THERMODYNAMICS

AND AN INTRODUCTION
TO
THERMOSTATISTICS
SECONDEDITION

HERBERT
B.CALLEN
Universitvof Pennsvlvania

JOHN WILEY & SONS

New York Chichester Brisbane Toronto Singapore
 UNIVERZITA KARLOVA V PRAZE
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Copyright @ 1985,by John Wiley & Sons,Inc.

All rights reserved.Publishedsimultaneouslyin Canada.

Reproduction or translationof any part of

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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.
QC311.C25 1985 536',.7 85-6387
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 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 characterizethe non-analytic behavior of ther-
modynamic 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 ex-
panded, 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
 uut Preface

Fourth, I have long been pnzzledby certain conceptualproblemslying pre

at the foundations of thermodynamics,and this has led me to an interpre- phv
tation of the "meaning" of thermodynamics.In the final chapter-an tion
"interpretive postlude" to the main body of the text-I developthe thesis con
that thermostatisticshas its roots in the symmetriesof the fundamental cas
laws of physicsrather than in the quantitative content of thoselaws. The T
discussionis qualitative and descriptive,seekingto establishan intuitive one
framework and to encouragethe student to see scienceas a coherent foll
structure in which thermodynamicshas a natural and fundamentalrole. is f,
Although both statisticalmechanicsand thermodynamicsare included stat
in this new edition, I have attemptedneither to separatethem completely Cha
nor to meld them into the undifferentiatedform now popular under the T
rubric of " thermal physics."I believethat eachof theseextremeoptions is resF
misdirected. To divorce thermodynamicscompletely from its statistical and
mechanical base is to rob thermodynamicsof its fundamental physical inse
origins. Without an insight into statistical mechanicsa scientist remains inse
rooted in the macroscopicempiricism of the nineteenthcentury, cut off ata
from contemporarydevelopmentsand from an integratedview of science. T
Conversely, the amalgamationof thermodynamicsand statistical me- first
chanics into an undifferentiated" thermal physics" tends to eclipsether- Per
modynamics.The fundamentalityand profundity of statisticalmechanics
are treacherouslyseductive;" thermal physics" coursesalmost perforce Phil
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
I wheneverthe generalmethodsof macroscopicthermodynamicsare suffi-
cient. 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 compo-
nents. 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 thermody-
namics above all other subjects as requiring increased emphasis in the undergraduate curriculum That
emphasis subsequently has decreaserl
 P reface lx

preservesand emphasizesthe hierarchicalstructureof science,organizing

physics into coherent units with clear and easily rememberedinterrela-
n tionships. Similarly, classical mechanicsis best understood as a self-
IS contained postulatory structure, only later to be validated as a limiting
rl 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
rt 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
d 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
l. Postulates I

15.
2. Conditions of Equilibrium
3. Formal Relations and SampleSys-
tems
4. ReversibleProcesses;
Engines
1 5 . Statistical Mechanics in Entropy
Representation
5 . LegendreTransformations PA
GE
6. Extremum Principles in Legendre
Representation
CL
7. Maxwell Relations lntr,
The
15.
1 6 . CanonicalFormalism t
1.1
7 7 . Generalized Canonical Formula-
1.2
tion
1.3
8 . Stability t.4
9. First-OrderPhaseTransitions 1.5
1.6
t.7
10. Critical Phenomena 1.8
1 8 . QuantumFluids
1.9
11. Nernst
19. Fluctuations 1.1
12. Summaryof Principles
20. Variational Properties and Mean 2
Field Theory 2.7
13. Propertiesof Materials
2.2
14. IrreversibleThermodynamics 2.3
2.4
2.5
21. Postlude: Symmetry and the Conceptual Foundations of Thermodynamics 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 2

I THE PROBLEM AND THE POSTULATES 5

1.1 The TemporalNature of MacroscopicMeasurements 5
1.2 The SpatialNature of MacroscopicMeasurements 6
1.3 The Compositionof ThermodynamicSystems 9
1.4 The Internal Energy 11
1.5 ThermodynamicEquilibrium 13
1.6 Walls and Constraints 15
1.7 Measurability of the Energy 16
1.8 QuantitativeDefinitionof Heat-Units 18
1.9 The Basic Problemof Thermodynamics 25
l.i0 The Entropy Maximum Postulates 2'l

2 THE CONDITIONS OF EQUILIBRIUM 35

2.1 IntensiveParameters 35
2.2 Equationsof State 37
2.3 Entropic IntensiveParameters 40
2.4 Thermal Equilibrium-Temperature 43
2.5 Agreementwith Intuitive Conceptof Temperature 45
2.6 TemperatureUnits 46
2.7 MechanicalEquilibrium 49
2.8 Equilibrium with Respectto Matter Flow 54
2.9 ChemicalEquilibrium 56
xlt

3 SOME FORMAL RELATIONSHIPS, 1 l \

AND SAMPLE SYSTEMS 59 7.7
3.1 The Euler Equation 59 7.2
3.2 The Gibbs-Duhem Relation 60 7.3
3.3 Summary of Formal Structure 63
3.4 The Simple Ideal Gas and Multicomponent 7.4
Simple Ideal Gases 66 7.5
3.5 The "Ideal van der WaalsFluid" 74
3.6 ElectromagneticRadiation 78 8 S
3.7 The "Rubber Band" 80 8.1
3.8 UnconstrainableVariables;Magnetic Systems 81 8.2
3.9 Molar Heat Capacityand Other Derivatives 84 8.3
8.4
4 REVERSIBLE PROCESSES AND THE
MAXIMUM WORK THEOREM 9L 8.5
4.1 Possibleand ImpossibleProcesses 97
4.2 Quasi-Staticand ReversibleProcesses 95 9 F
4.3 RelaxationTimes and Irreversibility 99 9.1
4.4 Heat Flow: Coupled Systemsand Reversalof processes 101 9.2
4.5 The Maximum Work Theorem 103 9.3
4.6 Coefficientsof Engine,Refrigerator,and 9.4
Heat Pump Performance 113 9.5
4.7 The Carnot Cycle 118 9.6
4.8 Measurability of the Temperatureand of the Entropy 123
4.9 Other Criteria of Engine Performance;PowerOutput and 9.7
"EndoreversibleEngines" 725
4.10 Other Cyclic Processes r28
5 ALTERNATIVE FORMULATIONS
AND LEGENDRE TRANSFORMATIONS 131
5.1 The Energy Minimum Principle 131
5.2 LegendreTransformations 737
5.3 ThermodynamicPotentials 746
5.4 GeneralizedMassieuFunctions 151
6 THE EXTREMUM PRINCIPLE IN THE
LEGENDRE TRANSFORMED REPRESENTATIONS 153
6.1 The Minimum Principlesfor the Potentials- 153
6.2 The Helmholtz Potential r57
6.3 The Enthalpy; The Joule-Thomsonor "Throttling" process 160
6.4 The Gibbs Potential; ChemicalReactions I67 S
6.5 Other Potentials 172 F
6.6 Compilations of Empirical Data; The Enthalpy of Formation 773 I
6.7 The Maximum Principlesfor the MassieuFunctions 179
 Contents xiii

7 MAXWELL RELATIONS 181

59 7.1 The MaxwellRelations 181
59 7.2 A ThermodynamicMnemonicDiagram 183
60 7.3 A Procedure for the Reduction of Derivatives in
63 Single-Component Systems 186
7.4 Some Simple Applications 190
'7.5
66 Generalizations: Magnetic Systems 199
74
78 I STABILITY OF THERMODYNAMIC SYSTEMS 203
BO 8.1 Intrinsic Stability of ThermodynarnicSystems 203
B1 8.2 Stability Conditionsfor ThermodynamicsPotentials 207
B4 8.3 PhysicalConsequences of Stability 209
8.4 Le Chatelier'sPrinciple; The QualitativeEffect
of Fluctuations 2r0
)1 8.5 The Le Chatelier-Braun Principle 2r2
)1
)5 9 FIRST-ORDER PHASE TRANSITIONS 275
,9 9.1 First-OrderPhaseTransitionsin Single-Component Systems 215
)l 9.2 The Discontinuityin the Entropy-LatentHeat 222
)3 9.3 The Slope of CoexistenceCurves;the ClapeyronEquation 228
9.4 Unstable Isothermsand First-Order PhaseTransitions 233
IJ 9.5 GeneralAttributesof First-OrderPhaseTransitions 243
.8 9-6 First-Order PhaseTransitionsin Multicomponent
r3 Systems-Gibbs PhaseRule 245
9.7 PhaseDiagramsfor Binary Systems 248
r5
E TO CRITICAL PHENOMENA 255
lO.1 Thermodynamicsin the Neighborhoodof the Critical Point 255
lO.2 Divergenceand Stability 261
I 10.3 Order Parametersand Critical Exponents 263
1 10.4 ClassicalTheory in the Critical Region; Landau Theory 265
7 10.5 Roots of the Critical Point Problem 270
6 10.6 Scalingand Universality 272
I
II THE NERNST POSTULATE 277
ll.1 Nernst'sPostulate,and the Principleof Thomsen
and Bertholot 277
ll.2 Heat Capacitiesand Other Derivativesat Low Temperatures 280
lf .3 The "Unattainability" of Zero Temperature 287

T2 SUMMARY OF PRINCIPLES
FOR GENERAL SYSTEMS 283
l2.I General Systems 283
12.2 The Postulates 283
XID Contents

12.3 The IntensiveParameters 284 16.3

72.4 LegendreTransforms 16.4
285
72.5 Maxwell Relations 285 16.5
72.6 Stability and PhaseTransitions 286 16.6
I2.7 CriticalPhenomena 287 16.7
I2.8 Propertiesat Zero Temperature 287 16.8
16.9
13 PROPERTTES OF MAT4RTALS 289 16.1
f 3.1 The General Ideal Gas 289 16.1
73.2 Chemical Reactionsin ldeal Gases 292
73.3 Small Deviationsfrom "Ideality"-The Virial Expansion l7 l
297 (
73.4 The "Law of CorrespondingStates"for Gases 299 17.I
13.5 Dilute Solutions:OsmoticPressureand Vapor pressure 302 17.2
13.6 Solid Systems 305 17.3
14 IRREVERSIBLE THERMODYNAMICS 307 Itt
I4.I General Remarks 307 18.1
I4.2 Affinities and Fluxes 308 t8.2
74.3 Purely-Resistiveand Linear Systems 372 18.3
14.4 The TheoreticalBasisof the OnsagerReciprocity 314 18.4
14.5 ThermoelectricEffects 376 18.5
14.6 TheConductivities 3r9 18.6
I4.7 The SeebeckEffect and the Thermoelectricpower 320
14.8 The Peltier Effect 323
14.9 The ThomsenEffect 324
19 l
19.1
PART II 19.2
STATISTICAL MECHANICS 19.3
15 STATISTICAL MECIIANICS IN THE a)
ENTROPY REPRESENTATION: I
THE MICROCANONICAL FORMALISM 329 n.7
15.1 PhysicalSignificance
of the Entropyfor ClosedSystems 329 n.2
75.2 The EinsteinModelof a CrystallineSolid 333 n.3
15.3 TheTwo-State System 337
75.4 A PolymerModel-The RubberBandRevisited 339
15.5 CountingTechniques and their Circumvention;
High Dimensionality

16 THE CANONICAL FORMALISM; STATISTICAL

MECHANICS IN HELMHOLTZ REPRESENTATION 349 I I
16.1 The ProbabilityDistribution 349 T
76.2 AdditiveEnergies of the partitionSum
andFactorizability 3s3
 Cofltents xU

16.3 Internal Modesin a Gas 355

16.4 Probabilitiesin FactorizableSystems 3s8
16.5 StatisticalMechanicsof Small Systems:Ensembles 360
16.6 Density of Statesand Density-of-Orbital States 362
16.7 The Debye Model of Non-metallic Crystals 364
16.8 ElectromagneticRadiation 368
16.9 The ClassicalDensityof States 370
f6.10 The ClassicalIdeal Gas 372
16.11 High TemperatureProperties-The Equipartition Theorem 375

17 BNTROPY AND DISORDER; GENERALIZED

CANONICAL FORMULATIONS 379
l7.I Entropy as a Measureof Disorder 379
17.2 Distributionsof Maximal Disorder 382
17.3 The Grand CanonicalFormalism 385

18 QUANTUM FLUIDS 393

18.1 QuantumParticles;A "Fermion Pre-GasModel" 393
18.2 The Ideal Fermi Fluid 399
18.3 The ClassicalLimit and the QuantumCriteria 402
18.4 The StrongQuantumRegime;Electronsin a Metal 405
18.5 The Ideal BoseFluid 470
18.6 Non-ConservedIdeal BoseFluids; Electromagnetic
Radiation Revisited 412
18.7 BoseCondensation 4r3
T9 FLUCTUATIONS 423
19.1 The ProbabilityDistributionof Fluctuations 423
19.2 Momentsand The EnergyFluctuations 424
19.3 GeneralMomentsand CorrelationMoments 426
20 VARIATIONAL PROPERTIES, PERTURBATION
EXPANSIONS, AND MEAN FIELD THEORY 433
20.1 The BogoliubovVariational Theorem 433
20.2 Mean Field Theory 440
20.3 Mean Field Theory in GeneralizedRepresentation;
the Binary Alloy 449

PART III
FOUNDATIONS
21 POSTLUDE: SYMMBTRY AND THE CONCEPTUAL
FOUNDATIONS OF THERMOSTATISTICS 455
21.7 Statistics 455
21.2 Symmetry 458
21.3 Noether's Theorem 460
2I.4 Energy, Momentum and Angular Momentum; the Generalized
"First Law" of Thermodynamics 467
21.5 Broken Symmetryand Goldstone'sTheorem 462
21.6 Other Broken SymmetryCoordinates-Electric and
Magnetic Moments 465
27.7 Mole Numbers and GaugeSymmetry 466
21.8 Time Reversal,the Equal Probability of Microstates,
and the Entropy Principle 467
21.9 Symmetry and Completeness 469

APPENDIX A
SOME RELATIONS IT{VOLVING
PARTIAL DERIVATIVES 473
A.1 Partial Derivatives 473
4.2 Taylor's Expansion 474
A.3 Differentials 475
A.4 CompositeFunctions 4',15
A.5 Implicit Functions 476

APPENDIX B
MAGNETIC SYSTEMS 479
GENERAL REFERENCES 485
INDEX 487