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The Thermodynamics of Phase and Reaction Equilibria - 1st Edition - ISBN: 9780444594976, 9780444595027

The Thermodynamics of Phase and Reaction Equilibria

1st Edition

Author: Ismail Tosun
eBook ISBN: 9780444595027
Paperback ISBN: 9781493302444
Hardcover ISBN: 9780444594976
Imprint: Elsevier
Published Date: 5th September 2012
Page Count: 744
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This book provides a sound foundation for understanding abstract concepts of phase and reaction equilibria (e.g. partial molar Gibbs energy, fugacity, and activity), and shows how to apply these concepts to solve practical problems using numerous clear examples. It also presents numerical methods necessary for solving real-world problems as well the basic mathematics needed, facilitating its use as a self-study reference work. In the example problems requiring MATHCAD® for the solution, the results of the intermediate steps are given, enabling the reader to easily track mistakes and understand the order of magnitude of the various quantities involved.

Key Features

  • Clear layout, coherent and logical organization of the content, and presentation suitable for self-study
  • Provides analytical equations in dimensionless form for the calculation of changes in internal energy, enthalpy, and entropy as well as departure functions and fugacity coefficients
  • Includes up-to-date information, comprehensive in-depth content and current examples in each chapter
  • Includes many well organized problems (with answers), which are extensions of the examples enabling conceptual understanding for quantitative/real problem solving
  • Includes the mathematical background required for solving problems encountered in phase and reaction equilibria


Graduate and undergraduate students in chemical, environmental, petroleum, and metallurgical engineering departments; graduate and undergraduate students in the departments of chemistry, biotechnology, food science and technology, and materials science as well as professional engineers in the above areas

Table of Contents




Chapter 1. Review of the First and Second Laws of Thermodynamics

1.1 Definitions

1.2 Concepts of the “Abstract World” of Thermodynamics

1.3 Work

1.4 Paths Followed During a Process

1.5 The First Law of Thermodynamics

1.6 The Second Law of Thermodynamics


Chapter 2. Thermodynamic Properties of Real Substances

2.1 Work Functions

2.2 Thermodynamic Properties of a Single-Phase System



Chapter 3. Calculation of Changes in Internal Energy, Enthalpy, and Entropy

3.1 Equations of State

3.2 Calculation of the Change in Internal Energy

3.3 Calculation of the Change in Enthalpy

3.4 Calculation of the Change in Entropy

3.5 The Principle of Corresponding States

3.6 Departure Functions

3.7 Which Equation of State to Use?



Chapter 4. Equilibrium and Phase Stability in One-Component Systems

4.1 Equilibrium Criteria for Closed Systems

4.2 Equilibrium Criteria for Open Systems

4.3 Phase Stability



Chapter 5. Fugacity of a Pure Component

5.1 Molar Gibbs Energy of a Pure Ideal Gas

5.2 Definition of Fugacity and Fugacity Coefficient

5.3 Fugacity of a Pure Gas

5.4 Fugacity of a Pure Liquid

5.5 Fugacity of a Pure Solid

5.6 Phase Transitions and Equilibrium Criteria

5.7 Analysis of Phase Diagrams Using Stability Criteria

5.8 Variation of Fugacity with Pressure and Temperature



Chapter 6. Thermodynamics of Mixtures

6.1 Equations of State for Mixtures

6.2 Partial Molar Property

6.3 Property Changes on Mixing

6.4 The Gibbs-Duhem Equation



Chapter 7. Fugacity of a Component in a Mixture

7.1 Fundamental Equations for a Multicomponent Mixture

7.2 Partial Molar Gibbs Energy of an Ideal Gas Mixture

7.3 Fugacity of a Component in a Mixture

7.4 Ideal Mixture

7.5 Calculation of Component Fugacities in a Gas Mixture

7.6 Calculation of Component Fugacities in a Liquid Mixture

7.7 Variation of Component Fugacity with Pressure and Temperature

7.8 The Use of Fugacity in Phase Equilibrium Calculations



Chapter 8. Excess Mixture Properties and Activity Coefficients

8.1 Property Changes on Mixing for an Ideal Mixture

8.2 Excess Properties

8.3 Activity and Activity Coefficient

8.4 Binary Activity Coefficient Models

8.5 Regular Mixture


8.7 Infinite Dilution Activity Coefficients

8.8 Testing Consistency of Experimental Data

8.9 Concluding Remarks



Chapter 9. Vapor-Liquid Equilibrium

9.1 Vapor-Liquid Equilibrium Calculations

9.2 Raoult’s Law

9.3 VLE Calculations When Raoult’s Law is Applicable

9.4 VLE Calculations by Numerical Techniques

9.5 VLE Calculations for Nonideal Liquid Mixtures

9.6 Positive and Negative Deviations from Raoult’s Law

9.7 Relative Volatility

9.8 VLE Calculations Using the Equation of State



Chapter 10. Solubility of Gases in Liquids

10.1 Henry’s Law

10.2 Factors Affecting Gas Solubility

10.3 Applications of Henry’s Law



Chapter 11. Liquid-Liquid Equilibrium

11.1 Mathematical Preliminaries

11.2 Stability of Liquid Mixtures

11.3 Liquid-Liquid Equilibrium Calculations

11.4 Liquid-Liquid Extraction

11.5 Applications of Liquid-Liquid Equilibrium



Chapter 12. Solid-Liquid Equilibrium

12.1 Equilibrium Between a Pure Solid and a Liquid Mixture

12.2 Colligative Properties



Chapter 13. Chemical Reaction Equilibrium

13.1 Stoichiometry of a Chemical Reaction

13.2 The Law of Combining Proportions

13.3 Equilibrium for a Single Reaction

13.4 Evaluation of the Equilibrium Constant

13.5 Gas Phase Reactions

13.6 Liquid (or Solid) Phase Reactions

13.7 An Alternative Way of Calculating Equilibrium Composition



Chapter 14. Heterogeneous Reactions and Multireaction Equilibria

14.1 Heterogeneous Reactions

14.2 Multiple Chemical Reactions

14.3 Determination of Independent Reactions From The Given Species

14.4 The Enthalpy and Gibbs Energy Change of Reaction

14.5 Carbon Formation

14.6 The Inverse Problem

14.7 Chemical Equilibrium Calculations by the Minimization of Gibbs Energy



Appendix A. Critical Constants and Acentric Factors

Compiled From

Appendix B. Heat Capacity of Ideal Gases

Compiled From

Appendix C. Antoine Constants

Compiled From

Appendix D. Corresponding States Using the Lee-Kesler Equation of State

Compressibility Factor

Enthalpy Departure Function

Entropy Departure Function

Appendix E. Enthalpy and Gibbs Energy of Formation at 298 K and 1bar

Compiled From

Appendix F. Matrices

F.1 Matrix Definition

F.2 Types of Matrices

F.3 Matrix Algebra

F.4 Determinants

F.5 Special Matrices

F.6 Linear Dependence

Appendix G. Databanks, Simulation Programs, Books, Websites


Simulation Programs





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© Elsevier 2012
5th September 2012
eBook ISBN:
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About the Author

Ismail Tosun

Ismail Tosun

The author has been teaching undergraduate and graduate level thermodynamics courses for over 30 years. Since 1989 he has been a professor at the Middle East Technical University (METU), Ankara, Turkey. He has also taught at the Turkish Military Academy and the University of Akron, Ohio. Professor Tosun received his BS and MS degrees from METU, and a PhD degree from the University of Akron, all in chemical engineering. He is the author of the book Modeling in Transport Phenomena, 2nd Ed., published by Elsevier. His research interests include mathematical modeling and transport phenomena. He is the author or co-author of over sixty publications.

Affiliations and Expertise

Department of Chemical Engineering, Middle East Technical University, Ankara, Turkey


"This detailed thermodynamics text from Tosun is designed for a graduate or upper-level undergraduate course…Differential calculus is utilized throughout, and each chapter opens with a summary of mathematical techniques needed to learn the upcoming material." --Reference and Research Book News, October 2013

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