Preface xv

About the companion website xvii

1 Introduction 1

1.1 Atoms and molecules 1

1.2 Phases 2

1.3 Energy 3

1.4 Chemical reactions 4

1.5 Problem solving 5

1.6 Some conventions 7

Exercises 11

Further reading 14

2 Ideal gases 15

2.1 Ideal gas equation of state 16

2.2 Molecular degrees of freedom 18

2.3 Translational energy: Distribution and relation to pressure 21

2.4 Maxwell distribution of molecular speeds 23

2.5 Principle of equipartition of energy 24

2.6 Temperature and the zeroth law of thermodynamics 25

2.7 Mixtures of gases 27

2.8 Molecular collisions 27

Exercises 29

Further reading 30

3 Non-ideal gases and intermolecular interactions 31

3.1 Non-ideal behavior 31

3.2 Interactions of matter with matter 32

3.3 Intermolecular interactions 34

3.4 Real gases 39

3.5 Corresponding states 42

3.6 Supercritical fluids 43

Exercises 43

Further reading 44

4 Liquids, liquid crystals, and ionic liquids 45

4.1 Liquid formation 45

4.2 Properties of liquids 45

4.3 Intermolecular interaction in liquids 47

4.4 Structure of liquids 50

4.5 Internal energy and equation of state of a rigid sphere liquid 52

4.6 Concentration units 53

4.7 Diffusion 55

4.8 Viscosity 57

4.9 Migration 59

4.10 Interface formation 60

4.11 Liquid crystals 62

4.12 Ionic liquids 64

Exercises 66

Further reading 67

5 Solids, nanoparticles, and interfaces 68

5.1 Solid formation 68

5.2 Electronic structure of solids 70

5.3 Geometrical structure of solids 72

5.4 Interface formation 76

5.5 Glass formation 78

5.6 Clusters and nanoparticles 78

5.7 The carbon family: Diamond, graphite, graphene, fullerenes, and carbon nanotubes 80

5.8 Porous solids 83

5.9 Polymers and macromolecules 84

Exercises 86

Endnotes 86

Further reading 86

6 Statistical mechanics 87

6.1 The initial state of the universe 88

6.2 Microstates and macrostates of molecules 89

6.3 The connection of entropy to microstates 91

6.4 The constant alpha: Introducing the partition function 93

6.5 Using the partition function to derive thermodynamic functions 94

6.6 Distribution functions for gases 96

6.7 Quantum statistics for particle distributions 98

6.8 The Maxwell-Boltzmann speed distribution 102

6.9 Derivation of the ideal gas law 103

6.10 Deriving the Sackur-Tetrode equation for entropy of a monatomic gas 104

6.11 The partition function of a diatomic molecule 106

6.12 Contributions of each degree of freedom to thermodynamic functions 106

6.13 The total partition function and thermodynamic functions 111

6.14 Polyatomic molecules 113

Exercises 115

Endnotes 116

Further reading 116

7 First law of thermodynamics 117

7.1 Some definitions and fundamental concepts in thermodynamics 118

7.2 Laws of thermodynamics 118

7.3 Internal energy and the first law 119

7.4 Work 121

7.5 Intensive and extensive variables 123

7.6 Heat 124

7.7 Non-ideal behavior changes the work 125

7.8 Heat capacity 126

7.9 Temperature dependence of Cp 12