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Chapter 1 First Law1

1.1 System and Surroundings1

1.2 Energy Transfer2

1.3 Energy of a System4

1.4 Energy as a State Function5

1.5 Work5

1.6 The Closed System7

1.7 Notation8

1.8 Intensive and Extensive Properties9

1.9 The Open System10

1.10 Enthalpy11

1.11 Steady State11

1.12 Heat Capacity at Constant Volume12

1.13 Heat Capacity at Constant Pressure13

1.14 Adiabatic Flow Through a Valve: Joule-Thomson Expansion16

1.15 Equations of State17

1.16 Nonideal Gases22

1.17 Adiabatic Compression or Expansion26

1.18 Enthalpies of Formation29

1.19 Enthalpy Changes in Chemical Reactions31

1.20 Adiabatic Temperature Change in Chemical Reactions34

References38

Problems38

Chapter 2 Second Law45

2.1 Entropy as a State Function46

2.2 Entropy Not Conserved49

2.3 Open System Entropy Balance50

2.4 Adiabatic, Reversible, Steady State System50

2.5 Heat Engines51

2.6 Diagrammatic Representation54

2.7 Refrigerators55

2.8 Heat Pumps57

2.9 Entropy Changes57

2.10 Entropy Changes in Chemical Reactions and the Third Law60

References62

Problems62

Chapter 3 Property Relationships67

3.1 The Property Relation69

3.2 The Functions F and G70

3.3 Chemical Potentials71

3.4 Partial Molar Quantities73

3.5 Property Relations Derived from U, H, F, and G75

3.6 Ideal Gas78

3.7 Entropy of Mixing78

3.8 Heat Capacity80

3.9 Variation of Heat Capacity81

3.10 Isentropic Pressure-Temperature Relationship82

3.11 Isentropic Compression of Solids83

3.12 Thermoelastic Effect84

3.13 Compressibility87

3.14 Magnetic Effects89

References93

Problems93

Chapter 4 Equilibrium97

4.1 Condition of Equilibrium98

4.2 Barometric Equation100

4.3 Phase Equilibria101

4.4 Special Case: Closed System, Constant Volume103

4.5 First-Order Transitions: Variation of Equilibrium Pressure with Temperature104

4.6 Clapeyron Equation in Vapor Equilibria107

4.7 Variation of Vapor Pressure of a Condensed Phase with Total Applied Pressure109

4.8 Variation of Vapor Pressure with Particle Size111

4.9 Second-Order Transitions112

4.10 Superconductivity: An Example114

References116

Problems116

Chapter 5 Chemical Equilibrium119

5.1 Thermodynamic Activity119

5.2 Chemical Equilibrium122

5.3 Gaseous Equilibria123

5.4 Solid-Vapor Equilibria125

5.5 Sources of Information on ？G°127

5.6 Ellingham Diagrams130

5.7 Variation of Equilibrium Constant with Temperature135

5.8 Gases Dissolved in Metals (Sievert's Law)138

5.9 Chemical Equilibrium and Adiabatic Flame Temperatures139

References144

Problems144

Chapter 6 Electrochemistry149

6.1 Electrochemical Cell150

6.2 Nomenclature151

6.3 Calculation of Cell Voltage152

6.4 Direction of Reaction153

6.5 Half-Cell Reactions154

6.6 Variation of Voltage with Concentration: Nernst Equation156

6.7 Pourbaix Diagrams156

6.8 Concentration Cells159

6.9 Oxygen Pressure Determination161

6.10 Temperature Dependence of Voltage162

6.11 Electrochemical Potential162

References164

Problems164

Chapter 7 Solutions169

7.1 Thermodynamic Activity169

7.2 Partial Molar Quantities171

7.3 Relative Partial Molar Quantities173

7.4 Entropy of Mixing: Ideal Solution174

7.5 Enthalpy of Mixing: Ideal Solution174

7.6 Graphical Representation175

7.7 Nonideal Solutions178

7.8 Gibbs-Duhem Relation181

7.9 Dilute Solutions and Colligative Properties183

7.10 Integrating the Gibbs-Duhem Equation184

7.11 Regular Solutions186

7.12 Regular Solutions: Atomistic Interpretation188

7.13 Polymer Solutions190

7.14 Osmotic Pressure192

References195

Problems195

Chapter 8 Phase Rule199

8.1 Phases199

8.2 Components200

8.3 Specifying a System200

8.4 Equilibrium Conditions201

8.5 Gibbs Phase Rule201

8.6 One-Component System201

8.7 Examples202

8.8 Phase Rule for Condensed Systems204

Problems205

Chapter 9 Phase Diagrams207

9.1 Freezing Point Depression208

9.2 The Lever Rule211

9.3 Simple Eutectic Diagram213

9.4 Cooling Curves214

9.5 Complete Miscibility216

9.6 Immiscibility220

9.7 Spinodal Points222

9.8 Peritectic Phase Diagrams224

9.9 Compounds225

9.10 Ternary Diagrams225

References234

Problems234

Chapter 10 Statistical Thermodynamics245

10.1 Average Velocity of Gas Molecules246

10.2 Macrostates and Microstates249

10.3 Isolated Systems and the Boltzmann Hypothesis252

10.4 The Third Law254

10.5 Systems at Constant Temperature255

10.6 Information and Entropy256

10.7 Boltzmann Distribution258

10.8 Degeneracy262

10.9 Partition Function263

10.10 Distinguishability of Particles264

10.11 Ideal Gas265

10.12 Maxwell-Boltzmann Distribution: Ideal Gas267

10.13 Fermi-Dirac Distribution270

10.14 Heat Capacity of Solids274

10.15 Molecular Weight Distribution in Polymers278

10.16 Entropy of Mixing of Polymer Solutions284

References287

Appendix 10.A: Proof that β = 1/kT287

Problems288

Appendix Background293

A.1 Length294

A.2 Mass and Amount of Material294

A.3 Time294

A.4 Electric Current295

A.5 Temperature295

A.6 Force296

A.7 Pressure296

A.8 Volume296

A.9 Energy296

A.10 Power297

A.11 Composition297

A.12 Checking Units298

A.13 Logarithms299

A.14 Differentials300

A.15 Partial Derivatives300

A.16 Total Differential301

A.17 Factorials301

A.18 Homogeneous Functions302

A.19 Lagrange Method of Undetermined Multipliers302

Exercises in Unit Conversions306

Index309