Thermodynamics and Introductory Statistical Mechanics - B.Linder, Wiley, 2004.pdf

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Frontmatter
THERMODYNAMICS
AND INTRODUCTORY
STATISTICAL MECHANICS
BRUNO LINDER
Department of Chemistry and Biochemistry
The Florida State University
A JOHN WILEY & SONS, INC. PUBLICATION
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Copyright # 2004 by John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey.
Published simultaneously in Canada.
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Library of Congress Cataloging-in-Publication Data:
Linder, Bruno.
Thermodynamics and introductory statistical mechanics/Bruno Linder.
p. cm.
Includes bibliographical references and index.
ISBN 0-471-47459-2
1. Thermodynamics. 2. Statistical mechanics. I Title.
QD504.L56 2005
541 0 .369–dc22
2004003022
Printed in the United States of America
10987654321
To Cecelia
... and to William, Diane, Richard, Nancy, and Carolyn
CONTENTS
PREFACE
xv
1 INTRODUCTORY REMARKS
1
1.1 Scope and Objectives / 1
1.2 Level of Course / 2
1.3 Course Outline / 2
1.4 Books / 3
PART I THERMODYNAMICS
5
2 BASIC CONCEPTS AND DEFINITIONS
7
2.1 Systems and Surroundings / 8
2.2 State Variables and Thermodynamic Properties / 8
2.3 Intensive and Extensive Variables / 9
2.4 Homogeneous and Heterogeneous Systems, Phases / 9
2.5 Work / 9
2.6 Reversible and Quasi-Static Processes / 10
2.6.1 Quasi-Static Process / 11
2.6.2 Reversible Process / 12
2.7 Adiabatic and Diathermal Walls / 13
2.8 Thermal Contact and Thermal Equilibrium / 13
vii
viii
CONTENTS
3 THE LAWS OF THERMODYNAMICS I
14
3.1 The Zeroth Law—Temperature / 15
3.2 The First Law—Traditional Approach / 16
3.3 Mathematical Interlude I: Exact and Inexact Differentials / 18
3.4 The First Law—Axiomatic Approach / 19
3.5 Some Applications of the First Law / 23
3.5.1 Heat Capacity / 23
3.5.2 Heat and Internal Energy / 23
3.5.3 Heat and Enthalpy / 24
3.6 Mathematical Interlude II: Partial Derivatives / 26
3.6.1 Relations Between Partials of Dependent Variables / 26
3.6.2 Relations Between Partials with
Different Subscripts / 27
3.7 Other Applications of the First Law / 27
3.7.1 C P C V /27
3.7.2 Isothermal Change, Ideal Gas / 28
3.7.3 Adiabatic Change, Ideal Gas / 28
3.7.4 The Joule and the Joule-Thomson Coefficients / 29
4 THE LAWS OF THERMODYNAMICS II
32
4.1 The Second Law—Traditional Approach / 32
4.2 Engine Efficiency: Absolute Temperature / 36
4.2.1 Ideal Gas / 36
4.2.2 Coupled Cycles / 36
4.3 Generalization: Arbitrary Cycle / 38
4.4 The Clausius Inequality / 39
4.5 The Second Law—Axiomatic Approach (Carath´odory) / 41
4.6 Mathematical Interlude III: Pfaffian Differential Forms / 43
4.7 Pfaffian Expressions in Two Variables / 44
4.8 Pfaffian Expressions in More Than Two Dimensions / 44
4.9 Carath´odory’s Theorem / 45
4.10 Entropy—Axiomatic Approach / 45
4.11 Entropy Changes for Nonisolated Systems / 48
4.12 Summary / 49
4.13 Some Applications of the Second Law / 50
4.13.1 Reversible Processes (PV Work Only) / 50
4.13.2 Irreversible Processes / 51

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