Introduction to the Thermodynamics of MaterialsPDF电子书下载

Part Ⅰ Thermodynamic Principles 1

Chapter 1 Introduction and Definition of Terms 3

1.1Introduction 3

1.2The Concept of State 4

1.3Example of Equilibrium 8

1.4The Equation of State of an Ideal Gas 9

1.5The Units of Energy and Work 12

1.6Extensive and Intensive Thermodynamic Variables 13

1.7Equilibrium Phase Diagrams and Thermodynamic Components 13

1.8Laws of Thermodynamics 16

1.8.1 The First Law of Thermodynamics 17

1.8.2 The Second Law of Thermodynamics 17

1.8.3 The Third Law of Thermodynamics 17

1.9Summary 17

1.10Concepts and Terms Introduced in Chapter 1 18

1.11Qualitative Example Problems 19

1.12Quantitative Example Problems 20

Problems 21

Chapter 2 The First Law of Thermodynamics 23

2.1Introduction 23

2.2The Relationship between Heat and Work 24

2.3Internal Energy and the First Law of Thermodynamics 25

2.4Constant-Volume Processes 29

2.5Constant-Pressure Processes and the Enthalpy，H 30

2.6Heat Capacity 31

2.7Reversible Adiabatic Processes 37

2.8Reversible Isothermal Pressure or Volume Changes of an Ideal Gas 40

2.9Other Forms of Work 41

2.9.1 Magnetic Work on a Paramagnetic Material 41

2.9.2 Electrical Work on a Dielectric Material 42

2.9.3 Work to Create or Extend a Surface 42

2.10Summary 43

2.11Concepts and Terms Introduced in Chapter 2 45

2.12 Qualitative Example Problems 45

2.13 Quantitative Example Problems 47

Problems 51

Appendix 2A：Note on the Sign Convention of δw 54

Chapter 3 The Second Law of Thermodynamics 57

3.1 Introduction 57

3.2 Spontaneous or Natural Processes 58

3.3 Entropy and the Quantification of Irreversibility 59

3.4 Reversible Processes 61

3.5 Illustration of Reversible and Irreversible Processes 61

3.5.1 The Reversible Isothermal Expansion of an Ideal Gas 62

3.5.2 The Free Expansion of an Ideal Gas 63

3.6 Further Differences between Reversible and Irreversible Expansion 64

3.7 Compression of an Ideal Gas 65

3.7.1 Reversible Isothermal Compression 65

3.8 The Adiabatic Expansion of an Ideal Gas 66

3.9 Summary Statements 67

3.10 The Properties of Heat Engines 67

3.11 The Thermodynamic Temperature Scale 71

3.12 The Second Law of Thermodynamics 74

3.13 Maximum Work 76

3.14 Entropy and the Criterion for Equilibrium 78

3.15 The Combined Statement of the First and Second Laws of Thermodynamics 79

3.16 Summary 81

3.17 Concepts and Terms Introduced in Chapter 3 83

3.18 Qualitative Example Problems 83

3.19 Quantitative Example Problems 85

Problems 90

Chapter 4 The Statistical Interpretation of Entropy 93

4.1 Introduction 93

4.2 Entropy and Disorder on an Atomic Scale 94

4.3 The Concept of Microstate 95

4.4 The Microcanonical Approach 96

4.4.1 Identical Particles on Distinguishable Sites with Different Assigned Energies 96

4.4.2 Configurational Entropy of Differing Atoms in a Crystal 98

4.4.3 Configurational Entropy of Magnetic Spins on an Array of Atoms 102

4.5 The Boltzmann Distribution 104

4.6 The Influence of Temperature 108

4.7 Thermal Equilibrium and the Boltzmann Equation 110

4.8 Heat Flow and the Production of Entropy 111

4.9 Summary 113

4.10 Concepts and Terms Introduced in Chapter 4 114

4.11 Qualitative Example Problems 115

4.12 Quantitative Example Problems 116

Problems 119

Chapter 5 Fundamental Equations and Their Relationships 121

5.1 Introduction 121

5.2 The Enthalpy，H 123

5.3 The Helmholtz Free Energy，A 123

5.4 The Gibbs Free Energy，G 128

5.5 The Fundamental Equations for a Closed System 129

5.6 The Variation of the Composition within a Closed System 131

5.7 The Chemical Potential 131

5.8 Thermodynamic Relations 134

5.9 Maxwell’s Relations 135

5.10 Examples of the Application of Maxwell Relations 137

5.10.1 The First TdS Equation 137

5.10.2 The Second TdS Equation 139

5.10.3 S and V as Dependent Variables and T and P as Independent Variables 141

5.10.4 An Energy Equation （Internal Energy） 142

5.10.5 Another Energy Equation （Enthalpy） 143

5.10.6 A Magnetic Maxwell Relation 143

5.10.7 S，V，and M with Independent Variables T，P，and ？ 144

5.11 Another Important Formula 145

5.12 The Gibbs-Helmholtz Equation 145

5.13 Summary 147

5.14 Concepts and Terms Introduced in Chapter 5 148

5.15 Qualitative Example Problems 148

5.16 Quantitative Example Problems 150

Problems 152

Chapter 6 Heat Capacity，Enthalpy，Entropy，and the Third Law of Thermodynamics 155

6.1 Introduction 155

6.2 Theoretical Calculation of the Heat Capacity 156

6.3 The Empirical Representation of Heat Capacities 162

6.4 Enthalpy as a Function of Temperature and Composition 162

6.5 The Dependence of Entropy on Temperature and the Third Law of Thermodynamics 172

6.5.1 Development of the Third Law of Thermodynamics 172

6.5.2 Apparent Contradictions to the Third Law of Thermodynamics 175

6.6 Experimental Verification of the Third Law 177

6.7 The Influence of Pressure on Enthalpy and Entropy 182

6.8 Summary 184

6.9 Concepts and Terms Introduced in Chapter 6 185

6.10 Qualitative Example Problems 186

6.11 Quantitative Example Problems 187

Problems 193

Appendix 6A 194

Part Ⅱ Phase Equilibria 199

Chapter 7 Phase Equilibrium in a One-Component System 199

7.1 Introduction 199

7.2 The Variation of Gibbs Free Energy with Temperature at Constant Pressure 200

7.3 The Variation of Gibbs Free Energy with Pressure at Constant Temperature 204

7.4 The Gibbs Free Energy as a Function of Temperature and Pressure 205

7.5 Equilibrium between the Vapor Phase and a Condensed Phase 210

7.6 Graphical Representation of Vapor Phase and Condensed Phase Equilibria 212

7.7 Solid-Solid Equilibria 212

7.8 The Effect of an Applied Magnetic Field on the P-T Diagram 217

7.9 Summary 218

7.10 Concepts and Terms Introduced in Chapter 7 219

7.11 Qualitative Example Problems 220

7.12 Quantitative Example Problems 222

Problems 226

Chapter 8 The Behavior of Gases 229

8.1 Introduction 229

8.2 The P-V-T Relationships of Gases 229

8.3 The Thermodynamic Properties of Ideal Gases and Mixtures of Ideal Gases 230

8.3.1 Mixtures of Ideal Gases 230

8.3.1.1 Mole Fraction 231

8.3.1.2 Dalton’s Law of Partial Pressures 231

8.3.1.3 Partial Molar Quantities 232

8.3.2 The Enthalpy of Mixing of Ideal Gases 234

8.3.3 The Gibbs Free Energy of Mixing of Ideal Gases 235

8.3.4 The Entropy of Mixing of Ideal Gases 236

8.4 Deviation From Ideality and Equations of State for Real Gases 236

8.5 The Van Der Waals Fluid 240

8.6 Other Equations of State for Nonideal Gases 250

8.7 Further Thermodynamic Treatment of Nonideal Gases 251

8.8 Summary 259

8.9 Concepts and Terms Introduced in Chapter 8 260

8.10 Qualitative Example Problems 260

8.11 Quantitative Example Problems 261

Problems 265

Chapter 9 The Behavior of Solutions 267

9.1 Introduction 267

9.2 Raoult’s Law and Henry’s Law 267

9.3 The Thermodynamic Activity of a Component in Solution 271

9.4 The Gibbs-Duhem Equation 273

9.5 The Gibbs Free Energy of Formation of a Solution 275

9.5.1 The Molar Gibbs Free Energy of a Solution and the Partial Molar Gibbs Free Energies of the Components of the Solution 275

9.5.2 The Change in Gibbs Free Energy due to the Formation of a Solution 277

9.5.3 The Method of Tangential Intercepts 278

9.6 The Properties of Ideal Solutions 279

9.6.1 The Change in Volume Accompanying the Formation of an Ideal Solution 279

9.6.2 The Enthalpy of Formation of an Ideal Solution 281

9.6.3 The Entropy of Formation of an Ideal Solution 282

9.7 Nonideal Solutions 285

9.8 Application of the Gibbs-Duhem Relation to the Determination of Activity 288

9.8.1 The Relationship between Henry’s and Raoult’s Laws 289

9.8.3 Direct Calculation of the Total Molar Gibbs Free Energy of Mixing 290

9.9 Regular Solutions 292

9.10 A Statistical Model of Solutions 298

9.10.1 Extensions of the Regular Solution Model：The Atomic Order Parameter 303

9.10.2 Including Second-Neighbor Interactions 306

9.11 Subregular Solutions 307

9.12 Modified Regular Solution Model for Application to Polymers 309

9.12.1 The Flory-Huggins Model 309

9.13 Summary 310

9.14 Concepts and Terms Introduced in Chapter 9 313

9.15 Qualitative Example Problems 313

9.16 Quantitative Example Problems 315

Problems 317

Chapter 10 Gibbs Free Energy Composition and Phase Diagrams of Binary Systems 321

10.1 Introduction 321

10.2 Gibbs Free Energy and Thermodynamic Activity 322

10.3 Qualitative Overview of Common Binary Equilibrium Phase Diagrams 324

10.3.1 The Lens Diagram：Regular Solution Model 324

10.3.2 Unequal Enthalpies of Mixing 325

10.3.3 The Low-Temperature Regions in Phase Diagrams 326

10.3.4 The Eutectic and Eutectoid Phase Diagrams 327

10.3.5 The Peritectic and Peritectoid Phase Diagrams 329

10.4 Liquid and Solid Standard States 331

10.5 The Gibbs Free Energy of Formation of Regular Solutions 338

10.6 Criteria for Phase Stability in Regular Solutions 341

10.7 Phase Diagrams，Gibbs Free Energy，and Thermodynamic Activity 346

10.8 The Phase Diagrams of Binary Systems That Exhibit Regular Solution Behavior in the Liquid and Solid States 356

10.9 Summary 362

10.10 Concepts and Terms Introduced in Chapter 10 364

10.11 Qualitative Example Problems 364

10.12 Quantitative Example Problems 366

Problems 371

Appendix 10A 373

Appendix 10B 376

Part Ⅲ Reactions and Transformations of Phases 381

Chapter 11 Reactions Involving Gases 381

11.1 Introduction 381

11.2 Reaction Equilibrium in a Gas Mixture and the Equilibrium Constant 382

11.3 The Effect of Temperature on the Equilibrium Constant 388

11.4 The Effect of Pressure on the Equilibrium Constant 390

11.5 Reaction Equilibrium as a Compromise between Enthalpy and Entropy 391

11.6 Reaction Equilibrium in the System SO2（g）-SO3（g）-O2（g） 394

11.6.1 The Effect of Temperature 395

11.6.2 The Effect of Pressure 396

11.6.3 The Effect of Changes in Temperature and Pressure 397

11.7 Equilibrium in H2O-H2 and CO2 -CO Mixtures 399

11.8 Summary 401

11.9 Concepts and Terms Introduced in Chapter 11 402

11.10 Qualitative Example Problems 403

11.11 Quantitative Example Problems 404

Problems 410

Chapter 12 Reactions Involving Pure Condensed Phases and a Gaseous Phase 413

12.1 Introduction 413

12.2 Reaction Equilibrium in a System Containing Pure Condensed Phases and a Gas Phase 414

12.3 The Variation of the Standard Gibbs Free Energy Change with Temperature 419

12.4 Ellingham Diagrams 422

12.5 The Effect of Phase Transformations 430

12.5.1 Example of the Oxidation of Copper 431

12.5.2 Example of the Chlorination of Iron 433

12.6 The Oxides of Carbon 435

12.6.1 The Equilibrium 2CO + O2 = 2CO2 440

12.7 Graphical Representation of Equilibria in the System Metal-Carbon-Oxygen 443

12.8 Summary 447

12.9 Concepts and Terms Introduced in Chapter 12 448

12.10 Qualitative Example Problems 448

12.11 Quantitative Example Problems 450

Problems 456

Appendix 12A 458

Appendix 12B 459

Chapter 13 Reaction Equilibria in Systems Containing Components in Condensed Solution 467

13.1 Introduction 467

13.2 The Criteria for Reaction Equilibrium in Systems Containing Components in Condensed Solution 469

13.3 Alternative Standard States 477

13.4 The Gibbs Equilibrium Phase Rule 484

13.5 Phase Stability Diagrams 489

13.6 Binary Systems Containing Compounds 503

13.7 Graphical Representation of Phase Equilibria 516

13.7.1 Phase Equilibria in the System Mg-Al-O 516

13.7.2 Phase Equilibria in the System Al-C-O-N Saturated with Carbon 520

13.8 The Formation of Oxide Phases of Variable Composition 523

13.9 The Solubility of Gases in Metals 532

13.10 Solutions Containing Several Dilute Solutes 537

13.11 Summary 547

13.12 Concepts and Terms Introduced in Chapter 13 550

13.13 Qualitative Example Problems 550

13.14 Quantitative Example Problems 551

Problems 561

Chapter 14 Electrochemistry 567

14.1 Introduction 567

14.2 The Relationship between Chemical and Electrical Driving Forces 569

14.3 The Effect of Concentration on EMF 574

14.4 Formation Cells 576

14.5 Concentration Cells 577

14.6 The Temperature Coefficient of the EMF 584

14.7 Thermal Energy （Heat） Effects 586

14.8 The Thermodynamics of Aqueous Solutions 587

14.9 The Gibbs Free Energy of Formation of Ions and Standard Reduction Potentials 591

14.9.1 Solubility Products 596

14.9.2 The Influence of Acidity 599

14.10 Pourbaix Diagrams 601

14.10.1 The Pourbaix Diagram for Aluminum 603

14.10.2 The Equilibrium between the Two Dissolved Substances 604

14.10.3 The Equilibrium between the Two Solids 605

14.10.4 One Solid in Equilibrium with a Dissolved Substance 607

14.10.5 The Solubility of Alumina in Aqueous Solutions 609

14.11 Summary 611

14.12 Concepts and Terms introduced in Chapter 14 613

14.13 Qualitative Example Problem 613

14.14 Quantitative Example Problems 614

Problems 618

Chapter 15 Thermodynamics of Phase Transformations 621

15.1 Thermodynamics and Driving Force 622

15.1.1 Phase Transformations with No Change in Composition 622

15.1.2 Phase Transformations with Change in Composition 624

15.2 Use of the T 0 Curves 626

15.2.1 Martensitic Transformation 628

15.2.2 Massive Transformations 628

15.2.3 The Formation of Amorphous Phases from the Liquid 629

15.3 Surface Energy 630

15.3.1 Equilibrium Shape 630

15.4 Nucleation and Surface Energy 632

15.4.1 Homogeneous Nucleation 632

15.4.2 Heterogeneous Nucleation 632

15.5 Capillarity and Local Equilibrium 634

15.6 Thermodynamics of the Landau Theory of Phase Transformations 636

15.7 Summary 643

15.8 Concepts and Terms Introduced in Chapter 15 643

15.9 Qualitative Example Problems 644

Problems 645

Appendix A：Selected Thermodynamic and Thermochemical Data 649

Appendix B：Exact Differential Equations 657

Appendix C：The Generation of Additional Thermodynamic Potentials as Legendre Transformations 659

Nomenclature 669

Answers to Selected Problems 671

Index 687