PART Ⅰ：THE PRINCIPLES OF THERMODYNAMICS

Chapter 1： First and Second Laws

1.1 Introduction

1.2 Thermodynamic systems

1.3 Thermodynamic variables

1.4 Temperature and the zeroth law

1.5 Work

1.6 Internal energy and the first law

1.7 Heat

1.8 Expression of the first law for an infinitesimal process

1.9 Adiabatically impossible processes

1.10 Natural and reversible processes

1.11 Systematic treatment of the second law

1.12 Final statement of the second law

1.13 A criterion of equilibrium.Reversible processes

1.14 Maximum work

1.15 The fundamental equation for a closed system

1.16 Summary of the basic laws

1.17 Natural processes as mixing processes

1.18 The molecular interpretation of the second law

Problems

Chapter 2：Auxiliary Functions and Conditions of Equilibrium

2.1 The functions H， A and G

2.2 Properties of the enthalpy

2.3 Properties of the Helmholtz free energy

2.4 Properties of the Gibbs function

2.5a Availability

2.5b Digression on the useful work of chemical reaction

2.6 The fundamental equations for a closed system in terms of H，A and G

2.7 The chemical potential

2.8 Criteria of equilibrium in terms of extensive properties

2.9 Criteria of equilibrium in terms of intensive properties

2.10 Mathematical relations between the various functions of state

2.11 Measurable quantities in thermodynamics

2.12 Calculation of changes in the thermodynamic functions over ranges of temperature and pressure

2.13 Molar and partial molar quantities

2.14 Calculation of partial molar quantities from experimental data

Problems

PART Ⅱ： REACTION AND PHASE EQUILIBRIA

Chapter 3： Thermodynamics of Gases

3.1 Models

3.2 The single perfect gas

3.3 The perfect gas mixture

3.4 Imperfect gases

3.5 The Joule-Thomson effect

3.6 The fugacity of a single imperfect gas

3.7 Fugacities in an imperfect gas mixture

3.8 Temperature coefficient of the fugacity and standard chemical potential

3.9 Ideal gaseous solutions and the Lewis and Randall rule

Problems

Chapter 4： Equilibria of Reactions Involving Gases

4.1 Introduction

4.2 The stoichiometry of chemical reaction

4.3 Preliminary discussion on reaction equilibrium

4.4 Concise discussion on reaction equilibrium

4.5 The equilibrium constant for a gas reaction

4.6 The temperature dependence of the equilibrium constant

4.7 Other forms of equilibrium constant for perfect gas mixtures

4.8 Free energies and enthalpies of formation from the elements

4.9 Some examples

4.10 Free energies of formation of non-gaseous substances or from non-gaseous elements

4.11 Preliminary discussion on reaction equilibria involving gases together with immiscible liquids and solids

4.12 Concise discussion on reaction equilibria involving gases together with immiscible liquids and solids

4.13 Example on the roasting of galena

4.14 Measurement of the free energy of reaction by use of galvanic cells

4.15 Alternative discussion of the galvanic cell

4.16 Number of independent reactions

4.17 Conditions of equilibrium for several independent reactions

4.18 General remarks on simultaneous reactions

4.19 General remarks on maximum attainable yield

problems

Chapter 5：Phase Rule

5.1 Introduction

5.2 The phase rule for non-reactive components

5.3 The phase rule for reactive components

5.4 Additional restrictions

5.5 Example of the application of the phase rule

5.6 Alternative approach

5.7 Two examples from the zinc smelting industry

Problems

Chapter 6：Phase Equilibria in Single Component Systems

6.1 Introduction

6.2 The Clausius-Clapeyron equation

6.3 The enthalpy of vaporization and its temperature coefficient

6.4 Integration of the Clausius-Clapeyron equation

6.5 The effect of a second gas on the vapour pressure of a liquid or solid

6.6 Lambda transitions

Problems

Chapter 7：General Properties of Solutions and the Gibbs-Duhem Equation

7.1 The Gibbs-Duhem equation

7.2 Pressure-temperature relations

7.3 Partial pressure-composition relations

7.4 The empirical partial pressure curves of binary solutions

7.5 Application of the Gibbs-Duhem equation to the partial pressure curves

7.6 Application of the Gibbs-Duhem equation to the total pressure curve

7.7 The Gibbs-Duhem equation in relation to Raoult’s and Henry’s laws

7.8 The Gibbs-Duhem equation in relation to the Margules and van Laar equations

Problems

Chapter 8：Ideal Solutions

8.1 Molecular aspects of solutions

8.2 Definition of the ideal solution

8.3 Raoult’s and Henry’s laws

8.4 Imperfect vapour phase

8.5 The mixing properties of ideal solutions

8.6 The dependence of vapour-solution equilibria on temperature and pressure

8.7 Nernst’s law

8.8 Equilibrium between an ideal solution and a pure crystalline component

8.9 Depression of the freezing-point

8.10 Elevation of the boiling-point

8.11 The osmotic pressure of an ideal solution

8.12 The ideal solubility of gases in liquids

8.13 The ideal solubility of solids in liquids

Problems

Chapter 9：Non-Ideal Solutions

9.1 Conventions for the activity coefficient on the mole fraction scale

9.2 The activity coefficient in relation to Raoult’s and Henry’s laws

9.3 The use of molality and concentration scales

9.4 Convention for the activity-coefficient on the molality scale

9.5 The effect of temperature and pressure

9.6 The determination of activity coefiicients

9.7 The Gibbs-Duhem equation applied to activity coefficients

9.8 The calculation of the activity coefficient of the solute

9.9 Excess functions of non-ideal solutions

9.10 The activity

9.11 The osmotic coefficient

Problems

Chapter 10： Reaction Equilibrium in Solution.Electrolytes

10.1 Reaction equilibrium in solution

10.2 Free energy of formation in solution.Convention concerning hydrates

10.3 Equilibrium constants expressed on the molality and volume concentration scales

10.4 Temperature and pressure dependence of the equilibrium constant

10.5 Ratio of an equilibrium constant in the gas phase and in solution

10.6 Notation for electrolytes

10.7 Lack of significance of certain quantities

10.8 Dissociation equilibrium and the chemical potential of the electrolyte

10.9 Activity coefficients

10.10 Phase equilibrium of an electrolyte.Solubility product

10.11 Equilibrium constant for ionic reactions

10.12 Magnitude of activity coefficients of charged and uncharged species

10.13 Free energy of dissociation

10.14 The hydrogen ion convention and the free energies and enthalpies of formation of individual ions

10.15 Activity coefficients and free energies as measured by the use of the galvanic cell

10.16 Activity coefficients by use of the Gibbs-Duhem equation

10.17 Partial pressure of a volatile electrolyte

10.18 Limiting behaviour at high dilution

Problems

PART Ⅲ：THERMODYNAMICS IN RELATION TO THE EXISTENCE OF MOLECULES

Chapter 11： Statistical Analogues of Entropy and Free Energy

11.1 Thermodynamics and molecular reality

11.2 The quantum states of macroscopic systems

11.3 Quantum states， energy states and thermodynamic states

11.4 Fluctuations

11.5 Averaging and the statistical postulate

11.6 Accessibility

11.7 The equilibrium state

11.8 Statistical methods

11.9 The ensemble and the averaging process

11.10 Statistical analogues of the entropy and Helmholtz free energy

11.11 Comparison of statistical analogues with thermodynamic functions

11.12 Thermal and configurational entropy

11.13 Appendix Ⅰ.Origin of the canonical distribution

11.14 Appendix Ⅱ.Entropy analogues

Problem

Chapter 12： Partition Function of a Perfect Gas

12.1 Distinguishable states of a gas and the molecular partition function

12.2 Schrodinger’s equation

12.3 Separability of the wave equation

12.4 Factorization of the molecular partition function

12.5 The translational partition function

12.6 The internal partition function

12.7 Thermodynamic properties of the perfect gas

12.8 The Maxwell-Boltzmann distribution

12.9 Distribution over translational and internal states

12.10 Number of translational sates of a given energy

12.11 The Maxwell velocity distribution

12.12 Principle of equipartition

12.13 Appendix.Some definite integrals

Problems

Chapter 13： Perfect Crystals and the Third Law

13.1 Normal co-ordinates

13.2 The Schrodinger equation for the crystal

13.3 The energy levels of the harmonic oscillator

13.4 The partition function

13.5 The Maxwell-Boltzmann distribution

13.6 The high temperature approximation

13.7 The Einstein approximation

13.8 The Debye approximation

13.9 Comparison with experiment

13.10 Vapour pressure at high temperature

13.11 The third law—preliminary

13.12 Statement of the third law

13.13 Tests and applications of the third law

Problems

Chapter 14：Configurational Energy and Entropy

14.1 Introduction

14.2 Example 1：the lattice model of mixtures

14.3 Example 2：the Langmuir isotherm

Chapter 15：Chemical Equilibrium in Relation to Chemical Kinetics

15.1 Introduction

15.2 Kinetic species

15.3 Variables determining reaction rate

15.4 Forward and backward processes

15.5 Thermodynamic restrictions on the form of the kinetic equations

15.6 The temperature coefficient in relation to thermodynamic quantities

15.7 Transition-state theory

15.8 The equilibrium assumption

15.9 The reaction rate

Appendix.Answers to Problems and Comments

Index