Modern Thermodynamics -- Contents -- Preface to the Second Edition -- Preface to the First Edition -- Acknowledgments -- Notes for Instructors -- List of Variables -- Part I Historical Roots: From Heat Engines to Cosmology -- 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 -- 1.4.1 The Laws of Gases -- 1.5 States of Matter and the van der Waals Equation -- 1.5.1 The Law of Corresponding States -- 1.5.2 Molecular Forces and the Law of Corresponding States -- 1.6 An Introduction to the Kinetic Theory of Gases -- 1.6.1 Kinetic Theory of Pressure -- 1.6.2 The Maxwell-Boltzmann Velocity Distribution -- 1.6.3 The Maxwell Speed Distribution -- Appendix 1.1 Partial Derivatives -- Derivatives of Many Variables -- Basic Identities -- Appendix 1.2 Elementary Concepts in Probability Theory -- Average Values -- Some Common Probability Distributions -- Some Useful Integrals -- 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 -- 2.3.1 Relation between Cmp and CmV -- 2.3.2 Adiabatic Processes in an Ideal Gas -- 2.3.3 Sound Propagation -- 2.4 Thermochemistry: Conservation of Energy in Chemical Reactions -- 2.4.1 Variation of Enthalpy with Temperature -- 2.4.2 Variation of Enthalpy with Pressure -- 2.4.3 Computation of DHr Using Bond Enthalpies -- 2.5 Extent of Reaction: A State Variable for Chemical Systems -- 2.6 Conservation of Energy in Nuclear Reactions and Some General Remarks -- 2.6.1 General Remarks.

2.7 Energy Flows and Organized States -- 2.7.1 Self-organization -- 2.7.2 Process Flows -- 2.7.3 Solar Energy Flow -- 2.7.4 Energy Flows in Biological Systems -- 2.7.5 Wind Energy and the Betz Law -- Appendix 2.1 Mathematica Codes -- Appendix 2.2 Energy Flow in the USA for the Year 2013 -- References -- Examples -- Exercises -- 3 The Second Law of Thermodynamics and the Arrow of Time -- 3.1 The Birth of the Second Law -- 3.1.1 Efficiency of a Reversible Engine -- 3.2 The Absolute Scale of Temperature -- 3.3 The Second Law and the Concept of Entropy -- 3.3.1 Statements of the Second Law -- 3.4 Modern Formulation of the Second Law -- 3.5 Examples of Entropy Changes due to Irreversible Processes -- 3.5.1 Heat Conduction -- 3.5.2 Irreversible Expansion of a Gas -- 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 -- 4.1.1 Chemical Potential -- 4.1.2 Chemical Reactions -- 4.1.3 Affinity -- 4.2 General Properties of Affinity -- 4.2.1 Affinity and Direction of Reaction -- 4.2.2 Additivity of Affinities -- 4.2.3 Coupling between Affinities -- 4.3 Entropy Production Due to Diffusion -- 4.3.1 Discrete Systems -- 4.4 General Properties of Entropy -- Appendix 4.1 Thermodynamics Description of Diffusion -- References -- Example -- Exercises -- Part II Equilibrium Thermodynamics -- 5 Extremum Principles and General Thermodynamic Relations -- Extremum Principles in Nature -- 5.1 Extremum Principles Associated with the Second Law -- 5.1.1 Maximum Entropy -- 5.1.2 Minimum Energy.

5.1.3 Minimum Helmholtz Energy -- 5.1.4 Minimum Gibbs Energy -- 5.1.5 Minimum Enthalpy -- 5.1.6 Extremum Principles and Stability of the Equilibrium State -- 5.1.7 Legendre Transformations -- 5.2 General Thermodynamic Relations -- 5.2.1 The Gibbs-Duhem Equation -- 5.2.2 The Helmholtz Equation -- 5.2.3 The Gibbs-Helmholtz Equation -- 5.3 Gibbs Energy of Formation and Chemical Potential -- 5.3.1 Tabulation of Gibbs Energies of Compounds -- 5.4 Maxwell Relations -- 5.4.1 General Relation between Cmp and CmV -- 5.5 Extensivity with Respect to N and Partial Molar Quantities -- 5.6 Surface Tension -- 5.6.1 Excess Pressure in a Liquid Drop -- 5.6.2 Capillary Rise -- References -- Examples -- Exercises -- 6 Basic Thermodynamics of Gases, Liquids and Solids -- Introduction -- 6.1 Thermodynamics of Ideal Gases -- 6.1.1 The Equation of State -- 6.1.2 The Total Internal Energy -- 6.1.3 Heat Capacities and Adiabatic Processes -- 6.1.4 Entropy and Thermodynamic Potentials -- 6.1.5 Chemical Potential -- 6.1.6 Entropy of Mixing and the Gibbs Paradox -- 6.2 Thermodynamics of Real Gases -- 6.2.1 Total Internal Energy -- 6.2.2 Molar Heat Capacities CmV and Cmp -- 6.2.3 Adiabatic Processes -- 6.2.4 Helmholtz and Gibbs Energies -- 6.2.5 Entropy -- 6.2.6 Chemical Potential -- 6.2.7 Chemical Affinities -- 6.3 Thermodynamics Quantities for Pure Liquids and Solids -- 6.3.1 Equation of State -- 6.3.2 Thermodynamic Quantities -- 6.3.3 Heat Capacities -- Reference -- Examples -- Exercises -- 7 Thermodynamics of Phase Change -- Introduction -- 7.1 Phase Equilibrium and Phase Diagrams -- 7.1.1 The Clapeyron Equation -- 7.1.2 The Clausius-Clapeyron Equation -- 7.2 The Gibbs Phase Rule and Duhems Theorem -- 7.3 Binary and Ternary Systems -- 7.3.1 Binary Liquid Mixtures in Equilibrium with the Vapor -- 7.3.2 Azeotropes -- 7.3.3 Solution in Equilibrium with Pure Solids: Eutectics.

7.3.4 Ternary Systems -- 7.4 Maxwells Construction and the Lever Rule -- 7.5 Phase Transitions -- 7.5.1 General Classification of Phase Transitions -- 7.5.2 Behavior near the Critical Point -- References -- Examples -- Exercises -- 8 Thermodynamics of Solutions -- 8.1 Ideal and Nonideal Solutions -- 8.2 Colligative Properties -- 8.2.1 Changes in Boiling and Freezing Points -- 8.2.2 Osmotic Pressure -- 8.3 Solubility Equilibrium -- 8.3.1 Nonionic Solutions -- 8.3.2 Ionic Solutions -- 8.3.3 Activity, Ionic Strength and Solubility -- 8.4 Thermodynamic Mixing and Excess Functions -- 8.4.1 Perfect Solutions -- 8.4.2 Ideal Solutions -- 8.4.3 Excess Functions -- 8.4.4 Regular and Athermal Solutions -- 8.5 Azeotropy -- References -- Examples -- Exercises -- 9 Thermodynamics of Chemical Transformations -- 9.1 Transformations of Matter -- 9.2 Chemical Reaction Rates -- 9.2.1 Rate Equations Using the Extent of Reactions -- 9.2.2 Reaction Rates and Activities -- 9.3 Chemical Equilibrium and the Law of Mass Action -- 9.3.1 Relation between the Equilibrium Constants and the Rate Constants -- 9.3.2 The vant Hoff Equation -- 9.3.3 Response to Perturbation from Equilibrium: The Le Chatelier-Braun Principle -- 9.4 The Principle of Detailed Balance -- 9.5 Entropy Production due to Chemical Reactions -- 9.5.1 An Example -- 9.6 Elementary Theory of Chemical Reaction Rates -- 9.6.1 The Arrhenius Theory of Rates -- 9.6.2 The Transition State Theory -- 9.7 Coupled Reactions and Flow Reactors -- 9.7.1 Zero-Order Reactions -- 9.7.2 Reversible First-Order Reaction -- 9.7.3 Consecutive First-Order Reactions -- 9.7.4 The Steady-State Assumption -- 9.7.5 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.

10.1.1 Entropy Production in a Continuous System -- 10.1.2 Entropy Production Due to Electrical Conduction and Ohms Law -- 10.2 Membranes and Electrochemical Cells -- 10.2.1 Membrane Potentials -- 10.2.2 Electrochemicl Affinity and Electromotive Force -- 10.2.3 Galvanic and Electrolytic Cells -- 10.2.4 Concentration Cell -- 10.2.5 Standard Electrode Potentials -- 10.3 Isothermal Diffusion -- 10.3.1 Diffusion in a Continuous System and Ficks Law -- 10.3.2 The Diffusion Equation -- 10.3.3 The Stokes-Einstein Relation -- 10.4 Chemical Potential for an Internal Degree of Freedom -- 10.4.1 The Debye Equation for Electric Dipole Relaxation -- References -- Examples -- Exercises -- 11 Thermodynamics of Radiation -- Introduction -- 11.1 Energy Density and Intensity of Thermal Radiation -- 11.2 The Equation of State -- 11.3 Entropy and Adiabatic Processes -- 11.4 Wiens Theorem -- 11.5 Chemical Potential of Thermal Radiation -- 11.5.1 Two Level Atom in Equilibrium with Radiation -- 11.6 Matter-Antimatter in Equilibrium with Thermal Radiation: The State of Zero Chemical Potential -- 11.7 Chemical Potential of Radiation not in Thermal Equilibrium with Matter -- 11.8 Entropy of Nonequilibrium Radiation -- References -- Example -- Exercises -- Part III Fluctuations and Stability -- 12 The Gibbs Stability Theory -- 12.1 Classical Stability Theory -- 12.2 Thermal Stability -- 12.3 Mechanical Stability -- 12.4 Stability and Fluctuations in Nk -- 12.4.1 Chemical Stability -- 12.4.2 Stability to Fluctuations Due to Diffusion -- References -- Exercises -- 13 Critical Phenomena and Configurational Heat Capacity -- Introduction -- 13.1 Stability and Critical Phenomena -- 13.2 Stability and Critical Phenomena in Binary Solutions -- 13.3 Configurational Heat Capacity -- Further Reading -- Exercises -- 14 Entropy Production, Fluctuations and Small Systems.

14.1 Stability and Entropy Production.