................................288
6.8 Heat of Mixing..........................................................................................................289
6.9 Heat of Crystallization..............................................................................................289
6.10 Flame Temperature...................................................................................................289
6.11 Heat of Condensation...............................................................................................289
6.12 Heat of Vaporisation.................................................................................................290
6.13 Hess’s Law................................................................................................................290
Exercises...............................................................................................................................319
Bibliography................................................................................................................................331
Index....................................................................................................................................333–335
 Foreword

Chemical Process Calculations is one of the core courses at the undergraduate level of Chemical
Engineering curriculum. In this course, more emphasis is given on the units and conversions,
basic concept of calculations, material balance with or without chemical reactions, combustion
of fuels and energy balances.
Professor D.C. Sikdar has written this book on Chemical Process Calculations with his
vast experience in teaching and research. He has received awards from the Government of
Karnataka for guiding M.Tech. thesis in the field of Bio-fuel. Professor Sikdar is well known
for his teaching skills. He has taken a keen interest in writing this book.
This book is meant to provide the fundamental concepts and practical tools needed by all
Chemical Engineers, regardless of the particular area they eventually enter. The chapters and
topics are organized in a systematic way in order that the students get a thorough knowledge
and understanding of the subject.
I strongly recommend the student to make use of this book and learn Chemical Process
Calculations in a very easy way.

Dr. R. RAVISHANKAR
Professor and Head
Department of Chemical Engineering
Dayananda Sagar College of Engineering
Bangalore

ix
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