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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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