Chemical

E ngineering hermodynamicsT

K.V. Narayanan

A Textbook of

A Textbook ofChemical Engineering Thermodynamics

A Textbook ofChemical Engineering

Thermodynamics

K.V. NARAYANANFormer Professor and Head

Department of Chemical Engineeringand

Former PrincipalGovernment Engineering College

Thrissur, Kerala

Delhi-1100922013

SECOND EDITION

A TEXTBOOK OF CHEMICAL ENGINEERING THERMODYNAMICS, Second EditionK.V. Narayanan

© 2013 by PHI Learning Private Limited, Delhi. All rights reserved. No part of this book maybe reproduced in any form, by mimeograph or any other means, without permission in writingfrom 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, PatparganjIndustrial Estate, Delhi-110092 and Printed by Mohan Makhijani at Rekha Printers Pvt. Ltd.,New Delhi-110020.

Preface xiiiPreface to the First Edition xv

1. INTRODUCTION AND BASIC CONCEPTS 1–23

1.1 Scope and Limitations of Thermodynamics 11.2 Definitions and Fundamental Concepts 2

1.2.1 Systems and Processes 21.2.2 Homogeneous and Heterogeneous Systems 31.2.3 Closed and Open Systems 31.2.4 State and Properties 31.2.5 Intensive and Extensive Properties 41.2.6 State and Path Functions 4

1.3 Force, Pressure and Energy 51.3.1 Force 51.3.2 Pressure 51.3.3 Energy 6

1.4 Equilibrium State and the Phase Rule 101.4.1 Steady State 101.4.2 Equilibrium State 101.4.3 Phase Rule 11

1.5 Temperature and Zeroth Law of Thermodynamics 111.5.1 Zeroth Law 111.5.2 Temperature 111.5.3 Ideal Gas Temperature Scale 12

1.6 Heat Reservoirs and Heat Engines 141.6.1 Heat Reservoir 141.6.2 Heat Engine 141.6.3 Heat Pump 15

1.7 Reversible and Irreversible Processes 16Summary 20Review Questions 21Exercises 22

2. FIRST LAW OF THERMODYNAMICS 24–48

2.1 General Statements of First Law of Thermodynamics 242.2 First Law of Thermodynamics for Cyclic Process 252.3 Internal Energy 25

Contents

v

vi Contents

2.4 First Law of Thermodynamics for Non-flow Process 262.5 Enthalpy 312.6 First Law of Thermodynamics for Flow Process 342.7 Heat Capacity 40Summary 44Review Questions 44Exercises 45

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

3.1 P-V-T Behaviour of Pure Fluids 493.2 Equations of State and the Concept of Ideal Gas 513.3 Processes involving Ideal Gases 52

3.3.1 Constant Volume Process 523.3.2 Constant Pressure Process 533.3.3 Constant Temperature Process 543.3.4 Adiabatic Process 553.3.5 Polytropic Process 57

3.4 Equations of State for Real Gases 603.4.1 Limiting Conditions 613.4.2 van der Waals Equation 613.4.3 Redlich–Kwong Equation 633.4.4 Redlich–Kwong–Soave Equation 643.4.5 Peng–Robinson Equation 643.4.6 Benedict–Webb–Rubin Equation 643.4.7 Virial Equation 65

3.5 Compressibility Charts 673.5.1 Principle of Corresponding States 683.5.2 Generalised Compressibility Charts 69

3.6 Heat Effects accompanying Chemical Reactions 693.6.1 The Standard Heat of Reaction 693.6.2 The Standard Heat of Combustion 703.6.3 The Standard Heat of Formation 703.6.4 Hess’s Law of Constant Heat Summation 713.6.5 Effect of Temperature on Standard Heat of Reaction 723.6.6 Temperature of Reaction 77

Summary 79Review Questions 80Exercises 81

4. SECOND LAW OF THERMODYNAMICS 89–125

4.1 Limitations of the First Law of Thermodynamics 894.1.1 Direction of Change 894.1.2 Qualitative Difference between Heat and Work 90

4.2 General Statements of the Second Law of Thermodynamics 904.2.1 The Equivalence of the Kelvin and Clausius Statements 91

Contents vii

4.3 Entropy 924.3.1 Why the Concept of Entropy? 924.3.2 Entropy and Heat 934.3.3 Entropy and Temperature 944.3.4 Entropy and the Nature of the Process 94

4.4 The Carnot Principle 954.4.1 Thermodynamic Temperature Scale 974.4.2 Ideal Gas as the Carnot Engine Working Substance 98

4.5 Entropy—A State Function 1014.6 Calculation of Entropy Changes 103

4.6.1 Phase Change 1034.6.2 Processes Involving Ideal Gases 1034.6.3 Adiabatic Mixing Process 1054.6.4 Isothermal Mixing of ideal Gases 1064.6.5 Chemical Reactions 107

4.7 Clausius Inequality 1084.8 Mathematical Statement of the Second Law of Thermodynamics 1114.9 Entropy and Irreversibility 1154.10 Statistical Explanation for Entropy 1184.11 Third Law of Thermodynamics 118Summary 120Review Questions 121Exercises 122

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

5.1 Flow Processes 1265.1.1 Continuity Equation 1265.1.2 Energy Equation 1275.1.3 Flow in Pipes 1355.1.4 Flow through Nozzles 1375.1.5 Ejectors 1425.1.6 Throttling Process (Joule–Thomson Expansion) 1435.1.7 Compressors 143

5.2 Refrigeration 1515.2.1 Coefficient of Performance (COP) 1525.2.2 Refrigerator Capacity 1525.2.3 Carnot Cycle 1525.2.4 Vapour-compression Cycle 1545.2.5 Choice of Refrigerant 1595.2.6 Air-refrigeration Cycle 1615.2.7 Absorption Refrigeration 1635.2.8 Heat Pumps 165

5.3 Liquefaction Processes 1665.3.1 Vaporisation of Liquid 1665.3.2 Free Expansion 1675.3.3 Isentropic Expansion 168

viii Contents

5.4 The Steam-Power Plant 1705.4.1 Rankine Cycle 1715.4.2 Reheat Cycle 1745.4.3 Regenerative Cycle 177

5.5 Internal Combustion Engines 1805.5.1 Otto Cycle 1805.5.2 Diesel Cycle 1835.5.3 Dual Cycle 187

5.6 Gas-turbine Power Plant 1885.6.1 Brayton Cycle 189

Summary 191Review Questions 192Exercises 193

6. THERMODYNAMIC PROPERTIES OF PURE FLUIDS 206–272

6.1 Classification of Thermodynamic Properties 2066.1.1 Reference Properties 2066.1.2 Energy Properties 2066.1.3 Derived Properties 207

6.2 Work Function (Helmholtz Free Energy) 2076.3 Gibbs Free Energy 2086.4 Relationships among Thermodynamic Properties 209

6.4.1 Exact Differential Equations 2096.4.2 Fundamental Property Relations 2106.4.3 Maxwell’s Equations 2116.4.4 Clapeyron Equation 2136.4.5 Entropy–Heat Capacity Relationships 2156.4.6 Differential Equations for Entropy 2166.4.7 Modified Equations for U and H 2176.4.8 Effect of Temperature, Pressure and Volume on U, H and S 2206.4.9 Relationship between CP and CV 2266.4.10 Ratio of Heat Capacities 2296.4.11 Effect of Pressure and Volume on CP and CV 2296.4.12 Joule–Thomson Coefficient 2336.4.13 Gibbs–Helmholtz Equation 235

6.5 Method of Jacobians 2366.5.1 Properties of Jacobians 2376.5.2 Thermodynamic Relations through the Method of Jacobians 238

6.6 Fugacity 2446.6.1 Standard State for Fugacity 2456.6.2 Fugacity Coefficient 2466.6.3 Effect of Temperature and Pressure on Fugacity 2466.6.4 Determination of Fugacity of Pure Gases 2476.6.5 Fugacities of Solids and Liquids 254

6.7 Activity 2556.7.1 Effect of Pressure and Temperature on Activity 256

Contents ix

6.8 Departure Functions and Generalised Charts 2566.9 Thermodynamic Diagrams 259

6.9.1 Types of Diagrams 2596.9.2 Construction of Thermodynamic Diagrams 262

Summary 265Review Questions 265Exercises 267

7. PROPERTIES OF SOLUTIONS 273–328

7.1 Partial Molar Properties 2737.1.1 Physical Meaning of Partial Molar Properties 2747.1.2 Partial Molar Properties and Properties of Solution 2767.1.3 Determination of Partial Molar Properties 279

7.2 Chemical Potential 2847.2.1 Effect of Temperature and Pressure on Chemical Potential 285

7.3 Fugacity in Solutions 2887.3.1 Fugacity in Gaseous Solutions 2887.3.2 Lewis–Randall Rule 2907.3.3 Fugacities in Liquid Solutions 2917.3.4 Ideal Solutions and Raoult’s Law 292

7.4 Henry’s Law and Dilute Solutions 2937.4.1 Ideal Behaviour of Real Solutions 2937.4.2 Henry’s Law and Gas Solubility 294

7.5 Activity in Solutions 2967.5.1 Selection of Standard States 296

7.6 Activity Coefficients 2977.6.1 Effect of Pressure on Activity Coefficients 2997.6.2 Effect of Temperature on Activity Coefficients 299

7.7 Gibbs–Duhem Equations 3027.8 Property Changes of Mixing 307

7.8.1 Activity and Property Change of Mixing 3087.8.2 Property Changes of Mixing for Ideal Solutions 310

7.9 Heat Effects of Mixing Processes 3117.10 Excess Properties 317

7.10.1 Excess Gibbs Free Energy 318Summary 320Review Questions 321Exercises 322

8. PHASE EQUILIBRIA 329–424

8.1 Criteria of Phase Equilibrium 3308.2 Criterion of Stability 3328.3 Phase Equilibria in Single-component Systems 3358.4 Phase Equilibria in Multicomponent Systems 3388.5 Phase Rule for Non-reacting Systems 3418.6 Duhem’s Theorem 343

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8.7 Vapour–Liquid Equilibria 3448.8 Phase Diagrams for Binary Solutions 346

8.8.1 Constant-pressure Equilibria 3468.8.2 Constant-temperature Equilibria 350

8.9 Vapour–Liquid Equilibria in Ideal Solutions 3518.10 Non-ideal Solutions 361

8.10.1 Azeotropes 3648.11 Vapour–Liquid Equilibria (VLE) at Low Pressures 368

8.11.1 Activity Coefficient Equations 3698.12 Vapour–Liquid Equilibria involving High Pressures and

Multicomponent Systems 3868.12.1 Equations of State Approach 3868.12.2 Vaporisation Equilibrium Constants 3878.12.3 Bubble-point Equilibria 3898.12.4 Dew-point Equilibria 3898.12.5 Flash Vaporisation 390

8.13 Consistency Test for VLE Data 3958.13.1 Using Slope of ln g Curves 3958.13.2 Using Data at the Mid-point 3968.13.3 Redlich–Kister Method 3968.13.4 Using the Coexistence Equation 3988.13.5 Using the Partial Pressure Data 399

8.14 Calculation of Activity Coefficients using Gibbs–Duhem Equation 4018.15 VLE for Systems of Limited Miscibility 403

8.15.1 Partially Miscible Systems 4038.15.2 Immiscible Systems 405

8.16 Liquid–Liquid Equilibrium Diagrams 4088.16.1 Binary Liquid–Liquid Equilibria 4088.16.2 Ternary Equilibrium Diagrams 408

Summary 411Review Questions 412Exercises 413

9. CHEMICAL REACTION EQUILIBRIA 425–481

9.1 Reaction Stoichiometry 4269.2 Criteria of Chemical Reaction Equilibrium 4299.3 Equilibrium Constant 4319.4 Equilibrium Constant and Standard Free Energy Change 433

9.4.1 Choice of Standard State 4349.4.2 Feasibility of a Reaction 434

9.5 Effect of Temperature on Equilibrium Constant 4369.5.1 Evaluation of Equilibrium Constants 4409.5.2 Giauque Functions 440

9.6 Effect of Pressure on Equilibrium 4469.6.1 Effect of Pressure on Equilibrium Constant 4469.6.2 Effect of Pressure on Equilibrium Composition 446

Textbook Of Chemical EngineeringThermodynamics

Publisher : PHI Learning ISBN : 9788120347472 Author : K. V. Narayanan

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