Materials Thermodynamics

The application of computational thermodynamic tools in the real world has been growing rapidly; the teaching of these skills needs to catch up. Meeting the demand for an updated, applications-driven text in Thermodynamics, Lecture Topics in Alloy Thermodynamics teaches the subject with a broader, more industry-oriented lens than any other book on the market to help prepare students and professionals for the real world. Stemming from the authorsÕ graduate course, this class-tested text reflects changes rapidly occurring in society at large, including the impact of computers on thermodynamics in MS&E university programs.

Y. Austin Chang is Wisconsin Distinguished Professor Emeritus in the Department of Materials Science and Engineering at the University of Wisconsin-Madison. He is a member of the National Academy of Engineering, Foreign Member of the Chinese Academy of Science, 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, all awarded by The Minerals, Metals and Materials Society (TMS). W. Alan Oates is a recipient of several wards, including the W. Hume-Rothery Award of TMS. Since 1992, Oates has held the position of Honorary Professor at the Science Research Institute, University of Salford, England.

Preface	p. xiii
Quantities, Units, and Nomenclature	p. xix
Review of Fundamentals	p. 1
Systems, Surroundings, and Work	p. 2
Thermodynamic Properties	p. 4
The Laws of Thermodynamics	p. 5
The Fundamental Equation	p. 8
Other Thermodynamic Functions	p. 9
Maxwell's Equations	p. 11
Defining Other Forms of Work	p. 11
Equilibrium State	p. 14
Exercises	p. 15
Thermodynamics of Unary Systems	p. 19
Standard State Properties	p. 19
The Effect of Pressure	p. 27
Gases	p. 28
Condensed Phases	p. 29
The Gibbs-Duhem Equation	p. 30
Experimental Methods	p. 31
Exercises	p. 32
Calculation of Thermodynamic Properties of Unary Systems	p. 35
Constant-Pressure/Constant-Volume Conversions	p. 36
Excitations in Gases	p. 37
Perfect Monatomic Gas	p. 37
Molecular Gases	p. 39
Excitations in Pure Solids	p. 39
The Thermodynamic Properties of a Pure Solid	p. 43
Inadequacies of the Model	p. 46
Exercises	p. 46
Phase Equilibria in Unary Systems	p. 49
The Thermodynamic Condition for Phase Equilibrium	p. 52
Phase Changes	p. 54
The Slopes of Boundaries in Phase Diagrams	p. 54
Gibbs Energy Change for Phase Transformations	p. 57
Stability and Critical Phenomena	p. 59
Gibbs's Phase Rule	p. 61
Exercises	p. 63
Thermodynamics of Binary Solutions I: Basic Theory and Application to Gas Mixtures	p. 67
Expressing Composition	p. 67
Total (Integral) and Partial Molar Quantities	p. 68
Relations between Partial and Integral Quantities	p. 70
Relation between Partial Quantities: the Gibbs-Duhem Equation	p. 72
Application to Gas Mixtures	p. 73
Partial Pressures	p. 73
Chemical Potentials in Perfect Gas Mixtures	p. 74
Real Gas Mixtures: Component Fugacities and Activities	p. 75
Exercises	p. 75
Thermodynamics of Binary Solutions II: Theory and Experimental Methods	p. 79
Ideal Solutions	p. 79
Real Solutions	p. 82
Dilute Solution Reference States	p. 83
Experimental Methods	p. 85
Chemical Potential Measurements	p. 86
Exercises	p. 89
Thermodynamics of Binary Solutions III: Experimental Results and Their Analytical Representation	p. 93
Some Experimental Results	p. 93
Liquid Alloys	p. 93
Solid Alloys	p. 95
Analytical Representation of Results for Liquid or Solid Solutions	p. 97
Exercises	p. 102
Two-Phase Equilibrium I: Theory	p. 103
Introduction	p. 103
Criterion for Phase Equilibrium Between Two Specified Phases	p. 104
Equilibrium between Two Solution Phases	p. 104
Equilibrium between a Solution Phase and a Stoichiometric Compound Phase	p. 107
Gibbs's Phase Rule	p. 108
Exercises	p. 110
Two-Phase Equilibrium II: Example Calculations	p. 113
Exercises	p. 121
Binary Phase Diagrams: Temperature-Composition Diagrams	p. 125
True Phase Diagrams	p. 126
T-x_i Phase Diagrams for Strictly Regular Solutions	p. 128
Some General Observations	p. 131
More on Miscibility Gaps	p. 133
The Chemical Spinodal	p. 134
Polymorphism	p. 135
Exercises	p. 136
Binary Phase Diagrams: Temperature-Chemical Potential Diagrams	p. 139
Some General Points	p. 140
Exercises	p. 146
Phase Diagram Topology	p. 149
Gibbs's Phase Rule	p. 151
Combinatorial Analysis	p. 151
Schreinemaker's Rules	p. 153
The Gibbs-Konovalov Equations	p. 154
Slopes of T-¿_i Phase Boundaries	p. 155
Slopes of T-x_i Phase Boundaries	p. 157
Some Applications of Gibbs-Konovalov Equations	p. 159
Exercises	p. 162
Solution Phase Models I: Configurational Entropies	p. 165
Substitutional Solutions	p. 168
Intermediate Phases	p. 169
Interstitial Solutions	p. 172
Exercises	p. 174
Solution Phase Models II: Configurational Energy	p. 177
Pair Interaction Model	p. 178
Ground-State Structures	p. 179
Nearest Neighbor Model	p. 180
Cluster Model	p. 183
Exercises	p. 188
Solution Models III: The Configurational Free Energy	p. 189
Helmholtz Energy Minimization	p. 190
Critical Temperature for Order/Disorder	p. 193
Exercises	p. 196
Solution Models IV: Total Gibbs Energy	p. 197
Atomic Size Mismatch Contributions	p. 199
Contributions from Thermal Excitations	p. 202
Coupling between Configurational and Thermal Excitations	p. 203
The Total Gibbs Energy in Empirical Model Calculations	p. 204
Exercises	p. 205
Chemical Equilibria I: Single Chemical Reaction Equations	p. 207
Introduction	p. 207
The Empirical Equilibrium Constant	p. 207
The Standard Equilibrium Constant	p. 208
Relation to ¿_r_G°	p. 208
Measurement of ¿_r _G°	p. 211
Calculating the Equilibrium Position	p. 213
Application of the Phase Rule	p. 217
Exercises	p. 218
Chemical Equilibria II: Complex Gas Equilibria	p. 221
The Importance of System Definition	p. 221
Calculation of Chemical Equilibrium	p. 224
Using the Extent of Reaction	p. 225
Using Lagrangian Multipliers	p. 227
Evaluation of Elemental Chemical Potentials in Complex Gas Mixtures	p. 229
Application of the Phase Rule	p. 231
Exercises	p. 232
Chemical Equilibria Between Gaseous and Condensed Phases I	p. 233
Graphical Presentation of Standard Thermochemical Data	p. 233
Ellingham Diagrams	p. 234
Chemical Potentials	p. 238
Exercises	p. 240
Chemical Equilibria Between Gaseous and Condensed Phases II	p. 243
Subsidiary Scales on Ellingham Diagrams	p. 244
System Definition	p. 247
Exercises	p. 252
Thermodynamics of Ternary Systems	p. 255
Analytical Representation of Thermodynamic Properties	p. 256
Substitutional Solution Phases	p. 256
Sublattice Phases	p. 259
Phase Equilibria	p. 260
Exercises	p. 264
Generalized Phase Diagrams for Ternary Systems	p. 267
System Definition	p. 276
Exercises	p. 278
Some Linearized Standard Gibbs Energies of Formation	p. 279
Some Useful Calculus	p. 281
Index	p. 289
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Materials Thermodynamics

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