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Preface

1 BASIC CONCEPTS AND THE LAWS OF GASES

Introduction

1.1 Thermodynamic Systems

1.2 Equilibrium and Nonequilibrium Systems

1.3 Biological and Other Open Systems

1.4 Temperature, Heat and Quantitative Laws of Gases

1.5 States of Matter and the van der Waals Equation

1.6 An Introduction to Kinetic Theory of Gases

Appendix 1.1: Partial Derivatives

Appendix 1.2: Elementary Concepts in Probability Theory

Appendix 1.3: Mathematica Codes

References

Examples

Exercises

2 THE FIRST LAW OF THERMODYNAMICS

The Idea of Energy Conservation amidst New Discoveries

2.1 The Nature of Heat

2.2 The First Law of Thermodynamics: The Conservation of Energy

2.3 Elementary Applications of the First Law

2.4 Thermochemistry: Conservation of Energy in Chemical Reactions

2.5 Extent of Reaction: A State Variable for Chemical Systems

2.6 Conservation of Energy in Nuclear Reactions and Some General Remarks

2.7 Energy Flows and Organized States

Appendix 2.1: Mathematica Codes

References

Examples

Exercises

3 THE SECOND LAW OF THERMODYNAMICS AND THE ARROW OF TIME

3.1 The Birth of the Second Law

3.2 The Absolute Scale of Temperature

3.3 The Second Law and the Concept of Entropy

3.4 Entropy, Reversible and Irreversible Processes

3.5 Examples of Entropy Changes due to Irreversible Processes

3.6 Entropy Changes Associated with Phase Transformations

3.7 Entropy of an Ideal Gas

3.8 Remarks about the Second Law and Irreversible Processes

Appendix 3.1: The Hurricane as a Heat Engine

Appendix 3.2: Entropy Production in Continuous Systems

References

Examples

Exercises

4 ENTROPY IN THE REALM OF CHEMICAL REACTIONS

4.1 Chemical Potential and Affinity: The Thermodynamic Force for Chemical Reactions

4.2 General Properties of Affinity

4.3 Entropy Production Due to Diffusion

4.4 General Properties of Entropy

Appendix 4.1: Thermodynamics Description of Diffusion

References

Examples

Exercises

5 EXTREMUM PRINCIPLES AND GENERAL THERMODYNAMIC RELATIONS

Extremum Principles in Nature

5.1 Extremum Principles Associated with the Second Law

5.2 General Thermodynamic Relations

5.3 Gibbs Energy of Formation and Chemical Potential

5.4 Maxwell Relations

5.5 Extensivity with Respect to N and Partial Molar Quantities

5.6 Surface Tension

References

Examples

Exercises

6 BASIC THERMODYNAMICS OF GASES, LIQUIDS AND SOLIDS

Introduction

6.1 Thermodynamics of Ideal Gases

6.2 Thermodynamics of Real Gases

6.3 Thermodynamics Quantities for Pure Liquids and Solids

Appendix 6.1 Equations of State

References

Examples

Exercises

7 THERMODYNAMICS OF PHASE CHANGE

Introduction

7.1 Phase Equilibrium and Phase Diagrams

7.2 The Gibbs Phase Rule and Duhem’s Theorem

7.3 Binary and Ternary Systems

7.4 Maxwell's Construction and the Lever Rule

7.5 Phase Transitions

References

Examples

Exercises

8 THERMODYNAMICS OF SOLUTIONS

8.1 Ideal and Nonideal Solutions

8.2 Colligative Properties

8.3 Solubility Equilibrium

8.4 Thermodynamic Mixing and Excess Functions

8.5 Azeotropy

References

Examples

Exercises

9 THERMODYNAMICS OF CHEMICAL TRANSFORMATIONS

9.1 Transformations of Matter

9.2 Chemical Reaction Rates

9.3 Chemical Equilibrium and the Law of Mass Action

9.4 The Principle of Detailed Balance

9.5 Entropy Production due to Chemical Reactions

9.6 Elementary Theory of Chemical Reaction Rates

9.7 Coupled Reactions and Flow Reactors

Appendix 9.1: Mathematica Codes

References

Examples

Exercises

10 FIELDS AND INTERNAL DEGREES OF FREEDOM

The Many Faces of Chemical Potential

10.1 Chemical Potential in a Field

10.2 Membranes and Electrochemical Cells

10.3 Isothermal Diffusion

References

Examples

Exercises

11 INTRODUCTION TO NONEQUILIBRIUM SYSTEMS

Introduction

11.1 Local Equilibrium

11.2 Local Entropy Production, Thermodynamic Forces and Flows

11.3 Linear Phenomenological Laws and Onsager Reciprocal Relations

11.4 Symmetry-Breaking Transition and Dissipative Structures

11.5 Chemical Oscillations

Appendix 11.1: Mathematica Codes

References

Further Reading

Exercises

12 THERMODYNAMICS OF RADIATION

Introduction

12.1 Energy Density and Intensity of Thermal Radiation

12.2 The Equation of State

12.3 Entropy and Adiabatic Processes

12.4 Wien’s Theorem

12.5 Chemical Potential of Thermal Radiation

12.6 Matter–Antimatter in Equilibrium with Thermal Radiation: The State of Zero Chemical Potential

References

Examples

Exercises

13 BIOLOGICAL SYSTEMS

13.1 The Nonequilibrium Nature of Life

13.2 Gibbs Energy Change in Chemical Transformations

13.3 Gibbs Energy Flow in Biological Systems

13.4 Biochemical Kinetics

References

Further Reading

Examples

Exercises

14 THERMODYNAMICS OF SMALL SYSTEMS

Introduction

14.1 Chemical Potential of Small Systems

14.2 Size-Dependent Properties

14.3 Nucleation

14.4 Fluctuations and Stability

References

Examples

Exercises

15 CLASSICAL STABILITY THEORY

15.1 Stability of Equilibrium States

15.2 Thermal Stability

15.3 Stability with Respect to Fluctuations in N

References

Exercises

16 CRITICAL PHENOMENA AND CONFIGURATIONAL HEAT CAPACITY

Introduction

16.1 Stability and Critical Phenomena

16.2 Stability and Critical Phenomena in Binary Solutions

16.3 Configurational Heat Capacity

Further Reading

Exercises

17 ELEMENTS OF STATISTICAL THERMODYNAMICS

Introduction

17.1 Fundamentals and Overview

17.2 Partition Function Factorization

17.3 The Boltzmann Probability Distribution and Average Values

17.4 Microstates, Entropy and the Canonical Ensemble

17.5 Canonical Partition Function and Thermodynamic Quantities

17.6 Calculating Partition Functions

17.7 Equilibrium Constants

Appendix 17.1: Approximations and Integrals

References

Examples

Exercises

LIST OF VARIABLES

STANDARD THERMODYNAMIC PROPERTIES

PHYSICAL CONTANTS AND DATA

INDEX

Library of Congress subject headings for this publication:

Thermodynamics.