CONTENTS

COVER

TITLE PAGE

PREFACE

1 INTRODUCTION

1.1 THE SIGNIFICANCE AND PHENOMENOLOGY OF IONS IN SOLUTION

1.2 LIST OF SYMBOLS AND ABBREVIATIONS

2 IONS AND THEIR PROPERTIES

2.1 IONS AS ISOLATED PARTICLES

2.2 SIZES OF IONS

2.3 IONS IN SOLUTION

REFERENCES

3 SOLVENTS FOR IONS

3.1 SOLVENT PROPERTIES THAT SUIT ION DISSOLUTION

3.2 PHYSICAL PROPERTIES OF SOLVENTS

3.3 CHEMICAL PROPERTIES OF SOLVENTS

3.4 PROPERTIES OF BINARY AQUEOUS COSOLVENT MIXTURES

REFERENCES

4 ION SOLVATION IN NEAT SOLVENTS

4.1 THE SOLVATION PROCESS

4.2 THERMODYNAMICS OF ION HYDRATION

4.3 TRANSFER THERMODYNAMICS INTO NONAQUEOUS SOLVENTS

4.4 THE STRUCTURE OF SOLVATED IONS

4.5 THE DYNAMICS OF SOLVATED IONS

4.6 ACID/BASE PROPERTIES OF IONS IN SOLUTION

REFERENCES

5 MUTUAL EFFECTS OF IONS AND SOLVENTS

5.1 ION EFFECTS ON THE STRUCTURE OF SOLVENTS

5.2 ION EFFECTS ON THE DYNAMICS OF THE SOLVENT

5.3 SOLVENT EFFECTS ON THE PROPERTIES OF IONS IN SOLUTION

REFERENCES

6 IONS IN MIXED SOLVENTS

6.1 ION TRANSFER INTO SOLVENT MIXTURES

6.2 PROPERTIES OF IONS IN SOLVENT MIXTURES

6.3 PREFERENTIAL SOLVATION OF IONS

REFERENCES

7 INTERACTIONS OF IONS WITH OTHER SOLUTES

7.1 ION–ION INTERACTIONS

7.2 ION ASSOCIATION

7.3 SALTING-IN AND SALTING-OUT

REFERENCES

8 APPLICATIONS OF SOLUTIONS OF IONS

8.1 APPLICATIONS IN ELECTROCHEMISTRY

8.2 APPLICATIONS IN HYDROMETALLURGY

8.3 APPLICATIONS IN SEPARATION CHEMISTRY

8.4 APPLICATIONS TO CHEMICAL REACTION RATES

8.5 SOLVATED IONS IN BIOPHYSICAL CHEMISTRY

REFERENCES

AUTHOR INDEX

SUBJECT INDEX

END USER LICENSE AGREEMENT

List of Tables

Chapter 02

Table 2.1 The names, Formulas, charge numbers, zI, and molar masses, MI, of common ions

Table 2.2 Ionization potentials leading to cations, electron affinities leading to anions, and proton affinities of anions, all converted to enthalpies

Table 2.3 The standard molar Gibbs energy and enthalpy of formation [1] and the standard molar entropy [13] and constant-pressure molar heat capacity [14] of isolated ions at the standard temperature T° = 298.15 K and pressure P° = 0.1 MPa

Table 2.4 The magnetic susceptibility, χIm[6], the molar refraction at the sodium D line, RD (normalized to the value for Na⁺) [6], and the softness parameter [6], modified by ±0.3 units, σ±0.3, of isolated ions

Table 2.5 The standard molar enthalpies of stepwise clustering of water molecules around ions in the ideal gas phase, −Δn−1,nH°/kJ·mol⁻¹, at T° = 298.15 K

Table 2.6 The standard molar Gibbs energies of stepwise clustering of water molecules around anions in the ideal gas phase, −Δn−1,nG°/kJ·mol⁻¹, at T° = 293.15 Ka

Table 2.7 The standard molar Gibbs energies of stepwise clustering of acetonitrile, methanol, and ammonia molecules around ions in the ideal gas phase, −Δn−1,nG°/kJ·mol⁻¹, at T° = 298.15 Ka

Table 2.8 Ionic Radii, rI[6], Thermochemical Ionic Radii, rIth[47], Ionic Volumes, vI[48], and Intrinsic Ionic Molar Volumes, VI intrM (see the text)

Table 2.9 Standard Molar Heat Capacities [21] and Entropies [13] of Aqueous Ions and their Standard Molar Enthalpies and Gibbs Energies of formation (see the text)

Table 2.10 Ionic Standard Partial Molar Volumes [6, 78], the Electrostriction Volumes Obtained from a Shell-by-shell Electrostatic Calculation [80], and the Ionic Standard Partial Molar Expansibilities and Compressibilities, all at 25°C

Table 2.11 Ionic Transport and Dynamic Properties in Aqueous Solutions: Limiting Molar Conductivities, λI∞ [90], Limiting Diffusion Coefficients, DI∞ [91], Viscosity B-coefficients, BηI [92], and NMR BnmrI Values [93] at 25°C

Table 2.12 Ionic static permittivity decrements, δ0I/dm³·mol⁻¹[130] and surface tension Increments, dσ/dci/mN·m⁻¹·mol⁻¹·dm3·year, in aqueous solutions at 20–30°C

Chapter 03

Table 3.1 Solvents, their Common Abbreviations, Formulas, and CAS Registry Numbers

Table 3.2 The Freezing/Melting Points, tm, Normal Boiling Points, tb, of Solvents, and their Molar Masses

Table 3.3 Volumetric Properties of Solvents at 25°C: Densities, ρ, Molar Volumes, V, Isobaric Expansibilities, αP, Isothermal Compressibilities, κT, and Intrinsic Volumes, VX

Table 3.4 Some Thermodynamic Properties of Solvents for Electrolytes: The Vapor Pressure, p, the Molar Enthalpy of Vaporization, ΔHV, the Molar Constant Pressure Heat Capacity, CP, the Surface Tension σ, and the Hildebrand Solubility Parameter, at 25°C

Table 3.5 The Relative Permittivities of Solvents at 25°C and Ambient Pressure, ε, and their Temperature and Pressure Derivatives (∂ε/∂T)P and (∂ε/∂P)T, their Refractive Indexes, nD, their Polarizabilities, α, and their Dipole Moments, μ

Table 3.6 Some Properties of Solvents at 25°C: their Surface Potential Δχ/V [18], their Electric Field Dependence of the Permittivity, β/GV⁻²·m²[4], their Limiting Slope of the Electrolyte Molar Volumes, SV/cm³·dm3/2·mol−1/2[4], their Molar Diamagnetic Susceptibility, χ/10⁻⁶ cm³·mol⁻¹[3, 20], and their Mean Molar Electrostriction, ΔelsVS/cm³·mol⁻¹[21]

Table 3.7 Transport Properties of Solvents at 25°C: their Specific Conductance κ[1], their Self-diffusion Coefficient D[27], their Dynamic Viscosity η, and its Temperature Derivative (∂η/∂T)P

Table 3.8 Measures of the Structuredness of Solvents At 25°C: Stiffness = U/V− Pint, order = ΔΔSV(T, P°)/R and ΔCP/V(l) [27], and the Kirkwood Dipole Orientation Correlation Parameter g[29]

Table 3.9 Indexes of Solvent Solvation Ability: Polarity ETN and π*, Electron Pair Donicity, DNand β, Hydrogen Bond Donicity, ANand α, and the Softness Parameter, μ

Table 3.10 The Standard Molar Gibbs Energy for Protonation of Gaseous Solvent Molecules Relative to HCl(g), ΔΔGA, their Proton Affinities (enthalpies) Relative to Ammonia, ΔPA, and Differences of the Logarithmic Equilibrium Constants of Solvents in Dilute Solutions in Water for Protonation, ΔpKa, and Deprotonation ΔpKb, Relative to the Autoprotolysis Constant of Water, and the Logarithmic Constants pKSfor Autoprotolysis of the Neat Solvents

Table 3.11 Mole Fraction Solubilities of Solvents in Water, xS, and of Water in Solvents, xW, and the Logarithm of the Octanol/Water Partition Coefficients of the Solvents, images, at 25°C

Table 3.12 Spectroscopic Windows of Solvents

Table 3.13 The Coefficients of Equation 3.44 for the Excess Molar Gibbs Energy (YE = GE with the yi ≡ gi) and Enthalpies (YE = HE with the yi  ≡ hi) in J·mol⁻¹ of Aqueous Mixtures with Cosolvents at 25°C From [56] Unless Otherwise Noted

Table 3.14 The Coefficients of Equation 3.45 for the Excess Molar Heat Capacity (YE = CPE with the yi ≡ ci) in J·K⁻¹·mol⁻¹ and Volumes (YE = VE with the yi ≡ vi) in cm³·mol⁻¹ of Aqueous Mixtures with Cosolvents at 25°C from [56] Unless Otherwise Noted

Table 3.15 The Coefficients of Equation 3.49 for the Surface Tension and of Equation 3.44 for the Permittivity and the Viscosity at 25°C Adapted from [56]

Table 3.16 The internal Pressure Increment, ΔPint/MPa, in a 1 mol·dm⁻³ Solution of the Cosolvent in Water, the Maximal Partial Molar Excess Volume of Water, VWEmax/cm³·mol⁻¹, in Water-rich Mixtures, the Incremental Maximal Partial Molar Excess Heat Capacity of Water, ΔCPWEmax/J·K⁻¹·mol⁻¹, in Water-rich Mixtures, and the Volume Corrected Preferential Solvation Parameters of Water Near Water, δ′xWW, and of Cosolvent Near Water, δ′xWS(for the symbols see the text)

Table 3.17 Coefficients of Equation 33.43 for the Polarity increments ΔY = ΔET(30) with yi ≡ ei in Kcal·mol⁻¹(1 cal = 4.148 J) and the Polarity/polarizability Increments ΔY = Δπ* with yi ≡ pi

Table 3.18 Coefficients of Equation 33.43 for the Electron Pair Donicity Increments ΔY = Δβ with the yi ≡ bi and the Hydrogen Bond Donicity Increments ΔY = Δα with yi ≡ ai

Table 3.19 The Equilibrium Quotients for the acid–base Interactions according to Equations 3.52–3.55, adapted from [56]

Chapter 04

Table 4.1 Standard Molar Enthalpies of Hydration [13] of Ions, and the Corresponding Entropies [13] and Gibbs Energies of Hydration at 25°C

Table 4.2 Ionic Standard Molar Gibbs Energies of Transfer from Water into Nonaqueous Solvents, ΔG∞(I±, W→S)/kJ·mol⁻¹, at 25°C a

Table 4.3 Ionic Standard Partial Molar Enthalpies of Transfer from Water into Nonaqueous Solvents, ΔtH∞(I±, W→S)/kJ·mol⁻¹, at 25°C a

Table 4.4 Ionic Standard Partial Molar Entropies of Transfer From Water into Nonaqueous Solvents, ΔtS∞(I±, W→S)/J·K⁻¹·mol⁻¹, at 25°Ca

Table 4.5 Ionic standard partial molar heat capacities in non-aqueous solvents, CP∞(I±, S)/J·K⁻¹·mol⁻¹, at 25°Ca

Table 4.6 Ionic Standard Partial Molar Volumes in Nonaqueous Solvents, V∞(I±, S)/cm³·mol⁻¹, at 25°Ca

Table 4.7 Ranges of Hydration Numbers of Ions Obtained x-ray and Neutron Diffraction [53]

Table 4.8 Average Hydration Numbers of Ions at infinite Dilution Obtained by QM-MM Computer Simulations

Table 4.9 Hydration Numbers of Ions At infinite Dilution Obtained from Electrostriction, Equation 4.36 [84], Compressibility, Equation 4.37 [52], Entropy of Hydration, Equation 4.41 [52], and Empirically, hIWemp∞ = 0.360│zI│/(rI/nm)

Table 4.10 Ionic Solvation Numbers at 25°C in Nonaqueous Solvents from Electrostriction (roman font) and Entropy of Immobilization (italic font)

Table 4.11 Lewis Acidity and Basicity indexes of ions from the Standard Molar Gibbs Energies of Transfer and from indicator Measurements in Poorly Solvating Solvents

Chapter 05

Table 5.1 Relative Self Diffusion (1 – DW(E)/DW) and Ionic B-coefficients of Viscosity and NMR Relaxation At 25°C

Table 5.2 Water Structural Entropy ΔstrSI/JK⁻¹ mol⁻¹ and Structural Heat Capacity ΔstrCPI/JK⁻¹ mol⁻¹ Effects [51] and the Changes of the Hydrogen Bond Geometrical Factors, ΔGHB(I), of Representative Ions [53]

Table 5.3 The internal Pressure Differences ΔPint At 25°C of Aqueous 1 M (or 1 m) Electrolytes (values in parentheses corrected for valency, see the text), their Structural Temperature Differences ΔT = Tstr–T, and their Osmotic Coefficient Differences φ(0.4 m)–φ(0.2 m)

Table 5.4 Water Exchange Rates From the Vicinity of Ions: Rate Constants, log(kr/s⁻¹) for Exchange from the First Hydration Shell, and the Relative Mean Residence Times (RMRT in %) of Second Hydration Shell Moleculesa

Table 5.5 The Molecular Reorientation Time Constants in the Presence of Ions Relative to the Time Constants of the Pure Solvents, τS(I)or/τSor, in Various Solvents for the Specified Coordination Numbers hI(S), Obtained by NMR

Table 5.6 Limiting Molar Ionic Conductivities, 𝝀I∞/S∙cm²∙mol⁻¹, in Nonaqueous Solvents at 25°C [150, 151]

Table 5.7 The Ionic Viscosity B-coefficients in Nonaqueous Solvents at 25°C

Table 5.8 The Relative Dielectric Decrement –δ/εs(cE=0)/dm³∙mol–1 of Salts in Nonaqueous Solvents and Water at 25°C a,b

Table 5.9 The Molar Surface Tension Increments, Δε/cE, of Salts in Nonaqueous Solvents and Water at 25°C

Table 5.10 Rotational orientation Correlation Times τr/ps of Several Polyatomic Ions in Various Solvents

Chapter 06

Table 6.1 Standard Molar Gibbs Energy of Transfer of Ions from Water into Equimolar Aqueous Mixtures with Cosolvents, ΔtG∞(I±, W→0.5W + 0.5S)/kJ·mol⁻¹from Refs. 10 and 11

Table 6.2 Standard Molar Enthalpies ΔtH∞(I±, W→0.5W + 0.5S)/kJ·mol⁻¹(roman font) and Entropies ΔtS∞(I±, W→0.5W + 0.5S)/J·K⁻¹·mol⁻¹(italicsfont) of Transfer of Ions from Water into Equimolar Aqueous Mixtures with Cosolventsa

Table 6.3 Pair interaction enthalpic parameters, hE,S(R)/J·kg·mol⁻², and heat capacity parameters cE, S(R)/J·mol⁻¹·kg·mol⁻²for electrolytes in mixtures of a reference solvent R (W or as specified) with cosolvents at 25°C

Table 6.4 Coefficients for Equation 6.4for Aqueous Mixtures with Cosolvents at 25°C from Ref. 35, with the Presumed Standard Electrolyte E1 Noted

Table 6.5 The Iso-solvation Points xA(is) Equaling the Local Mole Fractions xLB for Sodium Ions in Binary Mixtures of Solvents A and Ba

Chapter 07

Table 7.1 The Mean Ionic Activity Coefficients of Representative Aqueous Electrolytes at 25°C at Selected Molalities [2]

Table 7.2 Hydration Numbers h(c) of Electrolytes Obtained from Isothermal Compressibilities at 25°C [21] Compared with hcp Values Obtained From Colligative Properties at Several Temperatures [16], Independent of the Concentration

Table 7.3 The BET Parameters r and ΔH and K(if ≠ 1) for Highly Concentrated Aqueous Salts at 25°C [19]

Table 7.4 Thermodynamic Functions of Ion Pairing of Some Electrolytes in Several Solvents at 25°Ca

Table 7.5 Volume Change on Ion Pairing, ΔipV, and the Number of Solvent Molecules Released from the Ions on Pairing, Obtained from the Volume, Δiph(V), and Entropy, Δiph(S), Changes at 25°C [19, 29, 40, 41]

Table 7.6 Empirical Setschenow Constants and the Ionic Electrostriction Parameter

Chapter 08

Table 8.1 Comparison of Features of Widely Used Batteries

Table 8.2 The Coefficients of the Expression δSW = axS + bxS² for the Difference Between the Reference pH of (0.05 mol (kg solution)–1KHPh buffer) at 25°C in Several Aqueous Solvent Mixtures S from that in Water (4.005), According to Data in [15]

Table 8.3 Standard Electrode Potentials, E°/V, vs. the SHE at 25°C According to Various Extra-thermodynamic Assumptions

Table 8.4 Thermodynamics of Transfer (in KJ mol–1) from Pure Water into Aqueous Acetonitrile Pertinent to the Dissolution of Copper and Silver [17, 35]

Table 8.5 The Standard Molar Gibbs Energy for Transfer, Δ*G∞(I)/kJ mol–1, of Univalent Ions Between Mutually Saturated Water and o-nitrophenyloctyl Ether and Water and 1,2-dichloroethane at 25°C, Obtained from Exchange Equilibria [49]

Table 8.6 Relative Rates log(kin S/kin MeOH) of the Nucleophilic Reactions (8.22) and (8.23) at 25°C [71] Compared with the Normalized Polarity index images

Table 8.7 Rate Constants, 10–7kexch/M–1 s–1, for the Electron Exchange Reactions of the Redox Couples Fe(Cp)₂+/0[72] and Cr(Ph-Ph)₂+/0[73] in Various Solvents and their Values of the Function nD–2 – ε–1

Table 8.8 Rate Constants for Solvent Exchange, log(kexch/s⁻¹) at 25°C, at Solvated di- and Trivalent Metal Cations, Water From Table 5.4, Nonaqueous Solvents a

Table 8.9 Equilibrium Quotients, logKexch, for Exchange Reaction ((8.24) for PTCs: Dc₃MeN⁺Br–in Toluene [80] and Ph₄As⁺Br⁻in Chloroform [81] with Aqueous Anions X⁻

Table 8.10 Rate Constants, log(kr/s–1), for PTC Reactions A, B, C, D, and E Described in the Text in Solvents Arranged According to their Relative Pemittivities, with their Anion Solvating Abilities, the Acceptor Number AN, Also Shown

Table 8.11 Lyotropic Numbers, Nlyo, Applicable to Colloidal Systems [89, 90]

Table 8.12 Anion Parameters that Might be Relevant to their ordering in the Hofmeister Series

Table 8.13 Cation Parameters that Might be Relevant to their ordering in the Hofmeister Series

List of Illustrations

Chapter 02

Figure 2.1 Schematic representation of the stepwise molar enthalpy −Δn−1,nH° of the gas phase clustering of a solvent around an ion and a solvent molecule. The horizontal asymptote is the molar enthalpy of vaporization of the solvent and the area between the curves is the standard molar solvation enthalpy of the ion. (The circles are the experimental data for Li⁺ in water.)

Figure 2.2 The electric field, log(E/V·m⁻¹) (circles and dashed line); the relative permittivity, εr (triangles and dotted lines); and the electrostriction, ΔVI els/cm³·mol⁻¹ (squares and full lines) near aqueous fluoride anions at 25°C (filled symbols) and 100°C (empty symbols), as functions of the distance from the center of the ion.

Figure 2.3 Surface potential increment of aqueous 1:1 electrolyte solutions at 1 M over that of pure water, ΔΔχ. Left-hand panel: plotted against their molar surface tension increments, kE; right-hand panel: plotted against the difference between the cation and anion molar surface tension increments, k₊−k₋. Squares are for acids HX, circles are for NaX, upright triangles are for KX, and downward triangles are for NH₄X, with X being the anion.

Chapter 04

Figure 4.1 The relative permittivity of a solvent having a bulk permittivity ε(0), a high-field value of the permittivity of n² (the square of its refractive index), and b coefficient of the field dependence of the permittivity (Eq. 3.16) as indicated, as a function of the distance r/nm from a point charge producing the electric field.

Figure 4.2 Coordination numbers obtained from the pair correlation function g(r): the dashed curve represents 4πρr², the continuous thick curve is 4πρg(r)r². The cross-hatched area, symmetric with respect to rmax of the first peak, and the area with vertical lines up to rmin of the first trough are two versions of the coordination number of a solvent around an ion.

Chapter 06

Figure 6.1 Representative partial molar volumes of electrolytes in mixed aqueous DMSO solvents: NaBr (●), KBr (▲), Me₄NBr (▼) with 100 cm³·mol⁻¹ deducted, and Bu₄NBr (♦) with 250 cm³·mol⁻¹ deducted for the clarity of presentation.

Figure 6.2 Limiting conductivities ΛE2∞ of electrolytes in aqueous ethanol mixtures at 25°C adjusted to the value for E1 = KCl according to Equation 6.3. KCl (▪), LiCl (□), LiBr (●), LiNO₃ (o), NaCl (▲), NaNO₃ (Δ), KBr (▼), KClO₄ (▽), and also KNO₃, CsCl, Me₄NBr, Et₄NBr, Pr₄NBr, Bu₄NBr, Bu₄NI (►, ◄, ◊, ⊲, and ⊳).

Figure 6.3 Local mole fractions of water around Na⁺ ions in aqueous mixtures with formamide (●), N-methlformamide (▼), and N,N-dimethylformamide (▲), obtained from NMR relaxation rates [56].

Chapter 07

Figure 7.1 Molal scale mean ionic activity coefficients of aqueous LiCl(⦁), LiBr (▴), LiI (▾), NaCl (♦), and CsCl (▪) at 25°C (Data from Ref. 2).

Figure 7.2 BET plots for ≥3 mol∙kg⁻¹ aqueous cobalt bromide at 25°C: - - o - - Equation 7.18 yielding a physically inacceptable negative ordinate intercept, ─⦁─ Equation 7.19 with K = 0.86 (From Ref. 19with permission from the publisher, Springer).

Figure 7.3 The hydration numbers h(c) of aqueous salts at 25°C obtained from isothermal compressibility data for LiCl (-o-) and NaOH (-▫-). At the right-hand side are shown the BET parameters r (number of water-binding sites per formula unit of the salt) of these salts (large filled symbols)

Figure 7.4 The Eigen–Tamm scheme for stepwise formation from free solvated cations Xx+ and solvated anions Yy− of 2SIP ion pairs, then SIP ion pairs, and finally CIP ion pairs, with elimination of solvent molecules from the solvation shells of the ions

Figure 7.5 The static permittivities εs of aqueous CsF(⦁), KF(▴), and KOH(▾) at 25°C as functions of their molar concentration c and their fits according to Equation 7.28 (────)

Figure 7.6 Predicted salting coefficients of various solutes by aqueous sodium chloride according to Equation 7.42 (──) plotted against the experimental values [67] (⦁) and the differences (images) (From Ref. 65 by permission from the publisher, Elsevier).

Guide

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IONS IN SOLUTION AND THEIR SOLVATION

Yizhak Marcus

Hebrew University of Jerusalem

Copyright © 2015 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey
Published simultaneously in Canada

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at http://www.wiley.com/go/permissions.

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Library of Congress Cataloging-in-Publication Data:

Marcus, Y.
  Ions in solution and their solvation / Yizhak Marcus.
    pages  cm
  Includes indexes.

  ISBN 978-1-118-88914-5 (cloth)
1. Ionic solutions.  2. Ions.  3. Solution (Chemistry)  4. Solvation.  I. Title.
  QD561 .M3365
  541′.372–dc23
    2015020563

Cover credits: Art courtesy of the author & Background Image: Roman Okopny/iStockphoto

PREFACE

Thirty years ago, my book Ion Solvation was published, which became very popular and has been since then extensively cited, in particular for the numerical data concerning the properties of ions. However, much has happened during these years regarding experimental and computer simulation results pertinent to this subject as well as regarding physicochemical insights of the interactions that occur between ions and their surrounding solvents and other solutes too. It is therefore high time for an updated and revised edition of the early book to be available to scientists and engineers who deal with ions in solution. It is expected that the present book fulfills its mission to provide the needed up-to-date information.

It is appropriate to quote here some passages from the preface of my earlier book. “My main purpose … on the one hand is to look back on what has been accomplished in a given field, organize it in an orderly fashion, and present it in a comprehensible and unified manner. On the other hand, I use this opportunity to locate gaps in our knowledge, and either fill these with new research while the book is being written, or to do this to the best of my ability in the course of time.” The latter purposes I still pursue in spite of a rather advanced age.

A further quotation from the preface of my earlier book is as true at the present time as, if not even more so than, at the time my earlier book was written. “University research nowadays … is not conducive to the carrying out of extensive and systematic sets of measurements of high accuracy on the properties of systems. Both from the stand point of student interest and from that of the necessary financial support, work on systems that are not of immediate practical importance … is not encouraged.” Still, impressive amounts of work of high quality are produced in universities too, and where relevant have found their way into the present book.

Numerical tables were an essential part of my earlier book on ion solvation and are also necessarily so in the present book on ions in solution and their solvation. These are interspersed in the places in the text where the quantities are being discussed, rather than being relegated to appendices, although the tables may disrupt the smooth flow of the text. Their provision, it is hoped, should make the present book as useful as a source book of data as was its predecessor. However, it must be stressed that there are some newer and corrected numerical data, for example, the CODATA thermochemical compilations or data examined by the European Commission on Atomic Energy that could not find their way into the preset book. Readers are also encouraged to look up recent volumes of the Journal of Physical and Chemical Reference Data for the latest critically examined values.

The significance of ions in solution and of their solvation is dealt with in the introductory chapter, which also describes the organization of the material in the chapters, as is also reflected in the list of contents.

It remains for me to express my appreciation of my university, of which I am now an emeritus professor for 15 years, which has provided me with the facilities required for doing nonlaboratory research and for writing reviews and books. The academic environment and discussions with colleagues here as well as at conferences that I attend, being supported by my university, are invaluable for doing what I have undertaken in this book.

Jerusalem, August 2014

1
INTRODUCTION

1.1 THE SIGNIFICANCE AND PHENOMENOLOGY OF IONS IN SOLUTION

Lesen Sie weiter in der vollständigen Ausgabe!

Lesen Sie weiter in der vollständigen Ausgabe!

Lesen Sie weiter in der vollständigen Ausgabe!

Lesen Sie weiter in der vollständigen Ausgabe!

Lesen Sie weiter in der vollständigen Ausgabe!

Lesen Sie weiter in der vollständigen Ausgabe!

Lesen Sie weiter in der vollständigen Ausgabe!

Lesen Sie weiter in der vollständigen Ausgabe!

Lesen Sie weiter in der vollständigen Ausgabe!

Lesen Sie weiter in der vollständigen Ausgabe!