Thermodynamics

A complete undergraduate course

Andrew M. Steane

OXFORD
\JNIVERSITY PRESS
Contents

How to use this book (t)

1.1 For the student
1.2 For the teacher
2 Introducing thermodynamics 3

3 A survey of thermodynamic ideas 7

3.1 Energy and entropy 7
3.2 Concepts and terminology 12
3.2.1 System 12
3.2.2 State 14
3.2.3 Extensive, intensive 18
3.2.4 Thermodynamic equilibrium 20
3.2.5 Temperature 22
3.2.6 Quasistatic 22
3.2.7 Reversible and irreversible 23
3.2.8 Adiathermal, isentropic, adiabatic, isothermal 25
3.2.9 Expansion coefficients, heat capacities 26
3.2.10 Thermal reservoir 29
3.3 The laws of thermodynamics 29
3.4 Where we are heading 32
Exercises 33
4 Some gen eral knowledge 34
4.1 Density, heat capacity 34
4.2 Moles 35
4.3 Boltzmann constant, gas constant 36
4.4 Pressure and STP 37
4.5 Latentheat 37
4.6 Magnetic properties 38
s Mathem atical tools 40
5.1 Working with partial derivatives 40
5.1.1 Reciprocal and reciprocity theorems 42
5.1.2 lntegrating 45
5.1.3 Mixed derivatives 46

t sections rnarked with a dagger below are optional reading. They can be omitted without the loss of
inforrnation required later in the book.
vili Cont.ents
5 .2
Proper and improper differentials, function of state 46
5.2.1 Integrating factor 49
5.3 Some further observations 49
5.3.1 Alternative derivation of reciprocal and reciprocity theorems 49
5.3.2 Integration in general 50
Exercises 51

6 Zeroth law, equation of state 52

6.1Empirical temperature 54
6.1.1 Equation of state 55
6.1.2 Algebraic argument (t) 57
6.2 Some example equations of state 59
6.2.1 Ideal gas 59
6.2.2 Thermal radiation 61
6.2.3 Solids and wires 62
6.2.4 Paramagnetic material 63
6.2.5 Equations of state for other properties 65
6.3 Thermometry 66
Exercises 68
7 First law, internal energy 70
7 .1 Defining internal energy 70
7.1.1 Heat and work 73
7 .2 Work by compression 74
7 .3 Heat capacities 77
7.3.1 Energy equation 80
7.3.2 Relation of compressibilities
and heat capacities 82
7 .4 Solving thermodynamic problems 83
7.5 Expansion 85
7.5.1 Free expansion ofideal gas 85
7.5 .2 Adiabatic expansion of ideal gas 86
7.5.3 Adiabatic atmosphere 87
7.5.4 Fast and yet adiabatic? 88
Exercises 89
8 The second law and entropy 93
8.1 Heat engines and the Carnot cycle 93
8.1.1 Heat pumps and refrigerators 95
8.1.2 1\vo impossible things (equivalence ofKelvin and Clausius Statements) 96
8.2 Carnot's theorem and absolute temperature 97
8.2.1 Carnot's theorem: reversible engines are equally, and the most, efficient 97
8.2.2 Existence of an absolute temperature measure 98
8.2.3 Hot heat is more valuable than cold heat 101
 Contents ix

8.3 Clausius' theorem and entropy 102

8.4 Tue first and second laws together 105
8.5 Summary 106
Exercises 106

9 Understanding entropy 108

9.1 Examples 109
9.1.1 Entropy content 111
9.1.2 Enttopy production and enttopy flow 112
9.2 But what is it? 113
9.2.1 Entropy increase in a free expansion 115
9.3 Gibbs' paradox 116
9.3.1 Entropy ofmixing 118
9.3.2 Reversible mixing 119
9.4 Specific heat anomalies 120
9.5 Maxwell's daemon 122
9.5.1 Szilard engine 123
9.5.2 The Feynman-Smoluchowski ratchet 125
9.6 The principle of detailed balance 127
9. 7 Adiabatic surfaces et) 128
9.8 Irreversibility in the universe 131
Exercises 133

10 Heat ftow and thermal relaxation 136

10.1 Thermal conduction; diffusion equation 136
10.1.l Steady state 138
10.1.2 Time-dependent 139
10.2 Relaxation time 145
10.3 Speed of sound (t) 146
10.3.1 Ultra-relativistic gas 148
Exercises 148

11 Practical heat engines 150

11 .1 Tue maximum work theorem 152
11.1.1 lmperfections 152
11.2 Otto cycle 153
Exercises 155

12 Introducing chemical potential 157

12.1 Chemical potential of an
ideal gas 161
12.1.1 Example: the isothermal atmosphere 163
12.2 Saha equation (t) 165
Exercises 167
x Contents

13 Functions and methods 169

13.1 The fundamental relation 169
13.1.1 Euler relation, Gibbs-Duhem relation 170
13.2 Thermodynamic potentials 172
13.2.1 Free energy as a form of potential energy 174
13.2.2 Natural variables and thermodynamic potentials 175
13.2.3 Maxwell relations 176
13.2.4 Obtaining one potential function from another 177
13.3 Basic results for closed systems 177
13.3.1 Relating intemal energy to equation of state 178
13.3.2 Sackur-Tetrode equation 182
13.3.3 Complete thermodynamic information 186
Exercises 186
14 Elastic bands, rods, bubbles, magnets 188
14.1 Expressions for work 188
14.2 Rods, wires, elastic bands 188
14.3 Surface tension 190
14.4 Paramagnetism 192
14.4.1 Idealparamagnet 195
14.4.2 Cooling by adiabatic demagnetization 197
14.5 Electric and magnetic work (t) 200
14.5.1 Dielectrics and polarization 202
14.5.2 Magnetic work 207
14.6 lntroduction to the partition function (t) 210
Exercises 212
15 Modelling real gases 216
15 .1 van der Waals gas 219
15.1.1 Phase change 220
15.1.2 Critical parameters and the law of corresponding states 222
15.2 Redlich-Kwong, Dieterici, and Peng-Robinson gas 224
Exercises 226
16 Expansion and flow processes 228
16.1 Expansion coefficients 228
16.2 U: free expansion 229
16.2.1 Deriving the equation of state of an ideal gas 229
16.3 H: throttle process: Joule-Kelvin expansion 230
16.3 .1 Bernoulli equation 231
16.3.2 Cooling and liquification of gases 232
16.4 Generalflow process 236
16.4.1 S and H: the gas turbine 237
Exercises 239
 Contents xi
17 Stability and free energy 243
17.1 Isolated system: maximum entropy 243
17.1.1 Equilibrium condition with intemal restrictions 245
17.1.2 Tue minimum energy principle 246
17 .1.3 Stability 247
17.2 Phase change 249
17.3 Free energy and availability 250
17 .3.1 Free energy and equilibrium 253
Exercises 257
18 Reinventing the subject 259
18.1 Some basic derivations from maximum entropy 262
18.2 Caratheodory formulation ofthe second law (t) 263
18.3 Negative temperature (t) 265
19 Thermal radiation 268
19.1 Some general observations about thermal radiation 268
19.1.1 Black body radiation: a first look 274
19.2 Basic thermodynamic arguments 275
19.2.1 Equation of state and Stefan-Boltzmann law 279
19.2.2 Comparison with ideal gas 282
19.2.3 Adiabatic expansion and Wien's laws (t) 283
19.3 Cosmic microwave background radiation 288
Exercises 289
20 Radiative heat transfer 291
20.1 Tue greenhouse effect 294
Exercises 297
21 Chemical reactions 299
21.1 Basic considerations 299
21.1.1 Reaction rate 301
21.2 Chemical equilibrium and the law of mass action 301
21.2 .1 Van 't Hoff equation 305
21.2.2 Chemical terminology 306
21.3 Tue reversible electric cell (t) 307
Exercises 309
22 Phase change 311
22.1 General introduction 311
22.1.1 Phase diagram 312
22.1.2 Some interesting phase diagrams 314
22.2 Basic properties offirst-order phase transitions 317
22.3 Clausius-Clapeyron equation 320
xii Contents
22.3.1 Vapour-liquid and liquid-solid coexistence lines 323
22.3.2 Gibbs phase rule 325
22.3.3 Behaviour of the chemical potential 326
22.4 The type-! superconducting transition (t) 326
Exercises 329
23 The third law 331
23.1 Response functions 332
23.2 Unattainability theorem 333
23.3 Phase change 334
23.4 Absolute entropy and chemical potential 335
24 Phase change, nucleation, and solutes 336
24.1 Treatment of surface effects 336
24.2 Metastable phases 338
24.2.1 Nucleation 341
24.3 Colligative properties 347
24.3.1 Osmotic pressure 347
24.3.2 lnftuence of dissolved particles on phase transitions 350
24.4 Chapter summary 353
Exercises 353
25 Continuous phase transitions 355
25.1 Orderparameter 357
25.2 Critical exponents 359
25.3 Landau mean field theory 361
25.3.1 Application to ferromagnetism 366
25.4 Binary mixtures 370
Exercises 373
26 Self-gravitation and negative heat capacity 375
26.1 Negative heat capacity 375
26.1.1 Jeans length 377
26.2 Black holes and Hawking radiation 378
Exercises 381

27 Fluctuations 382
27 .1 Probability of a departure from the maximum entropy point 383
27.1.1 Is there a violation of the second law? 384
27.2 Calculating the ftuctuations 385
27.2.1 More general constraints 387
27 .2.2 Some general observations 391
27 .3 Interna! ftows 393
27.4 Fluctuation as a function oftime 395
 Conunts xili
27.5 Johnson noise 398
Exercises 401
28 Thermoelectricity and entropy flow 403
28.1 Thermoelectric effects 403
28.1.1 Thomson's treatment 406
28.2 Entropy gradients and Onsager's reciprocal relations 409
28.2.1 Derivation of Onsager's reciprocal relation 411
28.2.2 Application 416
28.2.3 Entropy current, entropy production rate 41 7
Exercises 418

Appendix A Electric and magnetic work 421

Appendix B More on natural variables and free energy 424
Appendix C Some mathematical results 428
Bibliography 431
Index 433