Contents

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 denition of heat 13
2.2 Heat capacity 14
Exercises 17
3 Probability 18
3.1 Discrete probability distributions 19
3.2 Continuous probability distributions 20
3.3 Linear transformation 21
3.4 Variance 22
3.5 Linear transformation and the variance 23
3.6 Independent variables 24
Further reading 27
Exercises 27
4 Temperature and the Boltzmann factor 30
4.1 Thermal equilibrium 30
4.2 Thermometers 31
4.3 The microstates and macrostates 33
4.4 A statistical denition of temperature 34
4.5 Ensembles 36
4.6 Canonical ensemble 36
4.7 Applications of the Boltzmann distribution 40
Further reading 44
Exercises 44
II Kinetic theory of gases 45
5 The MaxwellBoltzmann distribution 46
xii Contents
5.1 The velocity distribution 46
5.2 The speed distribution 47
5.2.1 v and v
2
48
5.2.2 The mean kinetic energy of a gas molecule 48
5.2.3 The maximum of f(v) 49
5.3 Experimental justication 49
Exercises 52
6 Pressure 54
6.1 Molecular distributions 55
6.1.1 Solid angles 55
6.1.2 The number of molecules travelling in a certain
direction at a certain speed 55
6.1.3 The number of molecules hitting a wall 56
6.2 The ideal gas law 56
6.3 Daltons law 58
Exercises 59
7 Molecular eusion 62
7.1 Flux 62
7.2 Eusion 64
Exercises 67
8 The mean free path and collisions 68
8.1 The mean collision time 68
8.2 The collision cross-section 69
8.3 The mean free path 71
Exercises 72
III Transport and thermal diusion 73
9 Transport properties in gases 74
9.1 Viscosity 74
9.2 Thermal conductivity 79
9.3 Diusion 81
9.4 More-detailed theory 84
Further reading 86
Exercises 87
10 The thermal diusion equation 88
10.1 Derivation of the thermal diusion equation 88
10.2 The one-dimensional thermal diusion equation 89
10.3 The steady state 92
10.4 The thermal diusion equation for a sphere 92
10.5 Newtons law of cooling 95
10.6 The Prandtl number 97
10.7 Sources of heat 98
Exercises 99
Contents xiii
IV The rst law 103
11 Energy 104
11.1 Some denitions 104
11.1.1 A system in thermal equilibrium 104
11.1.2 Functions of state 104
11.2 The rst law of thermodynamics 106
11.3 Heat capacity 108
Exercises 111
12 Isothermal and adiabatic processes 114
12.1 Reversibility 114
12.2 Isothermal expansion of an ideal gas 116
12.3 Adiabatic expansion of an ideal gas 117
12.4 Adiabatic atmosphere 117
Exercises 119
V The second law 121
13 Heat engines and the second law 122
13.1 The second law of thermodynamics 122
13.2 The Carnot engine 123
13.3 Carnots theorem 126
13.4 Equivalence of Clausius and Kelvin statements 127
13.5 Examples of heat engines 127
13.6 Heat engines running backwards 129
13.7 Clausius theorem 130
Further reading 133
Exercises 133
14 Entropy 136
14.1 Denition of entropy 136
14.2 Irreversible change 136
14.3 The rst law revisited 138
14.4 The Joule expansion 140
14.5 The statistical basis for entropy 142
14.6 The entropy of mixing 143
14.7 Maxwells demon 145
14.8 Entropy and probability 146
Exercises 149
15 Information theory 153
15.1 Information and Shannon entropy 153
15.2 Information and thermodynamics 155
15.3 Data compression 156
15.4 Quantum information 158
Further reading 161
Exercises 161
xiv Contents
VI Thermodynamics in action 163
16 Thermodynamic potentials 164
16.1 Internal energy, U 164
16.2 Enthalpy, H 165
16.3 Helmholtz function, F 166
16.4 Gibbs function, G. 167
16.5 Availability 168
16.6 Maxwells relations 170
Exercises 178
17 Rods, bubbles and magnets 182
17.1 Elastic rod 182
17.2 Surface tension 185
17.3 Paramagnetism 186
Exercises 192
18 The third law 193
18.1 Dierent statements of the third law 193
18.2 Consequences of the third law 195
Exercises 198
VII Statistical mechanics 199
19 Equipartition of energy 200
19.1 Equipartition theorem 200
19.2 Applications 203
19.2.1 Translational motion in a monatomic gas 203
19.2.2 Rotational motion in a diatomic gas 203
19.2.3 Vibrational motion in a diatomic gas 204
19.2.4 The heat capacity of a solid 205
19.3 Assumptions made 205
19.4 Brownian motion 207
Exercises 208
20 The partition function 209
20.1 Writing down the partition function 210
20.2 Obtaining the functions of state 211
20.3 The big idea 218
20.4 Combining partition functions 218
Exercises 219
21 Statistical mechanics of an ideal gas 221
21.1 Density of states 221
21.2 Quantum concentration 223
21.3 Distinguishability 224
21.4 Functions of state of the ideal gas 225
21.5 Gibbs paradox 228