ISBN-10:
0470484144
ISBN-13:
9780470484142
Pub. Date:
12/14/2009
Publisher:
Wiley
Materials Thermodynamics / Edition 1

Materials Thermodynamics / Edition 1

by Y. Austin Chang, W. Alan Oates

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Product Details

ISBN-13: 9780470484142
Publisher: Wiley
Publication date: 12/14/2009
Series: Wiley Series on Processing of Engineering Materials Series , #7
Pages: 320
Product dimensions: 6.30(w) x 9.30(h) x 0.80(d)

About the Author

Y. Austin Chang is Wisconsin Distinguished ProfessorEmeritus in the Department of Materials Science and Engineering atthe University of Wisconsin–Madison. He is a member of theNational Academy of Engineering, Foreign Member of the ChineseAcademy of Sciences, and the recipient of many honors and awards,including the J. Willard Gibbs Award, the Gold Medal, and A. E.White Distinguished Teacher Award of ASM International, and the W.Hume-Rothery Award, John Bardeen Award, and the Educator Award, allawarded by The Minerals, Metals and Materials Society (TMS).

W. Alan Oates is a recipient of several awards, includingthe W. Hume-Rothery Award of TMS.—Since 1992, Oates has heldthe position of Honorary Professor at the Science ResearchInstitute, University of Salford, England.

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Table of Contents

Preface xiii

Quantities, Units, and Nomenclature xix

1 Review of Fundamentals 1

1.1 Systems, Surroundings, and Work 2

1.2 Thermodynamic Properties 4

1.3 The Laws of Thermodynamics 5

1.4 The Fundamental Equation 8

1.5 Other Thermodynamic Functions 9

1.5.1 Maxwell's Equations 11

1.5.2 Defining Other Forms of Work 11

1.6 Equilibrium State 14

Exercises 15

2 Thermodynamics of Unary Systems 19

2.1 Standard State Properties 19

2.2 The Effect of Pressure 27

2.2.1 Gases 28

2.2.2 Condensed Phases 29

2.3 The Gibbs-Duhem Equation 30

2.4 Experimental Methods 31

Exercises 32

3 Calculation of Thermodynamic Properties of Unary Systems 35

3.1 Constant-Pressure/Constant-Volume Conversions 36

3.2 Excitations in Gases 37

3.2.1 Perfect Monatomic Gas 37

3.2.2 Molecular Gases 39

3.3 Excitations in Pure Solids 39

3.4 The Thermodynamic Properties of a Pure Solid 43

3.4.1 Inadequacies of the Model 46

Exercises 46

4 Phase Equilibria in Unary Systems 49

4.1 The Thermodynamic Condition for Phase Equilibrium 52

4.2 Phase Changes 54

4.2.1 The Slopes of Boundaries in Phase Diagrams 54

4.2.2 Gibbs Energy Change for Phase Transformations 57

4.3 Stability and Critical Phenomena 59

4.4 Gibbs's Phase Rule 61

Exercises 63

5 Thermodynamics of Binary Solutions I: Basic Theory and Application to Gas Mixtures 67

5.1 Expressing Composition 67

5.2 Total (Integral) and Partial Molar Quantities 68

5.2.1 Relations between Partial and Integral Quantities 70

5.2.2 Relation between Partial Quantities: the Gibbs-Duhem Equation 72

5.3 Application to Gas Mixtures 73

5.3.1 Partial Pressures 73

5.3.2 Chemical Potentials in Perfect Gas Mixtures 74

5.3.3 Real Gas Mixtures: Component Fugacities and Activities 75

Exercises 75

6 Thermodynamics of Binary Solutions II: Theory and Experimental Methods 79

6.1 Ideal Solutions 79

6.1.1 Real Solutions 82

6.1.2 Dilute Solution Reference States 83

6.2 Experimental Methods 85

6.2.1 Chemical Potential Measurements 86

Exercises 89

7 Thermodynamics of Binary Solutions III: Experimental Results and Their Analytical Representation 93

7.1 Some Experimental Results 93

7.1.1 Liquid Alloys 93

7.1.2 Solid Alloys 95

7.2 Analytical Representation of Results for Liquid or Solid Solutions 97

Exercises 102

8 Two-Phase Equilibrium I: Theory 103

8.1 Introduction 103

8.2 Criterion for Phase Equilibrium Between Two Specified Phases 104

8.2.1 Equilibrium between Two Solution Phases 104

8.2.2 Equilibrium between a Solution Phase and a Stoichiometric Compound Phase 107

8.3 Gibbs's Phase Rule 108

Exercises 110

9 Two-Phase Equilibrium II: Example Calculations 113

Exercises 121

10 Binary Phase Diagrams: Temperature-Composition Diagrams 125

10.1 True Phase Diagrams 126

10.2 T-xi Phase Diagrams for Strictly Regular Solutions 128

10.2.1 Some General Observations 131

10.2.2 More on Miscibility Gaps 133

10.2.3 The Chemical Spinodal 134

10.3 Polymorphism 135

Exercises 136

11 Binary Phase Diagrams: Temperature-Chemical Potential Diagrams 139

11.1 Some General Points 140

Exercises 146

12 Phase Diagram Topology 149

12.1 Gibbs's Phase Rule 151

12.2 Combinatorial Analysis 151

12.3 Schreinemaker's Rules 153

12.4 The Gibbs-Konovalov Equations 154

12.4.1 Slopes of T-μi Phase Boundaries 155

12.4.2 Slopes of T-xi Phase Boundaries 157

12.4.3 Some Applications of Gibbs-Konovalov Equations 159

Exercises 162

13 Solution Phase Models I: Configurational Entropies 165

13.1 Substitutional Solutions 168

13.2 Intermediate Phases 169

13.3 Interstitial Solutions 172

Exercises 174

14 Solution Phase Models II: Configurational Energy 177

14.1 Pair Interaction Model 178

14.1.1 Ground-State Structures 179

14.1.2 Nearest Neighbor Model 180

14.2 Cluster Model 183

Exercises 188

15 Solution Models III: The Configurational Free Energy 189

15.1 Helmholtz Energy Minimization 190

15.2 Critical Temperature for Order/Disorder 193

Exercises 196

16 Solution Models IV: Total Gibbs Energy 197

16.1 Atomic Size Mismatch Contributions 199

16.2 Contributions from Thermal Excitations 202

16.2.1 Coupling between Configurational and Thermal Excitations 203

16.3 The Total Gibbs Energy in Empirical Model Calculations 204

Exercises 205

17 Chemical Equilibria I: Single Chemical Reaction Equations 207

17.1 Introduction 207

17.2 The Empirical Equilibrium Constant 207

17.3 The Standard Equilibrium Constant 208

17.3.1 Relation to ΔrG° 208

17.3.2 Measurement of Δr G° 211

17.4 Calculating the Equilibrium Position 213

17.5 Application of the Phase Rule 217

Exercises 218

18 Chemical Equilibria II: Complex Gas Equilibria 221

18.1 The Importance of System Definition 221

18.2 Calculation of Chemical Equilibrium 224

18.2.1 Using the Extent of Reaction 225

18.2.2 Using Lagrangian Multipliers 227

18.3 Evaluation of Elemental Chemical Potentials in Complex Gas Mixtures 229

18.4 Application of the Phase Rule 231

Exercises 232

19 Chemical Equilibria Between Gaseous and Condensed Phases I 233

19.1 Graphical Presentation of Standard Thermochemical Data 233

19.2 Ellingham Diagrams 234

19.2.1 Chemical Potentials 238

Exercises 240

20 Chemical Equilibria Between Gaseous and Condensed Phases II 243

20.1 Subsidiary Scales on Ellingham Diagrams 244

20.2 System Definition 247

Exercises 252

21 Thermodynamics of Ternary Systems 255

21.1 Analytical Representation of Thermodynamic Properties 256

21.1.1 Substitutional Solution Phases 256

21.1.2 Sublattice Phases 259

21.2 Phase Equilibria 260

Exercises 264

22 Generalized Phase Diagrams for Ternary Systems 267

22.1 System Definition 276

Exercises 278

Appendix A Some Linearized Standard Gibbs Energies of Formation 279

Appendix B Some Useful Calculus 281

Index 289

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