Introduction to the thermodynamics of materials Fourth Edition2025|PDF|Epub|mobi|kindle电子书版本百度云盘下载

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1 Introduction and Definition of Terms1

1.1 Introduction1

1.2 The Concept of State1

1.3 Simple Equilibrium4

1.4 The Equation of State of an Ideal Gas5

1.5 The Units of Energy and Work8

1.6 Extensive and Intensive Properties8

1.7 Phase Diagrams and Thermodynamic Components9

2 The First Law of Thermodynamics15

2.1 Introduction15

2.2 The Relationship between Heat and Work16

2.3 Internal Energy and the First Law of Thermodynamics17

2.4 Constant-Volume Processes21

2.5 Constant-Pressure Processes and the Enthalpy H21

2.6 Heat Capacity21

2.7 Reversible Adiabatic Processes25

2.8 Reversible Isothermal Pressure or Volume Changes of an Ideal Gas27

2.9 Summary28

2.10 Numerical Examples29

Problems34

3 The Second Law of Thermodynamics37

3.1 Introduction37

3.2 Spontaneous or Natural Processes38

3.3 Entropy and the Quantification of Irreversibility39

3.4 Reversible Processes40

3.5 An Illustration of Irreversible and Reversible Processes41

3.6 Entropy and Reversible Heat43

3.7 The Reversible Isothermal Compression of an Ideal Gas46

3.8 The Reversible Adiabatic Expansion of an Ideal Gas47

3.9 Summary Statements48

3.10 The Properties of Heat Engines48

3.11 The Thermodynamic Temperature Scale51

3.12 The Second Law of Thermodynamics53

3.13 Maximum Work55

3.14 Entropy and the Criterion for Equilibrium57

3.15 The Combined Statement of the First and Second Laws of Thermodynamics58

3.16 Summary59

3.17 Numerical Examples61

Problems66

4 The Statistical Interpretation of Entropy69

4.1 Introduction69

4.2 Entropy and Disorder on an Atomic Scale70

4.3 The Concept of Microstate71

4.4 Determination of the Most Probable Microstate72

4.5 The Influence of Temperature76

4.6 Thermal Equilibrium and the Boltzmann Equation78

4.7 Heat Flow and the Production of Entropy79

4.8 Configurational Entropy and Thermal Entropy80

4.9 Summary83

4.10 Numerical Examples84

Problems86

5 Auxiliary Functions87

5.1 Introduction87

5.2 The Enthalpy H89

5.3 The Helmholtz Free Energy A89

5.4 The Gibbs Free Energy G94

5.5 Summary of the Equations for a Closed System95

5.6 The Variation of the Composition and Size of the System96

5.7 The Chemical Potential97

5.8 Thermodynamic Relations98

5.9 Maxwell's Equations99

5.10 The Upstairs-Downstairs-Inside-Out Formula101

5.11 The Gibbs-Helmholtz Equation102

5.12 Summary103

5.13 Example of the Use of the Thermodynamic Relations104

Problems106

6 Heat Capacity, Enthalpy, Entropy,and the Third Law of Thermodynamics109

6.1 Introduction109

6.2 Theoretical Calculation of the Heat Capacity110

6.3 The Empirical Representation of Heat Capacities115

6.4 Enthalpy as a Function of Temperature and Composition116

6.5 The Dependence of Entropy on Temperature and the Third Law of Thermodynamics125

6.6 Experimental Verification of the Third Law128

6.7 The Influence of Pressure on Enthalpy and Entropy134

6.8 Summary136

6.9 Numerical Examples137

Problems147

7 Phase Equilibrium in a One-Component System149

7.1 Introduction149

7.2 The Variation of Gibbs Free Energy with Temperature at Constant Pressure150

7.3 The Variation of Gibbs Free Energy with Pressure at Constant Temperature157

7.4 Gibbs Free Energy as a Function of Temperature and Pressure159

7.5 Equilibrium between the Vapor Phase and a Condensed Phase160

7.6 Graphical Representation of Phase Equilibria in a One-Component System162

7.7 Solid-Solid Equilibria168

7.8 Summary171

Numerical Examples172

Problems175

8 The Behavior of Gases177

8.1 Introduction177

8.2 The P-V-T Relationships of Gases177

8.3 Deviations from Ideality and Equations of State for Real Gases180

8.4 The van der Waals Gas182

8.5 Other Equations of State for Nonideal Gases191

8.6 The Thermodynamic Properties of Ideal Gases and Mixtures of Ideal Gases192

8.7 The Thermodynamic Treatment of Nonideal Gases198

8.8 Summary204

8.9 Numerical Examples206

Problems208

9 The Behavior of Solutions211

9.1 Introduction211

9.2 Raoult's Law and Henry's Law211

9.3 The Thermodynamic Activity of a Component in Solution215

9.4 The Gibbs-Duhem Equation216

9.5 The Gibbs Free Energy of Formation of a Solution218

9.6 The Properties of Raoultian Ideal Solutions221

9.7 Nonideal Solutions226

9.8 Application of the Gibbs-Duhem Relation to the Determination of Activity229

9.9 Regular Solutions240

9.10 A Statistical Model of Solutions245

9.11 Subregular Solutions252

9.12 Summary254

9.13 Numerical Examples257

Problems259

10 Gibbs Free Energy Composition and Phase Diagrams of Binary Systems263

10.1 Introduction263

10.2 Gibbs Free Energy and Thermodynamic Activity264

10.3 The Gibbs Free Energy of Formation of Regular Solutions266

10.4 Criteria for Phase Stability in Regular Solutions268

10.5 Liquid and Solid Standard States273

10.6 Phase Diagrams, Gibbs Free Energy, and Thermodynamic Activity283

10.7 The Phase Diagrams of Binary Systems That Exhibit Regular Solution Behavior in the Liquid and Solid States292

10.8 Summary298

10.9 Numerical Example299

Problems301

11 Reactions Involving Gases305

11.1 Introduction305

11.2 Reaction Equilibrium in a Gas Mixture and the Equilibrium Constant306

11.3 The Effect of Temperature on the Equilibrium Constant311

11.4 The Effect of Pressure on the Equilibrium Constant312

11.5 Reaction Equilibrium as a Compromise between Enthalpy and Entropy314

11.6 Reaction Equilibrium in the System SO2（g）-SO3（g）-O2（g）316

11.7 Equilibrium in H2O-H2 and CO2-CO Mixtures321

11.8 Summary323

11.9 Numerical Examples324

Problems335

12 Reactions Involving Pure Condensed Phases and a Gaseous Phase337

12.1 Introduction337

12.2 Reaction Equilibrium in a System Containing Pure Condensed Phases and a Gas Phase338

12.3 The Variation of the Standard Gibbs Free Energy Change with Temperature343

12.4 Ellingham Diagrams346

12.5 The Effect of Phase Transformations353

12.6 The Oxides of Carbon358

12.7 Graphical Representation of Equilibria in the System Metal-Carbon-Oxygen365

12.8 Summary368

12.9 Numerical Examples369

Problems380

13 Reaction Equilibria in Systems Containing Components in Condensed Solution383

13.1 Introduction383

13.2 The Criteria for Reaction Equilibrium in Systems Containing Components in Condensed Solution385

13.3 Alternative Standard States393

13.4 The Gibbs Phase Rule399

13.5 Binary Systems Containing Compounds417

13.6 Graphical Representation of Phase Equilibria429

13.7 The Formation of Oxide Phases of Variable Composition437

13.8 The Solubility of Gases in Metals446

13.9 Solutions Containing Several Dilute Solutes450

13.10 Summary460

13.11 Numerical Examples462

Problems470

14 Phase Diagrams for Binary Systems in Pressure-Temperature-Composition Space475

14.1 Introduction475

14.2 A Binary System Exhibiting Complete Mutual Solubility of the Components in the Solid and Liquid States475

14.3 A Binary System Exhibiting Complete Mutual Solubility in the Solid and Liquid States and Showing Minima on the Melting, Boiling, and Sublimation Curves480

14.4 A Binary System Containing a Eutectic Equilibrium and Having Complete Mutual Solubility in the Liquid485

14.5 A Binary System Containing a Peritectic Equilibrium and Having Complete Mutual Solubility in the Liquid State493

14.6 Phase Equilibrium in a Binary System Containing an Intermediate γ Phase That Melts, Sublimes,and Boils Congruently501

14.7 Phase Equilibrium in a Binary System Containing an Intermediate γ Phase That Melts and Sublimes Congruently and Boils Incongruently508

14.8 Phase Equilibrium in a Binary System with a Eutectic and One Component That Exhibits Allotropy513

14.9 A Binary Eutectic System in Which Both Components Exhibit Allotropy517

14.10 Phase Equilibrium at Low Pressure:The Cadmium-Zinc System524

14.11 Phase Equilibrium at High Pressure:The Na2O·Al2O3.2SiO2-SiO2 System525

14.12 Summary531

15 Electrochemistry533

15.1 Introduction533

15.2 The Relationship between Chemical and Electrical Driving Forces535

15.3 The Effect of Concentration on EMF540

15.4 Formation Cells541

15.5 Concentration Cells544

15.6 The Temperature Coefficient of the EMF549

15.7 Heat Effects551

15.8 The Thermodynamics of Aqueous Solutions552

15.9 The Gibbs Free Energy of Formation of Ions and Standard Reduction Potentials555

15.10 Pourbaix Diagrams564

15.11 Summary574

15.12 Numerical Examples576

Problems579

Appendices581

A Selected Thermodynamic and Thermochemical Data581

B Exact Differential Equations589

C The Generation of Auxiliary Functions as Legendre Transformations591

Nomenclature599

Answers603

Index615