Thermodynamics (eBook)

Front cover 1
Thermodynamics 4
Copyright page 5
Preface 6
Preface to the Second Edition 8
Preface to the First Edition 10
Contents 12
Chapter 1. Fundamentals 18
1.0 Introductory Remarks 18
1.1 Introductory Definitions 19
1.2 The Zeroth Law of Thermodynamics 22
1.3 Mathematical Apparatus 26
1.4 Thermodynamic Forces 35
1.5 Elements of Work 36
1.6 The Element of Work for a System Subjected to Electromagnetic Fields 46
1.7 The First Law of Thermodynamics 48
1.8 The First Law of Thermodynamics as a Parable 54
1.9 The Second Law of Thermodynamics 55
1.10 Cyclic processes in relation to reversibility and irreversibility 59
1.11 An Entropy Analogy 64
1.12 Constraints, Equilibrium, Functions of State 65
1.13 Systematics of Thermodynamic Functions of State 75
1.14 Interrelations Involving Heat Capacities 90
1.15 The Joule-Thomson Experiment 92
1.16 Heat Measurements and Calorimetry 97
1.17 Determination of Enthalpies and Entropies of Materials 99
1.18 The Third Law of Thermodynamics 103
1.19 The Gibbs-Duhem Relation and Its Analogs 105
1.20 Thermodynamics of Open Systems 110
1.21 Effect of Chemical Changes on Composition 120
1.22 Legendre Transforms and Stability of a System 123
Chapter 2. Equilibrium in Ideal Systems 128
2.0 Thermodynamics of Ideal Systems with Several Components and Phases 128
2.1 Coexistence of Phases: The Gibbs Phase Rule 128
2.2 Achievement of Equilibrium 131
2.3 System of one component and several phases 137
2.4 Properties of Ideal Gases 143
2.5 Properties of Ideal Solutions in Condensed Phases 147
2.6 The Duhem-Margules Equation and its Consequences 153
2.7 Temperature Dependence of Composition of Solutions 155
2.8 Lowering of the freezing point and elevation of the boiling point 156
2.9 Chemical Equilibrium: General Principles and Application to Ideal Gases 160
2.10 Chemical Equilibrium in Homogeneous Condensed Ideal Solutions 167
2.11 Chemical Equilibrium in Ideal Heterogeneous Systems 170
2.12 Equilibrium Between Two Ideal Phases 173
2.13 Chemical Irreversibility in Chemical Reactions The Affinity
Chapter 3. Characterization of Nonideal Solutions 176
3.0 Introductory Remarks 176
3.1 Thermodynamic Treatment of Nonideal Gas Mixtures 176
3.2 Temperature and Pressure Dependence of the Fugacity of a Gas 179
3.3 Thermodynamic Description of Real Solutions in the Condensed State 180
3.4 Characterization of Nonideal Solutions Preliminaries
3.5 Standardization of Thermodynamic Analysis for Nonideal Solutions 187
3.6 Reformulation of the Thermodynamic Description of Nonideal Solutions 193
3.7 Characterization of Equilibrium in Nonideal Solutions 195
3.8 Variation of Activity, Activity Coefficients with Temperature and Presssure 205
3.9 Calorimetric Functions of State in Chemical Processes 206
3.10 Equilibrium Calculations 214
3.11 Determination of Activity Coefficients 218
3.12 Oxidation Boundary for Magnetite-Zinc Ferrite Solid Solutions 225
3.13 Activity of Solvent and Solute 227
3.14 Mixing in Nonideal Solutions 231
3.15 Phase Stability: General Consequences of Deviations from Ideality 241
3.16 Discussion of Several Types of Phase Diagrams 247
3.17 Variation of Mutual Solubility with Temperature 256
Chapter 4. Thermodynamic Properties of Electrolytes 266
4.0 Introductory Comments 266
4.1 Activities of Strong Electrolytes 266
4.2 Theoretical Determination of Activities in Electrolyte Solutions 273
4.3 Experimental Determination of Activities and Activity Coefficients 275
4.4 Equilibrium Properties of Weak Electrolytes 278
4.5 Galvanic Cells 284
4.6 Operation of Galvanic Cells 286
4.7 Galvanic Cells Operational Analysis
4.8 Liquid Junction Potentials 295
4.9 EMF Dependence on Activities 296
4.10 Types of Operating Cells 299
4.11 Thermodynamic Information from Galvanic Cell Measurements 301
Chapter 5. Thermodynamic Properties of Materials in Externally Applied Fields 304
5.0 Introductory Comments 304
5.1 Thermodynamics of Gravitational Fields 304
5.2 Thermodynamics of Adsorption Processes 311
5.3 Heats of Adsorption 320
5.4 Surface vs. Bulk Effects Thermodynamics of Self-Assembly
5.5 Pressure of Electromagnetic Radiation 337
5.6 Thermodynamic Characterization of Electromagnetic Radiation 340
5.7 Effects of Electric Fields on Thermodynamic Properties of Matter 344
5.8 Systematization of Electromagnetic Field Effects in Thermodynamics 350
5.9 Adiabatic Demagnetization and Transitions to Superconductivity 360
Chapter 6. Irreversible Thermodynamics 364
6.0 Introductory Comments 364
6.1 Generalities 364
6.2 Shock Phenomena 374
6.3 Linear Phenomenological Equations 381
6.4 Steady State Conditions and Prigogine's Theorem 383
6.5 Onsager Reciprocity Conditions 384
6.6 Thermomolecular Mechanical Effects 386
6.7 Electrokinetic Phenomena 389
6.8 The Soret Effect 394
6.9 Thermoelectric Effects 396
6.10 Irreversible Thermomagnetic Phenomena in Two Dimensions 400
6.11 Chemical Processes 406
6.12 Coupled Reactions: Special Example 409
6.13 Coupled Reactions, General Case 411
Chapter 7. Critical Phenomena 414
7.0 Introductory Remarks 414
7.1 Properties of Materials Near Their Critical Point 414
7.2 Homogeneity Requirements, Correlation Lengths, Scaling Properties 421
7.3 Derivation of Griffith's and Rushbrooke's Inequality 424
7.4 Scaled Equation of State 432
7.5 Landau Theory of Critical Phenomena and Phase Transitions 432
Chapter 8. A Final Speculation About Ultimate Temperatures-A Fourth Law of Thermodynamics? 442
Chapter 9. Mathematical Proof of the Carathéodory Theorem and Resulting Interpretations Derivation of the Debye-Hückel Equation
9.1 Fundamentals 444
9.2 Proof of Holonomicity 446
9.3 Necessary Condition for Establishing the Carathéodory Theorem 450
9.4 Relevance to Thermodynamics 453
9.5 Derivation of the Limiting Form for the Debye-Hückel Equation 454
Index 462