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Introduction to the Thermodynamics of Materials, Fifth Edition

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CRC Press
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This is the 5th edition with a publication date of 3/13/2008.
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For more than thirty years, this text has been the definitive introduction to the thermodynamic principles of materials and their multitude of applications. New to this edition is a detailed discussion of acetylene combustion and a numerical explanation for the expansion of ideal gases, as well as additional worked examples covering a wide variety of applied thermodynamics concepts.

Author Biography

David R. Gaskell, School of Materials Engineering, Purdue University, West Lafayette, IN

Table of Contents

Prefacep. xiii
Introduction and Definition of Termsp. 1
Introductionp. 1
The Concept of Statep. 1
Simple Equilibriump. 4
The Equation of State of an Ideal Gasp. 5
The Units of Energy and Workp. 8
Extensive and Intensive Propertiesp. 8
Phase Diagrams and Thermodynamic Componentsp. 9
Numerical Examplesp. 12
The First Law of Thermodynamicsp. 15
Introductionp. 15
The Relationship between Heat and Workp. 16
Internal Energy and the First Law of Thermodynamicsp. 17
Constant-Volume Processesp. 21
Constant-Pressure Processes and the Enthalpy Hp. 21
Heat Capacityp. 21
Reversible Adiabatic Processesp. 25
Reversible Isothermal Pressure or Volume Changes of an Ideal Gasp. 27
Summaryp. 28
Numerical Examplesp. 29
Problemsp. 34
The Second Law of Thermodynamicsp. 37
Introductionp. 37
Spontaneous or Natural Processesp. 38
Entropy and the Quantification of Irreversibilityp. 39
Reversible Processesp. 40
An Illustration of Irreversible and Reversible Processesp. 41
Entropy and Reversible Heatp. 43
The Reversible Isothermal Compression of an Ideal Gasp. 46
The Reversible Adiabatic Expansion of an Ideal Gasp. 47
Summary Statementsp. 48
The Properties of Heat Enginesp. 48
The Thermodynamic Temperature Scalep. 51
The Second Law of Thermodynamicsp. 53
Maximum Workp. 55
Entropy and the Criterion for Equilibriump. 57
The Combined Statement of the First and Second Laws of Thermodynamicsp. 58
Summaryp. 59
Numerical Examplesp. 61
Problemsp. 66
The Statistical Interpretation of Entropyp. 69
Introductionp. 69
Entropy and Disorder on an Atomic Scalep. 70
The Concept of Microstatep. 71
Determination of the Most Probable Microstatep. 72
The Influence of Temperaturep. 76
Thermal Equilibrium and the Boltzmann Equationp. 78
Heat Flow and the Production of Entropyp. 79
Configurational Entropy and Thermal Entropyp. 80
Summaryp. 83
Numerical Examplesp. 84
Problemsp. 86
Auxiliary Functionsp. 87
Introductionp. 87
The Enthalpy Hp. 88
The Helmholtz Free Energy Ap. 89
The Gibbs Free Energy Gp. 94
Summary of the Equations for a Closed Systemp. 95
The Variation of the Composition and Size of the Systemp. 95
The Chemical Potentialp. 97
Thermodynamic Relationsp. 98
Maxwell's Equationsp. 98
The Upstairs-Downstairs-Inside-Out Formulap. 101
The Gibbs-Helmholtz Equationp. 102
Summaryp. 103
Example of the Use of the Thermodynamic Relationsp. 104
Numerical Examplep. 105
Problemsp. 107
Heat Capacity, Enthalpy, Entropy, and the Third Law of Thermodyanmicsp. 109
Introductionp. 109
Theoretical Calculation of the Heat Capacityp. 110
The Empirical Representation of Heat Capacitiesp. 114
Enthalpy as a Function of Temperature and Compositionp. 115
The Dependence of Entropy on Temperature and the Third Law of Thermodynamicsp. 124
Experimental Verification of the Third Lawp. 127
The Influence of Pressure on Enthalpy and Entropyp. 133
Summaryp. 135
Numerical Examplesp. 135
Problemsp. 147
Phase Equilibrium in a One-Component Systemp. 149
Introductionp. 149
The Variation of Gibbs Free Energy with Temperature at Constant Pressurep. 150
The Variation of Gibbs Free Energy with Pressure at Constant Temperaturep. 157
Gibbs Free Energy as a Function of Temperature and Pressurep. 159
Equilibrium between the Vapor Phase and a Condensed Phasep. 160
Graphical Representation of Phase Equilibria in a One-Component Systemp. 162
Solid-Solid Equilibriap. 168
Summaryp. 171
Numerical Examplesp. 172
Problemsp. 175
The Behavior of Gasesp. 177
Introductionp. 177
The P-V-T Relationships of Gasesp. 177
Deviations from Ideality and Equations of State for Real Gasesp. 180
The van der Waals Gasp. 182
Other Equations of State for Nonideal Gasesp. 191
The Thermodynamic Properties of Ideal Gases and Mixtures of Ideal Gasesp. 192
The Thermodynamic Treatment of Nonideal Gasesp. 198
Summaryp. 204
Numerical Examplesp. 206
Problemsp. 208
The Behavior of Solutionsp. 211
Introductionp. 211
Raoult's Law and Henry's Lawp. 211
The Thermodynamic Activity of a Component in Solutionp. 215
The Gibbs-Duhem Equationp. 216
The Gibbs Free Energy of Formation of a Solutionp. 218
The Properties of Raoultian Ideal Solutionsp. 221
Nonideal Solutionsp. 226
Application of the Gibbs-Duhem Relation to the Determination of Activityp. 229
Regular Solutionsp. 240
A Statistical Model of Solutionsp. 245
Subregular Solutionsp. 252
Summaryp. 254
Numerical Examplesp. 257
Problemsp. 259
Gibbs Free Energy Composition and Phase Diagrams of Binary Systemsp. 263
Introductionp. 263
Gibbs Free Energy and Thermodynamic Activityp. 264
The Gibbs Free Energy of Formation of Regular Solutionsp. 266
Criteria for Phase Stability in Regular Solutionsp. 268
Liquid and Solid Standard Statesp. 273
Phase Diagrams, Gibbs Free Energy, and Thermodynamic Activityp. 283
The Phase Diagrams of Binary Systems That Exhibit Regular Solution Behavior in the Liquid and Solid Statesp. 292
Summaryp. 298
Numerical Examplep. 299
Problemsp. 301
Reactions Involving Gasesp. 305
Introductionp. 305
Reaction Equilibrium in a Gas Mixture and the Equilibrium Constantp. 306
The Effect of Temperature on the Equilibrium Constantp. 311
The Effect of Pressure on the Equilibrium Constantp. 312
Reaction Equilibrium as a Compromise between Enthalpy and Entropyp. 314
Reaction Equilibrium in the System SO[subscript 2(g)]-SO[subscript 3(g)]-O[subscript 2(g)]p. 316
Equilibrium in H[subscript 2]O-H[subscript 2] and CO[subscript 2]-CO Mixturesp. 321
Summaryp. 323
Numerical Examplesp. 324
Problemsp. 335
Reactions Involving Pure Condensed Phases and a Gaseous Phasep. 337
Introductionp. 337
Reaction Equilibrium in a System Containing Pure Condensed Phases and a Gas Phasep. 338
The Variation of the Standard Gibbs Free Energy Change with Temperaturep. 343
Ellingham Diagramsp. 346
The Effect of Phase Transformationsp. 353
The Oxides of Carbonp. 358
Graphical Representation of Equilibria in the System Metal-Carbon-Oxygenp. 365
Summaryp. 368
Numerical Examplesp. 369
Problemsp. 380
Reaction Equilibria in Systems Containing Components in Condensed Solutionp. 383
Introductionp. 383
The Criteria for Reaction Equilibrium in Systems Containing Components in Condensed Solutionp. 385
Alternative Standard Statesp. 393
The Gibbs Phase Rulep. 399
Binary Systems Containing Compoundsp. 417
Graphical Representation of Phase Equilibriap. 429
The Formation of Oxide Phases of Variable Compositionp. 437
The Solubility of Gases in Metalsp. 446
Solutions Containing Several Dilute Solutesp. 450
Summaryp. 460
Numerical Examplesp. 462
Problemsp. 470
Phase Diagrams for Binary Systems in Pressure-Temperature-Composition Spacep. 475
Introductionp. 475
A Binary System Exhibiting Complete Mutual Solubility of the Components in the Solid and Liquid Statesp. 475
A Binary System Exhibiting Complete Mutual Solubility in the Solid and Liquid States and Showing Minima on the Melting, Boiling, and Sublimation Curvesp. 480
A Binary System Containing a Eutectic Equilibrium and Having Complete Mutual Solubility in the Liquidp. 485
A Binary System Containing a Peritectic Equilibrium and Having Complete Mutual Solubility in the Liquid Statep. 493
Phase Equilibrium in a Binary System Containing an Intermediate [gamma] Phase That Melts, Sublimes, and Boils Congruentlyp. 501
Phase Equilibrium in a Binary System Containing an Intermediate [gamma] Phase That Melts and Sublimes Congruently and Boils Incongruentlyp. 508
Phase Equilibrium in a Binary System with a Eutectic and One Component That Exhibits Allotropyp. 513
A Binary Eutectic System in Which Both Components Exhibit Allotropyp. 517
Phase Equilibrium at Low Pressure: The Cadmium-Zinc Systemp. 524
Phase Equilibrium at High Pressure: The Na[subscript 2]O-Al[subscript 2]O[subscript 3]-2SiO[subscript 2]-SiO[subscript 2] Systemp. 525
Summaryp. 531
Electrochemistryp. 533
Introductionp. 533
The Relationship between Chemical and Electrical Driving Forcesp. 535
The Effect of Concentration on EMFp. 540
Formation Cellsp. 541
Concentration Cellsp. 544
The Temperature Coefficient of the EMFp. 549
Heat Effectsp. 551
The Thermodynamics of Aqueous Solutionsp. 552
The Gibbs Free Energy of Formation of Ions and Standard Reduction Potentialsp. 555
Pourbaix Diagramsp. 564
Summaryp. 574
Numerical Examplesp. 576
Problemsp. 579
Selected Thermodynamic and Thermochemical Datap. 581
Exact Differential Equationsp. 589
The Generation of Auxiliary Functions as Legendre Transformationsp. 591
Nomenclaturep. 599
Answersp. 603
Indexp. 615
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