Professional Documents
Culture Documents
AND AN INTRODUCTION
TO
THERMOSTATISTICS
SECONDEDITION
HERBERT
B.CALLEN
Universitvof Pennsvlvania
V PRAZE
KARLOVA
UNIVERZITA
mat - fyz fakultY
Kninovna
- Knthovna
Fr.Z6vi6ky
Odd tyzikalrr:
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To Sara
.....and
to Jill,Jed,
Zacharyand Jessica
PREFACE
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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
PA
GE
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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
2
5
5
6
9
11
13
15
16
18
25
2'l
35
35
37
40
43
45
46
49
54
56
xlt
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
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
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B4
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)1
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,9
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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
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
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
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
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
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