Table of contents for Introduction to the thermodynamics of materials / David R. Gaskell.

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Contents
Preface	xiii
1 Introduction and DeÞnition of Terms	1
1.1 Introduction	1
1.2 The Concept of State	1
1.3 Simple Equilibrium	4
1.4 The Equation of State of an Ideal Gas	5
1.5 The Units of Energy and Work	8
1.6 Extensive and Intensive Properties	8
1.7 Phase Diagrams and Thermodynamic Components	9
1.8 Numerical Examples	13
2 The First Law of Thermodynamics	15
2.1 Introduction	15
2.2 The Relationship between Heat and Work	16
2.3 Internal Energy and the First Law of Thermodynamics	17
2.4 Constant-Volume Processes	21
2.5 Constant-Pressure Processes and the Enthalpy H	21
2.6 Heat Capacity	21
2.7 Reversible Adiabatic Processes	25
2.8 Reversible Isothermal Pressure or Volume Changes 
 of an Ideal Gas	27
2.9 Summary	28
2.10 Numerical Examples	29
 Problems	34
3 The Second Law of Thermodynamics	37
3.1 Introduction	37
3.2 Spontaneous or Natural Processes	38
3.3 Entropy and the QuantiÞcation of Irreversibility	39
3.4 Reversible Processes	40
3.5 An Illustration of Irreversible and Reversible Processes	41
3.6 Entropy and Reversible Heat	43
3.7 The Reversible Isothermal Compression of an Ideal Gas	46
3.8 The Reversible Adiabatic Expansion of an Ideal Gas	47
3.9 Summary Statements	48 
3.10 The Properties of Heat Engines	48 
3.11 The Thermodynamic Temperature Scale	51 
3.12 The Second Law of Thermodynamics	53 
3.13 Maximum Work	55 
3.14 Entropy and the Criterion for Equilibrium	57 
3.15 The Combined Statement of the First and Second Laws 
 of Thermodynamics	58 
3.16 Summary	59 
3.17 Numerical Examples 61 Problems	66 
4 The Statistical Interpretation of Entropy	69 
4.1 Introduction	69 
4.2 Entropy and Disorder on an Atomic Scale	70 
4.3 The Concept of Microstate	71 
4.4 Determination of the Most Probable Microstate	72 
4.5 The Inßuence of Temperature	76 
4.6 Thermal Equilibrium and the Boltzmann Equation	78 
4.7 Heat Flow and the Production of Entropy	79 
4.8 ConÞgurational Entropy and Thermal Entropy	80 
4.9 Summary	83 
4.10 Numerical Examples	84
 Problems	86 
5 Auxiliary Functions	87 
5.1 Introduction	87 
5.2 The Enthalpy H	89 
5.3 The Helmholtz Free Energy A	89 
5.4 The Gibbs Free Energy G	94 
5.5 Summary of the Equations for a Closed System	95 
5.6 The Variation of the Composition and Size of the System	96 
5.7 The Chemical Potential	97 
5.8 Thermodynamic Relations	98 
5.9 Maxwell's Equations	99 
5.10 The Upstairs-Downstairs-Inside-Out Formula	101 
5.11 The Gibbs-Helmholtz Equation	102 
5.12 Summary 	103 
5.13 Example of the Use of the Thermodynamic Relations	104
5.14 Numerical Examples	
 Problems	106 
6 Heat Capacity, Enthalpy, Entropy, and the Third Law of 
 Thermodynamics	109 
6.1 Introduction	109 
6.2 Theoretical Calculation of the Heat Capacity	110 
6.3 The Empirical Representation of Heat Capacities	115 
6.4 Enthalpy as a Function of Temperature and Composition	116 
6.5 The Dependence of Entropy on Temperature and the Third Law 
 of Thermodynamics 	125 
6.6 Experimental VeriÞcation of the Third Law	128 
6.7 The Inßuence of Pressure on Enthalpy and Entropy	134 
6.8 Summary	136 
6.9 Numerical Examples	137
Problems 147 
7 Phase Equilibrium in a One-Component System	149 
7.1 Introduction	149 
7.2 The Variation of Gibbs Free Energy with Temperature at 
 Constant Pressure	150 
7.3 The Variation of Gibbs Free Energy with Pressure at 
 Constant Temperature	157 
7.4 Gibbs Free Energy as a Function of Temperature and Pressure	159 
7.5 Equilibrium between the Vapor Phase and a Condensed Phase	160 
7.6 Graphical Representation of Phase Equilibria in a One-Component 
 System	162 
7.7 Solid-Solid Equilibria	168 
7.8 Summary 171 Numerical Examples 172 Problems	175 
8 The Behavior of Gases	177 
8.1 Introduction	177 
8.2 The P-V-T Relationships of Gases	177 
8.3 Deviations from Ideality and Equations of State for Real Gases	180 
8.4 The van der Waals Gas	182 
8.5 Other Equations of State for Nonideal Gases	191 
8.6 The Thermodynamic Properties of Ideal Gases and Mixtures 
 of Ideal Gases	192 
8.7 The Thermodynamic Treatment of Nonideal Gases	198 
8.8 Summary	204 
8.9 Numerical Examples 206 Problems	208 
9 The Behavior of Solutions	211 
9.1 Introduction	211 
9.2 Raoult's Law and Henry's Law	211 
9.3 The Thermodynamic Activity of a Component in Solution	215 
9.4 The Gibbs-Duhem Equation	216 
9.5 The Gibbs Free Energy of Formation of a Solution	218 
9.6 The Properties of Raoultian Ideal Solutions	221 
9.7 Nonideal Solutions	226 
9.8 Application of the Gibbs-Duhem Relation to the Determination 
 of Activity	229 
9.9 Regular Solutions	240 
9.10 A Statistical Model of Solutions	245 
9.11 Subregular Solutions	252 
9.12 Summary	254 
9.13 Numerical Examples	257 
 Problems	259 
10 Gibbs Free Energy Composition and Phase Diagrams of 
 Binary Systems	263 
10.1 Introduction	263 
10.2 Gibbs Free Energy and Thermodynamic Activity	264 
10.3 The Gibbs Free Energy of Formation of Regular Solutions	266 
10.4 Criteria for Phase Stability in Regular Solutions	268 
10.5 Liquid and Solid Standard States	273 
10.6 Phase Diagrams, Gibbs Free Energy, and Thermodynamic Activity	283 
10.7 The Phase Diagrams of Binary Systems That Exhibit Regular 
 Solution Behavior in the Liquid and Solid States	292 
10.8 Summary	298 
10.9 Numerical Example	299 
 Problems	301 
11 Reactions Involving Gases	305 
11.1 Introduction	305 
11.2 Reaction Equilibrium in a Gas Mixture and the Equilibrium Constant	306 
11.3 The Effect of Temperature on the Equilibrium Constant	311 
11.4 The Effect of Pressure on the Equilibrium Constant	312 
11.5 Reaction Equilibrium as a Compromise between Enthalpy 
 and Entropy	314 
11.6 Reaction Equilibrium in the System SO2(g)/SO3(g)/O2(g)	316 
11.7 Equilibrium in H2O/H2 and CO2/CO Mixtures	321 
11.8 Summary	323 
11.9 Numerical Examples	324 
 Problems	335 
12 Reactions Involving Pure Condensed Phases and a Gaseous 
 Phase	337 
12.1 Introduction	337 
12.2 Reaction Equilibrium in a System Containing Pure Condensed 
 Phases and a Gas Phase	338 
12.3 The Variation of the Standard Gibbs Free Energy Change 
 with Temperature	343 
12.4 Ellingham Diagrams	346 
12.5 The Effect of Phase Transformations	353 
12.6 The Oxides of Carbon	358 
12.7 Graphical Representation of Equilibria in the System 
 Metal/Carbon/Oxygen	365 
12.8 Summary	368 
12.9 Numerical Examples 369 Problems	380 
13 Reaction Equilibria in Systems Containing Components 
 in Condensed Solution	383 
13.1 Introduction	383 
13.2 The Criteria for Reaction Equilibrium in Systems Containing 
 Components in Condensed Solution	385 
13.3 Alternative Standard States	393 
13.4 The Gibbs Phase Rule	399 
13.5 Binary Systems Containing Compounds	417 
13.6 Graphical Representation of Phase Equilibria	429 
13.7 The Formation of Oxide Phases of Variable Composition	437 
13.8 The Solubility of Gases in Metals	446 
13.9 Solutions Containing Several Dilute Solutes	450 
13.10 Summary	460 
13.11 Numerical Examples	462 
 Problems	470 
14 Phase Diagrams for Binary Systems in Pressure-Temperature
 -Composition Space	475 
14.1 Introduction	475 
14.2 A Binary System Exhibiting Complete Mutual Solubility of the 
 Components in the Solid and Liquid States	475 
14.3 A Binary System Exhibiting Complete Mutual Solubility in the Solid 
 and Liquid States and Showing Minima on the Melting, Boiling, 
 and Sublimation Curves	480 
14.4 A Binary System Containing a Eutectic Equilibrium and Having 
 Complete Mutual Solubility in the Liquid	485 
14.5 A Binary System Containing a Peritectic Equilibrium and Having 
 Complete Mutual Solubility in the Liquid State	493 
14.6 Phase Equilibrium in a Binary System Containing an Intermediate 
 Phase That Melts, Sublimes, and Boils Congruently	501 
14.7 Phase Equilibrium in a Binary System Containing an Intermediate 
 Phase That Melts and Sublimes Congruently and Boils Incongruently	508 
14.8 Phase Equilibrium in a Binary System with a Eutectic and One 
 Component That Exhibits Allotropy	513 
14.9 A Binary Eutectic System in Which Both Components Exhibit 
 Allotropy	517 
14.10 Phase Equilibrium at Low Pressure: The Cadmium-Zinc System	524 
14.11 Phase Equilibrium at High Pressure: The Na2OAl2O32SiO2/SiO2 
 System	525 
14.12 Summary	531 
15 Electrochemistry	533 
15.1 Introduction 533 
15.2 The Relationship between Chemical and Electrical Driving Forces	535 
15.3 The Effect of Concentration on EMF	540 
15.4 Formation Cells	541 
15.5 Concentration Cells	544 
15.6 The Temperature CoefÞcient of the EMF	549 
15.7 Heat Effects	551 
15.8 The Thermodynamics of Aqueous Solutions	552 
15.9 The Gibbs Free Energy of Formation of Ions and Standard 
 Reduction Potentials	555 
15.10 Pourbaix Diagrams	564 
15.11 Summary	574 
15.12 Numerical Examples	576 
 Problems	579 
Appendices 
A Selected Thermodynamic and Thermochemical Data	581 
B Exact Differential Equations	589 
C The Generation of Auxiliary Functions as Legendre Transformations	591 
Nomenclature	599 
Answers	603 
Index	615 

Library of Congress Subject Headings for this publication:

Metallurgy.
Thermodynamics.
Materials -- Thermal properties.