1 Introduction and Definition of Terms 1
1.1 Introduction 1
1.2 The Concept of State 1
1.3 Simple Equilibrium 4
1.4 The Equation of State of an Ideal Gas 5
1.5 The Units of Energy and Work 8
1.6 Extensive and Intensive Properties 8
1.7 Phase Diagrams and Thermodynamic Components 9
2 The First Law of Thermodynamics 15
2.1 Introduction 15
2.2 The Relationship between Heat and Work 16
2.3 Internal Energy and the First Law of Thermodynamics 17
2.4 Constant-Volume Processes 21
2.5 Constant-Pressure Processes and the Enthalpy H 21
2.6 Heat Capacity 21
2.7 Reversible Adiabatic Processes 25
2.8 Reversible Isothermal Pressure or Volume Changes of an Ideal Gas 27
2.9 Summary 28
2.10 Numerical Examples 29
Problems 34
3 The Second Law of Thermodynamics 37
3.1 Introduction 37
3.2 Spontaneous or Natural Processes 38
3.3 Entropy and the Quantification of Irreversibility 39
3.4 Reversible Processes 40
3.5 An Illustration of Irreversible and Reversible Processes 41
3.6 Entropy and Reversible Heat 43
3.7 The Reversible Isothermal Compression of an Ideal Gas 46
3.8 The Reversible Adiabatic Expansion of an Ideal Gas 47
3.9 Summary Statements 48
3.10 The Properties of Heat Engines 48
3.11 The Thermodynamic Temperature Scale 51
3.12 The Second Law of Thermodynamics 53
3.13 Maximum Work 55
3.14 Entropy and the Criterion for Equilibrium 57
3.15 The Combined Statement of the First and Second Laws of Thermodynamics 58
3.16 Summary 59
3.17 Numerical Examples 61
Problems 66
4 The Statistical Interpretation of Entropy 69
4.1 Introduction 69
4.2 Entropy and Disorder on an Atomic Scale 70
4.3 The Concept of Microstate 71
4.4 Determination of the Most Probable Microstate 72
4.5 The Influence of Temperature 76
4.6 Thermal Equilibrium and the Boltzmann Equation 78
4.7 Heat Flow and the Production of Entropy 79
4.8 Configurational Entropy and Thermal Entropy 80
4.9 Summary 83
4.10 Numerical Examples 84
Problems 86
5 Auxiliary Functions 87
5.1 Introduction 87
5.2 The Enthalpy H 89
5.3 The Helmholtz Free Energy A 89
5.4 The Gibbs Free Energy G 94
5.5 Summary of the Equations for a Closed System 95
5.6 The Variation of the Composition and Size of the System 96
5.7 The Chemical Potential 97
5.8 Thermodynamic Relations 98
5.9 Maxwell's Equations 99
5.10 The Upstairs-Downstairs-Inside-Out Formula 101
5.11 The Gibbs-Helmholtz Equation 102
5.12 Summary 103
5.13 Example of the Use of the Thermodynamic Relations 104
Problems 106
6 Heat Capacity, Enthalpy, Entropy,and the Third Law of Thermodynamics 109
6.1 Introduction 109
6.2 Theoretical Calculation of the Heat Capacity 110
6.3 The Empirical Representation of Heat Capacities 115
6.4 Enthalpy as a Function of Temperature and Composition 116
6.5 The Dependence of Entropy on Temperature and the Third Law of Thermodynamics 125
6.6 Experimental Verification of the Third Law 128
6.7 The Influence of Pressure on Enthalpy and Entropy 134
6.8 Summary 136
6.9 Numerical Examples 137
Problems 147
7 Phase Equilibrium in a One-Component System 149
7.1 Introduction 149
7.2 The Variation of Gibbs Free Energy with Temperature at Constant Pressure 150
7.3 The Variation of Gibbs Free Energy with Pressure at Constant Temperature 157
7.4 Gibbs Free Energy as a Function of Temperature and Pressure 159
7.5 Equilibrium between the Vapor Phase and a Condensed Phase 160
7.6 Graphical Representation of Phase Equilibria in a One-Component System 162
7.7 Solid-Solid Equilibria 168
7.8 Summary 171
Numerical Examples 172
Problems 175
8 The Behavior of Gases 177
8.1 Introduction 177
8.2 The P-V-T Relationships of Gases 177
8.3 Deviations from Ideality and Equations of State for Real Gases 180
8.4 The van der Waals Gas 182
8.5 Other Equations of State for Nonideal Gases 191
8.6 The Thermodynamic Properties of Ideal Gases and Mixtures of Ideal Gases 192
8.7 The Thermodynamic Treatment of Nonideal Gases 198
8.8 Summary 204
8.9 Numerical Examples 206
Problems 208
9 The Behavior of Solutions 211
9.1 Introduction 211
9.2 Raoult's Law and Henry's Law 211
9.3 The Thermodynamic Activity of a Component in Solution 215
9.4 The Gibbs-Duhem Equation 216
9.5 The Gibbs Free Energy of Formation of a Solution 218
9.6 The Properties of Raoultian Ideal Solutions 221
9.7 Nonideal Solutions 226
9.8 Application of the Gibbs-Duhem Relation to the Determination of Activity 229
9.9 Regular Solutions 240
9.10 A Statistical Model of Solutions 245
9.11 Subregular Solutions 252
9.12 Summary 254
9.13 Numerical Examples 257
Problems 259
10 Gibbs Free Energy Composition and Phase Diagrams of Binary Systems 263
10.1 Introduction 263
10.2 Gibbs Free Energy and Thermodynamic Activity 264
10.3 The Gibbs Free Energy of Formation of Regular Solutions 266
10.4 Criteria for Phase Stability in Regular Solutions 268
10.5 Liquid and Solid Standard States 273
10.6 Phase Diagrams, Gibbs Free Energy, and Thermodynamic Activity 283
10.7 The Phase Diagrams of Binary Systems That Exhibit Regular Solution Behavior in the Liquid and Solid States 292
10.8 Summary 298
10.9 Numerical Example 299
Problems 301
11 Reactions Involving Gases 305
11.1 Introduction 305
11.2 Reaction Equilibrium in a Gas Mixture and the Equilibrium Constant 306
11.3 The Effect of Temperature on the Equilibrium Constant 311
11.4 The Effect of Pressure on the Equilibrium Constant 312
11.5 Reaction Equilibrium as a Compromise between Enthalpy and Entropy 314
11.6 Reaction Equilibrium in the System SO2（g）-SO3（g）-O2（g） 316
11.7 Equilibrium in H2O-H2 and CO2-CO Mixtures 321
11.8 Summary 323
11.9 Numerical Examples 324
Problems 335
12 Reactions Involving Pure Condensed Phases and a Gaseous Phase 337
12.1 Introduction 337
12.2 Reaction Equilibrium in a System Containing Pure Condensed Phases and a Gas Phase 338
12.3 The Variation of the Standard Gibbs Free Energy Change with Temperature 343
12.4 Ellingham Diagrams 346
12.5 The Effect of Phase Transformations 353
12.6 The Oxides of Carbon 358
12.7 Graphical Representation of Equilibria in the System Metal-Carbon-Oxygen 365
12.8 Summary 368
12.9 Numerical Examples 369
Problems 380
13 Reaction Equilibria in Systems Containing Components in Condensed Solution 383
13.1 Introduction 383
13.2 The Criteria for Reaction Equilibrium in Systems Containing Components in Condensed Solution 385
13.3 Alternative Standard States 393
13.4 The Gibbs Phase Rule 399
13.5 Binary Systems Containing Compounds 417
13.6 Graphical Representation of Phase Equilibria 429
13.7 The Formation of Oxide Phases of Variable Composition 437
13.8 The Solubility of Gases in Metals 446
13.9 Solutions Containing Several Dilute Solutes 450
13.10 Summary 460
13.11 Numerical Examples 462
Problems 470
14 Phase Diagrams for Binary Systems in Pressure-Temperature-Composition Space 475
14.1 Introduction 475
14.2 A Binary System Exhibiting Complete Mutual Solubility of the Components in the Solid and Liquid States 475
14.3 A Binary System Exhibiting Complete Mutual Solubility in the Solid and Liquid States and Showing Minima on the Melting, Boiling, and Sublimation Curves 480
14.4 A Binary System Containing a Eutectic Equilibrium and Having Complete Mutual Solubility in the Liquid 485
14.5 A Binary System Containing a Peritectic Equilibrium and Having Complete Mutual Solubility in the Liquid State 493
14.6 Phase Equilibrium in a Binary System Containing an Intermediate γ Phase That Melts, Sublimes,and Boils Congruently 501
14.7 Phase Equilibrium in a Binary System Containing an Intermediate γ Phase That Melts and Sublimes Congruently and Boils Incongruently 508
14.8 Phase Equilibrium in a Binary System with a Eutectic and One Component That Exhibits Allotropy 513
14.9 A Binary Eutectic System in Which Both Components Exhibit Allotropy 517
14.10 Phase Equilibrium at Low Pressure:The Cadmium-Zinc System 524
14.11 Phase Equilibrium at High Pressure:The Na2O·Al2O3.2SiO2-SiO2 System 525
14.12 Summary 531
15 Electrochemistry 533
15.1 Introduction 533
15.2 The Relationship between Chemical and Electrical Driving Forces 535
15.3 The Effect of Concentration on EMF 540
15.4 Formation Cells 541
15.5 Concentration Cells 544
15.6 The Temperature Coefficient of the EMF 549
15.7 Heat Effects 551
15.8 The Thermodynamics of Aqueous Solutions 552
15.9 The Gibbs Free Energy of Formation of Ions and Standard Reduction Potentials 555
15.10 Pourbaix Diagrams 564
15.11 Summary 574
15.12 Numerical Examples 576
Problems 579
Appendices 581
A Selected Thermodynamic and Thermochemical Data 581
B Exact Differential Equations 589
C The Generation of Auxiliary Functions as Legendre Transformations 591
Nomenclature 599
Answers 603
Index 615