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Chapter1 Thermodynamics：Review1

1.1 The First Law1

1.1.1 System and Surroundings1

1.1.2 Heat and Work2

1.1.3 Reversibility2

1.1.4 Internal Energy2

1.1.5 State Functions2

1.1.6 The First Law2

1.1.7 Enthalpy3

1.1.8 Intensive and Extensive Properties and Notation3

1.1.9 Heat Capacities3

1.1.10 Ideal Gas4

1.1.11 Enthalpy of Formation4

1.2 Entropy，and the Second Law5

1.2.1 Entropy Not Conserved5

1.2.2 Entropy Changes5

1.2.3 Entropy Changes in Chemical Reactions and the Third Law6

1.3 Property Relations7

1.3.1 Free Energies7

1.3.2 Maxwell Relations7

1.3.3 Chemical Potentials8

1.3.4 Partial Molar Quantities9

1.3.5 Other Definitions9

1.4 Equilibrium9

1.5 Thermodynamics Activity10

1.6 Chemical Equilibrium11

1.7 Electrochemical Cells11

1.8 Solutions12

1.8.1 Ideal Solutions12

1.8.2 Immiscibility12

1.8.3 Regular Solutions14

1.8.4 Spinodal Points16

1.8.5 Gibbs-Duhem Equation17

1.9 Phase Rule17

Problems18

Chapter2 Statistical Thermodynamics27

2.1 Macrostates and Microstates29

2.2 The Boltzmann Hypothesis31

2.3 Entropy of Mixing31

2.4 Systems at Constant Temperature and the Canonical Ensemble32

2.5 Boltzmann Distribution32

2.6 Patrtition Function33

2.7 Degeneracy33

2.8 Distinguishability of Particles35

2.9 Ideal Gas36

2.10 Maxwell-Boltmann Distribution：Ideal Gas36

2.11 Fermi-Dirac Distribution37

2.12 Effusion：Langmuir Equation39

2.13 Mean Free Path43

2.14 Diffusion in Gases45

2.15 Elasticity of Rubber50

References61

Appendix 2A61

Appendix 2B Evaluation of K62

Appendix 2C Calculation of x263

Problems64

Chapter3 Defects in Solids67

3.1 Structural Point Defects in Elemental Crystals68

3.2 Vacancies：Experimental Verification71

3.3 Interactions Between Vacancies and Impurities73

3.4 Interaction Between Imperfections and Impurities75

3.5 Electronic Defects77

3.6 Defects in Ionic Compounds80

3.7 Frenkel Defects81

3.8 Schottky-Wagner Defects83

3.9 Interactions Among Defects84

3.10 Intrinsic and Extrinsic Defects in Ionic Crystals86

3.11 Experimental Determination of Defect Type89

3.12 Nonstoichiometry91

References92

Problems93

Chapter4 Surfaces and Interfaces97

4.1 Surface Energy-Surface Tension98

4.2 Approximate Calculation of Solid Surface Energy99

4.3 Effect of Surface Curvature101

4.4 Vapor Pressure105

4.5 Solubility of Small Particles106

4.6 Melting Temperature of Small Particles109

4.7 Measurement of Surface Energy111

4.8 Surface Energy of Solids112

4.9 Relative Surface Energies114

4.10 Wetting of Surfaces115

4.11 Surface Energy and Impurity Segregation at Interfaces（Gibbs Absorption Isotherm）116

4.12 Adsorption on Solids（Adsorption Isotherms）119

4.13 Equilibrium Shape of a Crystal121

4.14 Effect of Temperature on Surface Energy123

References123

Problems123

Chapter5 Diffusion127

5.1 Fick’s First Law127

5.2 Fick’s Second Law133

5.3 Kirkendall Effect138

5.4 Mobility141

5.5 Diffusion in Ionic Solids145

5.6 Temperature Dependence of Diffusion146

5.7 High Diffusivity Paths148

5.8 Formation of Compounds152

5.9 Boltzmann-Matano Analysis154

References156

Appendix 5A：The Error Function156

Problems158

Chapter6 Transformations165

6.1 Types of Diffusional Transformation166

6.2 Homogeneous Nucleation168

6.3 Size Distribution of Nuclei170

6.4 Supercooling172

6.5 Heterogeneous Nucleation174

6.6 Rate of Nucleation178

6.7 Growth of Transformed Phase180

6.8 Spinodal Transformations182

References186

Appendix 6A186

Problems187

Chapter7 Reaction Kinetics191

7.1 Rate of Reaction192

7.2 Order of Reactions193

7.3 Equilibrium Constants：Relation to Reaction Rate Constants195

7.4 First-Order Reactions196

7.5 First-Order Reactions with Forward Reverse Rates198

7.6 Higher Order Reactions202

7.7 Reactions in Series204

7.8 Temperature Dependence of Reaction Rate205

7.9 Heterogeneous Reactions208

7.10 Solid State Transformation Kinetics213

References216

Problems216

Chapter8 Nonequilibrium Thermodynamics221

8.1 Entropy Generation223

8.2 Forces and Fluxes225

8.3 Onsager Reciprocity Relationship226

8.4 Thermal Diffusion227

8.5 Electromigration230

8.6 Thermal-Electrical Effects232

References238

Appendix 8A239

Index241