Introduction to the Thermodynamics of Materials, Fifth Edition

by Gaskell; David R.

• ISBN13: 9781591690436
• ISBN10: 1591690439
• Edition: 5th
• Format: Hardcover
• Copyright: 2008-03-13
• Publisher: CRC Press

Summary

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

Preface	p. xiii
Introduction and Definition of Terms	p. 1
Introduction	p. 1
The Concept of State	p. 1
Simple Equilibrium	p. 4
The Equation of State of an Ideal Gas	p. 5
The Units of Energy and Work	p. 8
Extensive and Intensive Properties	p. 8
Phase Diagrams and Thermodynamic Components	p. 9
Numerical Examples	p. 12
The First Law of Thermodynamics	p. 15
Introduction	p. 15
The Relationship between Heat and Work	p. 16
Internal Energy and the First Law of Thermodynamics	p. 17
Constant-Volume Processes	p. 21
Constant-Pressure Processes and the Enthalpy H	p. 21
Heat Capacity	p. 21
Reversible Adiabatic Processes	p. 25
Reversible Isothermal Pressure or Volume Changes of an Ideal Gas	p. 27
Summary	p. 28
Numerical Examples	p. 29
Problems	p. 34
The Second Law of Thermodynamics	p. 37
Introduction	p. 37
Spontaneous or Natural Processes	p. 38
Entropy and the Quantification of Irreversibility	p. 39
Reversible Processes	p. 40
An Illustration of Irreversible and Reversible Processes	p. 41
Entropy and Reversible Heat	p. 43
The Reversible Isothermal Compression of an Ideal Gas	p. 46
The Reversible Adiabatic Expansion of an Ideal Gas	p. 47
Summary Statements	p. 48
The Properties of Heat Engines	p. 48
The Thermodynamic Temperature Scale	p. 51
The Second Law of Thermodynamics	p. 53
Maximum Work	p. 55
Entropy and the Criterion for Equilibrium	p. 57
The Combined Statement of the First and Second Laws of Thermodynamics	p. 58
Summary	p. 59
Numerical Examples	p. 61
Problems	p. 66
The Statistical Interpretation of Entropy	p. 69
Introduction	p. 69
Entropy and Disorder on an Atomic Scale	p. 70
The Concept of Microstate	p. 71
Determination of the Most Probable Microstate	p. 72
The Influence of Temperature	p. 76
Thermal Equilibrium and the Boltzmann Equation	p. 78
Heat Flow and the Production of Entropy	p. 79
Configurational Entropy and Thermal Entropy	p. 80
Summary	p. 83
Numerical Examples	p. 84
Problems	p. 86
Auxiliary Functions	p. 87
Introduction	p. 87
The Enthalpy H	p. 88
The Helmholtz Free Energy A	p. 89
The Gibbs Free Energy G	p. 94
Summary of the Equations for a Closed System	p. 95
The Variation of the Composition and Size of the System	p. 95
The Chemical Potential	p. 97
Thermodynamic Relations	p. 98
Maxwell's Equations	p. 98
The Upstairs-Downstairs-Inside-Out Formula	p. 101
The Gibbs-Helmholtz Equation	p. 102
Summary	p. 103
Example of the Use of the Thermodynamic Relations	p. 104
Numerical Example	p. 105
Problems	p. 107
Heat Capacity, Enthalpy, Entropy, and the Third Law of Thermodyanmics	p. 109
Introduction	p. 109
Theoretical Calculation of the Heat Capacity	p. 110
The Empirical Representation of Heat Capacities	p. 114
Enthalpy as a Function of Temperature and Composition	p. 115
The Dependence of Entropy on Temperature and the Third Law of Thermodynamics	p. 124
Experimental Verification of the Third Law	p. 127
The Influence of Pressure on Enthalpy and Entropy	p. 133
Summary	p. 135
Numerical Examples	p. 135
Problems	p. 147
Phase Equilibrium in a One-Component System	p. 149
Introduction	p. 149
The Variation of Gibbs Free Energy with Temperature at Constant Pressure	p. 150
The Variation of Gibbs Free Energy with Pressure at Constant Temperature	p. 157
Gibbs Free Energy as a Function of Temperature and Pressure	p. 159
Equilibrium between the Vapor Phase and a Condensed Phase	p. 160
Graphical Representation of Phase Equilibria in a One-Component System	p. 162
Solid-Solid Equilibria	p. 168
Summary	p. 171
Numerical Examples	p. 172
Problems	p. 175
The Behavior of Gases	p. 177
Introduction	p. 177
The P-V-T Relationships of Gases	p. 177
Deviations from Ideality and Equations of State for Real Gases	p. 180
The van der Waals Gas	p. 182
Other Equations of State for Nonideal Gases	p. 191
The Thermodynamic Properties of Ideal Gases and Mixtures of Ideal Gases	p. 192
The Thermodynamic Treatment of Nonideal Gases	p. 198
Summary	p. 204
Numerical Examples	p. 206
Problems	p. 208
The Behavior of Solutions	p. 211
Introduction	p. 211
Raoult's Law and Henry's Law	p. 211
The Thermodynamic Activity of a Component in Solution	p. 215
The Gibbs-Duhem Equation	p. 216
The Gibbs Free Energy of Formation of a Solution	p. 218
The Properties of Raoultian Ideal Solutions	p. 221
Nonideal Solutions	p. 226
Application of the Gibbs-Duhem Relation to the Determination of Activity	p. 229
Regular Solutions	p. 240
A Statistical Model of Solutions	p. 245
Subregular Solutions	p. 252
Summary	p. 254
Numerical Examples	p. 257
Problems	p. 259
Gibbs Free Energy Composition and Phase Diagrams of Binary Systems	p. 263
Introduction	p. 263
Gibbs Free Energy and Thermodynamic Activity	p. 264
The Gibbs Free Energy of Formation of Regular Solutions	p. 266
Criteria for Phase Stability in Regular Solutions	p. 268
Liquid and Solid Standard States	p. 273
Phase Diagrams, Gibbs Free Energy, and Thermodynamic Activity	p. 283
The Phase Diagrams of Binary Systems That Exhibit Regular Solution Behavior in the Liquid and Solid States	p. 292
Summary	p. 298
Numerical Example	p. 299
Problems	p. 301
Reactions Involving Gases	p. 305
Introduction	p. 305
Reaction Equilibrium in a Gas Mixture and the Equilibrium Constant	p. 306
The Effect of Temperature on the Equilibrium Constant	p. 311
The Effect of Pressure on the Equilibrium Constant	p. 312
Reaction Equilibrium as a Compromise between Enthalpy and Entropy	p. 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 Mixtures	p. 321
Summary	p. 323
Numerical Examples	p. 324
Problems	p. 335
Reactions Involving Pure Condensed Phases and a Gaseous Phase	p. 337
Introduction	p. 337
Reaction Equilibrium in a System Containing Pure Condensed Phases and a Gas Phase	p. 338
The Variation of the Standard Gibbs Free Energy Change with Temperature	p. 343
Ellingham Diagrams	p. 346
The Effect of Phase Transformations	p. 353
The Oxides of Carbon	p. 358
Graphical Representation of Equilibria in the System Metal-Carbon-Oxygen	p. 365
Summary	p. 368
Numerical Examples	p. 369
Problems	p. 380
Reaction Equilibria in Systems Containing Components in Condensed Solution	p. 383
Introduction	p. 383
The Criteria for Reaction Equilibrium in Systems Containing Components in Condensed Solution	p. 385
Alternative Standard States	p. 393
The Gibbs Phase Rule	p. 399
Binary Systems Containing Compounds	p. 417
Graphical Representation of Phase Equilibria	p. 429
The Formation of Oxide Phases of Variable Composition	p. 437
The Solubility of Gases in Metals	p. 446
Solutions Containing Several Dilute Solutes	p. 450
Summary	p. 460
Numerical Examples	p. 462
Problems	p. 470
Phase Diagrams for Binary Systems in Pressure-Temperature-Composition Space	p. 475
Introduction	p. 475
A Binary System Exhibiting Complete Mutual Solubility of the Components in the Solid and Liquid States	p. 475
A Binary System Exhibiting Complete Mutual Solubility in the Solid and Liquid States and Showing Minima on the Melting, Boiling, and Sublimation Curves	p. 480
A Binary System Containing a Eutectic Equilibrium and Having Complete Mutual Solubility in the Liquid	p. 485
A Binary System Containing a Peritectic Equilibrium and Having Complete Mutual Solubility in the Liquid State	p. 493
Phase Equilibrium in a Binary System Containing an Intermediate [gamma] Phase That Melts, Sublimes, and Boils Congruently	p. 501
Phase Equilibrium in a Binary System Containing an Intermediate [gamma] Phase That Melts and Sublimes Congruently and Boils Incongruently	p. 508
Phase Equilibrium in a Binary System with a Eutectic and One Component That Exhibits Allotropy	p. 513
A Binary Eutectic System in Which Both Components Exhibit Allotropy	p. 517
Phase Equilibrium at Low Pressure: The Cadmium-Zinc System	p. 524
Phase Equilibrium at High Pressure: The Na[subscript 2]O-Al[subscript 2]O[subscript 3]-2SiO[subscript 2]-SiO[subscript 2] System	p. 525
Summary	p. 531
Electrochemistry	p. 533
Introduction	p. 533
The Relationship between Chemical and Electrical Driving Forces	p. 535
The Effect of Concentration on EMF	p. 540
Formation Cells	p. 541
Concentration Cells	p. 544
The Temperature Coefficient of the EMF	p. 549
Heat Effects	p. 551
The Thermodynamics of Aqueous Solutions	p. 552
The Gibbs Free Energy of Formation of Ions and Standard Reduction Potentials	p. 555
Pourbaix Diagrams	p. 564
Summary	p. 574
Numerical Examples	p. 576
Problems	p. 579
Appendices
Selected Thermodynamic and Thermochemical Data	p. 581
Exact Differential Equations	p. 589
The Generation of Auxiliary Functions as Legendre Transformations	p. 591
Nomenclature	p. 599
Answers	p. 603
Index	p. 615
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