Ions in Solution and their Solvation

Yizhak Marcus, PhD, is Professor Emeritus at the Hebrew University in Jerusalem. He was a researcher at the Soreq Nuclear Research Center, from where he was appointed in 1965 as Professor of Inorganic and Analytical Chemistry at the Hebrew University until his retirement in 1999. His main interest is the chemistry of liquids and solutions: aqueous, non-aqueous, and mixed solvents, solutions of electrolytes and non-electrolytes. He has published eight books and over 300 papers in refereed journals as well as roughly 30 contributions in multi-author books.

• Preface ix1 Introduction 11.1 The Significance and Phenomenology of Ions in Solution 11.2 List of Symbols and Abbreviations 52 Ions and Their Properties 102.1 Ions as Isolated Particles 102.1.1 Bare Ions 112.1.2 Ions in Clusters 262.2 Sizes of Ions 302.3 Ions in Solution 352.3.1 Thermodynamics of Ions in Aqueous Solutions 382.3.1.1 Heat Capacities of Aqueous Ions 382.3.1.2 Entropies of Aqueous Ions 392.3.1.3 Enthalpies of Formation of Aqueous Ions 432.3.1.4 Gibbs Energies of Formation of Aqueous Ions 442.3.1.5 Ionic Molar Volumes in Aqueous Solutions 442.3.2 Other Properties of Aqueous Ions 492.3.2.1 Ionic Conductivities in Aqueous Solutions 492.3.2.2 Ionic Self]Diffusion in Aqueous Solutions 502.3.2.3 Ionic Effects on the Viscosity 512.3.2.4 Ionic Effects on the Relaxation of NMR Signals 552.3.2.5 Ionic Dielectric Decrements 552.3.2.6 Ionic Effects on the Surface Tension 56References 583 Solvents for Ions 633.1 Solvent Properties that Suit Ion Dissolution 633.2 Physical Properties of Solvents 643.2.1 Volumetric Properties 643.2.2 Thermodynamic Properties 693.2.3 Electrical, Optical, and Magnetic Properties 703.2.4 Transport Properties 753.3 Chemical Properties of Solvents 773.3.1 Structuredness 773.3.2 Solvent Properties Related to their Ion Solvating Ability 803.3.2.1 Polarity 813.3.2.2 Electron Pair Donicity and Ability to Accept a Hydrogen Bond 833.3.2.3 Hydrogen Bond Donicity and Electron Pair Acceptance 843.3.2.4 Softness 853.3.3 Solvents as Acids and Bases 863.3.4 Miscibility with and Solubility in Water 883.3.5 Spectroscopic and Electrochemical Windows 903.4 Properties of Binary Aqueous Cosolvent Mixtures 903.4.1 Physical Properties of Binary Aqueous Mixtures with Cosolvents 903.4.1.1 Thermodynamic Properties of the Mixtures 923.4.1.2 Some Electrical, Optical, and Transport Properties of the Mixtures 983.4.2 Chemical Properties of Binary Aqueous Mixtures with Cosolvents 983.4.2.1 Structuredness 983.4.2.2 Properties Related to the Ion Solvating Ability 101References 1044 Ion Solvation in Neat Solvents 1074.1 The Solvation Process 1074.2 Thermodynamics of Ion Hydration 1094.2.1 Gibbs Energies of Ion Hydration 1094.2.1.1 Accommodation of the Ion in a Cavity 1104.2.1.2 Electrostatic Interactions 1104.2.2 Entropies of Ion Hydration 1164.2.3 Enthalpies of Ion Hydration 1164.3 Transfer Thermodynamics into Nonaqueous Solvents 1174.3.1 Selection of an Extra]Thermodynamic Assumption 1174.3.2 Thermodynamics of Transfer of Ions into Nonaqueous Solvents 1184.3.2.1 Gibbs Energies of Transfer 1184.3.2.2 Enthalpies of Transfer 1264.3.2.3 Entropies of Transfer 1304.3.2.4 Ionic Heat Capacities in Nonaqueous Solvents 1304.3.2.5 Ionic Volumes in Nonaqueous Solvents 1334.4 The Structure of Solvated Ions 1354.4.1 Hydration Numbers from Diffraction Studies 1384.4.2 Hydration Numbers from Computer Simulations 1394.4.3 Hydration Numbers from Bulk Properties 1414.4.4 Solvation Numbers in Nonaqueous Solvents 1474.5 The Dynamics of Solvated Ions 1474.5.1 The Mobility of Ions in Solution 1474.5.2 Rate of Solvent Exchange Near Ions 1504.6 Acid/Base Properties of Ions in Solution 151References 1535 Mutual Effects of Ions and Solvents 1565.1 Ion Effects on the Structure of Solvents 1565.1.1 Experimental Studies of Ion Effects on the Structure of Solvents 1565.1.1.1 Self]diffusion of Water Molecules 1565.1.1.2 Viscosity B]Coefficients 1575.1.1.3 NMR Signal Relaxation 1595.1.1.4 Dielectric Relaxation 1595.1.1.5 Vibrational Spectroscopy 1605.1.1.6 X]Ray Absorption and Scattering 1625.1.1.7 Structural Entropy 1635.1.1.8 Transfer from Light to Heavy Water 1655.1.1.9 Internal Pressure 1685.1.1.10 Some Other Experimental Results 1705.1.2 Computer Simulations of Ion Effects on the Structure of Solvents 1705.2 Ion Effects on the Dynamics of the Solvent 1715.2.1 Mean Residence Times of Solvent Molecules Near Ions 1715.2.2 Experimental Studies of Ion Effects on the Solvent Orientation Dynamics 1745.2.2.1 Ultrafast Infrared Spectroscopy 1745.2.2.2 High]frequency Dielectric Relaxation Spectroscopy 1765.2.2.3 NMR Relaxation Times 1785.2.3 Computer Simulations of Reorientation Times 1805.3 Solvent Effects on the Properties of Ions in Solution 1805.3.1 Bulk Properties 1805.3.2 Molecular Properties 186References 1876 Ions in Mixed Solvents 1936.1 Ion Transfer into Solvent Mixtures 1946.2 Properties of Ions in Solvent Mixtures 1996.2.1 Thermodynamic Properties of Ions in Mixed Solvents 1996.2.2 Transport Properties of Ions in Mixed Solvents 2036.3 Preferential Solvation of Ions 2056.3.1 Spectroscopic Studies 2076.3.2 Results from Thermodynamic Data 2106.3.2.1 The QLQC Method 2116.3.2.2 The IKBI Method 2136.3.2.3 Treatments Based on Stepwise Solvent Replacements 215References 2167 Interactions of Ions with Other Solutes 2197.1 Ion–Ion Interactions 2197.1.1 Activity Coefficients of Electrolyte Solutions 2207.1.2 Ion Hydration Related to Ion–Ion Interactions 2237.2 Ion Association 2277.2.1 Electrostatic Theory of Ion Association 2307.2.1.1 Activity Coefficients of Neutral Ion Pairs 2317.2.2 Methods for Studying Ion Association 2327.2.3 Thermodynamic Quantities Pertaining to Ion Association 2347.2.4 Aggregation of Ions in Solutions 2377.3 Salting]in and Salting]out 2397.3.1 Empirical Setschenow Constant Data 2407.3.2 Interpretation of Salting Phenomena 240References 2448 Applications of Solutions of Ions 2478.1 Applications in Electrochemistry 2488.1.1 Batteries and Supercapacitors 2488.1.2 Solvent]Independent pH and Electrode Potential Scales 2518.2 Applications in Hydrometallurgy 2578.3 Applications in Separation Chemistry 2598.3.1 Solvent Extraction of Alkali Metal Cations 2598.3.2 Solvation of Ionizable Drug Molecules 2628.4 Applications to Chemical Reaction Rates 2648.5 Solvated Ions in Biophysical Chemistry 2698.5.1 The Hofmeister Series 2708.5.1.1 The Anion Hofmeister Series 2708.5.1.2 The Cation Hofmeister Series 2718.5.1.3 Interpretation of the Hofmeister series 2728.5.2 Water Structure Effects of Ions 2758.5.3 Some Aspects of Protein Hydration 277References 279Author Index 000Subject Index 000