Thermodynamics and an introduction to thermostatistics - walter callen

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Textbook for thermodynamics
THERMODYNAMICS AND AN INTRODUCTION TO THERMOSTATISTICS SECOND EDITION HERBERT B, CALLEN University of pennsylvania JOHN WiLeY SONS New York Chichester Brisbane Toronto Singapore Copyright 1985, by John Wiley Sons, Inc. All rights reserved Published simultaneously in Canada Reproduction or translation of any part of his work beyond that permitted by Sections 107 and 108 of the 1976 UnIted States Copyright Act without the permission of the copyright owner is unlawful Requests for permIssion or further information should be addressed to the Permissions Department, John Wiley Sons I of Congress Cataloging in Publication Data: Calen herbert B Thermodynamics and an Introduction to Thermostatistics Rev ed of. Thermodynamics 1960 Bibliography p 485 Includes index 1 ThermodynamIcs 2 Statistical Mechanics I Callen, Herbert B ThermodynamIcs II Title III Title ThermostatistIcs QC3]C251985536785-6387 Printed in the Republic of Singapore 1098 To Sara and to jill. Jed Zachary and Jessica PREFACE Twenty-five years after writing the first edition of Thermodynamics I am gratified that the book is now the thermodynamic reference most fre quently cited in physics research literature, and that the postulational formulation which it introduced is now widely accepted. Nevertheless several considerations prompt this new edition and extension First, thermodynamics advanced dramatically in the 60s and 70s, pri- marily in the area of critical phenomena. Although those advances are largely beyond the scope of this book, I have attempted to at least describe the nature of the problem and to introduce the critical exponents and scaling functions that characterize the non-analytic behavior of ther- modynamic functions at a second-order phase transition This account is descriptive and simple. It replaces the relatively complicated theory of second-order transitions that, in the view of many students, was the most difficult section of the first edition Second, I have attempted to improve the pedagogical attributes of the book for use in courses from the junior undergraduate to the first year graduate level, for physicists, engineering scientists and chemists. This purpose has been aided by a large number of helpful suggestions from students and instructors. Many explanations are simplified and numerous examples are solved explicitly. The number of problems has been ex- panded and partial or complete answers are given for many Third, an introduction to the principles of statistical mechanics has been added Here the spirit of the first edition has been maintained; the emphasis is on the underlying simplicity of principles and on the central train of logic rather than on a multiplicity of applications. For this purpose, and to make the text accessible to advanced undergraduates, I have avoided explicit non-commutivity problems in quantum mechanics All that is required is familiarity with the fact that quantum mechanics predicts discrete energy levels in finite systems. However, the formulation is designed so that the more advanced student will properly interpret the theory in the non-commutative case DEIN reface Fourth, I have long been puzzled by certain conceptual problems iying at the foundations of thermodynamics, and this has led me to an interpre tation of the"meaning"of thermodynamics. In the final chapter-an interpretive postlude to the main body of the text-I develop the thesis that thermostatistics has its roots in the symmetries of the fundamental laws of physics rather than in the quantitative content of those laws. The discussion is qualitative and descriptive, seeking to establish an intuitive framework and to encourage the student to see science as a coherent structure in which thermod ynamics has a natural and fundamental role t Although both statistical mechanics and thermodynamics are included in this new edition, I have attempted neither to separate them completely nor to meld them into the undifferentiated form now popular under the rubric of "thermal physics. I believe that each of these extreme options is misdirected. To divorce thermodynamics completely from its statistical mechanical base is to rob thermodynamics of its fundamental physical origins. Without an insight into statistical mechanics a scientist remains rooted in the macroscopic empiricism of the nineteenth century, cut off from contemporary developments and from an integrated view of science Conversely, the amalgamation of thermodynamics and statistical me- chanics into an undifferentiated"thermal physics tends to eclipse ther- modynamics. The fundamentality and profundity of statistical mechanics are treacherously seductive; "thermal physics"courses almost perforce give short shrift to macroscopic operational principles. Furthermore the amalgamation of thermodynamics and statistical mechanics runs counter to the "principle of theoretical economy", the principle that predictions should be drawn from the most general and least detailed assumptions possible. Models, endemic to statistical mechanics, should be eschewed whenever the general methods of macroscopic thermodynamics are suffi- cient. Such a habit of mind is hardly encouraged by an organization of the subjects in which thermodynamics is little more than a subordinate clause. The balancing of the two distinct components of the thermal sciences is carried out in this book by introducing the subject at the macroscopic level, by formulating thermodynamics so that its macroscopic postulates are precisely and clearly the theorems of statistical mechanics, and by frequent explanatory allusions to the interrelationships of the two compo nents. Nevertheless, at the option of the instructor the chapters on statistical mechanics can be interleaved with those on thermodynamics in a sequence to be described. But even in that integrated option the basic macroscopic structure of thermodynamics is established before statistical reasoning is introduced Such a separation and sequencing of the subjects The Amercan Physical Society Committee on Applications of Physics reported i Bulletin of the APS, Vol 22#10, 1233(1971) that a survey of industrial research leaders designated thermody namics above all other subjects as requiring increased emphasis in the undergraduate curriculum. That emphasis subsequently has decreased Preface preserves and emphasizes the hierarchical structure of science, organizing physics into coherent units with clear and easily remembered interrela- tionships. Similarly, classical mechanics is best understood as a self- contained postulatory structure, only later to be validated as a limiting case of quantum mechanics Two primary curricular options are listed in the"menu"following. In one option the chapters are followed in sequence(Column A alone, or followed by all or part of column B). In the"integrated"option the menu is followed from top to bottom. Chapter 15 is a short and elementary statistical interpretation of entropy; it can be inserted immediately after Chapter 1, Chapter 4, or Chapter 7. The chapters listed below the first dotted line are freely flexible with respect to sequence, or to inclusion or omission. To balance the concrete and particular against more esoteric sections, instructors may choose to insert parts of Chapter 13 (Properties of materials) at various stages, or to insert the Postlude(Chapter 21, Symmetry and Conceptual Foundations) at any point in the course The minimal course, for junior year undergraduates, would involve the first seven chapters, with Chapter 15 and 16 optionally included as time permits. Philadelphia, Pennsylvania Herbert B. callen Preface to the Fourth Printing In the issuance of this fourth printing of the second edition, the publisher has graciously given me the opportunity to correct various misprints and "minor errors. I am painfully aware that no error, numerical or textual, is truly minor to the student reader. Accordingly, I am deeply grateful both to the numerous read- ers who have called errors to my attention, and to the charitable forbearance of the publisher in permitting their correction in this printing November 1987 Herbert callen x 1. Postulates 15 2. Conditions of equilibr Tul 3. Formal Relations and Sample Sys tems 4. Reversible Processes; Engines 15. Statistical Mechanics in Entropy Representation 5. Legendre Transformations 6. Extremum Principles in Legendre Representation 7. Maxwell Relations 15 16. Canonical Formalism 17, Generalized Canonical Formula tion 8. Stabilit 9. First-Order Phase Transitions 10. Critical Phenomena 18. Quantum Fluids 11. Nernst 19. Fluctuations 12. Summary of Principles 20. Variational Properties and Mean Field theor 13. Properties of materials 14. Irreversible Thermodynamics 21. Postlude: Symmetry and the Conceptual Foundations of Thermodynamics 【实例截图】
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