Molecular Thermodynamics of Fluid-Phase Equilibria / Edition 3

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Overview

The classic guide to mixtures, completely updated with new models, theories, examples, and data.

Efficient separation operations and many other chemical processes depend upon a thorough understanding of the properties of gaseous and liquid mixtures. Molecular Thermodynamics of Fluid-Phase Equilibria, Third Edition is a systematic, practical guide to interpreting, correlating, and predicting thermodynamic properties used in mixture-related phase-equilibrium calculations.

Completely updated, this edition reflects the growing maturity of techniques grounded in applied statistical thermodynamics and molecular simulation, while relying on classical thermodynamics, molecular physics, and physical chemistry wherever these fields offer superior solutions. Detailed new coverage includes:

  • Techniques for improving separation processes and making them more environmentally friendly.
  • Theoretical concepts enabling the description and interpretation of solution properties.
  • New models, notably the lattice-fluid and statistical associated-fluid theories.
  • Polymer solutions, including gas-polymer equilibria, polymer blends, membranes, and gels.
  • Electrolyte solutions, including semi-empirical models for solutions containing salts or volatile electrolytes.

Coverage also includes: fundamentals of classical thermodynamics of phase equilibria; thermodynamic properties from volumetric data; intermolecular forces; fugacities in gas and liquid mixtures; solubilities of gases and solids in liquids; high-pressure phase equilibria; virial coefficients for quantum gases; and much more.

Throughout, Molecular Thermodynamics of Fluid-Phase Equilibria strikes a perfect balance between empirical techniques and theory, and is replete with useful examples and experimental data. More than ever, it is the essential resource for engineers, chemists, and other professionals working with mixtures and related processes.

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Editorial Reviews

Booknews
A guide to interpreting, correlating, and predicting thermodynamic properties used in mixture-related phase-equilibrium calculations. Coverage includes empirical techniques and theory, with material on fundamentals of classical thermodynamics of phase equilibria, thermodynamic properties from volumetric data, intermolecular forces, fugacities in gas and liquid mixtures, viral coefficients for ordinary and quantum gases, polymer solutions, and osmotic systems. This third edition reflects the latest techniques in the field. Annotation c. by Book News, Inc., Portland, Or.
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Product Details

Meet the Author

JOHN M. PRAUSNITZ is Professor of Chemical Engineering at the University of California, Berkeley. A leading consultant on petroleum, natural gas, petrochemicals, cryogenic, and polymeric processes, he has published over 550 research articles. He has twice been named a Guggenheim Fellow, and received the 1997 Arthur K. Doolittle Award from the American Chemical Society.

RüDIGER N. LICHTENTHALER is Professor of Physical Chemistry and Applied Thermodynamics at the University of Heidelberg, Germany.

EDMUNDO GOMES DE AZEVEDO is Associate Professor of Chemical Engineering at the Instituto Superior Técnico, Lisbon, Portugal.

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Read an Excerpt

Preface
The first edition of this book appeared in 1969; the second edition in 1986. The purpose of this book remains unchanged: to present to senior or first-year graduate students in chemical engineering (and related sciences) a broad introduction to the thermodynamics of phase equilibria typically encountered in design of chemical products and processes, in particular, in separation operations. Thermodynamic tools are provided for efficient design and improvement of conventional and new separation processes including those that may be useful for environmental protection.

This book is suitable as a text for those students who have completed a first course in chemical engineering thermodynamics. While most of the material is based on classical thermodynamics, molecular properties are introduced to facilitate applications to real systems. Although no effort is made to teach statistical thermodynamics, useful results from statistical thermodynamics are included to connect thermodynamic and molecular properties.

The new edition presents an expanded discussion of theoretical concepts to describe and interpret solution properties, with emphasis on those concepts that bear promise for practical applications. Attention is given to a variety of models including the lattice-fluid theory and the statistical associated-fluid theory (SAFT).

A new chapter is devoted to polymer solutions including gas-polymer equilibria at ordinary and high pressures, polymer blends, polymeric membranes and gels. Other novel sections of the third edition include discussions of osmotic pressure and Donnan equilibria.

A serious omission in previous editions has now been corrected: the third edition contains an entirely new chapter on electrolyte solutions. This new chapter first gives the thermodynamic basis for describing activities of components in electrolyte solutions and then presents some semi-empirical models for solutions containing salts or volatile electrolytes. Also discussed are some applications of these models to phase-equilibrium calculations relevant to chemical, environmental and biochemical engineering.

All chapters have been updated primarily through presentation of some recent examples and some new homework problems.

It is a pleasure for the senior author to indicate here his thanks for the essential contributions of his two co-authors. Without their dedicated devotion and attention to numerous details, this third edition could not have been completed.

For helpful advice and comments, the authors are grateful to numerous colleagues, especially to Allan Harvey, Dan Kuehner, Huen Lee, Gerd Maurer, Van Nguyen, John O'Connell, and Jianzhong Wu.

Since 1986, the literature concerning fluid-phase thermodynamics has grown tremendously. To keep the book to a reasonable size, it has been necessary to omit many fine contributions. The authors apologize to their many colleagues whose important work could not be included lest the book become excessively long.

Chemical engineering thermodynamics is now in a state of transition. Classical thermodynamics is becoming increasingly replaced by new tools from applied statistical thermodynamics and molecular simulations. However, many - indeed most - of these new tools are not as yet sufficiently developed for practical applications. For the present and near future, it remains necessary to rely primarily on classical thermodynamics informed and extended through molecular physics and physical chemistry. Molecular thermodynamics, as presented here, is characterized by a combination of classical methods augmented by molecular science and supported by fundamental experimental data.

As in previous editions, this book is motivated by the authors' enthusiasm for explaining and extending the insights of thermodynamics towards useful applications in chemical engineering. If that enthusiasm can be communicated to students and to practicing engineers, the purpose of this book will be fulfilled. As in previous editions, the motto of the third remains, as before: Felix qui potuit rerum cognescere causas.

J. M. Prausnitz Berkeley, California

Effective teamwork that did not leave anything to be desired was the corner-stone for completing the third edition of this book during the time we spent in Berkeley. We thank John for preparing the ground correspondingly, for his leadership as senior author and for his support.

Because we were responsible for electronic typesetting, layout, artwork and figures (many from the previous edition), it was a challenge to take care of all details, requiring from us skills that we learned by doing. We did our best to prepare this book to meet professional standards.

Coming back to Berkeley and to collaborate once again with John was for us an enriching experience. In doing so we asked from our families even more sacrifices than we usually request as academic scientists.

I (R.N.L.) express most sincere thanks to my wife Brigitte, and to my children, Ulrike, Heike, Felix, Philipp, and Martin who provided the support necessary to commit myself in Berkeley exclusively to the revision of this book. I am also grateful to my colleagues at the Institute of Physical Chemistry of the University of Heidelberg for stepping in to meet my teaching duties while I was in Berkeley. Further, I want to thank Siegfried Kraft, Chancellor of the University of Heidelberg, whose understanding and advice made part of my stay in Berkeley possible.

I (E.G.A.) am thankful to my family, Cristina, Miguel and Marta, for their encouragement, understanding and support during the long and difficult months we were apart. Also I am grateful to Instituto Superior Técnico for a leave of absence, and to the Fulbright Program, Programa de Bolsas de Estudos da OTAN, and Funda‹o Luso-Americana para o Desenvolvimento for financial support of my residence in Berkeley during the academic year 1992/93 (when the preparation of the present edition started) and during the first semester of 1998.

R. N. Lichtenthaler Heidelberg, Germany E. Gomes de Azevedo Lisbon, Portugal

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Table of Contents

1. The Phase Equilibrium Problem.

2. Classical Thermodynamics of Phase Equilibria.

3. Thermodynamic Properties from Volumetric Data.

4. Intermolecular Forces, Corresponding States and Osmotic Systems.

5. Fugacities in Gas Mixtures.

6. Fugacities in Liquid Mixtures: Excess Functions.

7. Fugacities in Liquid Mixtures: Models and Theories of Solutions.

8. Polymers: Solutions, Blends, Membranes, and Gels.

9. Electrolyte Solutions.

10. Solubilities of Gases in Liquids.

11. Solubilities of Solids in Liquids.

12. High-Pressure Phase Equilibria.

Appendix A. Uniformity of Intensive Potentials as a Criterion of Phase Equilibrium.

Appendix B. A Brief Introduction to Statistical Thermodynamics.

Appendix C. Virial Coefficients for Quantum Gases.

Appendix D. The Gibbs-Duhem Equation.

Appendix E. Liquid-Liquid Equilibria in Binary and Multicomponent Systems.

Appendix F. Estimation of Activity Coefficients.

Appendix G. A General Theorem for Mixtures with Associating or Solvating Molecules.

Appendix H. Brief Introduction to Perturbation Theory of Dense Fluids.

Appendix I. The Ion-Interaction Model of Pitzer for Multielectrolyte Solutions.

Appendix J. Conversion Factors and Constants.

Index.

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Preface

Preface
The first edition of this book appeared in 1969; the second edition in 1986. The purpose of this book remains unchanged: to present to senior or first-year graduate students in chemical engineering (and related sciences) a broad introduction to the thermodynamics of phase equilibria typically encountered in design of chemical products and processes, in particular, in separation operations. Thermodynamic tools are provided for efficient design and improvement of conventional and new separation processes including those that may be useful for environmental protection.

This book is suitable as a text for those students who have completed a first course in chemical engineering thermodynamics. While most of the material is based on classical thermodynamics, molecular properties are introduced to facilitate applications to real systems. Although no effort is made to teach statistical thermodynamics, useful results from statistical thermodynamics are included to connect thermodynamic and molecular properties.

The new edition presents an expanded discussion of theoretical concepts to describe and interpret solution properties, with emphasis on those concepts that bear promise for practical applications. Attention is given to a variety of models including the lattice-fluid theory and the statistical associated-fluid theory (SAFT).

A new chapter is devoted to polymer solutions including gas-polymer equilibria at ordinary and high pressures, polymer blends, polymeric membranes and gels. Other novel sections of the third edition include discussions of osmotic pressure and Donnan equilibria.

A serious omission in previous editions has now been corrected: the third edition contains an entirely new chapter on electrolyte solutions. This new chapter first gives the thermodynamic basis for describing activities of components in electrolyte solutions and then presents some semi-empirical models for solutions containing salts or volatile electrolytes. Also discussed are some applications of these models to phase-equilibrium calculations relevant to chemical, environmental and biochemical engineering.

All chapters have been updated primarily through presentation of some recent examples and some new homework problems.

It is a pleasure for the senior author to indicate here his thanks for the essential contributions of his two co-authors. Without their dedicated devotion and attention to numerous details, this third edition could not have been completed.

For helpful advice and comments, the authors are grateful to numerous colleagues, especially to Allan Harvey, Dan Kuehner, Huen Lee, Gerd Maurer, Van Nguyen, John O'Connell, and Jianzhong Wu.

Since 1986, the literature concerning fluid-phase thermodynamics has grown tremendously. To keep the book to a reasonable size, it has been necessary to omit many fine contributions. The authors apologize to their many colleagues whose important work could not be included lest the book become excessively long.

Chemical engineering thermodynamics is now in a state of transition. Classical thermodynamics is becoming increasingly replaced by new tools from applied statistical thermodynamics and molecular simulations. However, many - indeed most - of these new tools are not as yet sufficiently developed for practical applications. For the present and near future, it remains necessary to rely primarily on classical thermodynamics informed and extended through molecular physics and physical chemistry. Molecular thermodynamics, as presented here, is characterized by a combination of classical methods augmented by molecular science and supported by fundamental experimental data.

As in previous editions, this book is motivated by the authors' enthusiasm for explaining and extending the insights of thermodynamics towards useful applications in chemical engineering. If that enthusiasm can be communicated to students and to practicing engineers, the purpose of this book will be fulfilled. As in previous editions, the motto of the third remains, as before: Felix qui potuit rerum cognescere causas.

J. M. Prausnitz
Berkeley, California

Effective teamwork that did not leave anything to be desired was the corner-stone for completing the third edition of this book during the time we spent in Berkeley. We thank John for preparing the ground correspondingly, for his leadership as senior author and for his support.

Because we were responsible for electronic typesetting, layout, artwork and figures (many from the previous edition), it was a challenge to take care of all details, requiring from us skills that we learned by doing. We did our best to prepare this book to meet professional standards.

Coming back to Berkeley and to collaborate once again with John was for us an enriching experience. In doing so we asked from our families even more sacrifices than we usually request as academic scientists.

I (R.N.L.) express most sincere thanks to my wife Brigitte, and to my children, Ulrike, Heike, Felix, Philipp, and Martin who provided the support necessary to commit myself in Berkeley exclusively to the revision of this book. I am also grateful to my colleagues at the Institute of Physical Chemistry of the University of Heidelberg for stepping in to meet my teaching duties while I was in Berkeley. Further, I want to thank Siegfried Kraft, Chancellor of the University of Heidelberg, whose understanding and advice made part of my stay in Berkeley possible.

I (E.G.A.) am thankful to my family, Cristina, Miguel and Marta, for their encouragement, understanding and support during the long and difficult months we were apart. Also I am grateful to Instituto Superior TŽcnico for a leave of absence, and to the Fulbright Program, Programa de Bolsas de Estudos da OTAN, and Funda‹o Luso-Americana para o Desenvolvimento for financial support of my residence in Berkeley during the academic year 1992/93 (when the preparation of the present edition started) and during the first semester of 1998.

R. N. Lichtenthaler
Heidelberg, Germany
E. Gomes de Azevedo
Lisbon, Portugal

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