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Chapter 1 Thermodynamics: Review 1

1.1 The First Law 1

1.1.1 System and Surroundings 1

1.1.2 Heat and Work 2

1.1.3 Reversibility 2

1.1.4 Internal Energy 2

1.1.5 State Functions 2

1.1.6 The First Law 2

1.1.7 Enthalpy 3

1.1.8 Intensive and Extensive Properties and Notation 3

1.1.9 Heat Capacities 3

1.1.10 Ideal Gas 4

1.1.11 Enthalpy of Formation 4

1.2 Entropy， and the Second Law 5

1.2.1 Entropy Not Conserved 5

1.2.2 Entropy Changes 5

1.2.3 Entropy Changes in Chemical Reactions and the Third Law 6

1.3 Property Relations 7

1.3.1 Free Energies 7

1.3.2 Maxwell Relations 7

1.3.3 Chemical Potentials 8

1.3.4 Partial Molar Quantities 9

1.3.5 Other Definitions 9

1.4 Equilibrium 9

1.5 Thermodynamics Activity 10

1.6 Chemical Equilibrium 11

1.7 Electrochemical Cells 11

1.8 Solutions 12

1.8.1 Ideal Solutions 12

1.8.2 Immiscibility 12

1.8.3 Regular Solutions 14

1.8.4 Spinodal Points 16

1.8.5 Gibbs-Duhem Equation 17

1.9 Phase Rule 17

problems 18

Chapter 2 Statistical Thermodynamics 27

2.1 Macrostates and Microstates 29

2.2 The Boltzmann Hypothesis 31

2.3 Entropy of Mixing 31

2.4 Systems at Constant Temperature and the Canonical Ensemble 32

2.5 Boltzmann Distribution 32

2.6 Partition Function 33

2.7 Degeneracy 33

2.8 Distinguishability of Particles 35

2.9 Ideal Gas 36

2.10 Maxwell-Boltmann Distribution: Ideal Gas 36

2.11 Fermi-Dirac Distribution 37

2.12 Effusion: Langmuir Equation 39

2.13 Mean Free Path 43

2.14 Diffusion in Gases 45

2.15 Elasticity of Rubber 50

References 61

Appendix 2A 61

Appendix 2B Evaluation of K 62

Appendix 2C Calculation of x2 63

Problems 64

Chapter 3 Defects in Solids 67

3.1 Structural Point Defects in Elemental Crystals 68

3.2 Vacancies: Experimental Veriflcation 71

3.3 Interactions Between Vacancies and Impurities 73

3.4 Interaction Between Imperfections and Impurities 75

3.5 Electronic Defects 77

3.6 Defects in Ionic Compounds 80

3.7 Frenkel Defects 81

3.8 Schottky-Wagner Defects 83

3.9 Interactions Among Defects 84

3.10 Intrinsic and Extrinsic Defects in Ionic Crystals 86

3.11 Experimental Determination of Defect Type 89

3.12 Nonstoichiometry 91

References 92

Problems 93

Chapter 4 Surfaces and Interfaces 97

4.1 Surface Energy-Surface Tension 98

4.2 Approximate Calculation of Solid Surface Energy 99

4.3 Effect of Surface Curvature 101

4.4 Vapor Pressure 105

4.5 Solubility of Small Particles 106

4.6 Melting Temperature of Small Particles 109

4.7 Measurement of Surface Energy 111

4.8 Surface Energy of Solids 112

4.9 Relative Surface Energies 114

4.10 Wetting of Surfaces 115

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

4.12 Adsolption on Solids （Adsorption Isotherms） 119

4.13 Equilibrium Shape of a Crystal 121

4.14 Effect of Temperature on Surface Energy 123

References 123

problems 123

Chapter 5 Diffusion 127

5.1 Fick’s First Law 127

5.2 Fick’s Second Law 133

5.3 Kirkendall Effect 138

5.4 Mobility 141

5.5 Diffusion in Ionic Solids 145

5.6 Temperature Dependence of Diffusion 146

5.7 High Diffusivity Paths 148

5.8 Formation of Compounds 152

5.9 Boltzmann-Matano Analysis 154

References 156

Appendix 5A: The Error Function 156

Problems 158

Chapter 6 Transformations 165

6.1 Types of Diffusional Transformation 166

6.2 Homogeneous Nucleation 168

6.3 Size Distribution of Nuclei 170

6.4 Supercooling 172

6.5 Heterogeneous Nucleation 174

6.6 Rate of Nucleation 178

6.7 Growth of Transformed Phase 180

6.8 Spinodal Transformations 182

References 186

Appendix 6A 186

Problems 187

Chapter 7 Reaction Kinetics 191

7.1 Rate of Reaction 192

7.2 Order of Reactions 193

7.3 Equilibrium Constants: Relation to Reaction Rate Constants 195

7.4 First-Order Reactions 196

7.5 First-Order Reactions with Forward Reverse Rates 198

7.6 Higher Order Reactions 202

7.7 Reactions in Series 204

7.8 Temperature Dependence of Reaction Rate 205

7.9 Heterogeneous Reactions 208

7.10 Solid State Transformation Kinetics 213

References 216

Problems 216

Chapter 8 Nonequilibrium Thermodynamics 221

8.1 Entropy Generation 223

8.2 Forces and Fluxes 225

8.3 Onsager Reciprocity Relationship 226

8.4 Thermal Diffusion 227

8.5 Electromigration 230

8.6 Thermal-Electrical Effects 232

References 238

Appendix 8A 239

Index 241