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El. knyga: Materials Thermodynamics [Wiley Online]

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Materials ThermodynamicsDidesnis paveikslėlis
Kitos knygos pagal šią temą:
Wiley Online E-booksMore info about Wiley Online
Partnerių interneto svetainė: https://onlinelibrary.wiley.com/doi/book/10.1002/9780470549940
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 largefrom 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.
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 –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 ΔrG°
208
17.3.2 Measurement of ΔrG°
211
17.4 Calculating the Equilibrium Position
213
17.5 Application of the Phase Rule
217
Exercises
218
18 Chemical Equilibria H: 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
Y. Austin Chang is Wisconsin Distinguished Professor Emeritus in the Department of Materials Science and Engineering at the University of WisconsinMadison. 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.æSince 1992, Oates has held the position of Honorary Professor at the Science Research Institute, University of Salford, England.
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