Molecular Thermodynamics of Fluid-Phase Equilibria (3rd Edition)

Cover......Page 1
Contents......Page 6
Preface......Page 14
 Preface to the Second Edition......Page 17
 Preface to the First Edition......Page 20
Nomenclature......Page 22
1 The Phase-Equilibrium Problem......Page 26
 1.1 Essence of the Problem......Page 28
 1.2 Application of Thermodynamics to Phase-Equilibrium Problems......Page 29
2 Classical Thermodynamics of Phase Equilibria......Page 34
 2.1 Homogeneous Closed Systems......Page 35
 2.2 Homogeneous Open Systems......Page 39
 2.3 Equilibrium in a Heterogeneous Closed System......Page 42
 2.4 The Gibbs-Duhem Equation......Page 43
 2.6 The Chemical Potential......Page 44
 2.7 Fugacity and Activity......Page 46
 2.8 A Simple Application: Raoult\'s Law......Page 49
 Problems......Page 51
3 Thermodynamic Properties from Volumetric Data......Page 56
 3.1 Thermodynamic Properties with Independent Variables P and T......Page 57
 3.2 Fugacity of a Component in a Mixture at Moderate Pressures......Page 62
 3.3 Fugacity of a Pure Liquid or Solid......Page 65
 3.4 Thermodynamic Properties with Independent Variables V and T......Page 68
 3.5 Fugacity of a Component in a Mixture According to van der Waals\' Equation......Page 72
 3.6 Phase Equilibria from Volumetric Properties......Page 76
 Problems......Page 79
4 Intermolecular Forces, Corresponding States and Osmotic Systems......Page 82
 4.1 Potential-Energy Functions......Page 84
 4.2 Electrostatic Forces......Page 85
 4.3 Polarizability and Induced Dipoles......Page 91
 4.4 Intermolecular Forces between Nonpolar Molecules......Page 93
 4.5 Mie\'s Potential-Energy Function for Nonpolar Molecules......Page 97
 4.6 Structural Effects......Page 102
 4.7 Specific (Chemical) Forces......Page 103
 4.8 Hydrogen Bonds......Page 106
 4.9 Electron Donor-Electron Acceptor Complexes......Page 113
 4.10 Hydrophobic Interaction......Page 119
 4.11 Molecular Interactions in Dense Fluid Media......Page 121
  Osmotic Pressure......Page 122
  Donnan Equilibria......Page 126
 4.12 Molecular Theory of Corresponding States......Page 129
 4.13 Extension of Corresponding-States Theory to More Complicated Molecules......Page 135
 4.14 Summary......Page 139
 References......Page 140
 Problems......Page 142
5 Fugacities in Gas Mixtures......Page 148
 5.1 The Lewis Fugacity Rule......Page 149
 5.2 The Virial Equation of State......Page 151
 5.3 Extension to Mixtures......Page 158
 5.4 Fugacities from the Virial Equation......Page 161
 5.5 Calculation of Virial Coefficients from Potential Functions......Page 164
 5.6 Third Virial Coefficients......Page 178
 5.7 Virial Coefficients from Corresponding-States Correlations......Page 184
 5.9 Strong Dimerization: Carboxylic Acids......Page 199
 5.10 Weak Dimerizations and Second Virial Coefficients......Page 204
 5.11 Fugacities at High Densities......Page 214
 5.12 Solubilities of Solids and Liquids in Compressed Gases......Page 216
 5.13 Summary......Page 225
 References......Page 227
 Problems......Page 230
6 Fugacities in Liquid Mixtures: Excess Functions......Page 238
 6.1 The Ideal Solution......Page 239
 6.2 Fundamental Relations of Excess Functions......Page 241
 6.3 Activity and Activity Coefficients......Page 243
 6.4 Normalization of Activity Coefficients......Page 247
 6.5 Activity Coefficients from Excess Functions in Binary Mixtures......Page 250
 6.6 Activity Coefficients for One Component from Those of the Other Components......Page 257
 6.7 Partial Pressures from Isothermal Total-Pressure Data......Page 261
 6.8 Partial Pressures from Isobaric Boiling-Point Data......Page 267
 6.9 Testing Equilibrium Data for Thermodynamic Consistency......Page 270
 6.10 Wohl\'s Expansion for the Excess Gibbs Energy......Page 275
 6.11 Wilson, NRTL, and UNIQUAC Equations......Page 283
 6.12 Excess Functions and Partial Miscibility......Page 294
 6.13 Upper and Lower Consolute Temperatures......Page 300
 6.14 Excess Functions for Multicomponent Mixtures......Page 304
 6.15 Wilson, NRTL, and UNIQUAC Equations for Multicomponent Mixtures......Page 312
 6.16 Summary......Page 319
 References......Page 322
 Problems......Page 324
7 Fugacities in Liquid Mixtures: Models and Theories of Solutions......Page 332
 7.1 The Theory of van Laar......Page 334
 7.2 The Scatchard-Hildebrand Theory......Page 338
 7.3 Excess Functions from an Equation of State......Page 351
 7.4 The Lattice Model......Page 354
 7.5 Calculation of the Interchange Energy from Molecular Properties......Page 359
 7.6 Nonrandom Mixtures of Simple Molecules......Page 361
 7.7 The Two-Liquid Theoryh......Page 369
 7.8 Activity Coefficients from Group-Contribution Methods......Page 375
 7.9 Chemical Theory......Page 377
 7.10 Activity Coefficients in Associated Solutions......Page 379
 7.11 Associated Solutions with Physical Interactions......Page 388
 7.12 Activity Coefficients in Solvated Solutions......Page 394
 7.13 Solutions Containing Two (or More) Complexes......Page 399
 7.14 Distribution of a Solute between Two Immiscible Solvents......Page 403
 7.15 The Generalized van der Waals Partition Function......Page 407
 7.16 Perturbed-Hard-Chain Theory......Page 412
 7.17 Hard-Sphere-Chain Models......Page 414
  Statistical Associated-Fluid Theory......Page 415
  Perturbed Hard-Sphere-Chain Theory......Page 425
 7.18 Summary......Page 428
 References......Page 431
 Problems......Page 436
8 Polymers: Solutions, Blends, Membranes, and Gels......Page 442
 8.1 Properties of Polymers......Page 443
 8.2 Lattice Models: The Flory-Huggins Theory......Page 446
 8.3 Equations of State for Polymer Solutions......Page 465
  Prigogine-Flory-Patterson Theory......Page 466
  Perturbed-Hard-Chain Theory......Page 484
  Lattice-Fluid Theory......Page 485
  Statistical Associated Fluid Theory......Page 495
  Perturbed Hard-Sphere-Chain Theory......Page 496
  Nonporous Membranes......Page 500
  Polymer Gels......Page 513
 8.5 Summary......Page 520
 References......Page 523
 Problems......Page 528
9 Electrolyte Solutions......Page 532
 9.1 Activity Coefficient of a Nonvolatile Solute in Solution and Osmotic Coefficient for the Solvent......Page 533
 9.2 Solution of an Electrolyte. Electroneutrality......Page 537
 9.3 Osmotic Coefficient in an Electrolyte Solution......Page 541
 9.4 Relation of Osmotic Coefficient to Mean Ionic Activity Coefficient......Page 544
 9.5 Temperature and Pressure Dependence of the Mean Ionic Activity Coefficient......Page 546
 9.6 Excess Properties of Electrolyte Solutions......Page 547
 9.7 Debye-Hückel Limiting Law......Page 549
 9.8 Weak Electrolytes......Page 555
 9.9 Salting-out and Salting-in of Volatile Solutes......Page 556
 9.10 Models for Concentrated Ionic Solutions......Page 562
 9.11 Fundamental Models......Page 563
 9.12 Semi-Empirical Models......Page 564
 9.13 Models Based on the Local-Composition Concept......Page 565
 9.14 The Model of Pitzer......Page 568
 9.15 The \"Chemical\" Hydration Model of Robinson and Stokes......Page 577
 9.16 Conversion from McMillan-Mayer to Lewis-Randall Formalisms......Page 581
 9.17 Phase Equilibria in Aqueous Solutions of Volatile Electrolytes......Page 582
 9.18 Protein Partitioning in Aqueous Two-Phase Systems......Page 590
 9.19 Summary......Page 597
 References......Page 600
 Problems......Page 603
10 Solubilities of Gases in Liquids......Page 608
 10.1 The Ideal Solubility of a Gas......Page 609
 10.2 Henry\'s Law and Its Thermodynamic Significance......Page 611
 10.3 Effect of Pressure on Gas Solubility......Page 613
 10.4 Effect of Temperature on Gas Solubility......Page 621
 10.5 Estimation of Gas Solubility......Page 628
 10.6 Gas Solubility in Mixed Solvents......Page 638
 10.7 Chemical Effects on Gas Solubility......Page 644
 References......Page 655
 Problems......Page 656
 11.1 Thermodynamic Framework......Page 660
 11.2 Calculation of the Pure-Solute Fugacity Ratio......Page 663
 11.3 Ideal Solubility......Page 666
 11.4 Nonideal Solutions......Page 669
 11.5 Solubility of a Solid in a Mixed Solvent......Page 678
 11.6 Solid Solutions......Page 683
 11.7 Solubility of Antibiotics in Mixed Nonaqueous Solvents......Page 689
 Problems......Page 692
12 High-Pressure Phase Equilibria......Page 696
 12.1 Fluid Mixtures at High Pressures......Page 698
  Interpretation of Phase Diagrams......Page 700
  Classification of Phase Diagrams for Binary Mixtures......Page 702
  Critical Phenomena in Binary Fluid Mixtures......Page 708
  Liquid-Liquid Equilibria......Page 712
  Gas-Gas Equilibria......Page 721
 12.4 Thermodynamic Analysis......Page 724
 12.5 Supercritical-Fluid Extraction......Page 731
 12.6 Calculation of High-Pressure Vapor-Liquid Equilibria......Page 737
 12.7 Phase Equilibria from Equations of State......Page 738
  Non-Quadratic Mixing Rules......Page 745
 12.8 Phase Equilibria from a Corresponding-States Correlation......Page 748
 12.9 Vapor-Liquid Equilibria from the Perturbed-Hard-Chain Theory......Page 751
 12.10 Phase Equilibria Using the Chemical Theory......Page 755
 12.11 Summary......Page 763
 References......Page 764
 Problems......Page 768
A: Uniformity of Intensive Potentials as a Criterion of Phase Equilibrium......Page 774
B: A Brief Introduction to Statistical Thermodynamics......Page 778
 Ensembles and Basic Postulates......Page 779
 The Canonical Ensemble......Page 781
 The Grand Canonical Ensemble......Page 787
 The Semiclassical Partition Function......Page 792
 Appendix B.2: Maximum-Term Method......Page 796
 Appendix B.3: Stirling\'s Formula......Page 797
 References......Page 798
 Virial Equation as a Power Series in Density or Pressure......Page 800
 Virial Coefficients for Hydrogen, Helium, and Neon......Page 804
 References......Page 808
D: The Gibbs-Duhem Equation......Page 810
E: Liquid-Liquid Equilibria in Binary and Multicomponent Systems......Page 816
 References......Page 826
F: Estimation of Activity Coefficients......Page 828
 Estimation from Activity Coefficients at Infinite Dilution......Page 829
 Estimation from Group-Contribution Methods......Page 833
 References......Page 839
G: A General Theorem for Mixtures with Associating or Solvating Molecules......Page 842
H: Brief Introduction to Perturbation Theory of Dense Fluids......Page 846
 References......Page 852
I: The Ion-Interaction Model of Pitzer for Multielectrolyte Solutions......Page 854
 References......Page 864
 SI Units and Conversion Factors......Page 866
 Some Fundamental Constants in Various Units......Page 868
 Critical Constants and Acentric Factors for Selected Fluids......Page 869
 A......Page 872
 C......Page 873
 E......Page 874
 F......Page 876
 H......Page 877
 I......Page 878
 M......Page 879
 P......Page 880
 S......Page 882
 V......Page 884
 W......Page 885