About the book
This book is the first part of a course on “Thermodynamics and Statistical Physics” held at present in physical and physico-mathematical faculties of our universities. In comparison with existing courses of thermodynamics the book has the following distinctive features:
1. Greater attention than in other books is devoted to a discussion of the initial propositions of thermodynamics, which enables us to establish both the limitations of thermodynamics and its organic connexion with statistical physics.
2. The content of the second law of thermodynamics is analysed
logically and with greater consistency, by taking into account the existence of negative absolute temperatures.
3. The methods of thermodynamics are considered and discussed in detail.
4. The theory of critical phenomena is expounded according to
Gibbs, which enables us to establish the connexion of these phenomena with phase transitions of the second kind.
5. The thermodynamics of systems with negative absolute temperatures is treated.
6. The fundamentals of the thermodynamics of irreversible processes are given.
7. The large number of problems included in the book form an integral part of the course. Many are devoted to certain additional questions that are not always treated in the course and do not enter in the main text of the book. For these reasons the solutions of the problems are set out in as much detail as possible.
The book was translated from Russian by F. Immirzi and translation edited by A.E.J. Hayes. The book was published in 1964.
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Chapter I: Basic concepts and initial propositions of thermodynamics 1
§ 1 Thermodynamic system and thermodynamic parameters. Thermodynamic equilibrium from the molecular viewpoint 1
§ 2 Initial propositions of thermodynamics and their discussion 4
§ 3 Quasi-static and non-static processes 9
§ 4 The internal energy of a system. Work and heat 10
§ 5 Thermic and caloric equations of state 16
Chapter II: Fundamental laws and equations of thermodynamics. The first law of thermodynamics 22
§6 The equation of the first law of thermodynamics 23
§7 Thermic and caloric properties. Thermal capacities and latent heats. Connexion between thermal capacities 26
§8 Fundamental thermodynamic processes and their equations 30
§9 The connexion between elasticity coefficients and thermal capacities 33
§ 10 Hess’s rule. Thermochemical equations 35
Chapter III: The second law of thermodynamics 38
§ 11 General features and initial formulation of the second law 38
§ 12 Reversible and irreversible processes 43
§ 13 The second law of thermodynamics for quasi-static processes. Entropy and absolute temperature 45
§ 14 Mathematical justification for the existence of entropy and absolute temperature 47
$ 15 The fundamental equation of thermodynamics for quasi-static processes. The evaluation of entropy 58
§ 16 The second law of thermodynamics for non-static processes 62
§ 17 Connexion between the thermic and caloric equations of state 65
§ 18 The efficiency of heat-engines. Carnot’s cycle and Carnot’s theorem. Types of heat-engines 69
§ 19 Spontaneous flow of heat 73
§ 20 Limits of applicability of the second law. The “theory” of the thermal death of the universe 74
Chapter IV: Methods of thermodynamics 84
§ 21 The method of cyclical processes 84
§ 22 The method of thermodynamic potentials 86
Chapter V: Certain applications of thermodynamics 100
§ 23 The Gibbs-Helmholtz equation and its application to a galvanic cell 100
§ 24 The cooling of gas in reversible and irreversible adiabatic expansion. The Joule-Thomson effect. Kapitsa’s turbo-cooler 103
§ 25 The thermodynamics of dielectrics and magnetic substances 108
§ 26 Radiation thermodynamics 117
§ 27 Thermodynamics of plasma 127
§ 28 The thermodynamics of systems with a variable number of particles 131
Chapter VI: Conditions of thermodynamic equilibrium and their application 136
§ 29 Homogeneous and heterogeneous systems. Phases and components 136
§ 30 General conditions of thermodynamic equilibrium 138
§ 31 Stability conditions for the equilibrium of a homogeneous system 145
§ 32 Equilibrium in a homogeneous system 149
§ 33 Equilibrium in a heterogeneous system 152
Chapter VII: Surface phenomena 161
§ 34 Surface tension and surface pressure 162
§ 35 Equilibrium form of a crystal. Wulf’s theorem 164
§ 36 The role of surface tension in the formation of a new phase. Initial stages 166
§ 37 Gibbs’ equation for adsorption. Surface-active substances 169
Chapter VIII: Phase transformations and critical phenomena 172
§ 38 Phase transitions of the first kind. Clapeyron-Clausius equation 174
§ 39 Phase transitions of the second kind. Ehrenfest’s equation 178
§ 40 The theory of phase transitions of the second kind 182
§ 41 Critical phenomena 185
Chapter IX: Nernst’s heat theorem 194
§ 42 Nernst’s theorem 194
§ 43 Corollaries of Nernst’s theorem 197
Chapter X: Negative absolute temperatures 202
§ 44 The possibility of the existence of states with a negative absolute temperature 202
§ 45 A system with negative absolute temperature 204
§ 46 The thermodynamics of systems at negative absolute temperatures 208
§ 47 Stability of the state of a system at negative absolute temperature 214
Chapter XI: Fundamentals of the thermodynamics of irreversible processes 216
§ 48 The fundamental propositions of the thermodynamics of irreversible processes 216
§ 49 Thermoelectrical phenomena 222
Solutions to problems 228