A timely, applications-driven text in thermodynamics Materials Thermodynamics provides both students and professionals with the in-depth explanation they need to prepare for the real-world application of thermodynamic tools. Based upon an actual graduate course taught by the authors, this class-tested text covers the subject with a broader, more industry-oriented lens than can be found in any other resource available. This modern approach: * Reflects changes rapidly occurring in society at large--from the impact of computers on the teaching of thermodynamics in materials science and…mehr
A timely, applications-driven text in thermodynamics Materials Thermodynamics provides both students and professionals with the in-depth explanation they need to prepare for the real-world application of thermodynamic tools. Based upon an actual graduate course taught by the authors, this class-tested text covers the subject with a broader, more industry-oriented lens than can be found in any other resource available. This modern approach: * Reflects changes rapidly occurring in society at large--from the impact of computers on the teaching of thermodynamics in materials science and engineering university programs to the use of approximations of higher order than the usual Bragg-Williams in solution-phase modeling * Makes students aware of the practical problems in using thermodynamics * Emphasizes that the calculation of the position of phase and chemical equilibrium in complex systems, even when properly defined, is not easy * Relegates concepts like equilibrium constants, activity coefficients, free energy functions, and Gibbs-Duhem integrations to a relatively minor role * Includes problems and exercises, as well as a solutions manual This authoritative text is designed for students and professionals in materials science and engineering, particularly those in physical metallurgy, metallic materials, alloy design and processing, corrosion, oxidation, coatings, and high-temperature alloys.Hinweis: Dieser Artikel kann nur an eine deutsche Lieferadresse ausgeliefert werden.
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 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, all awarded by The Minerals, Metals and Materials Society (TMS). W. Alan Oates is a recipient of several awards, 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.
Inhaltsangabe
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 Changes 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 - i 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 r G 208 17.3.2 Measurement of r 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
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 Changes 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 - i 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 r G 208 17.3.2 Measurement of r 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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