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## 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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