Thermodynamics

by Patrick Jacobs

Overview

This textbook on thermodynamics is intended primarily for honours and B. Sc students majoring in physical chemistry. However, students of physics, engineering and biochemistry will also find the book relevant to their studies.Its principal features are a much shorter presentation of the laws of thermodynamics than is customary, made possible by the definition of the thermodynamic scale of temperature using only one fixed point (the triple point of water) which immediately follows the Zeroth Law. The author's first exposure to thermodynamics revealed that its usefulness seemed to be mostly confined to the study of gases in equilibrium. Readers of this book will find that applications of thermodynamics to liquids and solids as well as gases are emphasized, and they will learn that thermodynamics can be applied to systems which are not in equilibrium.This book contains three learning aids. Fully worked out examples are included at appropriate places in the text, which also includes numerous exercises. These are designed to help the reader stop and think about what he or she has just read. Answers to the exercises are given at the end of each section and there are also problems at the end of each chapter which readers can work out on their own.

Product Details

ISBN-13:	9781848169715
Publisher:	Imperial College Press
Publication date:	05/06/2013
Pages:	456
Product dimensions:	5.90(w) x 8.90(h) x 1.00(d)

Table of Contents

Preface ix

1 Temperature and Energy 1

1.1 Introduction 1

1.2 The Zeroth Law of Thermodynamics 4

1.3 The Ideal Gas 6

1.4 Work 10

1.5 The First Law of Thermodynamics 20

1.6 Heat Capacity and Internal Energy of an Ideal Gas 22

1.7 Generalized Forces 23

2 Entropy 27

2.1 The Second Law of Thermodynamics 27

2.2 The Fundamental Equations for a Closed Phase 29

2.3 Calculation of Entropy Changes 31

2.4 Physical Meaning of the Thermodynamic Potentials 35

2.5 Conditions for Equilibrium in a Closed System 39

2.6 Entropy of Mixing 41

2.7 Thermodynamic Potentials for an Open Phase 42

2.8 Other Forms of the Second Law and the Unattainability of T = 0K 45

3 An Introduction to Statistical Thermodynamics 53

3.1 Need for a Microscopic Description 53

3.2 Postulates of Quantum Mechanics 54

3.3 A Model for the Ideal Gas 56

3.4 The Number of Translational States 59

3.5 The Boltzmann Distribution 62

3.6 Translational Motion in an Ideal Gas 66

3.7 Some Applications of the Boltzmann Distribution 68

3.8 The Partition Function 71

3.9 Evaluation of Thermodynamic Functions from Q 74

3.10 Internal Degrees of Freedom 78

3.11 Thermodynamic Functions for a Monatomic Ideal Gas 91

4 The Third Law of Thermodynamics 95

4.1 Entropy and Probability 95

4.2 The Boltzmann Entropy Equation 96

4.3 The Third Law of Thermodynamics 98

4.4 Experimental Observations Concerning the Third Law 100

4.5 The Thomsen and Berthelot Rule 104

4.6 Unattainability of T = 0 K 105

5 Systems of One Component 113

5.1 Real Gases 113

5.2 Intermolecular Potentials 117

5.3 The Joule-Thomson Effect 120

5.4 Thermodynamic Functions for Gases 124

5.5 Gases at High Pressures 127

5.6 Liquids 128

5.7 Solids 136

5.8 Triple Point 139

5.9 Higher-order Phase Transitions 140

6 Systems of More Than One Component 145

6.1 The Phase Rule 145

6.2 Partial Molar Properties 146

6.3 Mixtures of Gases 149

6.4 Liquid Mixtures 152

6.5 Liquid-Solid Equilibrium 172

6.6 Solutions 179

7 Surfaces and Interfaces 189

7.1 Plane Interface 189

7.2 Curved Interface 191

7.3 Thermodynamics of Interfaces 193

7.4 Some Typical Results 197

7.5 Thermodynamics of Wetting 200

7.6 The Gas-Solid Interface 201

7.7 Thermodynamics of Adsorption 206

7.8 Nucleation 213

8 Chemical Equilibrium 219

8.1 Stoichiometry 219

8.2 Affinity and Reaction Enthalpy 220

8.3 Temperature Dependence of the Reaction Enthalpy 227

8.4 The Standard Affinity, Reaction Isotherm and Equilibrium Constant 232

8.5 Effect of Pressure on Reactions Involving Gases 243

8.6 The Giaque Function 244

8.7 Theoretical Calculation of Equilibrium Constants 246

8.8 Reaction Rate Theory 249

9 Electrolytes 255

9.1 Electrolysis 255

9.2 Conductivity of Electrolyte Solutions 257

9.3 Ionic Mobility and Transport Number 260

9.4 Electrochemical Potential 266

9.5 Electrode Potential 266

9.6 The Cell Potential of an Electrochemical Cell 270

9.7 Activity Coefficients in Electrolyte Solutions 272

9.8 The Standard Cell Potential 282

9.9 pH 284

9.10 Thermodynamic Functions of Ions in Aqueous Solution 285

9.11 Electrochemical Cells with Transport 287

9.12 Some Applications 290

10 Fermi-Dirac and Bose-Einstein Statistics 295

10.1 Ensembles 295

10.2 The Canonical Ensemble 296

10.3 The Microcanonical Ensemble 298

10.4 The Grand Canonical Ensemble 299

10.5 Fermi-Dirac and Bose-Einstein Statistics 302

10.6 The Ideal Bose-Einstein Gas 307

10.7 The Ideal Fermi-Dirac Gas 312

10.8 Temperature Dependence of Thermodynamic Functions for a FD gas 314

11 Thermodynamics of Solids 319

11.1 Symmetry and the Physical Properties of Crystals 319

11.2 Stress and Strain 321

11.3 Thermodynamics of Stress and Strain 324

11.4 Point Defects in Ionic Crystals 329

11.5 Thermodynamics of Ionic Crystals with Point Defects 332

11.6 Semiconductors 337

12 Thermodynamics of Non-equilibrium Systems 343

12.1 Reprise 343

12.2 Entropy Production 346

12.3 Assumptions Upon Which TDNEP is Based 350

12.4 Examples of Non-equilibrium Processes 351

12.5 Thermoelectric Effects 353

12.6 Diffusion and Conduction in Electrolyte Solutions 355

Solutions to the Problems 363

Appendices 417

A1 Partial Differentiation 417

A2 The Classical Electromagnetic Field 423

A3 Sources of Thermo dynamic Data 429

References 431

Index 437