Preface v
Preface to the Second Edition vii
Preface to the First Edition ix
Fundamentals 1
Introductory Remarks 1
Introductory Definitions 2
The Zeroth Law of Thermodynamics 5
Mathematical Apparatus 9
Thermodynamic Forces 18
Elements of Work 19
The Element of Work for a System Subjected to Electromagnetic Fields 29
The First Law of Thermodynamics 31
The First Law of Thermodynamics as a Parable 37
The Second Law of Thermodynamics 38
Cyclic Processes in Relation to Reversibility and Irreversibility. Carnot Efficiency 42
An Entropy Analogy 47
Constraints, Equilibrium, Functions of State 48
Systematics of Thermodynamic Functions of State 58
Interrelations Involving Heat Capacities 73
The Joule-Thomson Experiment 75
Heat Measurements and Calorimetry 80
Determination of Enthalpies and Entropies of Materials 82
The Third Law of Thermodynamics 86
The Gibbs-Duhem Relation and Its Analogs 88
Thermodynamics of Open Systems 93
Effect of Chemical Changes on Composition 103
Legendre Transforms and Stability of a System 106
Equilibrium in Ideal Systems 111
Thermodynamics of Ideal Systems with Several Components and Phases 111
Coexistence of Phases: The Gibbs Phase Rule 111
Achievement of Equilibrium 114
System of One Component and Several Phases; The Clausius-Clapeyron Equation 120
Properties of Ideal Gases 126
Properties of Ideal Solutions in Condensed Phases 130
The Duhem-Margules Equation and its Consequences 136
Temperature Dependence of Composition of Solutions 138
Lowering of the Freezing Point and Elevation of the Boiling Point of a Solution 139
Chemical Equilibrium: General Principles and Application to Ideal Gases 143
Chemical Equilibrium in Homogeneous Condensed Ideal Solutions 150
Chemical Equilibrium in Ideal Heterogeneous Systems 153
Equilibrium Between Two Ideal Phases 156
Chemical Irreversibility in Chemical Reactions; The Affinity 156
Characterization of Nonideal Solutions 159
Introductory Remarks 159
Thermodynamic Treatment of Nonideal Gas Mixtures 159
Temperature and Pressure Dependence of the Fugacity of a Gas 162
Thermodynamic Description of Real Solutions in the Condensed State 163
Characterization of Nonideal Solutions; Preliminaries 165
Standardization of Thermodynamic Analysis for Nonideal Solutions 170
Reformulation of the Thermodynamic Description of Nonideal Solutions 176
Characterization of Equilibrium in Nonideal Solutions 178
Variation of Activity, Activity Coefficients with Temperature and Presssure 188
Calorimetric Functions of State in Chemical Processes 189
Equilibrium Calculations 197
Determination of Activity Coefficients by Vapor Pressure Measurements 201
Oxidation Boundary for Magnetite-Zinc Ferrite Solid Solutions 208
Activity of Solvent and Solute from Lowering of the Freezing Point of the Solution 210
Mixing in Nonideal Solutions 214
Phase Stability: General Consequences of Deviations from Ideality 224
Discussion of Several Types of Phase Diagrams 230
Variation of Mutual Solubility with Temperature; Second Order Transitions 239
Thermodynamic Properties of Electrolytes 249
Introductory Comments 249
Activities of Strong Electrolytes 249
Theoretical Determination of Activities in Electrolyte Solutions; The Debye-Huckel Equation 256
Experimental Determination of Activities and Activity Coefficients of Strong Electrolytes 258
Equilibrium Properties of Weak Electrolytes 261
Galvanic Cells 267
Operation of Galvanic Cells 269
Galvanic Cells; Operational Analysis 272
Liquid Junction Potentials 278
EMF Dependence on Activities 279
Types of Operating Cells 282
Thermodynamic Information from Galvanic Cell Measurements 284
Thermodynamic Properties of Materials in Externally Applied Fields 287
Introductory Comments 287
Thermodynamics of Gravitational Fields 287
Thermodynamics of Adsorption Processes 294
Heats of Adsorption 303
Surface vs. Bulk Effects; Thermodynamics of Self-Assembly 310
Pressure of Electromagnetic Radiation 320
Thermodynamic Characterization of Electromagnetic Radiation 323
Effects of Electric Fields on Thermodynamic Properties of Matter 327
Systematization of Electromagnetic Field Effects in Thermodynamics 333
Adiabatic Demagnetization and Transitions to Superconductivity 343
Irreversible Thermodynamics 347
Introductory Comments 347
Generalities 347
Shock Phenomena 357
Linear Phenomenological Equations 364
Steady State Conditions and Prigogine's Theorem 366
Onsager Reciprocity Conditions 367
Thermomolecular Mechanical Effects 369
Electrokinetic Phenomena 372
The Soret Effect 377
Thermoelectric Effects 379
Irreversible Thermomagnetic Phenomena in Two Dimensions 383
Chemical Processes 389
Coupled Reactions: Special Example 392
Coupled Reactions, General Case 394
Critical Phenomena 397
Introductory Remarks 397
Properties of Materials Near Their Critical Point 397
Homogeneity Requirements, Correlation Lengths, and Scaling Properties 404
Derivation of Griffith's and Rushbrooke's Inequality 407
Scaled Equation of State 415
Landau Theory of Critical Phenomena and Phase Transitions 415
A Final Speculation About Ultimate Temperatures-A Fourth Law of Thermodynamics? 425
Mathematical Proof of the Caratheodory Theorem and Resulting Interpretations; Derivation of the Debye-Huckel Equation 427
Fundamentals 427
Proof of Holonomicity 429
Necessary Condition for Establishing the Caratheodory Theorem 433
Relevance to Thermodynamics 436
Derivation of the Limiting Form for the Debye-Huckel Equation 437
Index 445