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Ud [B91}S1}21S SoIsA Statistical Physics Second Revised and Enlarged Edition Course of Theoretical Physics Volume 5 L. D. Landau and E. M. Lifshitz Institute of Physical Problems USSR Academy of Sciences i -Vee Tete Ct} Course of Theoretical Physics Volume 5 STATISTICAL PHYSICS ‘Second Revised and Enlarged Edition L.D. LANDAU and E. M. LIFSHITZ Institute of Physical Problems, USSR Academy of Sciences For this edition the book has been enlarged and the treatment in some places revised. The volume is devoted to an exposition of statistical physics and thermodynamics, these two subjects being closely interconnected and with good reason therefore presented together in these pages. In accordance with practice for other volumes in this Course of Theoretical Physics general principles ited as clearly as possible while addition their many specific applications are presented as fully as possible. This volume, in common with the series as, a whole, received acclaim when published id this second revised and enlarged edition will be enthusiastically welcomed. a, COURSE OF THEORETICAL PHYSICS Volume 5 STATISTICAL PHYSICS STATISTICAL PHYSICS by L.D. LANDAU anv E. M. LIFSHITZ )F PHYSICAL PROBLEMS, USB: ACADEMY OF SCIENCES Volume 5 of Course of Theoretical Physics Translated from the Russian by J.B. SYKES anp M.J. KEARSLEY SECOND REVISED AND ENLARGED EDITION PERGAMON PRESS OXFORD « NEW YORK + TORONTO SYDNEY - BRAUNSCHWEIG Pergamon Press Ltd., Headington Hill Hall, Oxford Pergamon Press Inc., Maxwell House, Fairview Park, Elmsford, New York 10523 Pergamon of Canada Ltd., 207 Queen's Quay West, Toronto 1 Pergamon Press (Aust.) Pty. Ltd., 19a Boundary Street, Rusheutters Bay, NSW. 2011, Australia Vieweg & Sohn GmbH, Burgplatz 1, Braunschweig Copyright © 1958 and 1969 Pergamon Press Lid. AURA Rese No port of he pabletion may be ered Mem, cet me anal eco recording others, ‘tho he prior person af Petjamon Press Lis First published in English 1959 2nd Impression 1959 34d Impression 1963, 2nd Revised and Enlarged Edition 1969 2nd Impression 1970 Library of Congress Catalog Card No. 68-18526 Printed in Huneary and reprinted thosraphiclly by A. Wheaton & Cox Exeter 08 o0p103 2 CONTENTS Preface to the second English edition From the preface to the first English edition Notation 510. gs. 30. BI. 2, $33. I. THE FUNDAMENTAL PRINCIPLES OF STATISTICAL PHYSICS Statistical distributions Statistical independence Liowville's theorem ‘The significance of energy The statistical matrix Statistical distributions in quantum statistics Entropy ‘The law of increase of entropy II, THERMODYNAMIC QUANTITIES ‘Temperature Macroscopic motion ‘Adiabatic processes Pressure Work and quantity of heat ‘The heat function ‘The free energy and the thermodynamic potential Relations between the derivatives of thermodynamic quantities 1. The thermodynamic scale of temperature Maximum work done by a body in an external medium |. Thermodynamic inequalities Le Chatelier’s pri ‘Nemst’s theorem ‘The dependence of the thermodynamic quantities on the number of particles Equilibrium of a body in an external field Rotating bodies ‘Thermodynamic relations in the relativistic region le III. THE GIBBS DISTRIBUTION The Gibbs distribution The Maxwellian distribution ‘The probability distribution for an oscillator ‘The free energy in the Gibbs distribution ‘Thermodynamic perturbation theory Expansion in powers of # ix % n 14 20 2 28 33 35 37 3 45 46 49 3 3 35 6 6 or n 16 ~ 33 86 93 vi 34. 5. 836. §50. $51. $52. §53. $54. $55. $56. §s7. $58. $59. $60, got. $62. $63. sn. 72. 73. 4, Contents ‘The Gibbs distribution for rotating bodies ‘The Gibbs distribution for a variable number of particles ‘The derivation of the thermodynamic relations from the IV. IDEAL GASES ‘The Boltzmann distribution ‘The Boltzmann distribution in classical statistics Molecular collisions deal gases not in equilibrium ‘The free energy of an ideal Boltzmann gas ‘The equation of state of an ideal gas Ideal gases with constant specific heat ‘The law of equipartition ‘Monatomic ideal gases Monatomic gases. The effect of the electronic angular momentum Diatomic gases with molecules of unlike atoms. Rotation of molecules Diatomic gases with molecules of like atoms. Rotation of molecules Diatomic gases. Vibrations of atoms Diatomic gases. The effect of the electronic angular momentum Polyatomie gases V. THE FERMI AND BOSE DISTRIBUTIONS ‘The Fermi distribution ‘The Bose distribution Fermi and Bose gases not in equilibrium Fermi and Bose gases of elementary particles ‘A degenerate electron gas The specific heat of a degenerate electron gas A relativistic degenerate electron gas ‘A degenerate Bose gas Black-body radiation VI. THE CONDENSED STATE Solids at low temperatures Solids at high temperatures Debye's interpolation formula ‘Thermal expansion of solids Phonons ‘Quantum liquids with Bose-type spectrum Superfluidity Quantum liquids with Fermi-type spectrum ‘The electronic spectra of metals ‘The electronic spectra of solid dielectrics Negative temperatures VIL. NON-IDEAL GASES. Deviations of gases from the ideal state Expansion in powers of the density ‘Van der Waals’ formula 101 104 106 110 nz ng 116 119 12 125 127 129 133 135 138 144 145 146 148 152 154 157 159 162 170 174 17 180 181 187 191 196 203 210 2a 25 220 22 pl. $103, $104, $105. $106. si07. $108, $109, s110, au, gu2. gus. Contents ‘Completely ionised gases ‘The method of correlation functions Calculation of the virial coefficient in quantum mechanics A degenerate “almost ideal” Bose gas ‘A degenerate “almost ideal” Fermi gas with repulsion between the particles ‘A degenerate “almost ideal” Fermi gas with attraction betwoen the particles ‘VIII. PHASE EQUILIBRIUM Conditions of phase equilibrium ‘The Clapeyron-Clausius formula The critical point Properties of matter near the critical point The law of corresponding states IX. SOLUTIONS Systems containing different particles ‘The phase rule Weak solutions Osmotic pressure Solvent phases in contact, Equilibrium with respect to the solute Evolution of heat and change of volume on dissolution ‘The mutual interaction of solutes Solutions of strong electrolytes Mixtures of ideal gases Mixtures of isotopes ‘Vapour pressure over concentrated solutions ‘Thermodynamic inequalities for solutions Equilibrium curves Examples of phase diagrams Intersection of singular curves on the equilibrium surface Gases and liquids X. CHEMICAL REACTIONS ‘The condition for chemical equilibrium ‘The law of mass action Heat of reaction Tonisation equilibrium Equilibrium with respect to pair production XI. PROPERTIES OF MATTER AT VERY HIGH DENSITY ‘The equation of state of matter at high density Equilibrium of bodies of large mass ‘The energy of a gravitating body Equilibrium of a “neutron” sphere XII. FLUCTUATIONS ‘The Gaussian distribution ‘The Gaussian distribution for more than one variable 225 234 m1 237 263 266 270 223 214 215 2 278 281 283 285 287 289 291 294 296 310 312 geese viii sua, gus. S116. su7. 4118, 119, $120. 121. 9122. $123. $124. $125. $126. $127. 5128. $129. $130. sil, 9132, 9133. $34, 8135. $136. 9137. $38, $139. gio. gid. 142, 9143, gua. 514s. $146, $147. $148, g149, $150. gsi. 152. Index Contents Fluctuations of the fundamental thermodynamic quantities Fluctuations in an ideal gas Poisson's formula Fluctuations in solutions Correlations of fluctuations Fluctuations at the critical point Correlations of fluctuations in an ideal gas Correlations of fluctuations in time ‘The symmetry of the kinetic coefficients ‘The dissipative function ‘Time correlations of the fluctuations of more than one variable The generalised susceptibility Non-thermodynamic fluctuations of a single variable Non-thermodynamie fluctuations of more than one vai ble XIII, THE SYMMETRY OF CRYSTALS ‘Symmetry of particle configuration in a body Symmetry with respect to orientation of molecules Symmetry elements of a crystal lattice ‘The Bravais lattice Crystal systems Crystal classes. Space groups The reciprocal lattice Irreducible representations of space groups XIV. PHASE TRANSITIONS OF THE SECOND KIND Phase transitions of the second kind The discontinuity of specific heat ‘Change in symmetry in a phase transition of the second kind Isolated and critical points of continuous transition Phase transitions of the second kind in a two-dimensional lattice XV. SURFACES Surface tension Surface tension of crystals Surface pressure Surface tension of solutions Surface tension of solutions of strong electrolytes ‘Adsorption Wetting The angle of contact ‘Nucleation in phase transitions Fluctuations in the curvature of long molecules ‘The impossibility of the existence of phases in one-dimensional systems 348 354 356 359 365 370 374 318 384 301 395 401 405 412 414 416 418 ass 458 460 462 463 465 470 an 415 48 481 PREFACE TO THE SECOND ENGLISH EDITION For this edition the book has been enlarged and the treatment in some places revised. The revision has, however, been incomplete to the extent that the book does not include topics related to the successful application in recent years of the methods of quantum field theory to statistical physics. The reason for this is that we have always attempted to construct the Course of Theoretical Physics as describing a single science, interlinking the discussion of its various branches in the different volumes. According to the general plan of the Course, this volume should have followed the one on quantum field theory, and the discussion of the above-mentioned methods in this book should have been based on the development of them in the previous volume. Since the latter has not yet been completed, it was not possible to include these methods in the present edition. To my profound regret, L. D. Landau, my teacher and friend, has been pre~ vented by injuries received in a road accident from personally contributing to the preparation of this new edition. April 1966 EM. Lirsuirz: The publishers learnt with deep regret of the death of Professor L. D. Landau in April 1968 while this volume was in press. FROM THE PREFACE TO THE FIRST ENGLISH EDITION ‘Tu present volume of the Theoretical Physics seties is devoted to an exposi- tion of statistical physics and thermodynamics. These two subjects are firmly interconnected, and in our opinion it is rational to present them together as one whole, ‘Asin the other volumes, we have endeavoured, on the one hand, tostate the general principles as clearly as possible, and, on the other hand, to present their many specific applications as fully as possible. However, the present book does not contain the theory of electric and magnetic properties of mat- ter, which are treated in another volume which is dealing with the electrody- namics of material media. Similarly, problems of non-equilibrium phenomena are not treated; we propose to consider these in a separate volume. ‘We have not included in this book the various theories of ordinary liquids and of strong solutions, which to us appear neither convincing nor useful. We do not share the view, which one encounters sometimes, that statistical physics is the least well-founded branch of theoretical physics (as regards its basic principles), We believe that the difficulties are created artificially, because the problems are often not stated sufficiently rationally. If one talks from the very beginning about the statistical distribution for small parts of a system (Subsystems) and not for a closed system as a whole, then one avoids the whole question of the ergodic or similar hypotheses, which are not really essential for physical statistics. Moscow L. D. Lanpav M. Lirsurrz NOTATION ‘Orenarors are denoted by a circumflex Phase space 4 generalised momenta and co-ordinates dp dg = dps dps »-- dP, gs das «- dg, Volume element in phase space (with s degrees of freedom) aL = gp dgi@zay [/ --- a? integral over all physically different states Thermodynamie quantities r v P E s w F ® Q temperature volume pressure ‘energy entropy E-PY heat function E-TS free energy E~TS+PY thermodynamic potential PV thermodynamic potential Gy C, specific heats