CONTENTS
Preface = ⅷ
1 Introduction = 1
2 The Structure of Thermodynamics = 5
2.1 A Classification of Thermodynamic Systems = 7
2.2 Classification of Thermodynamic Variables = 9
2.2.1 State Functions = 9
2.2.2 Process Variables = 11
2.2.3Extensive and Intensive Properties = 12
2.3 Classification of Relationships = 14
2.4 Criterion for Equilibrium = 15
2.5 Summary of Chapter 2 = 16
3 The Laws of Thermodynamics = 19
3.1 The First Law of Thermodynamics = 20
3.2 The Second Law of Thermodynamics = 23
3.3 Intuitive Meaning of Entropy Productions = 25
3.4 Relation between Entropy Transfer and Heat = 29
3.5 Combined Statement of the First and Second Laws = 31
3.6 The Third Law of Thermodynamics = 32
3.7 Summary of Chapter = 3
4 Thermodynamic Variables and Relations = 38
4.1 Classification of Thermodynamic Relationships = 39
4.1.1 The Laws of Thermodynamics = 40
4.1.2 Definitions in Thermodynamics = 40
4.1.3 Coefficient Relations = 46
4.2 Maxwell Relations = 48
4.3 General Strategy for Deriving Thermodynamic Relations = 51
4.3.1 Entropy and Volume Relations tp T and P = 52
4.3.2 Energy Functions Expressed in Terms of T and P = 54
4.3.3 The General Procedure = 56
4.3.4 Application to an Ideal Gas = 62
4.3.5 Applications to Solid and Liquids = 71
4.4 Summary of Chapter 4 = 77
5 Equilibrium in Thermodynamic Systems = 83
5.1 Intuitive Notions of Equilibrium = 84
5.2 Thermodynamic Formulation of a General Criterion for Equilibrium = 85
5.3 Mathematical Formulation of The General Criterion for Equilibrium = 88
5.4 Application of the General Strategy for Finding Conditions for Thermodynamic Equilibrium : The Unary Two Phase System = 93
5.5 Alternate Formulations of the Criterion for Equilibrium = 96
5.6 Summary of Chapter 5 = 99
6 Statistical Thermodynamics = 102
6.1 Microstates, Macrostates and Entropy = 104
6.2 Conditions for Equilibrium in Statistical Thermodynamics = 109
6.2.1 Evaluation of Entropy = 109
6.2.2 Evaluation of the Isolation Constraints = 112
6.2.3 The Constrained Maximum in the Entropy Function = 113
6.2.4 Calculation of the Macroscopic Properties from the Partition Function = 116
6.3 Applications of the Algorithm = 118
6.3.1 A Model with Two Energy Levels = 118
6.3.2 Einstein's Model of a Crystal = 119
6.3.3 Monatomic Gas Model = 122
6.4 Alternate Statistical Formulations = 128
6.5 Summary of Chapter = 6
7 Unary Heterogeneous Systems = 132
7.1 Structure of Unary Phase Diagrams in(P, T) Space = 135
7.1.1 Chemical Potential and the Gibbs Free Energy = 136
7.1.2 Chemical Potential Surfaces and the Structure of Unary Phase Diagrams = 137
7.1.3 Calculation of Chemical Potential Surfaces = 140
7.1.4 Competing Equilibria : Metastability = 141
7.2 The Clausius-Clapeyron Equation = 142
7.3 Integration of the Clausius-Clapeyron Equation = 145
7.3.1 Vaporization and Sublimation Curves = 147
7.3.2 Phase Boundaries between Condensed Phases = 149
7.4 Triple Points = 150
7.5 Computer Calculations of(P, T) Unary Phase Diagrams = 153
7.6 Alternate Representations of Unary Phase Diagrams = 155
7.7. Summary of Chapter 7 = 157
8 Multicomponent, Homogeneous Nonreacting Systems : Solutions = 160
8.1 Partial Molal Properties = 161
8.1.1 Definition of Partial Molal Properties = 162
8.1.2 Consequences of the Definitions of Partial Molal Properties = 163
8.1.3 The Mixing Process = 165
8.1.4 Molar Values of the Properties of Mixtures = 166
8.2 Evaluation of Partial Molal Properties = 168
8.2.1 Partial Molal Properties from Total Properties = 168
8.2.2 Graphical Determination of Partial molal Properties = 170
8.2.3 Evaluation of the PMP's of One Component from Measured Values of PMPs of the Other = 172
8.3 Relationships among Partial Molal Properties = 173
8.4 Chemical Potential in Multicomponent Systems = 176
8.5 Fugacities, Actvities and Activity Coefficients = 179
8.5.1 Properties of Ideal Gas Mixtures = 180
8.5.2 Mixtures of Real Gases : Fugacity = 184
8.5.3 Activity and the Behavior of Real Solutions = 185
8.5.4 Use of the Activity Coefficient to Describe the Behavior of Real Solutions = 187
8.6 The Behavior of Dilute Solutions = 189
8.7 Solution Models = 191
8.7.1 The Regular Solution Model = 191
8.7.2 Nonregular Solution Models = 194
8.7.3 Atomistic Models for Solution Behavior = 196
8.8 Summary of Chapter 8 = 203
9 Multicomponent Heterogeneous Systems = 208
9.1 The Description of Multiphase, Multicomponent, Nonreacting Systems = 209
9.2 Conditions for Equilibrium = 211
9.3 The Gibbs Phase Rule = 214
9.4 The Structure of Phase Diagrams = 216
9.4.1 Phase Diagrams Plotted in Thermodynamic Potential Space = 218
9.4.2 Unary Systems = 220
9.4.3 Binary Phase Diagrams = 223
9.4.4 Ternary Phase Diagrams = 225
9.5 The Interpretation of Phase Diagrams = 228
9.5.1 The Lever Rule for Tie Lines = 229
9.5.2 The Lever Rule for Tie Triangles = 231 =
9.6 Applications of Phase Diagrams in Materials Science = 232
9.7 Summary of Chapter 9 = 237
10 Thermodynamics of Phase Diagrams = 241
10.1 Free Energy-Composition(G-X) Diagrams = 242
10.1.1 Reference States for(G-X) Curves = 243
10.1.2 The Common Tangent Construction and Two Phase Equilibrium = 248
10.1.3 Two Phase Fields on Binary Phase Diagrams = 251
10.1.4 Three Phase Equilibria = 261
10.1.5 Intermediate Phases = 265
10.1.6 Metastable Phase Diagrams = 269
10.2 Thermodynamic Models for Binary Phase Diagrams = 271
10.2.1 Ideal Solution Models for Phase Diagrams = 271
10.2.2 Regular Solution Model for Phase Diagrams = 275
10.2.3 The Midrib Curve = 277
10.2.4 Pattern of Regular Solution Phase Diagrams with Two Phases = 281
10.2.5 Diagrams with Three of More Phases = 282
10.2.6 Modelling Phase Diagrams with Line Compounds = 284
10.3 Thermodynamic Molels for Three Component Systems = 287
10.4 Calculation of Phase Diagrams in Potential Space = 291
10.5 Computer Calculations of Phase Diagrams = 293
10.6 Summary of Chapter 10 = 296
11 Multicomponent, Multiphase Reacting Systems = 301
11.1 Reactions in the Gas Phase = 303
11.1.1 Univariant Reactions in the Gas Phase = 304
11.1.2 Multivariant Reactions in the Gas Phase = 312
11.2 Reactions in Multiphase Systems = 319
11.3 Patterns of Behavior in Common Reacting Systems = 322
11.3.1 Richardson-Ellingham Charts for Oxidation = 322
11.3.2 Oxidation in CO／CO₂ and H₂／H₂O Mixtures = 332
11.4 Predominance Diagrams and Multivariant Equilibria = 336
11.4.1 Pourbaix High Temperature Oxidation Diagrams = 336
11.4.2 Predominance Diagrams with Two Compositional Axes = 342
11.4.3 Interpretation of Predominance Diagrams = 346
11.5 Compounds as Components in Phase Digrams = 348
11.6 Summary of Chapter 11 = 349
12 Capillarity Effects in Thermodynamics = 355
12.1 The Geometry of Surfaces = 356
12.2 Surface Excess Properties = 360
12.3 Conditions for Equilibrium in Systems with Curved Interfaces = 363
12.4 Surface Tension : The Mechanical Analog of Surface Free Energy = 368
12.5 Capillarity Effects on Phase Diagrams = 370
12.5.1 Phase Boundary Shifts in Unary Systems = 370
12.5.2 Vapor Pressure in Equilibrium with Curved Surfaces = 371
12.5.3 Effect of Curvature Upon the Melting Temperature = 375
12.5.4 Phase Boundary Shifts in Binary Systems = 377
12.5.5 Local Equilibrium and the Application of Capillarity Shifts = 382
12.6 The Equilibrium Shape of Crystals : The Gibbs-Wulff Construction = 384
12.7 Equilibrium at Triple Lines = 389
12.8 Adsorption at Surfaces = 395
12.8.1 Measures of Adsorption = 395
12.8.2 The Gibbs Adsorption Equation = 398
12.9 Summary of Chapter 12 = 400
13 Defects in Crystals = 405
13.1 Point Defects in Elemental Crystals = 406
13.1.1 Conditions for Equilibrium in a Crystal with Vacant Lattice Sites = 407
13.1.2 The Concentration of Vacancies in a Vrystal at Equilibrium = 408
13.1.3 Interstitial Defects and Divacancies = 410
13.2 Point Defects in Stoichiometric Compound Crystals = 412
13.2.1 Frenkel Defects = 414
13.2.2 Schottky Defects = 417
13.2.3 Combined Defects in Binary Compounds = 419 =
13.2.4 Multi Equilibrium among Defects in a Stoichiometric Compound Crystals = 420
13.3 Nonstoichiometric Compound Crystals = 422
13.3.1 Equilibrium in Compound Crystals with a Variety of Defects = 424
13.3.2 Illustration of the Conditions for Equilibrium for Alumina = 427
13.4 Impurities in Nonstoichiometric Compounds = 428
13.5 Summary of Chapter 13 = 430
14 Equilibrium in Continuous Systems : Thermodynamic Effects of External Fields = 432
14.1 Thermodynamic Densities and the Description of Nonuniform Systems = 434
14.2 Conditions for Equilibrium in the Absence of External Fields = 435
14.3 Conditions for Equilibrium in the Presence of External Fields = 438
14.3.1 Potential Energy of a Continuous System = 438
14.3.2 Conditions for Equilibrum = 440
14.3.3 Equilibrium in a Gravitational Field = 441
14.3.4 Equilibrium in a Centrifugal Field = 444
14.3.5 Equilibrium in an Electrostatic Field = 445
14.4 The Gradient Energy in Nonuniform Systems = 447
14.5 Summary of Chapter 14 = 452
15 Electrochemistry = 455
15.1 Equilibrium within an Electrolyte Solution = 456
15.1.1 Equilibrium in Weak Electrolytes = 458
15.1.2 Equilibrium in a Strong Electrolyte = 464
15.2 Equilibrium in Two Phase Systems Involving an Electrolyte = 465
15.3 Equilibrium in an Electrochemical Cell = 469
15.3.1 Conditions for Equilibrium in a General Galvanic cell = 471
15.3.2 Temperature Dependence of the Electromotive Force of a Cell = 474
15.3.3 The Standard Hydrogen Electrode = 475
15.4 Pourbaix Diagrams = 477
15.4.1 The Stability of Water = 478
15.4.2 Pourbaix Diagram for Copper = 480
15.5 Summary of Chapter 15 = 484
Appendixes = 487
A Universal Constants and Conversion Factors = 487
B Atomic Numbers and Atomic Weights = 489
C Volumetric Properties of the Elements = 491
D Absolute Entropies and Heat Capacities of Solid Elements = 493
E Phase Transitions : Temperature and Entropies of Melting and Vaporization = 495
F Surface Tensions and Interfacial Free Energies = 497
G Termochemisty of Oxides = 499
H Termochemisty Nitrides = 501
I Termochemisty Carbides = 503
J Electrochemical Series = 505
K The Carnot Cycle = 507
L Answers to Homework Problems = 513
Index = 521
