General Commentary ............................................. xi
Preface ...................................................... xiii
CHAPTER 1 Fundamentals ......................................... i
1.1 Introductory Definitions ................................... 1
Remarks and Queries ........................................ 4
1.2 The Zeroth Law of Thermodynamics ........................... 5
Additional Information ..................................... 8
1.3 Mathematical Apparatus ..................................... 9
Remarks ................................................... 20
1.4 Thermodynamic Forces ...................................... 20
Reference ................................................. 21
1.5 Elements of Work .......................................... 21
Comment and Queries ....................................... 30
1.6 The Element of Work for a System Subjected to
Electromagnetic Fields .................................... 30
Remark and Reference ...................................... 32
1.7 The First Law of Thermodynamics ........................... 32
Reference ................................................. 37
Notes ..................................................... 37
1.8 The Second Law of Thermodynamics .......................... 38
Footnotes and Query ....................................... 42
1.9 Consequences of the First and Second Laws ................. 42
Remarks and Questions ..................................... 50
1.10 Functions of State; Reprise ............................... 51
Appendix A: Remarks Concerning Irreversible Processes ..... 59
Appendix B: Time-Dependent Irreversible Processes ......... 60
Reference ................................................. 64
Notes ..................................................... 64
1.11 Statements of the Second Law; Thermodynamic Operation
of Heat Engines; Kelvin and Planck Statements;
Temperature Scale ......................................... 65
Exercise .................................................. 67
1.12 Systematization of Results Based on Functions of State .... 67
Review of Electronic Properties of Metals ................. 87
Exercises and Remark ...................................... 88
1.13 The Third Law of Thermodynamics ........................... 88
Remarks and Queries ....................................... 90
1.14 The Gibbs-Duhem Relation and Its Analogs .................. 90
Query and Reference ....................................... 94
1.15 Heat Capacities; Fundamentals and Applications ............ 94
Acknowledgment ........................................... 105
Exercises and Comments ................................... 105
1.16 Effect of Chemical Changes on the Energy of a System ..... 105
Remarks .................................................. 106
1.17 Stability of a System; Fluctuations ...................... 107
Appendices ............................................... 114
Reference ................................................ 115
CHAPTER 2 Thermodynamic Properties of Ideal Systems .......... 117
2.1 Equilibrium in a System of Several Components and
Phases ................................................... 117
Exercises ................................................ 119
2.2 Achievement of Equilibrium ............................... 120
Comment and Exercise ..................................... 124
2.3 System of One Component and Several Phases;
the Clausius-Clapeyron Equation .......................... 124
Reference and Footnote ................................... 129
2.4 Properties of Ideal Gases ................................ 129
Exercises ................................................ 134
2.5 Properties of Ideal Solutions in Condensed Phases ........ 134
Reference ................................................ 136
2.6 The Duhem-Margules Equation and Its Consequences ......... 137
2.7 Temperature Dependence of Composition of Solutions ....... 138
2.8 Lowering of the Freezing Point and Elevation of the
Boiling Point of a Solution .............................. 139
Exercise ................................................. 142
2.9 General Description of Chemical Reactions and Chemical
Equilibrium; Application to Gases ........................ 142
Remarks .................................................. 148
2.10 Chemical Equilibrium in Homogeneous Condensed Ideal
Solutions ................................................ 149
Comments ................................................. 152
2.11 Chemical Equilibrium in Ideal Heterogeneous Systems ...... 152
2.12 Equilibrium between Two Ideal Phases ..................... 154
CHAPTER 3 Characterization of Nonideal Solutions ............. 155
3.0 Introductory Remarks ..................................... 155
3.1 Thermodynamic Treatment of Nonideal Gas Mixtures ......... 155
Notes and Exercise ....................................... 158
3.2 Temperature and Pressure Dependence of the Fugacity of
a Gas .................................................... 158
3.3 Thermodynamic Description of Real Solutions in the
Condensed State .......................................... 159
Query and Reference ...................................... 161
3.4 Characterization of Chemical Equilibrium in Nonideal
Solutions ................................................ 161
3.5 Pressure and Temperature Dependence of Activities and
Activity Coefficients .................................... 168
3.6 Determination of Activity Coefficients and Calorimetric
Quantities in Chemical Processes ......................... 168
References and Commentary ................................ 181
3.7 Determination of Activities from Freezing Point
Lowering of Solutions .................................... 181
3.8 Thermodynamic Properties of Nonideal Solutions ........... 184
Exercises ................................................ 192
Exercises ................................................ 206
3.9 Dependence of Higher Order Phase Transitions on
Temperature .............................................. 207
Exercises and References ................................. 217
3.10 Elements of Order-Disorder Theory and Applications ....... 217
References ............................................... 229
CHAPTER 4 Thermodynamic Properties of Electrolytes and of
EMF Cells ..................................................... 231
4.0 Introductory Comments .................................... 231
4.1 Activities of Strong Electrolytes ........................ 231
Exercise and Comment ..................................... 235
4.2 Theoretical Determination of Activities in Electrolyte
Solutions; the Debye-Hückel Equation ..................... 235
Comment and Exercises .................................... 237
Experimental Determination of Activities and Activity
Coefficients of Strong Electrolytes ...................... 238
Equilibrium Properties of Weak Electrolytes .............. 240
Exercise ................................................. 245
4.3 Galvanic Cells ........................................... 245
Remarks .................................................. 247
4.4 Operation of Galvanic Cells .............................. 247
Remarks .................................................. 250
4.5 Galvanic Cells; Operational Analysis ..................... 250
4.6 Liquid Junction Potentials ............................... 253
4.7 EMF Dependence on Activities ............................. 254
Examples of Operating Cells .............................. 255
Types of Operating Cells ................................. 256
Queries .................................................. 258
4.8 Thermodynamic Information from Galvanic Cells ............ 258
Assignment ............................................... 259
CHAPTER 5 Thermodynamic Properties of Materials in
Externally Applied Fields ..................................... 261
5.0 Introductory Comments .................................... 261
5.1 Thermodynamics of Gravitational and Centrifugal Fields ... 261
Comment and Exercises .................................... 267
5.2 Thermodynamics of Adsorption Processes ................... 267
References and Exercises ................................. 275
5.3 Heats of Adsorption ...................................... 276
Reference and Exercises .................................. 280
5.4 Surface vs Bulk Effects: Thermodynamics of Self-
Assembly ................................................. 281
References ............................................... 290
5.5 Pressure of Electromagnetic Radiation .................... 290
5.6 Thermodynamic Characterization of Electrodynamic
Radiation ................................................ 292
Exercises ................................................ 297
5.7 Effects of Electric Fields on Thermodynamic Properties
of Matter ................................................ 297
Reference and Exercises .................................. 302
5.8 Systematization of Electromagnetic Field Effects in
Thermodynamics ........................................... 302
Comments and Assignments ................................. 310
5.9 Adiabatic Diamagnetization and Transitions to
Superconductivity ........................................ 311
5.10 Thermodynamic Characterization of Anisotropic Media ...... 314
Reference ................................................ 322
5.11 Thermodynamic Properties of Anisotropic Media ............ 322
Reference and Exercise ................................... 327
5.12 Thermodynamics of Interacting Electron Assemblies ........ 327
Remarks and References ................................... 335
CHAPTER 6 Irreversible Thermodynamics ........................ 337
6.0 Introductory Comments .................................... 337
6.1 Generalities ............................................. 337
Notes and Queries ........................................ 345
6.2 Shock Phenomena .......................................... 345
Exercises ................................................ 351
6.3 Linear Phenomenological Equations ........................ 352
6.4 Steady-State Conditions and Prigogine's Theorem .......... 353
Comments and Questions ................................... 354
6.5 Onsager Reciprocity Conditions ........................... 355
Reference ................................................ 356
6.6 Thermomolecular Mechanical Effects ....................... 356
6.7 Electrokinetic Phenomena ................................. 359
Exercises ................................................ 362
6.8 The Soret Effect ......................................... 363
Exercises ................................................ 364
6.9 Thermoelectric Effects ................................... 364
Comments and Exercises ................................... 369
6.10 Irreversible Thermomagnetic Phenomena in Two Dimensions .. 369
Exercises ................................................ 373
CHAPTER 7 Critical Phenomena ................................. 375
7.0 Introductory Remarks ..................................... 375
7.1 Properties of Materials Near Their Critical Point ........ 375
Notes and References ..................................... 380
7.2 Homogeneity Requirements, Correlation Lengths, and
Scaling Properties ....................................... 381
Footnotes ................................................ 386
7.3 Derivation of Griffith's and Rushbrooke's Inequality ..... 386
Reference and Exercise ................................... 392
7.4 Scaled Equation of State ................................. 393
Reference ................................................ 393
7.5 Landau Theory of Critical Phenomena and Phase
Transitions .............................................. 393
Reference ................................................ 405
CHAPTER 8 A Final Speculation about Ultimate Temperatures -
A Fourth Law of Thermodynamics? ............................... 407
Reference ................................................ 408
CHAPTER 9 Reprise to the Second Law. Mathematical Proof
of the Caratheodory's Theorem and Resulting Interpretations ... 409
9.1 Fundamentals ............................................. 409
9.2 Proof of Holonomicity .................................... 411
9.3 Necessary Condition for Establishing the Caratheodory's
Theorem .................................................. 414
9.4 Relevance to Thermodynamics .............................. 416
9.5 Derivation of the Limiting Form for the Debye-Hückel
Equation ................................................. 417
References and Query ..................................... 422
CHAPTER 10 Elements of Statistical Thermodynamics ............. 425
10.1 Distributions and Statistics ............................. 425
10.2 The Boltzmann Relation for the Entropy ................... 429
10.3 Distribution Functions ................................... 429
10.4 Digression on the Concepts of Work and Heat .............. 432
10.5 Statistical Representation of Functions of State ......... 432
10.6 Summary .................................................. 433
10.7 Alternative Statistical Interpretation for Entropy in
Terms of Properties of a System .......................... 434
Footnotes ................................................ 436
10.8 Derivation of Curie's Law and Ohm's Law .................. 437
Index ......................................................... 439
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