Table of Contents

Chapter 1 The Properties of Gases 1
1.1 State Equation of the Ideal Gas 1
1.1.1 Empirical Laws of Gases 1
1.1.2 State Equation of Ideal Gas 2
1.1.3 Model and Definition of Ideal Gas 4
1.2 The Properties of Mixtures of the Ideal Gases 5
1.2.1 Composition of Mixtures 5
1.2.2 Dalton’s Law of Partial Pressures 6
1.2.3 Amagat’s Law of Partial Volumes 7
1.3 State Equations of Real Gas 8
1.3.1 The van der Waals Equation 8
1.3.2 Generalized Equation of State for Real Gases 9
1.4 Isothermal Curves and Liquefaction of Real Gas 10
1.4.1 Saturated Vapor Pressure of the Liquid 10
1.4.2 Isothermal Curves and Liquefaction 12
1.4.3 Critical Parameters and Critical Compression Factor Zc 14
1.5 Exercises 15

Chapter 2 The First Law of Thermodynamics 17
2.1 Basic Concepts 17
2.1.1 System and Surroundings 17
2.1.2 Property, State, and State Function 18
2.1.3 Process and Route 19
2.1.4 Work, Heat, and Energy 20
2.2 The First Law of Thermodynamics 22
2.2.1 The First Law of Thermodynamics 22
2.2.2 Internal Energy 23
2.3 Heat, Enthalpy, and Heat Capacities 23
2.3.1 Heat in Isochoric Conditions, and Internal Energy 23
2.3.2 Heat in Isobaric Conditions, and Enthalpy 25
2.3.3 Hess’s Law 26
2.3.4 Heat Capacities 27
2.4 Pressure-Volume Work and Reversible Processes 29
2.4.1 Pressure-Volume Work 29
2.4.2 Reversible Processes 30
2.5 Isoenthalpic Processes 36
2.5.1 The Joule-Thomson Effect 36
2.5.2 Adiabatic Joule-Thomson Coefficient 37
2.6 Thermochemistry 37
2.6.1 Standard Enthalpy of Formation 38
2.6.2 Enthalpy of Reaction 39
2.6.3 Temperature-Dependence of Standard Enthalpy of Reaction 40
2.7 Exercises 41

Chapter 3 The Second Law of Thermodynamics 42
3.1 Statements of the Second Law of Thermodynamics 42
3.1.1 Spontaneous Process 42
3.1.2 Conversion of Heat and Work 43
3.1.3 Statements of the Second Law of Thermodynamics 43
3.2 Carnot Cycle and Carnot Theorem 44
3.2.1 Carnot Cycle 44
3.2.2 Carnot Theorem 45
3.3 Entropy and Clausius Inequality 46
3.3.1 Derivation and Definition of Entropy 46
3.3.2 The Clausius Inequality 47
3.3.3 The Principle of the Increase of Entropy 47
3.3.4 Physical Significance of Entropy 48
3.4 The Calculation of Entropy Changes 49
3.4.1 The Calculation of Entropy Changes in Simple pVT Process 49
3.4.2 The Calculation of Entropy Changes for Phase Changes 51
3.5 The Standard Molar Reaction Entropy Change of Chemical Reaction 52
3.5.1 The Third Law of Thermodynamics 52
3.5.2 Absolute Entropy and Standard Molar Entropy of Matter 52
3.5.3 Calculation of Entropy Changes for Chemical Reactions 53
3.6 The Gibbs and Helmholtz Functions 55
3.6.1 Helmholtz Function 55
3.6.2 Gibbs Function 56
3.7 The Calculation of ΔA and ΔG 57
3.7.1 Simple pVT Change Process 57
3.7.2 Phase Change Processes 57
3.7.3 Chemical Change Processes 58
3.8 The Fundamental Equation of Thermodynamics 59
3.8.1 The Fundamental Equations of Thermodynamics 59
3.8.2 The Relations of Characteristic Function 60
3.8.3 The Maxwell Relations 61
3.9 The Application of the Second Law of Thermodynamics in the Phase Equilibria of Single Component Systems 62
3.9.1 The Clapeyron Equation 62
3.9.2 The Clausius-Clapeyron Equation 63
3.9.3 The Effect of Total Pressure on the Vapor Pressure 64
3.10 Exercises 65

Chapter 4 The Thermodynamics of Multi-Component Systems 68
4.1 Composition scale of multi-component systems 68
4.1.1 Mass Concentration 68
4.1.2 Amount of Substance concentration 68
4.1.3 Molality 69
4.2 Partial Molar Quantities 69
4.2.1 Definition of Partial Molar Quantity 70
4.2.2 Collected Formula of Partial Molar Quantity 71
4.2.3 The Gibbs-Duhem Equation 71
4.3 Chemical Potential 72
4.3.1 Definition of Chemical Potential 72
4.3.2 Equilibrium Criterion of Material 73
4.3.3 Application of Chemical Potential in Phase Equilibrium 74
4.4 Chemical Potential of Gas 75
4.4.1 Chemical Potential of a Pure Ideal Gas 75
4.4.2 Chemical Potentials in an Ideal Gas Mixture 76
4.5 Raoult’s law and Henry’s law 77
4.5.1 Raoult’s Law 77
4.5.2 Henry’s Law 78
4.5.3 Comparison of Raoult’s Law and Henry’s Law 79
4.6 Mixture of Ideal Liquid 79
4.6.1 Definition and Features of Mixture of Ideal Liquid 79
4.6.2 Chemical Potential of Arbitrary Component in Mixture of Ideal Liquid 80
4.6.3 Mixing Properties of Mixture of Ideal Liquid 81
4.7 Ideal Dilute Solution 82
4.7.1 Definition of Ideal Dilute Solution 82
4.7.2 Chemical Potential of the Solvent and Solute in Ideal Dilute Solution 82
4.8 Real Liquid Solution 83
4.8.1 The Solvent Activity 83
4.8.2 The Solute Activity 84
4.9 Colligative Properties 84
4.9.1 Depression of Vapor Pressure (Vapor Pressure of Solvent A) 85
4.9.2 Depression of Freezing Point 85
4.9.3 Elevation of Boiling Point 87
4.9.4 Osmotic Pressure 89
4.10 Exercises 90

Chapter 5 Chemical Equilibrium 92
5.1 Direction of Chemical Reaction and Condition of Equilibrium 92
5.1.1 Relationship between Condition of Equilibrium and Extent of Chemical Reaction 92
5.1.2 Chemical Affinity and Direction of Chemical Reaction 93
5.2 Equilibrium Constant Expressions for Gas Reaction 95
5.2.1 Isothermal Equation for Ideal Gas Reaction 95
5.2.2 Standard Equilibrium Constant Expression for Ideal Gas Reaction 96
5.2.3 Standard Equilibrium Constant Expression for Ideal Gas Reaction involving Pure Condensed Matter 97
5.2.4 Other Equilibrium Constant Expressions for Ideal Gas Reaction 99
5.2.5 Relationship between Dissociation Pressure and Standard Equilibrium Constant for Dissociation Reaction of Solid 100
5.2.6 Inherent Relation between Standard Equilibrium Constants of Relative Reactions 101
5.3 Calculation of Chemical Equilibrium 102
5.3.1 Calculation of Standard Molar Gibbs Function Change of Reaction and Standard Equilibrium Constant 102
5.3.2 Calculation of Equilibrium Composition of System and Equilibrium Conversion of Reactant 104
5.4 Response of Equilibrium to Conditions 106
5.4.1 Response of Equilibrium to Temperature 106
5.4.2 Response of Equilibrium to Pressure 107
5.4.3 Response of Equilibrium to Inert Component 108
5.4.4 Response of Equilibrium to Starting Materials Ratio 108
5.5 Exercises 109

Chapter 6 Phase Equilibrium 112
6.1 Phase Rule 113
6.1.1 Basic Concept 113
6.1.2 Phase Rule 114
6.2 Phase Diagram of One-Component System 116
6.2.1 Phase Diagram of Water 117
6.2.2 Phase Diagram of Sulfur 119
6.3 Gas-Liquid Phase Diagram of Two-Component Ideal Liquid Mixture System 120
6.3.1 Pressure-composition Phase Diagram 121
6.3.2 Lever Rule 123
6.3.3 Temperature-composition Phase Diagram 123
6.4 Gas-Liquid Phase Diagram of Two-Component Real Liquid Mixture System 124
6.4.1 Pressure-composition Phase Diagram 124
6.4.2 Temperature-composition Phase Diagram 126
6.5 Distillation Principle 128
6.6 Gas-Liquid Phase Diagrams of Partially Miscible and Nonmiscible Two-Component Liquid Systems 130
6.6.1 Solubility Relation of Partially Miscible Liquids 130
6.6.2 Temperature-composition Phase Diagrams of Partially Miscible Systems 131
6.6.3 Temperature-composition Phase Diagram of Nonmiscible System 131
6.7 Liquid-Solid Phase Diagram of Two-Component Condensed System with Solid-Phase Immiscibility 132
6.7.1 Phase Diagram Analysis 133
6.7.2 Thermal Analysis Method 134
6.7.3 Solubility Method 137
6.8 Liquid-Solid Phase Diagram of Condensed System for the Formation of Compounds 138
6.8.1 Liquid-solid Phase Diagram for the Formation of a Stable Compound System 138
6.8.2 Liquid-solid Phase Diagram for the Formation of an Unstable Compound System 139
6.9 Liquid-Solid Phase Diagram of Two-Component Condensed Systems with Solid-Phase Miscibility and Partial Miscibility 140
6.9.1 Liquid-solid Phase Diagram of Solid-phase Complete Miscibility System 140
6.9.2 Liquid-solid Phase Diagram of Solid-phase Partially Miscible System 141
6.10 Liquid-Solid Phase Diagram of Two-Component Systems with Solid-Phase Immiscible and Liquid-Phase Miscible 143
6.11 Liquid-Liquid Equilibrium Phase Diagram for Three-Component System 145
6.11.1 Graphical Representation of a Three-component System 145
6.11.2 Liquid-liquid Phase Diagram of Three-liquid System with One Pair of Partially Soluble Liquids at Constant Temperature 147
6.12 Exercises 147