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WATER A COMPREHENSIVE TREATISE
Volume 3
Aqueous Solutions of Simple Electrolytes
Volume 1
Volume 2
Volume 3
Volume 4
WATER A COMPREHENSIVE TREATISE
Edited by Felix Franks
The Physics and Physical Chemistry of Water
Water in Crystalline Hydrates; Aqueous Solutions of Simple Nonelectrolytes Aqueous Solutions of Simple Electrolytes
Aqueous Solutions of Macromolecules; Water in Disperse Systems
WATER A COMPREHENSIVE TREATISE
Edited by Felix Franks Unilever Research Laboratory
Sharnbrook, Bedford, England
Volume 3 Aqueous Solutions
of Simple Electrolytes
g:>PLENUM PRESS. NEW YORK-LONDON. 1973
200435
First Printing - May 1973 Second Printing - May 1977
Library of Congress Catalog Card Number 78-165694 ISBN 978-1-4684-2957-2 ISBN 978-1-4684-2955-8 (eBook) DOI 10.1007/978-1-4684-2955-8
© 1973 Plenum Press, New York Softcover reprint of the hardcover 1 st edition 1973
A Division of Plenum Publishing Corporation 227 West 17th Street, New York N.Y. 10011
United Kingdom edition published by Plenum Press, London A Division of Plenum Publishing Company, Ud.
Davis House (4th Floor), 8 Scrubs Lane, Harlesden, London, NWI0 6SE, England
All rights reserved
No part of this publication may be reproduced in any form without written permission from the publisher
Preface
The chapters making up this volume had originally been planned to form part of a single volume covering solid hydrates and aqueous solutions of simple molecules and ions. However, during the preparation of the manuscripts it became apparent that such a volume would turn out to be very unwieldy and I reluctantly decided to recommend the publication of separate volumes. The most sensible way of dividing the subject matter seemed to lie in the separation of simple ionic solutions.
The emphasis in the present volume is placed on ion-solvent effects, since a number of excellent texts cover the more general aspects of electrolyte solutions, based on the classical theories of Debye, Huckel, On sager, and Fuoss. It is interesting to speculate as to when a theory becomes "classical." Perhaps this occurs when it has become well known, well liked, and much adapted. The above-mentioned theories of ionic equilibria and transport certainly fulfill these criteria.
There comes a time when the refinements and modifications can no longer be related to physical significance and can no longer hide the fact that certain fundamental assumptions made in the development of the theory are untenable, especially in the light of information obtained from the application of sophisticated molecular and thermodynamic techniques.
There is now general agreement that the description of ionic solutions in terms of only a simple electrostatic potential fU'nction modified by a bulk dielectric permittivity. can hardly represent the true situation and we are now beginning to see the development and acceptance of the second generation of electrolyte theories. The present state of flux is reflected in most of the following chapters, which might suggest that the timing of the publication of this volume is premature. However, within the framework of this treatise properties of electrolyte solutions play an important part, and I hope that bringing together some of the more recent experimental
v
vi Preface
and theoretical results in one volume will advance the development of useful working models for ion solvation and ionic interactions.
As before I should like to express my gratitude to the contributing authors for their enthusiastic cooperation which is mainly responsible for the short interval between the publication of this and the preceding volume.
Biophysics Division Unilever Research Laboratory Colworth/Welwyn Colworth House, Sharnbrook, Bedford
F. FRANKS
Contents
Contents of Volume 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Xlll
Contents of Volume 2........................................ xv
Contents of Volume 4........................................ XVII
Chapter 1
Thermodynamics of Ion Hydration
H. L. Friedman and C. V. Krishnan
I. The Thermodynamic Theory of Solvation ............. . 1.1. General Remarks ............................... I 1.2. Resolution of Data into Solvation and Excess Properties 2 1.3. Standard States..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.4. Reference Solvents .............................. II 1.5. Pair Interaction Coefficients ...................... 13 1.6. Temperature and Pressure. . . . . . . . . . . . . . . . . . . . . . . . 21 1.7. Single-Ion Properties ............................ 21
2. Molecular Interpretation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.1. Introduction..................................... 24 2.2. The Born Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 2.3. The Debye-Pauling Model ....................... 30 2.4. Hamiltonian Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 2.5. A Chemical Model..... . . . . . . . . . . . . . . . . . . . . . . . . . 47
vii
viii Contents
3. Hydration of Gaseous Ions ........................... 54 3.1. Free Energies, Enthalpies, and Entropies of Hydration 54 3.2. Equations for Entropies of Aqueous Ions ......... 54 3.3. The Chemical Model Interpretation of Ionic Entropies 62 3.4. Transition and Rare Earth Metal Ions at Infinite Dilution 64
4. Other Thermodynamic Properties of Ions at Infinite Dilution in Water............................................. 66 4.1. Partial Molar Volume of Solute X at infinite Dilution,
VX(aq) .......................................... 66 4.2. Partial Molar Heat Capacity of Solute X at Infinite
Dilution, CX(aq).................................. 71 4.3. Partial Molar Isothermal Compressibility of Solute X
at Infinite Dilution, KTx(aq) , and Partial Molar Adiabatic Compressibility of Solute X at Infinite Dilution, KSx(aq) ......................................... 73
4.4. Partial Molal Expansibility of Solute X at Infinite Dilution, Ex (aq) ................................. 76
4.5. Variation of Heat Capacity of Solute X at Infinite Dilution with Temperature, oCx(aq)/oT ............ 78
4.6. Variation of Partial Molal Isothermal Compressibility of Solute X at Infinite Dilution with Temperature, oKTx(aq)/oT ......... ,' . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
4.7. Variation of Partial Molal Expansibility of Solute X at Infinite Dilution with Temperature, (oEx(aq)/oT)p . . . 80
5. Solvent-Isotope Effect in Hydration.................... 81 5.1. Introduction..................................... 81 5.2. Free Energies ................................... 82 5.3. Enthalpies...................................... 85 5.4. Entropies....................................... 100 5.5. Volumes........................................ 103 5.6. Heat Capacities ................................. 105
6. Reference Solvents ................................... 105 6.1. Free Energies in Nonaqueous Solvents ............ 105 6.2. Entropies in Nonaqueous Solvents ................ 105 6.3. Enthalpies in Nonaqueous Solvents........... . . . . . 108 6.4. Heat Capacities in Nonaqueous Solvents...... . . . . . 113
7. Ionic Hydration and Excess Properties ................. 113
Contents ix
Chapter 2
Thermodynamics of Aqueous Mixed Electrolytes
Henry L. Anderson and Robert H. Wood
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
2. Theoretical Framework ............................... 121
2.1. Symmetric, Common-Ion Mixtures................ 121
2.2. Symmetric, Multicomponent Mixtures... . . . . . . . . .. 124
2.3. Nomenclature................................... 126
3. Experimental Techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
4. Experimental Results and Discussion................... 128
4.1. Concentration and Common-Ion Dependence....... 128
4.2. Young's Sign Rule .............................. 139
4.3. Temperature Dependence of JmHE . . . . . . . . . . . . . . . . 140
4.4. Tetraalkylammonium Electrolytes ................. 141
Chapter 3
Hydration Effects and Acid-Base Equilibria
Loren G. Hepler and Earl M. Woolley
1. Ionization of Liquid Water ............................ 145
1.1. Ionization of Water in Aqueous Electrolyte Solutions 158
1.2. Ionization of Water in Aqueous Organic Mixtures.. 158
2. Hydration of H+ and OH- ........................... 160
2.1. Gas-Phase Hydration of H+ and OH-............. 160
2.2. Hydration of H+ and OH- in Aqueous Solution... 161
3. Organic Acids and Bases in Aqueous Solution.......... 163
3.1. Thermodynamics of Ionization Reactions .......... 165
3.2. Substituent Effects on Ionization of Organic Acids. . . 167
3.3. Examples of Hydration Effects on Acid-Base Ionization Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
x Contents
Chapter 4
Ionic Transport in Water and Mixed Aqueous Solvents
Robert L. Kay
I. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
2. Measurement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 174
3. Limiting Ionic Conductances in Binary Solutions. . . . . . .. 178
4. Mechanism of Ionic Conductance. . . . . . . . . . . . . . . . . . . . . . 180 4.1. Stokes' Law.................................... 184 4.2. Solvent Dipole Relaxation Effect ................. 186 4.3. Cosphere Effects ................................ 189 4.4. Temperature Coefficient... . . . . . . . . . . . . . . . . . . . . . . . 192 4.5. Pressure Coefficient..... . . . . . . . . . . . . . . . . . . . . . . . . . 196
5. Limiting Ionic Conductance in Aqueous Solvent Mixtures 204
Chapter 5
Infrared Spectroscopy of Aqueous Electrolyte Solutions
Ronald Ernest Verrall
I. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 211
2. Information on Aqueous Ionic Solutions Obtainable from Infrared Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 212 2.1. General......................................... 212 2.2. The Effects of Ions on the Structure of Water .... 213 2.3. Far Infrared ................................... . 2.4. Fundamental Infrared ........................... 215 2.5. Near Infrared.... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 218
3. Experimental Methods... . . . . . . . . . . . . .. . . . . . . . . . . . . . .. 219 3.1. General ........................................ 219 3.2. Atmospheric Absorptions ........................ 220 3.3. Cells and Cell Path Lengths ..................... 220 3.4. Temperature Variation of Sample. . . . . . . . . . . . . . . .. 222 3.5. Reflection Losses........ . . . . . . . . . . . . . . . . . . . . . . .. 223 3.6. Isotopically Dilute HDO as a Solvent ............ 224
Contents xi
4. Critical Review of Available Infrared Data ....... . . . . .. 225 4.1. Far Infrared .................................... 225 4.2. Fundamental Infrared ........................... 233 4.3. Near Infrared . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 249 4.4. Effect of Water on Infrared Spectra of Inorganic Ions 261
5. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 263
Chapter 6
Raman Spectroscopy of Aqueous Electrolyte Solutions
T. H. Lilley
1. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 265
2. Raman Bands Arising from Solutes . . . . . . . . . . . . . . . . . . .. 267
3. Raman Bands Arising from the Solvent: Liquid Water.. 275 3.1. Intermolecular Region Vibrations ................. 277 3.2. Intramolecular Bands of the Solvent .............. 283
4. Addendum. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 296
Chapter 7
Nuclear Magnetic Relaxation Spectroscopy
H. G. Hertz
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 30 I
2. Nuclear Magnetic Relaxation . . . . . . . . . . . . . . . . . . . . . . . . .. 304 2.1. Principles....................................... 304 2.2. Proton Relaxation Times and Correlation Times of
Water in Paramagnetic Electrolyte Solutions. . . . . .. 313 2.3. Oxygen-17 Relaxation in Aqueous Solutions of Para
magnetic Ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 338 2.4. Proton Relaxation Times and Correlation Times of
Water in Diamagnetic Electrolyte Solutions...... .. 349 2.5. Quadrupolar Relaxation of Water in Diamagnetic
Electrolyte Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 379
xii Contents
2.6. Relaxation Times of Ionic Nuclei Relaxing by Magnetic Dipole-Dipole Interaction . . . . . . . . . . . . . . . . . . . . . . .. 384
2.7. Self-Diffusion Coefficients in Electrolyte Solutions ., 389 2.8. Structural Interpretation of Microdynamic Data.... 395
Chapter 8
Dielectric Properties
Reinhard Pottel
1. Basic Theory ........................................ 401 1.1. Types of Dielectric Polarization and Its Decay .... 401 1.2. Dielectric Relaxation in a Model of Pure Water. .. 404 1.3. Dielectric Relaxdtion in a Model of Aqueous Ionic
Solutions ....................................... 407 1.4. Comparison of the Molecular Rotational Correlation
Times as Derived from Dielectric Relaxation and Proton Magnetic Resonance Relaxation ........... 409
2. Experimental Methods................................ 412
3. Characteristic Quantities Derived from Complex Permittivity Measurements ....................................... , 414
4. Information from the "Static" Permittivity ............. 420
5. Information Obtainable from the Dielectric Relaxation Time with the Help of the Proton Magnetic Relaxation Rate... 423
6. The Influence of Small Cations on the Dielectric Relaxation Time................................................ 426 6.1. Electrostatic Interaction Mechanisms Independent of
the Water Structure.. . . . . . . . .. . . . . . . . . . . . . . . .. 427 6.2. Mech~ni5iils Depending on the Water Structure. . .. 428
7. Summary ........................................... , 431
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 433
Subject Index ............................................... 457
Compound Index. .. ...... . . ... ... . .. ...... .. .... ... .. ..... ... 465
Formula Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 469
Contents of Volume 1: The Physics and Physical Chemistry of Water
Chapter 1. Introduction-Water, the Unique Chemical, by F. Franks
Chapter 2. The Water Molecule, by C. W. Kern and M. Karplus
Chapter 3. Theory of Hydrogen Bonding in Water, by C. N. R. Rao
Chapter 4. The Properties of Ice, by F. Franks
Chapter 5. Raman and Infrared Spectral Investigations of Water Structure, by G. E. Walrafen
Chapter 6. Nuclear Magnetic Resonance Studies on Water and Ice, by Jay A. Glasel
Chapter 7. Liquid Water: Dielectric Properties, by J. B. Hasted
Chapter 8. Liquid Water: Scattering of X-Rays, by A. H. Narten and H. A. Levy
Chapter 9. The Scattering of Neutrons by Liquid Water, by D. I. Page
Chapter 10. Thermodynamic and Transport Properties of Fluid Water, by G. S. Kell
Chapter 11. Application of Statistical Mechanics in the Study of Liquid Water, by A. Ben-Naim
Chapter 12. Liquid Water-Acoustic Properties: Absorption and Relaxation, by Charles M. Davis, Jr., and Jacek Jarzynski
Chapter 13. Water at High Temperatures and Pressures, by Klaus TOdheide
Chapter 14. Structural Models, by Henry S. Frank
xiii
Contents of Volume 2: Water in Crystalline Hydrates; Aqueous Solutions of Simple N onelectrolytes
Chapter 1. The Solvent Properties of Water, by F. Franks
Chapter 2. Water in Stoichiometric Hydrates, by M. Falk and O. Knop
Chapter 3. Clathrate Hydrates, by D. W. Davidson
Chapter 4. Infrared Studies of Hydrogen Bonding in Pure Liquids and Solutions, by W. A. P. Luck
Chapter 5. Thermodynamic Properties, by F. Franks and D. S. Reid
Chapter 6. Phase Behavior of Aqueous Solutions at High Pressures, by G. M. Schneider
Chapter 7. Dielectric Properties, by J. B. Hasted
Chapter 8. Spectroscopic Properties, by M. J. Blandamer and M. F. Fox
Chapter 9. Acoustic Properties, by M. J. Blandamer
Chapter 10. NMR Spectroscopic Studies, by M. D. Zeidler
Chapter 11. Molecular Theories and Models of Water and of Dilute Aqueous Solutions, by A. Ben-Nairn
xv
Contents of Volume 4: Aqueous Solutions of Macromolecules; Water in Disperse Systems
Chapter 1. The Hydrophobic Interaction, by F. Franks
Hydration and Reversible Aggregation Phenomena in Aqueous Solutions of Simple Solutes
Chapter 2. Surfactants, by G. C. Kresheck
Chapter 3. Dyestuffs, by G. H. Giles and D. G. Duff
Chapter 4. Lipids, by H. Hauser
The Role of Solute-Water Interactions in Aqueous Solutions and Gels of Macromolecules
Chapter 5.
Chapter 6.
Chapter 7.
Nucleic Acids, Peptides, and Proteins, by D. Eagland
Polysaccharides, by A. Suggett
Synthetic Polymers, by P. Molyneux
Disperse Systems
Chapter 8. Role of Water in the Stability of Hydrophobic Colloids, by D. Eagland
Chapter 9. Properties of Water in Capillaries and Thin Films, by J. Clifford
Chapter 10. The Aqueous Interface-Foams, Emulsions, by M. C. Phillips
Chapter 11. Clay-Water Systems, by E. Forslind
Chapter 12. Adsorption of Water on Well-Characterized Inorganic Surfaces, by A. C. Zettlemoyer
Chapter 13. Specific Interactions of Water with Biopolymers, by H. Berendsen
xvii