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Concepts in Thermal
Physics

Second Edition

STEPHEN J. BLUNDELL AND

KATHERINE M. BLUNDELL
Department of Physics,
University of Oxford, UK

OXFORD
UNIVERSITY PRESS
Contents

Preface vi i
Preface to the second edition x

I Preliminaries 1

1 Introduction 2
1.1 What is a mole? 3
1.2 The thermodynamic limit 4
1.3 The ideal gas 6
1.4 Combinatorial problems 7
1.5 Plan of the book 9
Exercises 12

2 Heat 13
2.1 A definition of heat 13
2.2 Heat capacity 14
Exercises 17

3 Probability 18
3.1 Discrete probability distributions 19
3.2 Continuous prob abil ity dist ributions 20
3.3 Linear transformation 21
3.4 Variance 22
3.5 Linear transformation and the variance 23
3.6 Independent variables 24
3.7 Binomial distribution 26
Further reading 29
Exercises 29

4 Temperature and the Boltzmann factor 32

4.1 Thermal equilibrium 32
4.2 Thermometers 33
4.3 The microstates and macrostates 35
4.4 A statistical definition of temperature 36
4.5 Ensembles 38
4.6 Canonical ensemble 38
4.7 Applications of the Boltzmann distribution 42
Further reading 46
Exercises 46
xii Contents

II Kin.etic theory of gases 47

5 The Maxwell—Boltzmann distribution 48

5.1 The velocity distribution 48
5.2 The speed distribution 49
5.3 Experimental justification 51
Exercises 54

6 Pressure 56
6.1 Molecular distributions 57
6.2 The ideal gas law 58
6.3 Dalton's law 60
Exercises 61

7 Molecular effusion 64
7.1 Flux 64
7.2 Effusion 66
Exercises 69

8 The mean free path and collisions 70

8.1 The mean collision time 70
8.2 The collision cross-section 71
8.3 The mean free path 73
Exercises 74

III Transport and thermal diffusion 75

9 Transport properties in gases 76

9.1 Viscosity 76
9.2 Thermal conductivity 81
9.3 Diffusion 83
9.4 More detailed theory 86
Further reading 88
Exercises 89

10 The thermal diffusion equation 90

10.1 Derivation of the thermal diffusion equation 90
10.2 The one-dimensional thermal diffusion equation 91
10.3 The steady state 94
10.4 The thermal diffusion equation for a sphere 94
10.5 Newton's law of cooling 99
10.6 The Prandtl number 100
10.7 Sources of heat 101
10.8 Particle diffusion 102
Exercises 103
 Contents xiii

IV The first law 107

11 Energy 108
11.1 Some definitions 108
11.2 The first law of thermodynamics 110
11.3 Heat capacity 112
Exercises 115

12 Isothermal and adiabatic processes 118

12.1 Reversibility 118
12.2 Isothermal expansion of an ideal gas 120
12.3 Adiabatic expansion of an ideal gas 121
12.4 Adiabatic atmosphere 121
Exercises 123

V The second law 125

13 Heat engines and the second law 126

13.1 The second law of thermodynamics 126
13.2 The Carnot engine 127
13.3 Carnot's theorem 130
13.4 Equivalence of Clausius' and Kelvin's st atements 131
13.5 Examples of heat engines 131
13.6 Heat engines running backwards 133
13.7 Clausius' theorem 134
Further reading 137
Exercises 137

14 Entropy 140
14.1 Definition of entropy 140
14.2 Irreversible change 140
14.3 The first law revisited 142
14.4 The Joule expansion 144
14.5 The statistical basis for entropy 146
14.6 The entropy of mixing 147
14.7 Maxwell's demon 149
14.8 Entropy and probability 150
Exercises 153

15 Information theory 157

15.1 Information and Shannon entropy 157
15.2 Information and thermodynamics 159
15.3 Data compression 160
15.4 Quantum information 162
15.5 Conditional and joint probabilities 165
15.6 Bayes' theorem 165
Further reading 168
Exercises 169
xiv Contents

VI Thermodynamics in action 171

16 Thermodynamic potentials 172

16.1 Internal energy, U 172
16.2 Enthalpy, H 173
16.3 Helmholtz function, F 174
16.4 Gibbs function, G 175
16.5 Constraints 176
16.6 Maxwell's relations 179
Exercises 187

17 Rods, bubbles, and magnets 191

17.1 Elastic rod 191
17.2 Surface tension 194
17.3 Electric and magnetic dipoles 195
17.4 Paramagnetism 196
Exercises 201

18 The third law 203

18.1 Different statements of the third law 203
18.2 Consequences of the third law 205
Exercises 208

VII Statistical mechanics 209

19 Equipartition of energy 210

19.1 Equipartition theorem 210
19.2 Applications 213
19.3 Assumptions made 215
19.4 Brownian motion 217
Exercises 218

20 The partition function 219

20.1 Writing down the partition funetion 220
20.2 Obtaining the functions of state 221
20.3 The big idea 228
20.4 Combining partition functions 228
Exercises 232

21 Statistical mechanics of an ideal gas 233

21.1 Density of states 233
21.2 Quantum concentration 235
21.3 Distinguishability 236
21.4 Functions of state of the ideal gas 237
21.5 Gibbs paradox 240
21.6 Heat capacity of a diatomic gas 241
Exercises 243
 Contents xv

22 The chemical potential 244

22.1 A definition of the chemical potential 244
22.2 The meaning of the chemical potential 245
22.3 Grand partition function 247
22.4 Grand potential 248
22.5 Chemical potential as Gibbs function per particle 250
22.6 Many types of particle 250
22.7 Particle number conservation laws 251
22.8 Chemical potential and chemical reactions 252
22.9 Osmosis 257
Further reading 261
Exercises 262

23 Photons 263
23.1 The classical thermodynamics of electromagnetic radiation 264
23.2 Spectral energy density 265
23.3 Kirchhoff's law 266
23.4 Radiation pressure 268
23.5 The statistical mechanics of the photon gas 269
23.6 Black-body distribution 270
23.7 Cosmic microwave background radiation 273
23.8 The Einstein A and B coefficients 274
Further reading 277
Exercises 278

24 Phonons 279
24.1 The Einstein model 279
24.2 The Debye model 281
24.3 Phonon dispersion 284
Further reading 287
Exercises 287

VIII Beyond the ideal gas 289

25 Relativistic gases 290

25.1 Relativistic dispersion relation for massive particles 290
25.2 The ultrarelativistic gas 290
25.3 Adiabatic expansion of an ultrarelativistic gas 293
Exercises 295

26 Real gases 296

26.1 The van der Waals gas 296
26.2 The Dieterici equation 304
26.3 Virial expansion 306
26.4 The law of corresponding states 310
Exercises 312
xvi Contents

27 Cooling real gases 313

27.1 The Joule expansion 313
27.2 Isothermal expansion 315
27.3 Joule—Kelvin expansion 316
27.4 Liquefaction of gases 318
Exercises 320

28 Phase transitions 321

28.1 Latent heat 321
28.2 Chemical potential and phase changes 324
28.3 The Clausius—Clapeyron equation 324
28.4 Stability and metastability 329
28.5 The Gibbs phase rule 332
28.6 Colligative properties 334
28.7 Classification of phase transitions 335
28.8 The Ising model 338
Further reading 343
Exercises 343

29 Bose—Einstein and Fermi—Dirac distributions 345

29.1 Exchange and symmetry 345
29.2 Wave functions of identical particles 346
29.3 The statistics of identical particles 349
Further reading 353
Exercises 354

30 Quantum gases and condensates 358

30.1 The non-interacting quantum fiuid 358
30.2 The Fermi gas 361
30.3 The Bose gas 366
30.4 Bose—Einstein condensation (BEC) 367
Further reading 373
Exercises 373

IX Special topics 375

31 Sound waves 376

31.1 Sound waves under isothermal conditions 377
31.2 Sound waves under adiabatic conditions 377
31.3 Are sound waves in general adiabatic or isothermal? 378
31.4 Derivation of the speed of sound within fluids 379
Further reading 382
Exercises 382

32 Shock waves 383

32.1 The Mach number 383
32.2 Structure of shock waves 383
32.3 Shock conservation laws 385
 Contents xvii

32.4 The Rankine--Hugoniot conditions 386

Further reading 389
Exercises 389

33 Brownian motion and fluctuations 390

33.1 Brownian motion 390
33.2 Johnson noise 393
33.3 Fluctuations 394
33.4 Fluctuations and the availability 395
33.5 Linear response 397
33.6 Correlation functions 400
Further reading 407
Exercises 407

34 Non-equilibrium thermodynamics 408

34.1 Entropy production 408
34.2 The kinetic coefficients 409
34.3 Proof of the Onsager reciprocal relations 410
34.4 Thermoelectricity 413
34.5 Time reversal and the arrow of time 417
Further reading 419
Exercises 419

35 Stars 420
35.1 Gravitational interaction 421
35.2 Nuclear reactions 426
35.3 Heat transfer 427
Further reading 434
Exercises 434

36 Compact objects 435

36.1 Electron degeneracy pressure 435
36.2 White dwarfs 437
36.3 Neutron stars 438
36.4 Black holes 440
36.5 Accretion 441
36.6 Black holes and entropy 442
36.7 Life, the Universe, and entropy 443
Further reading 445
Exercises 445

37 Earth's atmosphere 446

37.1 Solar energy 446
37.2 The temperature profile in the atmosphere 447
37.3 Radiative transfer 449
37.4 The greenhouse effect 452
37.5 Global warming 456
Further reading 460
Exercises 460
xviii Contents

A Fundamental constants 461

B Useful formulae 462

C Useful mathematics 464

C.1 The factorial integral 464
C.2 The Gaussian integral 464
C.3 Stirling's formula 467
C.4 Riemann zeta function 469
C.5 The polylogarithm 470
C.6 Partial derivatives 471
C.7 Exact differentials 472
C.8 Volume of a hypersphere 473
C.9 Jacobians 473
C.10 The Dirac delta function 475
C.11 Fourier transforms 475
C.12 Solution of the diffusion equation 476
C.13 Lagrange multipliers 477

D The electromagnetic spectrum 479

E Some thermodynamical definitions 480

F Thermodynamic expansion formulae 481

G Reduced mass 482

H Glossary of main symbols 483

Bibliography 485

Index 489