Introduction To The Thermodynamics Of Materials, Fourth Edition

by Gaskell,David

• ISBN13: 9781560329923
• ISBN10: 1560329920
• Edition: 4th
• Format: Hardcover
• Copyright: 2003-02-07
• Publisher: Taylor & Franci

Summary

The Fourth Edition of this classic textbook is a complete and authoritative introductory text on the thermodynamics of materials. With a new chapter (Chapter 14) and two new appendices providing thermodynamic and thermochemical data, the Fourth Edition includes extensive references to scientific reviews and original articles. Introduction to the Thermodynamics of Materialsis used universally as an introduction to the application of the thermodynamic method to understanding the behavior of materials systems. Aimed primarily at third-year undergraduate students of metallurgy, metallurgical engineering, ceramics, or materials science, this book will also be useful to graduate students and working professionals in need of a reference or a refresher course. A solutions manual is available to qualified instructors. NEW IN THE 4TH EDITION: - A new chapter covering Phase Diagrams for Binary Systems in Pressure-Temperature-Composition Space -Two new appendices: ExactDifferential Equations and Generation of Auxiliary Functions as Legendre Transformations - A CD containing thermodynamic properties of 50 commonly used compounds. The data and descriptive material on the CD enables students to make detailed thermodynamic calculations involving materials processing.

Author Biography

David R. Gaskell is currently a Professor of Materials Engineering at the University of Pennsylvania.

Table of Contents

Preface	xiii
Introduction and Definition of Terms	1	(14)
Introduction	1	(1)
The Concept of State	1	(3)
Simple Equilibrium	4	(1)
The Equation of State of an Ideal Gas	5	(3)
The Units of Energy and Work	8	(1)
Extensive and Intensive Properties	8	(1)
Phase Diagrams and Thermodynamic Components	9	(6)
The First Law of Thermodynamics	15	(22)
Introduction	15	(1)
The Relationship between Heat and Work	16	(1)
Internal Energy and the First Law of Thermodynamics	17	(4)
Constant-Volume Processes	21	(1)
Constant-Pressure Processes and the Enthalpy H	21	(1)
Heat Capacity	21	(4)
Reversible Adiabatic Processes	25	(2)
Reversible Isothermal Pressure or Volume Changes of an Ideal Gas	27	(1)
Summary	28	(1)
Numerical Examples	29	(8)
Problems	34	(3)
The Second Law of Thermodynamics	37	(32)
Introduction	37	(1)
Spontaneous or Natural Processes	38	(1)
Entropy and the Quantification of Irreversibility	39	(1)
Reversible Processes	40	(1)
An Illustration of Irreversible and Reversible Processes	41	(2)
Entropy and Reversible Heat	43	(3)
The Reversible Isothermal Compression of an Ideal Gas	46	(1)
The Reversible Adiabatic Expansion of an Ideal Gas	47	(1)
Summary Statements	48	(1)
The Properties of Heat Engines	48	(3)
The Thermodynamic Temperature Scale	51	(2)
The Second Law of Thermodynamics	53	(2)
Maximum Work	55	(2)
Entropy and the Criterion for Equilibrium	57	(1)
The Combined Statement of the First and Second Laws of Thermodynamics	58	(1)
Summary	59	(2)
Numerical Examples	61	(8)
Problems	66	(3)
The Statistical Interpretation of Entropy	69	(18)
Introduction	69	(1)
Entropy and Disorder on an Atomic Scale	70	(1)
The Concept of Microstate	71	(1)
Determination of the Most Probable Microstate	72	(4)
The Influence of Temperature	76	(2)
Thermal Equilibrium and the Boltzmann Equation	78	(1)
Heat Flow and the Production of Entropy	79	(1)
Configurational Entropy and Thermal Entropy	80	(3)
Summary	83	(1)
Numerical Examples	84	(3)
Problems	86	(1)
Auxiliary Functions	87	(22)
Introduction	87	(2)
The Enthalpy H	89	(1)
The Helmholtz Free Energy A	89	(5)
The Gibbs Free Energy G	94	(1)
Summary of the Equations for a Closed System	95	(1)
The Variation of the Composition and Size of the System	96	(1)
The Chemical Potential	97	(1)
Thermodynamic Relations	98	(1)
Maxwell's Equations	99	(2)
The Upstairs-Downstairs-Inside-Out Formula	101	(1)
The Gibbs-Helmholtz Equation	102	(1)
Summary	103	(1)
Example of the Use of the Thermodynamic Relations	104	(5)
Problems	106	(3)
Heat Capacity, Enthalpy, Entropy, and the Third Law of Thermodynamics	109	(40)
Introduction	109	(1)
Theoretical Calculation of the Heat Capacity	110	(5)
The Empirical Representation of Heat Capacities	115	(1)
Enthalpy as a Function of Temperature and Composition	116	(9)
The Dependence of Entropy on Temperature and the Third Law of Thermodynamics	125	(3)
Experimental Verification of the Third Law	128	(6)
The Influence of Pressure on Enthalpy and Entropy	134	(2)
Summary	136	(1)
Numerical Examples	137	(12)
Problems	147	(2)
Phase Equilibrium in a One-Component System	149	(28)
Introduction	149	(1)
The Variation of Gibbs Free Energy with Temperature at Constant Pressure	150	(7)
The Variation of Gibbs Free Energy with Pressure at Constant Temperature	157	(2)
Gibbs Free Energy as a Function of Temperature and Pressure	159	(1)
Equilibrium between the Vapor Phase and a Condensed Phase	160	(2)
Graphical Representation of Phase Equilibria in a One-Component System	162	(6)
Solid-Solid Equilibria	168	(3)
Summary	171	(6)
Numerical Examples	172	(3)
Problems	175	(2)
The Behavior of Gases	177	(34)
Introduction	177	(1)
The P-V-T Relationships of Gases	177	(3)
Deviations from Ideality and Equations of State for Real Gases	180	(2)
The van der Waals Gas	182	(9)
Other Equations of State for Nonideal Gases	191	(1)
The Thermodynamic Properties of Ideal Gases and Mixtures of Ideal Gases	192	(6)
The Thermodynamic Treatment of Nonideal Gases	198	(6)
Summary	204	(2)
Numerical Examples	206	(5)
Problems	208	(3)
The Behavior of Solutions	211	(52)
Introduction	211	(1)
Raoult's Law and Henry's Law	211	(4)
The Thermodynamic Activity of a Component in Solution	215	(1)
The Gibbs-Duhem Equation	216	(2)
The Gibbs Free Enrgy of Formation of a Solution	218	(3)
The Properties of Raoultian Ideal Solutions	221	(5)
Nonideal Solutions	226	(3)
Application of the Gibbs-Duhem Relation to the Determination of Activity	229	(11)
Regular Solutions	240	(5)
A Statistical Model of Solutions	245	(7)
Subregular Solutions	252	(2)
Summary	254	(3)
Numerical Examples	257	(6)
Problems	259	(4)
Gibbs Free Energy Composition and Phase Diagrams of Binary Systems	263	(42)
Introduction	263	(1)
Gibbs Free Energy and Thermodynamic Activity	264	(2)
The Gibbs Free Energy of Formation of Regular Solutions	266	(2)
Criteria for Phase Stability in Regular Solutions	268	(5)
Liquid and Solid Standard States	273	(10)
Phase Diagrams, Gibbs Free Energy, and Thermodynamic Activity	283	(9)
The Phase Diagrams of Binary Systems That Exhibit Regular Solution Behavior in the Liquid and Solid States	292	(6)
Summary	298	(1)
Numerical Examples	299	(6)
Problems	301	(4)
Reactions Involving Gases	305	(32)
Introduction	305	(1)
Reaction Equilibrium in a Gas Mixture and the Equilibrium Constant	306	(5)
The Effect of Temperature on the Equilibrium Constant	311	(1)
The Effect of Pressure on the Equilibrium Constant	312	(2)
Reaction Equilibrium as a Compromise between Enthalpy and Entropy	314	(2)
Reaction Equilibriu in the System SO2(g)-SO3(g)-O2(g)	316	(5)
Equilibrium in H2O-H2 and CO2-CO Mixtures	321	(2)
Summary	323	(1)
Numerical Examples	324	(13)
Problems	335	(2)
Reactions Involving Pure Condensed Phases and a Gaseous Phase	337	(46)
Introduction	337	(1)
Reaction Equilibrium in a System Containing Pure Condensed Phases and a Gas Phase	338	(5)
The Variation of the Standard Gibbs Free Energy Change with Temperature	343	(3)
Ellingham Diagrams	346	(7)
The Effect of Phase Transformations	353	(5)
The Oxides of Carbon	358	(7)
Graphical Representation of Equilibria in the System Metal-Carbon-Oxygen	365	(3)
Summary	368	(1)
Numerical Examples	369	(14)
Problems	380	(3)
Reaction Equilibria in Systems Containing Components in Condensed Solution	383	(92)
Introduction	383	(2)
The Criteria for Reaction Equilibrium in Systems Containing Components in Condensed Solution	385	(8)
Alternative Standard States	393	(6)
The Gibbs Phase Rule	399	(18)
Binary Systems Containing Compounds	417	(12)
Graphical Representation of Phase Equilibria	429	(8)
The Formation of Oxide Phases of Variable Composition	437	(9)
The Solubility of Gases in Metals	446	(4)
Solutions Containing Several Dilute Solutes	450	(10)
Summary	460	(2)
Numerical Examples	462	(13)
Problems	470	(5)
Phase Diagrams for Binary Systems in Pressure-Temperature-Composition Space	475	(58)
Introduction	475	(1)
A Binary System Exhibiting Complete Mutual Solubility of the Components in the Solid and Liquid States	475	(5)
A Binary System Exhibiting Complete Mutual Solubility in the Solid and Liquid States and Showing Minima on the Melting, Boiling, and Sublimation Curves	480	(5)
A Binary System Containing a Eutectic Equilibrium and Having Complete Mutual Solubility in the Liquid	485	(8)
A Binary System Containing a Peritectic Equilibrium and Having Complete Mutual Solubility in the Liquid State	493	(8)
Phase Equilibrium in a Binary System Containing an Intermediate γ Phase That Melts, Sublimes, and Boils Congruently	501	(7)
Phase Equilibrium in a Binary System Containing an Intermediate γ Phase That Melts and Sublimes Congruently and Boils Incongruently	508	(5)
Phase Equilibrium in a Binary System with a Eutectic and One Component That Exhibits Allotropy	513	(4)
A Binary Eutectic System in Which Both Components Exhibit Allotropy	517	(7)
Phase Equilibrium at Low Pressure: The Cadmium-Zinc System	524	(1)
Phase Equilibrium at High Pressure: The Na2O.Al2O3.2SiO2-SiO2 System	525	(6)
Summary	531	(2)
Electrochemistry	533	(66)
Introduction	533	(2)
The Relationship between Chemical and Electrical Driving Forces	535	(5)
The Effect of Concentration on EMF	540	(1)
Formation Cells	541	(3)
Concentration Cells	544	(5)
The Temperature Coefficient of the EMF	549	(2)
Heat Effects	551	(1)
The Thermodynamics of Aqueous Solutions	552	(3)
The Gibbs Free Energy of Formation of Ions and Standard Reduction Potentials	555	(9)
Pourbaix Diagrams	564	(10)
Summary	574	(2)
Numerical Examples	576	(5)
Problems	579	(2)
Appendices
A Selected Thermodynamic and Thermochemical Data	581	(8)
B Exact Differential Equations	589	(2)
C The Generation of Auxiliary Functions as Legendre Transformations	591	(8)
Nomenclature	599	(4)
Answers	603	(12)
Index	615