Thermodynamics (eBook)

Front Cover 1
THERMODYNAMICS 4
Copyright Page 5
Contents 6
PREFACE TO THE SECOND EDITION 10
PREFACE TO THE FIRST EDITION 12
Chapter 1. Fundamentals 14
1.0 Introductory Comments 14
1.1 Introductory Definitions 14
1.2 Temperature and the Zeroth Law of Thermodynamics 21
1.3 Temperatures, Temperature Scales, and Temperature Measurements 25
1.4 Mathematical Apparatus 31
1.5 Thermodynamic Forces 45
1.6 The Concept of Work 48
1.7 Appendix: Derivation for the Element of Work in the Presence of Electromagnetic Fields 62
1.8 The First Law of Thermodynamics and the Concept of Heat 65
1.9 The First Law of Thermodynamics as a Parable 80
1.10 The Carathiéodory Approach to the Second Law of Thermodynamics: Preliminaries 81
1.11 Appendix. Mathematical Preparations for the Second Law of Thermodynamics: Holonomicity 85
1.12 Appendix. Mathematical Proof for the Necessary Condition of Carathiéodory's Theorem 91
1.13 The Second Law of Thermodynamics 96
1.14 An Entropy Analogy 103
1.15 Cyclic Processes in Relation to Reversibility and Irreversibility: Carnot Efficiency 104
1.16 Constraints and Equilibrium 112
1.17 Correlation of Temperatures, Entropies, and Energies 122
1.18 Functions of State in Thermodynamics 128
1.A Illustrative Example: Deductions Based on the Joule–Thomson Coefficient 146
1.19 Heat, Calorimetry, and Thermochemistry 152
1.20 Numerical Calculation of Entropies 158
1.21 The Third Law of Thermodynamics 167
1.22 The Gibbs–Duhem Equation and Its Analogs 173
1.23 Thermodynamics of Open Systems 180
1.24 Inequalities in Thermodynamics 189
1.25 A Generalization of Euler's Theorem 190
1.26 The Legendre Transform and Stability Conditions 196
Chapter 2. Equilibrium in Ideal Systems 203
2.0 Thermodynamics of Ideal Systems with Several Components and Phases 203
2.1 Coexistence of Phases: The Gibbs Phase Rule 203
2.2 Achievement of Equilibrium 209
2.3 Systems of One Component and Several Phases: The Clausius–Clapeyron Equation 218
2.4 Properties of Ideal Gases 229
2.5 Properties of Ideal Solutions in Condensed Phases 236
2.6 The Duhem–Margules Equation and Its Consequences 241
2.7 Temperature Dependence of Composition of Solutions 243
2.8 Lowering of the Freezing Point and Elevation of the Boiling Point of a Solution 245
2.9 Chemical Equilibrium: General Principles and Application to Ideal Gases 250
2.10 Chemical Equilibrium in Homogeneous Ideal Solutions 261
2.11 Chemical Equilibrium in Ideal Heterogeneous Systems 267
2.12 Equilibrium Involving Ideal Mixtures in Two Phases 273
2.13 Entropy Production during Irreversible Processes 275
2.14 Entropy and Irreversibility in Chemical Reactions: The Chemical Affinity 277
Chapter 3. Characterization of Nonideal Systems 279
3.0 Introductory Remarks 279
3.1 Thermodynamic Treatment of Nonideal Gases 279
3.2 Temperature and Pressure Dependence of Activity Coefficients foraGas 285
3.3 Thermodynamic Treatment of Real Solutions 287
3.4 Characterization of Nonideal Solutions: Preliminaries 289
3.5 Standardization of Thermodynamic Descriptions of Nonideal Solutions 296
3.6 Reformulation of the Thermodynamic Description of Nonideal Solutions 305
3.7 Characterization of Equilibrium in Nonideal Solutions 307
3.A The Oxidation Boundary for Magnetite-Zinc Ferrite Solid Solutions 321
3.8 Thermochemistry 324
3.B Equilibrium Calculations 329
3.9 Reduction to Ideal Cases 331
3.C Energetics of Chemical Processes 333
3.10 Variations of Activity, Activity Coefficients, and Equilibrium Constants with Temperature and Pressure 335
3.11 Determination of Activity Coefficients by Measurement of Vapor Pressures 340
3.12 Activity of Solvent and Solute from Lowering of Freezing Point Data 354
3.13 Mixing in Nonideal Solutions 359
3.14 Phase Stability: General Consequences of Deviations from Ideality 370
3.15 Discussion of Several Types of Phase Diagrams 377
3.16 Variation of Mutual Solubility with Temperature 386
Chapter 4. Thermodynamic Properties of Electrolytes 397
4.0 Introductory Comments 397
4.1 Activities and Activity Coefficients for Strong Electrolytes 397
4.2 Theoretical Determination of Activities in Electrolyte Solutions: The Debye–HückelEquation 403
4.3 Experimental Determination of Activities and Activity Coefficients of Strong Electrolytes 406
4.4 Equilibrium Properties of Weak Electrolytes 413
4.5 The Electrochemical Potential 419
4.6 Galvanic and Electrolysis Cells: General Discussion 421
4.7 Galvanic Cells: General Treatment 429
4.8 Types of Electrodes 438
4.9 Liquid Junction Potentials 440
4.10 Concentration and Activity Dependence of the EMF 444
4.11 Types of Operating Cells 448
4.12 Thermodynamic Quantities from EMF Measurements 454
4.13 Applications of EMF Measurements 457
Chapter 5. Thermodynamic Properties of Systems in External Fields 463
5.0 Introductory Commentary 463
5.1 Thermodynamics of Gravitational Fields 463
5.2 Adsorption Thermodynamics 471
5.3 Heats of Adsorption 487
5.4 Thermodynamics of Radiation 497
5.5 Appendix. Alternative Derivation for Radiation Pressure 502
5.6 Effects of Electric Fields on Thermodynamic Properties of Matter 506
5.7 Appendix. Methods for Treatment of Integrals with Variable Limits 518
5.8 Thermodynamic Properties of Electromagnetic Fields: Systematics and Low Temperature Effects 520
5.9 Transitions to the Superconducting State (Soft Superconductors) 534
Chapter 6. Irreversible Thermodynamics 537
6.0 Introduction 537
6.1 Shock Phenomena 537
6.2 Irreversible Thermodynamics: Introductory CommentsnThe First and Second Laws in Local Form 546
6.3 The Linear Phenomenological Equations and the Onsager Reciprocity Conditions 558
6.4 Steady-State Conditions and Prigogine's Theorem 563
6.5 The Onsager Reciprocity Relations 565
6.6 Thermomolecular Mechanical Effects 567
6.7 The Soret Effect 571
6.8 Electrokinetic Phenomena 574
6.9 Thermoelectric Effects 580
6.10 Irreversible Phenomena in Two Dimensions 585
6.11 Chemical Processes 592
6.12 Coupled Reactions: Special Example 595
6.13 Coupled Reactions: General Case 598
Chapter 7. Final Speculation about Ultimate Temperatures~ The Fourth Law of Thermodynamics 602
Text 602
SUBJECT INDEX 604