| |

| |

Preface | |

| |

| |

| |

Introduction and Definition of Terms | |

| |

| |

| |

Introduction | |

| |

| |

| |

The Concept of State | |

| |

| |

| |

Simple Equilibrium | |

| |

| |

| |

The Equation of State of an Ideal Gas | |

| |

| |

| |

The Units of Energy and Work | |

| |

| |

| |

Extensive and Intensive Properties | |

| |

| |

| |

Phase Diagrams and Thermodynamic Components | |

| |

| |

| |

Numerical Examples | |

| |

| |

| |

The First Law of Thermodynamics | |

| |

| |

| |

Introduction | |

| |

| |

| |

The Relationship between Heat and Work | |

| |

| |

| |

Internal Energy and the First Law of Thermodynamics | |

| |

| |

| |

Constant-Volume Processes | |

| |

| |

| |

Constant-Pressure Processes and the Enthalpy H | |

| |

| |

| |

Heat Capacity | |

| |

| |

| |

Reversible Adiabatic Processes | |

| |

| |

| |

Reversible Isothermal Pressure or Volume Changes of an Ideal Gas | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

| |

The Second Law of Thermodynamics | |

| |

| |

| |

Introduction | |

| |

| |

| |

Spontaneous or Natural Processes | |

| |

| |

| |

Entropy and the Quantification of Irreversibility | |

| |

| |

| |

Reversible Processes | |

| |

| |

| |

An Illustration of Irreversible and Reversible Processes | |

| |

| |

| |

Entropy and Reversible Heat | |

| |

| |

| |

The Reversible Isothermal Compression of an Ideal Gas | |

| |

| |

| |

The Reversible Adiabatic Expansion of an Ideal Gas | |

| |

| |

| |

Summary Statements | |

| |

| |

| |

The Properties of Heat Engines | |

| |

| |

| |

The Thermodynamic Temperature Scale | |

| |

| |

| |

The Second Law of Thermodynamics | |

| |

| |

| |

Maximum Work | |

| |

| |

| |

Entropy and the Criterion for Equilibrium | |

| |

| |

| |

The Combined Statement of the First and Second Laws of Thermodynamics | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

| |

The Statistical Interpretation of Entropy | |

| |

| |

| |

Introduction | |

| |

| |

| |

Entropy and Disorder on an Atomic Scale | |

| |

| |

| |

The Concept of Microstate | |

| |

| |

| |

Determination of the Most Probable Microstate | |

| |

| |

| |

The Influence of Temperature | |

| |

| |

| |

Thermal Equilibrium and the Boltzmann Equation | |

| |

| |

| |

Heat Flow and the Production of Entropy | |

| |

| |

| |

Configurational Entropy and Thermal Entropy | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

| |

Auxiliary Functions | |

| |

| |

| |

Introduction | |

| |

| |

| |

The Enthalpy H | |

| |

| |

| |

The Helmholtz Free Energy A | |

| |

| |

| |

The Gibbs Free Energy G | |

| |

| |

| |

Summary of the Equations for a Closed System | |

| |

| |

| |

The Variation of the Composition and Size of the System | |

| |

| |

| |

The Chemical Potential | |

| |

| |

| |

Thermodynamic Relations | |

| |

| |

| |

Maxwell's Equations | |

| |

| |

| |

The Upstairs-Downstairs-Inside-Out Formula | |

| |

| |

| |

The Gibbs-Helmholtz Equation | |

| |

| |

| |

Summary | |

| |

| |

| |

Example of the Use of the Thermodynamic Relations | |

| |

| |

| |

Numerical Example | |

| |

| |

Problems | |

| |

| |

| |

Heat Capacity, Enthalpy, Entropy, and the Third Law of Thermodyanmics | |

| |

| |

| |

Introduction | |

| |

| |

| |

Theoretical Calculation of the Heat Capacity | |

| |

| |

| |

The Empirical Representation of Heat Capacities | |

| |

| |

| |

Enthalpy as a Function of Temperature and Composition | |

| |

| |

| |

The Dependence of Entropy on Temperature and the Third Law of Thermodynamics | |

| |

| |

| |

Experimental Verification of the Third Law | |

| |

| |

| |

The Influence of Pressure on Enthalpy and Entropy | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

| |

Phase Equilibrium in a One-Component System | |

| |

| |

| |

Introduction | |

| |

| |

| |

The Variation of Gibbs Free Energy with Temperature at Constant Pressure | |

| |

| |

| |

The Variation of Gibbs Free Energy with Pressure at Constant Temperature | |

| |

| |

| |

Gibbs Free Energy as a Function of Temperature and Pressure | |

| |

| |

| |

Equilibrium between the Vapor Phase and a Condensed Phase | |

| |

| |

| |

Graphical Representation of Phase Equilibria in a One-Component System | |

| |

| |

| |

Solid-Solid Equilibria | |

| |

| |

| |

Summary | |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

| |

The Behavior of Gases | |

| |

| |

| |

Introduction | |

| |

| |

| |

The P-V-T Relationships of Gases | |

| |

| |

| |

Deviations from Ideality and Equations of State for Real Gases | |

| |

| |

| |

The van der Waals Gas | |

| |

| |

| |

Other Equations of State for Nonideal Gases | |

| |

| |

| |

The Thermodynamic Properties of Ideal Gases and Mixtures of Ideal Gases | |

| |

| |

| |

The Thermodynamic Treatment of Nonideal Gases | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

| |

The Behavior of Solutions | |

| |

| |

| |

Introduction | |

| |

| |

| |

Raoult's Law and Henry's Law | |

| |

| |

| |

The Thermodynamic Activity of a Component in Solution | |

| |

| |

| |

The Gibbs-Duhem Equation | |

| |

| |

| |

The Gibbs Free Energy of Formation of a Solution | |

| |

| |

| |

The Properties of Raoultian Ideal Solutions | |

| |

| |

| |

Nonideal Solutions | |

| |

| |

| |

Application of the Gibbs-Duhem Relation to the Determination of Activity | |

| |

| |

| |

Regular Solutions | |

| |

| |

| |

A Statistical Model of Solutions | |

| |

| |

| |

Subregular Solutions | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

| |

Gibbs Free Energy Composition and Phase Diagrams of Binary Systems | |

| |

| |

| |

Introduction | |

| |

| |

| |

Gibbs Free Energy and Thermodynamic Activity | |

| |

| |

| |

The Gibbs Free Energy of Formation of Regular Solutions | |

| |

| |

| |

Criteria for Phase Stability in Regular Solutions | |

| |

| |

| |

Liquid and Solid Standard States | |

| |

| |

| |

Phase Diagrams, Gibbs Free Energy, and Thermodynamic Activity | |

| |

| |

| |

The Phase Diagrams of Binary Systems That Exhibit Regular Solution Behavior in the Liquid and Solid States | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Example | |

| |

| |

Problems | |

| |

| |

| |

Reactions Involving Gases | |

| |

| |

| |

Introduction | |

| |

| |

| |

Reaction Equilibrium in a Gas Mixture and the Equilibrium Constant | |

| |

| |

| |

The Effect of Temperature on the Equilibrium Constant | |

| |

| |

| |

The Effect of Pressure on the Equilibrium Constant | |

| |

| |

| |

Reaction Equilibrium as a Compromise between Enthalpy and Entropy | |

| |

| |

| |

Reaction Equilibrium in the System SO[subscript 2(g)]-SO[subscript 3(g)]-O[subscript 2(g)] | |

| |

| |

| |

Equilibrium in H[subscript 2]O-H[subscript 2] and CO[subscript 2]-CO Mixtures | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

| |

Reactions Involving Pure Condensed Phases and a Gaseous Phase | |

| |

| |

| |

Introduction | |

| |

| |

| |

Reaction Equilibrium in a System Containing Pure Condensed Phases and a Gas Phase | |

| |

| |

| |

The Variation of the Standard Gibbs Free Energy Change with Temperature | |

| |

| |

| |

Ellingham Diagrams | |

| |

| |

| |

The Effect of Phase Transformations | |

| |

| |

| |

The Oxides of Carbon | |

| |

| |

| |

Graphical Representation of Equilibria in the System Metal-Carbon-Oxygen | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

| |

Reaction Equilibria in Systems Containing Components in Condensed Solution | |

| |

| |

| |

Introduction | |

| |

| |

| |

The Criteria for Reaction Equilibrium in Systems Containing Components in Condensed Solution | |

| |

| |

| |

Alternative Standard States | |

| |

| |

| |

The Gibbs Phase Rule | |

| |

| |

| |

Binary Systems Containing Compounds | |

| |

| |

| |

Graphical Representation of Phase Equilibria | |

| |

| |

| |

The Formation of Oxide Phases of Variable Composition | |

| |

| |

| |

The Solubility of Gases in Metals | |

| |

| |

| |

Solutions Containing Several Dilute Solutes | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

| |

Phase Diagrams for Binary Systems in Pressure-Temperature-Composition Space | |

| |

| |

| |

Introduction | |

| |

| |

| |

A Binary System Exhibiting Complete Mutual Solubility of the Components in the Solid and Liquid States | |

| |

| |

| |

A Binary System Exhibiting Complete Mutual Solubility in the Solid and Liquid States and Showing Minima on the Melting, Boiling, and Sublimation Curves | |

| |

| |

| |

A Binary System Containing a Eutectic Equilibrium and Having Complete Mutual Solubility in the Liquid | |

| |

| |

| |

A Binary System Containing a Peritectic Equilibrium and Having Complete Mutual Solubility in the Liquid State | |

| |

| |

| |

Phase Equilibrium in a Binary System Containing an Intermediate [gamma] Phase That Melts, Sublimes, and Boils Congruently | |

| |

| |

| |

Phase Equilibrium in a Binary System Containing an Intermediate [gamma] Phase That Melts and Sublimes Congruently and Boils Incongruently | |

| |

| |

| |

Phase Equilibrium in a Binary System with a Eutectic and One Component That Exhibits Allotropy | |

| |

| |

| |

A Binary Eutectic System in Which Both Components Exhibit Allotropy | |

| |

| |

| |

Phase Equilibrium at Low Pressure: The Cadmium-Zinc System | |

| |

| |

| |

Phase Equilibrium at High Pressure: The Na[subscript 2]O-Al[subscript 2]O[subscript 3]-2SiO[subscript 2]-SiO[subscript 2] System | |

| |

| |

| |

Summary | |

| |

| |

| |

Electrochemistry | |

| |

| |

| |

Introduction | |

| |

| |

| |

The Relationship between Chemical and Electrical Driving Forces | |

| |

| |

| |

The Effect of Concentration on EMF | |

| |

| |

| |

Formation Cells | |

| |

| |

| |

Concentration Cells | |

| |

| |

| |

The Temperature Coefficient of the EMF | |

| |

| |

| |

Heat Effects | |

| |

| |

| |

The Thermodynamics of Aqueous Solutions | |

| |

| |

| |

The Gibbs Free Energy of Formation of Ions and Standard Reduction Potentials | |

| |

| |

| |

Pourbaix Diagrams | |

| |

| |

| |

Summary | |

| |

| |

| |

Numerical Examples | |

| |

| |

Problems | |

| |

| |

Appendices | |

| |

| |

| |

Selected Thermodynamic and Thermochemical Data | |

| |

| |

| |

Exact Differential Equations | |

| |

| |

| |

The Generation of Auxiliary Functions as Legendre Transformations | |

| |

| |

Nomenclature | |

| |

| |

Answers | |

| |

| |

Index | |