9780139777455

Molecular Thermodynamics of Fluid-Phase Equilibria

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  • ISBN13:

    9780139777455

  • ISBN10:

    0139777458

  • Edition: 3rd
  • Format: Paperback
  • Copyright: 10/22/1998
  • Publisher: Prentice Hall

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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

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