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THERMODYNAMICS

AND AN INTRODUCTION
TO

THERMOSTATISTICS
SECONDEDITION

HERBERT
B.CALLEN

Universitvof Pennsvlvania

JOHN WILEY & SONS


New York Chichester Brisbane Toronto Singapore

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Copyright @ 1985,by John Wiley & Sons,Inc.


All rights reserved.Publishedsimultaneouslyin Canada.
Reproduction or translationof any part of
this work beyond that permitted by Sections
107 and 108 of the 1976United StatesCopyright
Act without the permissionof the copyright
owner is unlawful. Requestsfor permission
or further information shouldbe addressedto
the PermissionsDepartment,John Wiley & Sons.
Lihrary of CongressCataloging in Publication Datu
Callen, Herbert B.
Thermodynamicsand an Introduction to
Thermostatistics.
Rev. ed of: Thermodynamics.1960.
Bibliography: p. 485
Includes index.
1. Thermodynamics. 2. StatisticalMechanics.
I. Callen, Herbert B. Thermodynamics. II. Title.
III. Title: Thermostatistics.
536',.7 85-6387
QC311.C25 1985
ISBN 0-471-86256-8
Printedand boundin the UnitedStatesof America
20 19

To Sara
.....and
to Jill,Jed,
Zacharyand Jessica

PREFACE

Twenty-five years after writing the first edition of Thermodynamics I am


gratified that the book is now the thermodynamic reference most frequently 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, primarily 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 characterizethe non-analytic behavior of thermodynamic functions at a second-orderphase 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 suggestionsfrom
students and instructors. Many explanations are simplified, and numerous
examples are solved explicitly. The number of problems has been expanded, and partial or complete answersare 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 accessibleto 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.
uu

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Preface

Fourth, I have long been pnzzledby certain conceptualproblemslying


at the foundations of thermodynamics,and this has led me to an interpretation of the "meaning" of thermodynamics.In the final chapter-an
"interpretive postlude" to the main body of the text-I developthe thesis
that thermostatisticshas its roots in the symmetriesof the fundamental
laws of physicsrather than in the quantitative content of thoselaws. The
discussionis qualitative and descriptive,seekingto establishan intuitive
framework and to encouragethe student to see scienceas a coherent
structure in which thermodynamicshas a natural and fundamentalrole.
Although both statisticalmechanicsand thermodynamicsare included
in this new edition, I have attemptedneither to separatethem completely
nor to meld them into the undifferentiatedform now popular under the
rubric of " thermal physics."I believethat eachof theseextremeoptions is
misdirected. To divorce thermodynamicscompletely from its statistical
mechanical base is to rob thermodynamicsof its fundamental physical
origins. Without an insight into statistical mechanicsa scientist remains
rooted in the macroscopicempiricism of the nineteenthcentury, cut off
from contemporarydevelopmentsand from an integratedview of science.
Conversely, the amalgamationof thermodynamicsand statistical mechanics into an undifferentiated" thermal physics" tends to eclipsethermodynamics.The fundamentalityand profundity of statisticalmechanics
are treacherouslyseductive;" thermal physics" coursesalmost perforce
give short shrift to macroscopicoperationalprinciples.* Furthermore the
amalgamationof thermodynamicsand statistical mechanicsruns counter
to the "principle of theoreticaleconomy";the principle that predictions
should be drawn from the most generaland least detailed assumptions
possible.Models, endemicto statisticalmechanics,should be eschewed
wheneverthe generalmethodsof macroscopicthermodynamicsare sufficient. Such a habit of mind is hardly encouragedby an organizationof the
subjectsin which thermodynamicsis little more than a subordinateclause.
The balancing of the two distinct componentsof the thermal sciencesis
carried out in this book by introducing the subject at the macroscopic
level, by formulating thermodynamicsso that its macroscopicpostulates
are precisely and clearly the theoremsof statistical mechanics,and by
frequent explanatoryallusionsto the interrelationshipsof the two components. Nevertheless,at the option of the instructor, the chapters on
statistical mechanicscan be interleavedwith thoseon thermodvnamicsin
a sequenceto be described.But even in that integratedoption the basic
macroscopicstructure of thermodynamicsis establishedbeforestatistical
reasoningis introduced. Sucha separationand sequencingof the subjects
*The American Physical Society Committee on Applications of Physics reported
lBulletin of the
lPS, Vol 22 #10, 1233 (I9'1L)l that a survey of industrial research leaders designated thermodynamics above all other subjects as requiring increased emphasis in the undergraduate curriculum That
emphasis subsequently has decreaserl

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preservesand emphasizesthe hierarchicalstructureof science,organizing


physics into coherent units with clear and easily rememberedinterrelationships. Similarly, classical mechanicsis best understood as a selfcontained postulatory structure, only later to be validated as a limiting
caseof quantum mechanics.
Two primary curricular options are listed in the "menu" following. In
one option the chaptersare followed in sequence(Column A alone, or
followedby all or part of columnB). In the "integrated"option the menu
is followed from top to bottom. Chapter 15 is a short and elementary
statisticalinterpretationof entropy; it can be insertedimmediatelyafter
Chapter1, Chapter4, or Chapter7.
The chapterslisted below the first dotted line are freely flexible with
respectto sequence,
or to inclusionor omission.To balancethe concrete
and particular againstmore esotericsections,instructorsmay chooseto
insertparts of Chapter13 (Propertiesof Materials)at variousstages,or to
insert the Postlude(Chapter21, Symmetryand ConceptualFoundations)
at any point in the course.
The minimal course,for junior year undergraduates,
would involvethe
first sevenchapters,with Chapter15 and 16 optionally includedas time
pernuts.
Philadelphia, P ennsyluania

Herbert B. Callen

Preface

Qi
I

l. Postulates
15.
2. Conditions of Equilibrium
3. Formal Relations and SampleSystems
4. ReversibleProcesses;
Engines
1 5 . Statistical Mechanics in Entropy
Representation
5 . LegendreTransformations
6. Extremum Principles in Legendre
Representation
7. Maxwell Relations
15.
1 6 . CanonicalFormalism
7 7 . Generalized Canonical Formulation
8 . Stability
9. First-OrderPhaseTransitions
10. Critical Phenomena
11. Nernst
12. Summaryof Principles
13. Propertiesof Materials

1 8 . QuantumFluids
19. Fluctuations
20. Variational Properties and Mean
Field Theory

14. IrreversibleThermodynamics

21. Postlude: Symmetry and the Conceptual Foundations of Thermodynamics

PA
GE
CL

lntr,
The

1.1
1.2
1.3
t.4
1.5
1.6
t.7
1.8
1.9
1.1

2.7
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9

CONTENTS

PART I
GENERAL PRINCIPLES OF
CLASSICAL THERMODYNAMICS
lntroduction The Nature of Thermodvnamics and the Basis of
Thermostatistics
I

THE PROBLEM AND THE POSTULATES


1.1 The TemporalNature of MacroscopicMeasurements
1.2 The SpatialNature of MacroscopicMeasurements
1.3 The Compositionof ThermodynamicSystems
1.4 The Internal Energy
1.5 ThermodynamicEquilibrium
1.6 Walls and Constraints
1.7 Measurability of the Energy
1.8 QuantitativeDefinitionof Heat-Units
1.9 The Basic Problemof Thermodynamics
l.i0 The Entropy Maximum Postulates

2 THE CONDITIONS OF EQUILIBRIUM


2.1 IntensiveParameters
2.2 Equationsof State
2.3 Entropic IntensiveParameters
2.4 Thermal Equilibrium-Temperature
2.5 Agreementwith Intuitive Conceptof Temperature
2.6 TemperatureUnits
2.7 MechanicalEquilibrium
2.8 Equilibrium with Respectto Matter Flow
2.9 ChemicalEquilibrium

2
5
5
6
9
11
13
15
16
18
25
2'l

35
35
37
40
43
45
46
49
54
56

xlt

SOME FORMAL RELATIONSHIPS,


AND SAMPLE SYSTEMS
3.1 The Euler Equation
3.2 The Gibbs-Duhem Relation
3.3 Summary of Formal Structure
3.4 The Simple Ideal Gas and Multicomponent
Simple Ideal Gases
3.5 The "Ideal van der WaalsFluid"
3.6 ElectromagneticRadiation
3.7 The "Rubber Band"
3.8 UnconstrainableVariables;Magnetic Systems
3.9 Molar Heat Capacityand Other Derivatives

REVERSIBLE PROCESSES AND THE


MAXIMUM
WORK THEOREM
4.1 Possibleand ImpossibleProcesses
4.2 Quasi-Staticand ReversibleProcesses
4.3 RelaxationTimes and Irreversibility
4.4 Heat Flow: Coupled Systemsand Reversalof processes
4.5 The Maximum Work Theorem
4.6 Coefficientsof Engine,Refrigerator,and
Heat Pump Performance
4.7 The Carnot Cycle
4.8 Measurability of the Temperatureand of the Entropy
4.9 Other Criteria of Engine Performance;PowerOutput and
"EndoreversibleEngines"
4.10 Other Cyclic Processes

59
59
60
63
66
74
78
80
81
84

ALTERNATIVE FORMULATIONS
AND LEGENDRE TRANSFORMATIONS
5.1 The Energy Minimum Principle
5.2 LegendreTransformations
5.3 ThermodynamicPotentials
5.4 GeneralizedMassieuFunctions

9L
97
95
99
101
103
113
118
123

1 l \
7.7
7.2
7.3
7.4
7.5

8 S
8.1
8.2
8.3
8.4
8.5

9 F
9.1
9.2
9.3
9.4
9.5
9.6
9.7

725

r28

THE EXTREMUM PRINCIPLE IN THE


LEGENDRE TRANSFORMED REPRESENTATIONS
6.1 The Minimum Principlesfor the Potentials6.2 The Helmholtz Potential
6.3 The Enthalpy; The Joule-Thomsonor "Throttling" process
6.4 The Gibbs Potential; ChemicalReactions
6.5 Other Potentials
6.6 Compilations of Empirical Data; The Enthalpy of Formation
6.7 The Maximum Principlesfor the MassieuFunctions

131
131
737
746
151

153
153
r57
160
I67
172
773
179

S
F
I

Contents

59
59
60
63
66
74
78
BO
B1
B4
)1
)1
)5
,9
)l
)3
IJ

.8

r3
r5
E
I
1
7
6
I

7 MAXWELL RELATIONS
7.1 The MaxwellRelations
MnemonicDiagram
7.2 A Thermodynamic
7.3
7.4
'7.5

A Procedure for the Reduction of Derivatives in


Single-Component Systems
Some Simple Applications
Generalizations: Magnetic Systems

STABILITY OF THERMODYNAMIC
SYSTEMS
8.1 Intrinsic Stability of ThermodynarnicSystems
8.2 Stability Conditionsfor ThermodynamicsPotentials
of Stability
8.3 PhysicalConsequences
8.4 Le Chatelier'sPrinciple; The QualitativeEffect
of Fluctuations
8.5 The Le Chatelier-Braun Principle

xiii

181
181
183
186
190
199

203
203
207
209
2r0
2r2

9 FIRST-ORDER PHASE TRANSITIONS


9.1 First-OrderPhaseTransitionsin Single-Component
Systems
9.2 The Discontinuityin the Entropy-LatentHeat
9.3 The Slope of CoexistenceCurves;the ClapeyronEquation
9.4 Unstable Isothermsand First-Order PhaseTransitions
9.5 GeneralAttributesof First-OrderPhaseTransitions
9-6 First-Order PhaseTransitionsin Multicomponent
Systems-Gibbs PhaseRule
9.7 PhaseDiagramsfor Binary Systems

275
215
222
228
233
243

TO CRITICAL PHENOMENA
lO.1 Thermodynamicsin the Neighborhoodof the Critical Point
lO.2 Divergenceand Stability
10.3 Order Parametersand Critical Exponents
10.4 ClassicalTheory in the Critical Region; Landau Theory
10.5 Roots of the Critical Point Problem
10.6 Scalingand Universality

255
255
261
263
265
270
272

II THE NERNST POSTULATE


Nernst'sPostulate,and the Principleof Thomsen
ll.1
and Bertholot
Heat Capacitiesand Other Derivativesat Low Temperatures
ll.2
lf .3 The "Unattainability" of Zero Temperature

277

T2 SUMMARY OF PRINCIPLES
FOR GENERAL SYSTEMS
General Systems
l2.I
12.2 The Postulates

245
248

277
280
287
283
283
283

XID

12.3
72.4
72.5
72.6
I2.7
I2.8

Contents

The IntensiveParameters
LegendreTransforms
Maxwell Relations
Stability and PhaseTransitions
CriticalPhenomena
Propertiesat Zero Temperature

284
285
285
286
287
287

13 PROPERTTES OF MAT4RTALS
f 3.1 The General Ideal Gas
73.2 Chemical Reactionsin ldeal Gases
73.3 Small Deviationsfrom "Ideality"-The Virial Expansion
73.4 The "Law of CorrespondingStates"for Gases
13.5 Dilute Solutions:OsmoticPressureand Vapor pressure
13.6 Solid Systems

289
289
292
297
299
302
305

14 IRREVERSIBLE THERMODYNAMICS
I4.I
General Remarks
I4.2
Affinities and Fluxes
74.3 Purely-Resistiveand Linear Systems
14.4 The TheoreticalBasisof the OnsagerReciprocity
14.5 ThermoelectricEffects
14.6 TheConductivities
I4.7
The SeebeckEffect and the Thermoelectricpower
14.8 The Peltier Effect
14.9 The ThomsenEffect

307
307
308
372
314
376
3r9
320
323
324

PART II
STATISTICAL MECHANICS
15 STATISTICAL MECIIANICS IN THE
ENTROPY REPRESENTATION:
THE MICROCANONICAL FORMALISM
15.1 PhysicalSignificance
of the Entropyfor ClosedSystems
75.2 The EinsteinModelof a CrystallineSolid
15.3 TheTwo-State
System
75.4 A PolymerModel-The RubberBandRevisited
15.5 CountingTechniques
and their Circumvention;
High Dimensionality
16 THE CANONICAL FORMALISM; STATISTICAL
MECHANICS IN HELMHOLTZ REPRESENTATION
16.1 The ProbabilityDistribution
76.2 AdditiveEnergies
andFactorizability
of the partitionSum

16.3
16.4
16.5
16.6
16.7
16.8
16.9
16.1
16.1

l7 l
(
17.I
17.2
17.3

Itt

18.1
t8.2
18.3
18.4
18.5
18.6

19 l
19.1
19.2
19.3

a)

I
329
329
333
337
339

n.7
n.2
n.3

349
349
3s3

I I
T

Cofltents

16.3
16.4
16.5
16.6
16.7
16.8
16.9
f6.10
16.11

Internal Modesin a Gas


Probabilitiesin FactorizableSystems
StatisticalMechanicsof Small Systems:Ensembles
Density of Statesand Density-of-Orbital States
The Debye Model of Non-metallic Crystals
ElectromagneticRadiation
The ClassicalDensityof States
The ClassicalIdeal Gas
High TemperatureProperties-The Equipartition Theorem

17 BNTROPY AND DISORDER; GENERALIZED


CANONICAL FORMULATIONS
l7.I
Entropy as a Measureof Disorder
17.2 Distributionsof Maximal Disorder
17.3 The Grand CanonicalFormalism

xU

355

3s8
360
362
364
368
370
372
375
379
379
382
385

18 QUANTUM FLUIDS
18.1 QuantumParticles;A "Fermion Pre-GasModel"
18.2 The Ideal Fermi Fluid
18.3 The ClassicalLimit and the QuantumCriteria
18.4 The StrongQuantumRegime;Electronsin a Metal
18.5 The Ideal BoseFluid
18.6 Non-ConservedIdeal BoseFluids; Electromagnetic
Radiation Revisited
18.7 BoseCondensation

393
393

T9 FLUCTUATIONS
19.1 The ProbabilityDistributionof Fluctuations
19.2 Momentsand The EnergyFluctuations
19.3 GeneralMomentsand CorrelationMoments

423

20 VARIATIONAL PROPERTIES, PERTURBATION


EXPANSIONS, AND MEAN FIELD THEORY
20.1 The BogoliubovVariational Theorem
20.2 Mean Field Theory
20.3 Mean Field Theory in GeneralizedRepresentation;
the Binary Alloy

399
402
405
470
412

4r3
423
424
426

433
433
440
449

PART III
FOUNDATIONS
21 POSTLUDE: SYMMBTRY AND THE CONCEPTUAL
FOUNDATIONS OF THERMOSTATISTICS
21.7 Statistics

455
455

21.2
21.3
2I.4
21.5
21.6
27.7
21.8
21.9

Symmetry
Noether's Theorem
Energy, Momentum and Angular Momentum; the Generalized
"First Law" of Thermodynamics
Broken Symmetryand Goldstone'sTheorem
Other Broken SymmetryCoordinates-Electric and
Magnetic Moments
Mole Numbers and GaugeSymmetry
Time Reversal,the Equal Probability of Microstates,
and the Entropy Principle
Symmetry and Completeness

458
460
467
462
465
466
467
469

APPENDIX A
SOME RELATIONS IT{VOLVING
PARTIAL DERIVATIVES
Partial Derivatives
A.1
4.2
Taylor's Expansion
A.3
Differentials
A.4
CompositeFunctions
A.5
Implicit Functions

473
473
474
475
4',15
476

APPENDIX B
MAGNETIC SYSTEMS

479

GENERAL REFERENCES

485

INDEX

487