Thermodynamics

Chapter 1. Fundamentals

Abstract

1.1 Introductory Definitions

Remarks and Queries

1.2 The Zeroth Law of Thermodynamics

Additional Information

1.3 Mathematical Apparatus

Remarks

1.4 Thermodynamic Forces

Reference

1.5 Elements of Work

Comment and Queries

1.6 The Element of Work for a System Subjected to Electromagnetic Fields

Remark and Reference

1.7 The First Law of Thermodynamics

Reference

Notes

1.8 The Second Law of Thermodynamics

Footnotes and Query

1.9 Consequences of the First and Second Laws

Remarks and Questions

1.10 Functions of State; Reprise

Appendix A: Remarks Concerning Irreversible Processes

Appendix B: Time-Dependent Irreversible Processes

Reference

Notes

1.11 Statements of the Second Law; Thermodynamic Operation of Heat Engines; Kelvin and Planck Statements; Temperature Scale

Exercise

1.12 Systematization of Results Based on Functions of State

Review of Electronic Properties of Metals

Exercises and Remark

1.13 The Third Law of Thermodynamics

Remarks and Queries

1.14 The Gibbs–Duhem Relation and Its Analogs

Query and Reference

1.15 Heat Capacities; Fundamentals and Applications

Acknowledgment

Exercises and Comments

1.16 Effect of Chemical Changes on the Energy of a System¹

Remarks

1.17 Stability of a System; Fluctuations

Appendices

Reference

Chapter 2. Thermodynamic Properties of Ideal Systems

Abstract

2.1 Equilibrium in a System of Several Components and Phases

Exercises

2.2 Achievement of Equilibrium

Comment and Exercise

2.3 System of One Component and Several Phases; the Clausius–Clapeyron Equation

Reference and Footnote

2.4 Properties of Ideal Gases

Exercises

2.5 Properties of Ideal Solutions in Condensed Phases

Reference

2.6 The Duhem–Margules Equation and Its Consequences

2.7 Temperature Dependence of Composition of Solutions

2.8 Lowering of the Freezing Point and Elevation of the Boiling Point of a Solution

Exercise

2.9 General Description of Chemical Reactions and Chemical Equilibrium; Application to Gases

Remarks

2.10 Chemical Equilibrium in Homogeneous Condensed Ideal Solutions

Comments

2.11 Chemical Equilibrium in Ideal Heterogeneous Systems

2.12 Equilibrium between Two Ideal Phases

Chapter 3. Characterization of Nonideal Solutions

Abstract

3.0 Introductory Remarks

3.1 Thermodynamic Treatment of Nonideal Gas Mixtures

Notes and Exercise

3.2 Temperature and Pressure Dependence of the Fugacity of a Gas

3.3 Thermodynamic Description of Real Solutions in the Condensed State

Query and Reference

3.4 Characterization of Chemical Equilibrium in Nonideal Solutions

3.5 Pressure and Temperature Dependence of Activities and Activity Coefficients

3.6 Determination of Activity Coefficients and Calorimetric Quantities in Chemical Processes

References and Commentary

3.7 Determination of Activities from Freezing Point Lowering of Solutions

3.8 Thermodynamic Properties of Nonideal Solutions

Exercises

Exercises

3.9 Dependence of Higher Order Phase Transitions on Temperature

Exercises and References

3.10 Elements of Order–Disorder Theory and Applications

References

Chapter 4. Thermodynamic Properties of Electrolytes and of EMF Cells

Abstract

4.0 Introductory Comments

4.1 Activities of Strong Electrolytes

Exercise and Comment

4.2 Theoretical Determination of Activities in Electrolyte Solutions; the Debye–Hückel Equation

Comment and Exercises

Experimental Determination of Activities and Activity Coefficients of Strong Electrolytes

Equilibrium Properties of Weak Electrolytes

Exercise

4.3 Galvanic Cells

Remarks

4.4 Operation of Galvanic Cells

Remarks

4.5 Galvanic Cells; Operational Analysis

4.6 Liquid Junction Potentials

4.7 EMF Dependence on Activities

Examples of Operating Cells

Types of Operating Cells

Queries

4.8 Thermodynamic Information from Galvanic Cells

Assignment

Chapter 5. Thermodynamic Properties of Materials in Externally Applied Fields

Abstract

5.0 Introductory Comments

5.1 Thermodynamics of Gravitational and Centrifugal Fields

Comment and Exercises

5.2 Thermodynamics of Adsorption Processes

References and Exercises

5.3 Heats of Adsorption

Reference and Exercises

5.4 Surface vs Bulk Effects: Thermodynamics of Self-Assembly

References

5.5 Pressure of Electromagnetic Radiation

5.6 Thermodynamic Characterization of Electrodynamic Radiation

Exercises

5.7 Effects of Electric Fields on Thermodynamic Properties of Matter

Reference and Exercises

5.8 Systematization of Electromagnetic Field Effects in Thermodynamics

Comments and Assignments

5.9 Adiabatic Diamagnetization and Transitions to Superconductivity

5.10 Thermodynamic Characterization of Anisotropic Media

Reference

5.11 Thermodynamic Properties of Anisotropic Media

Reference and Exercise

5.12 Thermodynamics of Interacting Electron Assemblies

Remarks and References

Chapter 6. Irreversible Thermodynamics

Abstract

6.0 Introductory Comments

6.1 Generalities

Notes and Queries

6.2 Shock Phenomena

Exercises

6.3 Linear Phenomenological Equations

6.4 Steady-State Conditions and Prigogine's Theorem

Comments and Questions

6.5 Onsager Reciprocity Conditions

Reference

6.6 Thermomolecular Mechanical Effects

6.7 Electrokinetic Phenomena

Exercises

6.8 The Soret Effect

Exercises

6.9 Thermoelectric Effects

Comments and Exercises

6.10 Irreversible Thermomagnetic Phenomena in Two Dimensions

Exercises

Chapter 7. Critical Phenomena

Abstract

7.0 Introductory Remarks

7.1 Properties of Materials Near Their Critical Point

Notes and References

7.2 Homogeneity Requirements, Correlation Lengths, and Scaling Properties

Footnotes

7.3 Derivation of Griffith's and Rushbrooke's Inequality

Reference and Exercise

7.4 Scaled Equation of State

Reference

7.5 Landau Theory of Critical Phenomena and Phase Transitions

Reference

Chapter 8. A Final Speculation about Ultimate Temperatures—A Fourth Law of Thermodynamics?

Abstract

Reference

Chapter 9. Reprise to the Second Law. Mathematical Proof of the Caratheodory's Theorem and Resulting Interpretations

Abstract

9.1 Fundamentals

9.2 Proof of Holonomicity

9.3 Necessary Condition for Establishing the Carathéodory's Theorem

9.4 Relevance to Thermodynamics

9.5 Derivation of the Limiting Form for the Debye–Hűckel Equation

References and Query

Chapter 10. Elements of Statistical Thermodynamics

Abstract

10.1 Distributions and Statistics

10.2 The Boltzmann Relation for the Entropy

10.3 Distribution Functions

10.4 Digression on the Concepts of Work and Heat

10.5 Statistical Representation of Functions of State

10.6 Summary

10.7 Alternative Statistical Interpretation for Entropy in Terms of Properties of a System

Footnotes:

10.8 Derivation of Curie’s Law and Ohm’s Law