A Textbook of

Chemical
Engineering
Thermodynamics
K.V. Narayanan
 A Textbook of
Chemical Engineering Thermodynamics
 A Textbook of
Chemical Engineering
Thermodynamics
SECOND EDITION

K.V. NARAYANAN
Former Professor and Head
Department of Chemical Engineering
and
Former Principal
Government Engineering College
Thrissur, Kerala

Delhi-110092
2013
A TEXTBOOK OF CHEMICAL ENGINEERING THERMODYNAMICS, Second Edition
K.V. Narayanan

© 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-978-81-203-4747-2

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

Seventeenth Printing (Second Edition) ... ... ... May, 2013

Published by Asoke K. Ghosh, PHI Learning Private Limited, Rimjhim House, 111, Patparganj
Industrial Estate, Delhi-110092 and Printed by Mohan Makhijani at Rekha Printers Pvt. Ltd.,
New Delhi-110020.
 Contents

Preface xiii
Preface to the First Edition xv

1. INTRODUCTION AND BASIC CONCEPTS 1–23

1.1 Scope and Limitations of Thermodynamics 1
1.2 Definitions and Fundamental Concepts 2
1.2.1 Systems and Processes 2
1.2.2 Homogeneous and Heterogeneous Systems 3
1.2.3 Closed and Open Systems 3
1.2.4 State and Properties 3
1.2.5 Intensive and Extensive Properties 4
1.2.6 State and Path Functions 4
1.3 Force, Pressure and Energy 5
1.3.1 Force 5
1.3.2 Pressure 5
1.3.3 Energy 6
1.4 Equilibrium State and the Phase Rule 10
1.4.1 Steady State 10
1.4.2 Equilibrium State 10
1.4.3 Phase Rule 11
1.5 Temperature and Zeroth Law of Thermodynamics 11
1.5.1 Zeroth Law 11
1.5.2 Temperature 11
1.5.3 Ideal Gas Temperature Scale 12
1.6 Heat Reservoirs and Heat Engines 14
1.6.1 Heat Reservoir 14
1.6.2 Heat Engine 14
1.6.3 Heat Pump 15
1.7 Reversible and Irreversible Processes 16
Summary 20
Review Questions 21
Exercises 22

2. FIRST LAW OF THERMODYNAMICS 24–48

2.1 General Statements of First Law of Thermodynamics 24
2.2 First Law of Thermodynamics for Cyclic Process 25
2.3 Internal Energy 25
v
vi Contents

2.4 First Law of Thermodynamics for Non-flow Process 26

2.5 Enthalpy 31
2.6 First Law of Thermodynamics for Flow Process 34
2.7 Heat Capacity 40
Summary 44
Review Questions 44
Exercises 45

3. P-V-T BEHAVIOUR AND HEAT EFFECTS 49–88

3.1 P-V-T Behaviour of Pure Fluids 49
3.2 Equations of State and the Concept of Ideal Gas 51
3.3 Processes involving Ideal Gases 52
3.3.1 Constant Volume Process 52
3.3.2 Constant Pressure Process 53
3.3.3 Constant Temperature Process 54
3.3.4 Adiabatic Process 55
3.3.5 Polytropic Process 57
3.4 Equations of State for Real Gases 60
3.4.1 Limiting Conditions 61
3.4.2 van der Waals Equation 61
3.4.3 Redlich–Kwong Equation 63
3.4.4 Redlich–Kwong–Soave Equation 64
3.4.5 Peng–Robinson Equation 64
3.4.6 Benedict–Webb–Rubin Equation 64
3.4.7 Virial Equation 65
3.5 Compressibility Charts 67
3.5.1 Principle of Corresponding States 68
3.5.2 Generalised Compressibility Charts 69
3.6 Heat Effects accompanying Chemical Reactions 69
3.6.1 The Standard Heat of Reaction 69
3.6.2 The Standard Heat of Combustion 70
3.6.3 The Standard Heat of Formation 70
3.6.4 Hess’s Law of Constant Heat Summation 71
3.6.5 Effect of Temperature on Standard Heat of Reaction 72
3.6.6 Temperature of Reaction 77
Summary 79
Review Questions 80
Exercises 81

4. SECOND LAW OF THERMODYNAMICS 89–125

4.1 Limitations of the First Law of Thermodynamics 89
4.1.1 Direction of Change 89
4.1.2 Qualitative Difference between Heat and Work 90
4.2 General Statements of the Second Law of Thermodynamics 90
4.2.1 The Equivalence of the Kelvin and Clausius Statements 91
 Contents vii

4.3 Entropy 92
4.3.1 Why the Concept of Entropy? 92
4.3.2 Entropy and Heat 93
4.3.3 Entropy and Temperature 94
4.3.4 Entropy and the Nature of the Process 94
4.4 The Carnot Principle 95
4.4.1 Thermodynamic Temperature Scale 97
4.4.2 Ideal Gas as the Carnot Engine Working Substance 98
4.5 Entropy—A State Function 101
4.6 Calculation of Entropy Changes 103
4.6.1 Phase Change 103
4.6.2 Processes Involving Ideal Gases 103
4.6.3 Adiabatic Mixing Process 105
4.6.4 Isothermal Mixing of ideal Gases 106
4.6.5 Chemical Reactions 107
4.7 Clausius Inequality 108
4.8 Mathematical Statement of the Second Law of Thermodynamics 111
4.9 Entropy and Irreversibility 115
4.10 Statistical Explanation for Entropy 118
4.11 Third Law of Thermodynamics 118
Summary 120
Review Questions 121
Exercises 122

5. SOME APPLICATIONS OF THE LAWS OF THERMODYNAMICS 126–205

5.1 Flow Processes 126
5.1.1 Continuity Equation 126
5.1.2 Energy Equation 127
5.1.3 Flow in Pipes 135
5.1.4 Flow through Nozzles 137
5.1.5 Ejectors 142
5.1.6 Throttling Process (Joule–Thomson Expansion) 143
5.1.7 Compressors 143
5.2 Refrigeration 151
5.2.1 Coefficient of Performance (COP) 152
5.2.2 Refrigerator Capacity 152
5.2.3 Carnot Cycle 152
5.2.4 Vapour-compression Cycle 154
5.2.5 Choice of Refrigerant 159
5.2.6 Air-refrigeration Cycle 161
5.2.7 Absorption Refrigeration 163
5.2.8 Heat Pumps 165
5.3 Liquefaction Processes 166
5.3.1 Vaporisation of Liquid 166
5.3.2 Free Expansion 167
5.3.3 Isentropic Expansion 168
viii Contents

5.4 The Steam-Power Plant 170

5.4.1 Rankine Cycle 171
5.4.2 Reheat Cycle 174
5.4.3 Regenerative Cycle 177
5.5 Internal Combustion Engines 180
5.5.1 Otto Cycle 180
5.5.2 Diesel Cycle 183
5.5.3 Dual Cycle 187
5.6 Gas-turbine Power Plant 188
5.6.1 Brayton Cycle 189
Summary 191
Review Questions 192
Exercises 193

6. THERMODYNAMIC PROPERTIES OF PURE FLUIDS 206–272

6.1 Classification of Thermodynamic Properties 206
6.1.1 Reference Properties 206
6.1.2 Energy Properties 206
6.1.3 Derived Properties 207
6.2 Work Function (Helmholtz Free Energy) 207
6.3 Gibbs Free Energy 208
6.4 Relationships among Thermodynamic Properties 209
6.4.1 Exact Differential Equations 209
6.4.2 Fundamental Property Relations 210
6.4.3 Maxwell’s Equations 211
6.4.4 Clapeyron Equation 213
6.4.5 Entropy–Heat Capacity Relationships 215
6.4.6 Differential Equations for Entropy 216
6.4.7 Modified Equations for U and H 217
6.4.8 Effect of Temperature, Pressure and Volume on U, H and S 220
6.4.9 Relationship between CP and CV 226
6.4.10 Ratio of Heat Capacities 229
6.4.11 Effect of Pressure and Volume on CP and CV 229
6.4.12 Joule–Thomson Coefficient 233
6.4.13 Gibbs–Helmholtz Equation 235
6.5 Method of Jacobians 236
6.5.1 Properties of Jacobians 237
6.5.2 Thermodynamic Relations through the Method of Jacobians 238
6.6 Fugacity 244
6.6.1 Standard State for Fugacity 245
6.6.2 Fugacity Coefficient 246
6.6.3 Effect of Temperature and Pressure on Fugacity 246
6.6.4 Determination of Fugacity of Pure Gases 247
6.6.5 Fugacities of Solids and Liquids 254
6.7 Activity 255
6.7.1 Effect of Pressure and Temperature on Activity 256
 Contents ix

6.8 Departure Functions and Generalised Charts 256

6.9 Thermodynamic Diagrams 259
6.9.1 Types of Diagrams 259
6.9.2 Construction of Thermodynamic Diagrams 262
Summary 265
Review Questions 265
Exercises 267

7. PROPERTIES OF SOLUTIONS 273–328

7.1 Partial Molar Properties 273
7.1.1 Physical Meaning of Partial Molar Properties 274
7.1.2 Partial Molar Properties and Properties of Solution 276
7.1.3 Determination of Partial Molar Properties 279
7.2 Chemical Potential 284
7.2.1 Effect of Temperature and Pressure on Chemical Potential 285
7.3 Fugacity in Solutions 288
7.3.1 Fugacity in Gaseous Solutions 288
7.3.2 Lewis–Randall Rule 290
7.3.3 Fugacities in Liquid Solutions 291
7.3.4 Ideal Solutions and Raoult’s Law 292
7.4 Henry’s Law and Dilute Solutions 293
7.4.1 Ideal Behaviour of Real Solutions 293
7.4.2 Henry’s Law and Gas Solubility 294
7.5 Activity in Solutions 296
7.5.1 Selection of Standard States 296
7.6 Activity Coefficients 297
7.6.1 Effect of Pressure on Activity Coefficients 299
7.6.2 Effect of Temperature on Activity Coefficients 299
7.7 Gibbs–Duhem Equations 302
7.8 Property Changes of Mixing 307
7.8.1 Activity and Property Change of Mixing 308
7.8.2 Property Changes of Mixing for Ideal Solutions 310
7.9 Heat Effects of Mixing Processes 311
7.10 Excess Properties 317
7.10.1 Excess Gibbs Free Energy 318
Summary 320
Review Questions 321
Exercises 322

8. PHASE EQUILIBRIA 329–424

8.1 Criteria of Phase Equilibrium 330
8.2 Criterion of Stability 332
8.3 Phase Equilibria in Single-component Systems 335
8.4 Phase Equilibria in Multicomponent Systems 338
8.5 Phase Rule for Non-reacting Systems 341
8.6 Duhem’s Theorem 343
x Contents

8.7 Vapour–Liquid Equilibria 344

8.8 Phase Diagrams for Binary Solutions 346
8.8.1 Constant-pressure Equilibria 346
8.8.2 Constant-temperature Equilibria 350
8.9 Vapour–Liquid Equilibria in Ideal Solutions 351
8.10 Non-ideal Solutions 361
8.10.1 Azeotropes 364
8.11 Vapour–Liquid Equilibria (VLE) at Low Pressures 368
8.11.1 Activity Coefficient Equations 369
8.12 Vapour–Liquid Equilibria involving High Pressures and
Multicomponent Systems 386
8.12.1 Equations of State Approach 386
8.12.2 Vaporisation Equilibrium Constants 387
8.12.3 Bubble-point Equilibria 389
8.12.4 Dew-point Equilibria 389
8.12.5 Flash Vaporisation 390
8.13 Consistency Test for VLE Data 395
8.13.1 Using Slope of ln g Curves 395
8.13.2 Using Data at the Mid-point 396
8.13.3 Redlich–Kister Method 396
8.13.4 Using the Coexistence Equation 398
8.13.5 Using the Partial Pressure Data 399
8.14 Calculation of Activity Coefficients using Gibbs–Duhem Equation 401
8.15 VLE for Systems of Limited Miscibility 403
8.15.1 Partially Miscible Systems 403
8.15.2 Immiscible Systems 405
8.16 Liquid–Liquid Equilibrium Diagrams 408
8.16.1 Binary Liquid–Liquid Equilibria 408
8.16.2 Ternary Equilibrium Diagrams 408
Summary 411
Review Questions 412
Exercises 413

9. CHEMICAL REACTION EQUILIBRIA 425–481

9.1 Reaction Stoichiometry 426
9.2 Criteria of Chemical Reaction Equilibrium 429
9.3 Equilibrium Constant 431
9.4 Equilibrium Constant and Standard Free Energy Change 433
9.4.1 Choice of Standard State 434
9.4.2 Feasibility of a Reaction 434
9.5 Effect of Temperature on Equilibrium Constant 436
9.5.1 Evaluation of Equilibrium Constants 440
9.5.2 Giauque Functions 440
9.6 Effect of Pressure on Equilibrium 446
9.6.1 Effect of Pressure on Equilibrium Constant 446
9.6.2 Effect of Pressure on Equilibrium Composition 446
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Thermodynamics

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