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–Huckel 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
