Molecular Thermodynamics of Fluid-Phase Equilibria

by Prausnitz, John M.; Lichtenthaler, Rudiger N.; de Azevedo, Edmundo Gomes

• ISBN13: 9780139777455
• ISBN10: 0139777458
• Edition: 3rd
• Format: Paperback
• Copyright: 1998-10-22
• Publisher: PEARSO

Summary

97774-4 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.

Author Biography

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.

Table of Contents

Preface	xiii	(8)
Preface to the Second Edition	xvi	(3)
Preface to the First Edition	xix	(2)
Nomenclature	xxi
1 The Phase-Equilibrium Problem	1	(8)
1.1 Essence of the Problem	3	(1)
1.2 Application of Thermodynamics to Phase-Equilibrium Problems	4	(5)
2 Classical Thermodynamic of Phase Equilibria	9	(22)
2.1 Homogeneous Closed System	10	(4)
2.2 Homogeneous Open Systems	14	(3)
2.3 Equilibrium in a Heterogeneous Closed System	17	(1)
2.4 The Gibbs-Duhem Equation	18	(1)
2.5 The Phase Rule	19	(1)
2.6 The Chemical Potential	19	(2)
2.7 Fugacity and Activity	21	(3)
2.8 A Simple Application: Raoult's Law	24	(2)
References	26	(1)
Problems	26	(5)
3 Thermodynamic Properties from Volumetric Data	31	(26)
3.1 Thermodynamic Properties with Independent Variables P and T	32	(5)
3.2 Fugacity of a Component in a Mixture at Moderate Pressure	37	(3)
3.3 Fugacity of a Pure Liquid or Solid	40	(3)
3.4 Thermodynamic Properties with Independent Variables V and T	43	(4)
3.5 Fugacity of a Component in a Mixture According to van der Waals' Equation	47	(4)
3.6 Phase Equilibria from Volumetric Properties	51	(3)
References	54	(1)
Problems	54	(3)
4 Intermolecular Forces, Corresponding States and Osmotic Systems	57	(66)
4.1 Potential-Energy Functions	59	(1)
4.2 Electrostatic Forces	60	(6)
4.3 Polarizability and Induced Dipoles	66	(2)
4.4 Intermolecular Forces between Nonpolar Molecules	68	(4)
4.5 Mie's Potential-Energy Function for Non-polar Molecules	72	(5)
4.6 Structural Effects	77	(1)
4.7 Specific (Chemical) Forces	78	(3)
4.8 Hydrogen Bonds	81	(7)
4.9 Electron Donor-Electron Acceptor Complexes	88	(6)
4.10 Hydrophobic Interactions	94	(2)
4.11 Molecular Interactions in Fluid Media	96	(8)
Osmotic Pressure	97	(4)
Donnan Equilibria	101	(3)
4.12 Molecular Theory of Corresponding States	104	(6)
4.13 Extension of Corresponding-States Theory to More Complicated Molecules	110	(4)
4.14 Summary	114	(1)
References	115	(2)
Problems	117	(6)
5 Fugacities in Gas Mixtures	123	(90)
5.1 The Lewis Fugacity Rule	124	(2)
5.2 The Virial Equation of State	126	(7)
5.3 Extension to Mixtures	133	(3)
5.4 Fugacities from the Virial Equation	136	(3)
5.5 Calculation of Virial Coefficients from Potential Functions	139	(14)
5.6 Third Virial Coefficients	153	(6)
5.7 Virial Coefficients from Corresponding-States Correlations	159	(15)
5.8 The "Chemical" Interpretation of Deviations from Gas-Phase Ideality	174	(1)
5.9 Strong Dimerization: Carboxylic Acids	174	(5)
5.10 Weak Dimerizations and Second Virial Coefficients	179	(10)
5.11 Fugacities at High Densities	189	(2)
5.12 Solubilities of Solids and Liquids in Compressed Gases	191	(9)
5.13 Summary	200	(2)
References	202	(3)
Problems	205	(8)
6 Fugacities in Liquid Mixtures: Excess Functions	213	(94)
6.1 The Ideal Solution	214	(2)
6.2 Fundamental Relations of Excess Functions	216	(2)
6.3 Activity and Activity Coefficients	218	(4)
6.4 Normalization of Activity Coefficients	222	(3)
6.5 Activity Coefficients from Excess Functions in Binary Mixtures	225	(7)
6.6 Activity Coefficients for One Component from Those of the Other Components	232	(4)
6.7 Partial Pressures from Isothermal Total-Pressure Data	236	(6)
6.8 Partial Pressures from Isobaric Boiling-Point Data	242	(3)
6.9 Testing Equilibrium Data for Thermodynamic Consistency	245	(5)
6.10 Wohl's Expansion for the Excess Gibbs Energy	250	(8)
6.11 Wilson, NRTL, and UNIQUAC Equations	258	(11)
6.12 Excess Functions and Partial Miscibility	269	(6)
6.13 Upper and Lower Consolute Temperatures	275	(4)
6.14 Excess Functions for Multicomponent Mixtures	279	(8)
6.15 Wilson, NRTL, and UNIQUAC Equations for Multicomponent Mixtures	287	(7)
6.16 Summary	294	(3)
References	297	(2)
Problems	299	(8)
7 Fugacities in Liquid Mixtures: Models and Theories of Solutions	307	(110)
7.1 The Theory of van Laar	309	(4)
7.2 The Scatchard-Hildebrand Theory	313	(13)
7.3 Excess Functions from an Equation of State	326	(3)
7.4 The Lattice Model	329	(5)
7.5 Calculation of the Interchange Energy from Molecular Properties	334	(2)
7.6 Nonrandom Mixtures of Simple Molecules	336	(8)
7.7 The Two-Liquid Theory	344	(6)
7.8 Activity Coefficients from Group-Contribution Methods	350	(2)
7.9 Chemical Theory	352	(2)
7.10 Activity Coefficients in Associated Solutions	354	(9)
7.11 Associated Solutions with Physical Interactions	363	(6)
7.12 Activity Coefficients in Solvated Solutions	369	(5)
7.13 Solutions Containing Two (or More) Complexes	374	(4)
7.14 Distribution of a Solute between Two Immiscible Solvents	378	(4)
7.15 The Generalized van der Waals Partition Function	382	(5)
7.16 Perturbed-Hard-Chain Theory	387	(2)
7.17 Hard-Sphere-Chain Models	389	(1)
Statistical Associated-Fluid Theory	390	(10)
Perturbed Hard-Sphere-Chain Theory	400	(3)
7.18 Summary	403	(3)
References	406	(5)
Problems	411	(6)
8 Polymers: Solutions, Blends, Memberanes, and Gels	417	(90)
8.1 Properties of Polymers	418	(3)
8.2 Lattice Models: The Flory-Huggins Theory	421	(19)
8.3 Equations of States for Polymer Solutions	440	(35)
Prigogine-Flory-Patterson Theory	441	(18)
Perturbed-Hard-Chain Theory	459	(1)
Lattice-Fluid Theory	460	(10)
Statistical Associatied Fluid Theory	470	(1)
Perturbed Hard-Sphere-Chain Theory	471	(4)
8.4 Nonporous Polymeric Membranes and Polymer Gels	475	(20)
Nonporous Membranes	475	(13)
Polymer Gels	488	(7)
8.5 Summary	495	(3)
References	498	(5)
Problems	503	(4)
9 Electroyte Solutions	507	(76)
9.1 Activity Coefficient of a Nonvolatile Solute in Solution and Osmotic Coefficient for the Solvent	508	(4)
9.2 Solution of an Electrolyte. Electroneutrality	512	(4)
9.3 Osmotic Coefficient in a Electrolyte Solution	516	(3)
9.4 Relation of Osmotic Coefficient to Mean Ionic Activity Coefficient	519	(2)
9.5 Temperature and Pressure Dependence of the Mean Ionic Activity Coefficient	521	(1)
9.6 Excess Properties of Electrolyte Solutions	522	(2)
9.7 Debye-Huckel Limiting Law	524	(6)
9.8 Weak Electrolytes	530	(1)
9.9 Salting-Out and Salting-in of Volatile Solutes	531	(6)
9.10 Models for Concentrated Ionic Solutions	537	(1)
9.11 Fundamental Models	538	(1)
9.12 Semi-Empirical Models	539	(1)
9.13 Models Based on the Local-Composition Concept	540	(3)
9.14 The Model of Pitzer	543	(9)
9.15 The "Chemical" Hydration Model of Robinson and Stokes	552	(4)
9.16 Conversion from McMillan-Mayer to Lewis-Randall Formalisms	556	(1)
9.17 Phase Equilibria in Aqueous Solutions of Volatile Electrolytes	557	(8)
9.18 Protein Partitioning in Aqueous Two-Phase Systems	565	(7)
9.19 Summary	572	(3)
References	575	(3)
Problems	578	(5)
10 Solubilities of Gases in Liquids	583	(52)
10.1 The Ideal Solubility of a Gas	584	(2)
10.2 Henry's Law and Its Thermodynamic Significance	586	(2)
10.3 Effect of Pressure on Gas Solubility	588	(8)
10.4 Effect of Temperature on Gas Solubility	596	(7)
10.5 Estimation of Gas Solubility	603	(10)
10.6 Gas Solubility in Mixed Solvents	613	(6)
10.7 Chemical Effects on Gas Solubility	619	(11)
References	630	(1)
Problems	631	(4)
11 Solubilities of Solids in Liquids	635	(36)
11.1 Thermodynamic Framework	635	(3)
11.2 Calculation of the Pure-Solute Fugacity Ratio	638	(3)
11.3 Ideal Solubility	641	(3)
11.4 Nonideal Solutions	644	(9)
11.5 Solubility of a Solid in a Mixed Solvent	653	(5)
11.6 Solid Solutions	658	(6)
11.7 Solubility of Antibiotics in Mixed Nonaqueous Solvents	664	(3)
References	667	(1)
Problems	667	(4)
12 High-Pressure Phases Equilibria	671	(78)
12.1 Fluid Mixtures at High Pressures	673	(2)
12.2 Phase Behavior at High Pressure	675	(12)
Interpretation of Phase Diagrams	675	(2)
Classification of Phase Diagrams for Binary Mixtures	677	(6)
Critical Phenomena in Binary Fluid Mixtures	683	(4)
12.3 Liquid-Liquid and Gas-Gas Equilibria	687	(12)
Liquid-Liquid Equilibria	687	(9)
Gas-Gas Equilibria	696	(3)
12.4 Thermodynamic Analysis	699
12.5 Supercritical-Fluid Extraction	706	(6)
12.6 Calculation of High-Pressure Vapor-Liquid Equilibria	712	(1)
12.7 Phase Equilibria form Equations of State	713	(10)
Non-Quadratic Mixing Rules	720	(3)
12.8 Phase Equilibria from a Corresponding-States Correlation	723	(3)
12.9 Vapor-Liquid Equilibria from the Perturbed-Hard-Chain Theory	726	(4)
12.10 Phase Equilibria Using the Chemical Theory	730	(8)
12.11 Summary	738	(1)
References	739	(4)
Problems	743	(6)
A Uniformity of Intensive Potentials as a Criterion of Phase Equilibrium	749	(4)
B A Brief Introduction to Statistical Thermodynamics	753	(22)
Thermodynamic States and Quantum States of a System	754	(1)
Ensembles and Basic Postulates	754	(2)
The Canonical Ensemble	756	(6)
The Grand Canonical Ensemble	762	(5)
The Semiclassical Partition Function	767	(4)
Appendix B.1: Two Basic Combinatorial Relations	771	(1)
Appendix B.2: Maximum-Term Method	771	(1)
Appendix B.3: Stirling's Formula	772	(1)
References	773	(2)
C Virial Coefficients for Quantum Gases	775	(10)
Virial Equation as a Power Series in Density or Pressure	775	(4)
Virial Coefficients for Hydrogen, Helium, and Neon	779	(4)
References	783	(2)
D The Gibbs-Duhem Equation	785	(6)
E Liquid-Liquid Equilibria in Binary and Multicomponent Systems	791	(12)
References	801	(2)
F Estimation of Activity Coefficients	803	(14)
Estimation from Activity Coefficients of Infinite Dilution	804	(4)
Estimation form Group-Contribution Methods	808	(6)
References	814	(3)
G A General Theorem for Mixtures with Associating or Solvating Molecules	817	(4)
H Brief Introduction to Perturbation Theory of Dense Fluids	821	(8)
References	827	(2)
I The Ion-Interaction Models of Pitzer for Multielectrolyte Solutions	829	(12)
References	839	(2)
J Conversion Factors and Constants	841	(6)
SI Units and Conversion Factors	841	(2)
Some Fundamental Constants in Various Units	843	(1)
Critical Constants and Acentric Factors For Selected Fluids	844	(3)
Index	847

Excerpts

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 com