Thermodynamics - 4th Edition - ISBN: 9780124167056, 9780124201101


4th Edition

Principles Characterizing Physical and Chemical Processes

Authors: Jurgen Honig
eBook ISBN: 9780124201101
eBook ISBN:
Paperback ISBN: 9780128101407
Hardcover ISBN: 9780124167056
Imprint: Academic Press
Published Date: 9th December 2013
Page Count: 462
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Thermodynamics is a self-contained analysis of physical and chemical processes based on classical thermodynamic principles. Emphasis is placed on the fundamental principles with a combination of theory and practice, demonstrating their application to a variety of disciplines. This edition has been completely revised and updated to include new material and novel formulations, including new formulation and interpretation of The Second Law, discussions of heat vs. work, uniqueness of chemical potential, and construction of functions of state. This book will appeal to graduate students and professional chemists and physicists who wish to acquire a more sophisticated overview of thermodynamics and related subject matter.

Key Features

  • Clear explanations of abstract theoretical concepts
  • Complete revision and update, including novel formulations not described elsewhere
  • Exhaustive coverage of graphical, numerical, and analytical computational techniques
  • The latest applications in science and engineering


Chemists, chemical engineers, physicists, and graduate-level students in these disciplines

Table of Contents

General Commentary


Chapter 1. Fundamentals


1.1 Introductory Definitions

Remarks and Queries

1.2 The Zeroth Law of Thermodynamics

Additional Information

1.3 Mathematical Apparatus


1.4 Thermodynamic Forces


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



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



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


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


Exercises and Comments

1.16 Effect of Chemical Changes on the Energy of a System1


1.17 Stability of a System; Fluctuations



Chapter 2. Thermodynamic Properties of Ideal Systems


2.1 Equilibrium in a System of Several Components and Phases


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


2.5 Properties of Ideal Solutions in Condensed Phases


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


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


2.10 Chemical Equilibrium in Homogeneous Condensed Ideal Solutions


2.11 Chemical Equilibrium in Ideal Heterogeneous Systems

2.12 Equilibrium between Two Ideal Phases

Chapter 3. Characterization of Nonideal Solutions


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



3.9 Dependence of Higher Order Phase Transitions on Temperature

Exercises and References

3.10 Elements of Order–Disorder Theory and Applications


Chapter 4. Thermodynamic Properties of Electrolytes and of EMF Cells


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


4.3 Galvanic Cells


4.4 Operation of Galvanic Cells


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


4.8 Thermodynamic Information from Galvanic Cells


Chapter 5. Thermodynamic Properties of Materials in Externally Applied Fields


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


5.5 Pressure of Electromagnetic Radiation

5.6 Thermodynamic Characterization of Electrodynamic Radiation


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


5.11 Thermodynamic Properties of Anisotropic Media

Reference and Exercise

5.12 Thermodynamics of Interacting Electron Assemblies

Remarks and References

Chapter 6. Irreversible Thermodynamics


6.0 Introductory Comments

6.1 Generalities

Notes and Queries

6.2 Shock Phenomena


6.3 Linear Phenomenological Equations

6.4 Steady-State Conditions and Prigogine's Theorem

Comments and Questions

6.5 Onsager Reciprocity Conditions


6.6 Thermomolecular Mechanical Effects

6.7 Electrokinetic Phenomena


6.8 The Soret Effect


6.9 Thermoelectric Effects

Comments and Exercises

6.10 Irreversible Thermomagnetic Phenomena in Two Dimensions


Chapter 7. Critical Phenomena


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


7.3 Derivation of Griffith's and Rushbrooke's Inequality

Reference and Exercise

7.4 Scaled Equation of State


7.5 Landau Theory of Critical Phenomena and Phase Transitions


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



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


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


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


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



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About the Author

Jurgen Honig

Jurgen Honig

Prof. Honig received a BS degree from Amherst College in 1945 and a PhD degree from the University of Minnesota in 1952. After a postdoctoral appointment year at the James Forrestal Center of Princeton University in 1953, he joined the Department of Chemistry at Purdue University in 1953, and was promoted to Associate Professor in 1958. From 1959-1967, Prof. Honig was Associate Group leader and Group leader at the MIT Lincoln Laboratory in Lexington, MA. He returned as Professor of Chemistry to Purdue University in 1967 and retired from that position in 2000. During the latter years, he was Editor of the Journal of Solid State Chemistry (1982-2000), the Chairman of the Materials Sciences Council (1968-1982), and published over 420 refereed publications and five books.

Prof. Honig has earned an honorary degree from the University of Science and Technology (2009, Krakow, Poland; fellow of the New York Academy of Sciences; Wetherill medal (1995); Editor, Journal of Solid State Chemistry (1982- 2000); Honorary Member, Materials Research Society of India; two issues of the Journal of Solid State Chemistry (1990 and 2000) and an issue of Solid State Sciences (2000) dedicated to him; and a session at a Materials Research Society meeting (2000) held in honor of his retirement.

Affiliations and Expertise

Department of Chemistry, Purdue University, West Lafayette, IN, USA

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