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Thermal Physics
 Thermal Physics
Thermodynamics and Statistical Mechanics
for Scientists and Engineers

Robert F. Sekerka
Carnegie Mellon University
Pittsburgh, PA 15213, USA

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD

PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK
225 Wyman Street, Waltham, MA 02451, USA

Copyright © 2015 Elsevier Inc. All rights reserved.

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ISBN: 978-0-12-803304-3
Dedication

To Care . . . .

who cared about every word

and helped me write what I meant to say
rather than what I had written

v
 •••
•••
•••
Tableof Contents

About the Cover xv

Preface XVII

PART I Thermodynamic s 1
1 Intr oduct ion 3
1.1 Temper ature 3
1.2 Thermodynamics Versus Statistical Mechanics 5
1.3 Classification of State Variabl es 6
1.4 Energy in Mechanics 8
1.5 Elementary Kinetic Theory 12

2 First Law of Thermodynamics 15

2.1 Statement of the First Law 15
2.2 Quasistatic Work 17
2.3 Heat Capacities 19
2.4 Work Due to Expansion of an Ideal Gas 24
2.5 Enthalpy 28

3 Second Law of Thermod ynamics 31

3.1 Statement of the Second Law 32
3.2 Carnot Cycle and Engines 35
3.3 Calculation of th e Entropy Chang e 39
3.4 Combined First and Second Laws 41
3.5 Statistical Interpretation of Entrop y 47

vii
viii Table of Contents

4 Third Law of Thermodynamics 49

4.1 Statement of the Third Law 49
4.2 Implications of the Third Law 50

5 Open Systems 53
5.1 Single Component Open System 53
5.2 Mu lticomponent Open Systems 55
5.3 Euler Theorem of Homogeneous Functions 59
5.4 Chemical Potential of Real Gases, Fugacity 64
5.5 Legen dre Transformations 67
5.6 Partial Molar Quantities 71
5.7 Entropy of Chemical Reaction 75

6 Equilibrium and Thermodynamic Potentia ls 79

6.1 Entropy Criterion 79
6.2 Energy Criterion 84
6.3 Other Equilibrium Criteria 88
6.4 Summary of Criteria 92

7 Requirements for Stabi lity 95

7.1 Stability Requirements for Entrop y 95
7.2 Stability Requirements for Internal Energy 100
7.3 Stability Requirements for Other Potentials 102
7.4 Consequences of Stability Requiremen ts 105
7.5 Extension to Many Variables 106
7.6 Principles of Le Chatlier and Le Chatlier-Braun 107

8 Monocomponent Phase Equi librium 109

8.1 Clausius-Clapeyron Equation 110
8.2 Sketches of the Thermodynamic Function s 115
8.3 Phas e Diagram in th e v, p Plane 118
 Table of Contents ix

9 Two -Phase Equilibrium for a van der Waa ls Fluid 121

9.1 van der Waals Equation of State 121
9.2 Thermodynamic Functions 124
9.3 Phase Equilibrium and Miscibility Gap 127
9.4 Gibbs Free Energy 131

10 Binary Solutions 137

10.1 Thermodynamics of Binary Solutions 137
10.2 Ideal Soluti ons 142
10.3 Phase Diagram for an Ideal Solid and an Ideal Liquid 145
10.4 Regular Solution 148
10.5 General Binary Solutions 153

11 Externa l Forces and Rotating Coordinate Systems 155

11.1 Conditions for Equilibrium 155
11.2 Uniform Gravitational Field 157
11.3 Non-Uniform Gravitational Field 164
11.4 Rotating Systems 164
11.5 Electric Fields 166

12 Chemica l Reactions 167

12.1 Reactions at Constant Volume or Pressure 168
12.2 Standard States 171
12.3 Equilibr ium and Affinity 173
12.4 Explicit Equilibrium Conditions 175
12.5 Simul taneous Reactions 182

13 Thermodynam ics of Fluid-Fluid Interf aces 185

13.1 Planar Interfaces in Fluids 186
13.2 Curved Interfaces in Flu ids 197
x Table of Contents

13.3 Interface Junctions and Contact Angles 202

13.4 Liquid Surface Shape in Gravity 205

14 Thermodynamics of Solid-Flu i d Interfaces 215

14.1 Planar Solid-Fluid Interfaces 216
14.2 Anisotropy of y 22 1
14.3 Curved Solid-Fluid Interfaces 227
14.4 Faceting of a Large Planar Face 233
14.5 Equilibrium Shape from the~ -Vector 236
14.6 Herring Formula 240
14.7 Legendre Transform of the Equilibrium Shape 241
14.8 Remarks About Solid-Solid Interfaces 242

PART II Statistical Mechanics 245

15 Entropy and Information Theory 247
15.1 Entropy as a Measure of Disorder 247
15.2 Boltzmann Eta Theorem 251

16 Microcanonical Ensemble 257

16.1 Fundamenta l Hypothesis of Statistical Mechanics 258
16.2 Two-Stat e Subsystems 261
16.3 Harmonic Oscillators 265
16.4 Ideal Gas 267
16.5 Multicomponent Ideal Gas 273

17 Classical Microcanonical Ensemble 277

17.1 Liouville's Theorem 278
17.2 Classical Microcanonical Ensemble 280
 Tab le of Contents xi

18 Distinguishable Part icles with Negligible

Interaction Energies 285
18.1 Derivation of the Boltzmann Distribution 285
18.2 Two-State Subsystems 289
18.3 Harmonic Oscillators 293
18.4 Rigid Linear Rotator 303

19 Canonical Ensemble 305

19. 1 Three Derivations 305
19.2 Factorizat ion Theorem 312
19.3 Classica l Idea l Gas 313
19.4 Maxwell-Boltzmann Distribution 317
19.5 Energy Dispersion 320
19.6 Paramagnetism 321
19.7 Partition Function and Densit y of States 330

20 Classical Canonical Ensemble 337

20.1 Classical Ideal Gas 338
20.2 Law of Dulong and Petit 342
20.3 Averaging Theorem and Equipartition 343
20.4 Virial Theorem 346
20.5 Virial Coefficients 348
20.6 Use of Canonical Transforma tions 354
20.7 Rotating Rigid Polya tomi c Molecu les 356

21 Grand Canonical Ensemble 359

21.1 Derivation from Microcanonical Ensemble 360
21.2 Ideal Systems: Orbitals and Factorization 368
xii Table of Contents

21.3 Classical Ideal Gas with Internal Structure 380

21.4 Multicomponent Systems 388
21.5 Pressure Ensemb le 389

22 Entropy for Any Ensemb le 397

22.1 General Ensemble 397
22.2 Summation over Energy Levels 402

23 Un ified Treatment of Idea l Fermi, Bose, and Classical Gases 405

23.1 Integr al Formulae 406
23.2 The Functions hv(A, a) 408
23.3 Virial Expansio ns for Ideal Fermi and Bose Gases 410
23.4 Heat Capacity 412

24 Bose Condensat ion 413

24.l Bosons at Low Temperatures 413
24.2 Thermodynamic Functions 416
24.3 Condensate Region 421

25 Degenerate Fermi Gas 425

25.1 Ideal Fermi Gas at Low Temperatures 425
25.2 Free Electron Model of a Metal 428
25.3 Thermal Activation of Electrons 429
25.4 Pauli Paramagnetism 433
25.5 Landau Diamagnetism 436
25.6 Thermionic Emission 439
25.7 Semiconductors 442

26 Quantum Statistics 451

26.1 Pure States 451
26.2 Statistical States 453
 Table of Contents xiii

26.3 Random Phases and External Influ ence 454

26.4 Time Evoluti on 455
26.5 Densit y Operators for Specific Ensembles 456
26.6 Examp les of th e Density Matrix 459
26.7 Indi stinguishable Particles 465

27 Ising Model 469

27.1 Ising Mod el, Mean Fie ld Treatment 470
27.2 Pair Sta tistics 477
27.3 Soluti on in One Dimension for Zero Field 479
27.4 Transfer Matrix 480
27.5 Oth er Methods of Soluti on 483
27.6 Monte Carlo Simulation 484

PARTIll Appendices 495

A Stirl ing 's Approximation 497
A.l Elem entary Mot ivation ofEq. (A.l ) 498
A.2 Asymptotic Series 499

B Use of Jacobians to Convert Partial Derivatives 503

B.l Properties of Jacobians 503
B.2 Connect ion to Thermody namic s 504

C Differential Geometry of Surfaces 509

C.l Alterna tive Formulae for ~ Vector 509
C.2 Sur face Differe nti al Geome try 511
C.3 ~ Vector for Genera l Surfaces 516
C.4 Herring Form ula 518

D Equi librium of Two-State Systems 523

xiv Table of Contents

E Aspects of Canonical Transformations 529

E.1 Necessary and Sufficient Conditions 530
E.2 Restricted Canonical Transformations 534

F Rotation of Rigid Bodies 537

El Moment oflnertia 537
F.2 Angular Momentum 539
F.3 Kinetic Energy 540
F.4 Time Derivatives 540
F.5 Rotating Coordinate System 541
F.6 Matrix Formulation 544
F.7 Canonical Variables 546
F.8 Quantum Energy Levels for Diatomic Molecule 547

G Thermodynamic Perturbation Theory 549

G.1 Classical Case 549
G.2 Quantum Case 550

H Selected Mathematical Relations 553

H.1 Bernoulli Numbers and Polynomials 553
H.2 Euler-Maclaur in Sum Formula 554

Creation and Annihilation Operators 559

1.1 Harmonic Oscillator 559
1.2 Boson Operators 560
1.3 Fermion Operators 562
1.4 Boson and Fermion Number Operators 563

References 565
Index 569
About the Cover

To represent the many scientists who have made major contributions to the foundations of
thermodynamics and statistical mechanics, the cover of this book depicts four significant
scientists along with some equations and graphs associated with each of them.
• James Clerk Maxwell (1831-1879) for his work on thermodynamics and especially the
kinetic theory of gases, including the Maxwell relations derived from perfect differen-
tials and the Maxwell-Boltzmann Gaussian distribution of gas velocities, a precursor of
ensemble theory (see Sections 5.2, 19.4, and 20.1).
• Ludwig Boltzmann (1844-1906) for his statistical approach to mechanics of many
particle systems, including his Eta function that describes the decay to equilibrium
and his formula showing that the entropy of thermodynamics is proportional to the
logarithm of the number of microscopic realizations of a macrosystem (see Chapters
15–17).
• J. Willard Gibbs (1839-1903) for his systematic theoretical development of the ther-
modynamics of heterogeneous systems and their interfaces, including the definition
of chemical potentials and free energy that revolutionized physical chemistry, as well
as his development of the ensemble theory of statistical mechanics, including the
canonical and grand canonical ensembles. The contributions of Gibbs are ubiquitous
in this book, but see especially Chapters 5–8, 12–14, 17, 20, and 21.
• Max Planck (1858-1947, Nobel Prize 1918) for his quantum hypothesis of the energy of
cavity radiation (hohlraum blackbody radiation) that connected statistical mechanics
to what later became quantum mechanics (see Section 18.3.2); the Planck distribution
of radiation flux versus frequency for a temperature 2.725 K describes the cosmic
microwave background, first discovered in 1964 as a remnant of the Big Bang and later
measured by the COBE satellite launched by NASA in 1989.
The following is a partial list of many others who have also made major contributions
to the field, all deceased. Recipients of a Nobel Prize (first awarded in 1901) are denoted
by the letter “N” followed by the award year. For brief historical introductions to thermo-
dynamic and statistical mechanics, see Cropper [11, pp. 41-136] and Pathria and Beale [9,
pp. xxi-xxvi], respectively. The scientists are listed in the order of their year of birth:
Sadi Carnot (1796-1832); Julius von Mayer (1814-1878); James Joule (1818-1889);
Hermann von Helmholtz (1821-1894); Rudolf Clausius (1822-1888); William Thomson,
Lord Kelvin (1824-1907); Johannes van der Waals (1837-1923, N1910); Jacobus van’t
Hoff (1852-1911, N1901); Wilhelm Wien (1864-1928, N1911); Walther Nernst (1864-
1941, N1920); Arnold Sommerfeld (1868-1951); Théophile de Donder (1872-1957); Albert

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of Morris detestation

to these

office feet

change

at embrace

and bishop cabin

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