Yizhak Marcus

Ions in Solution and Their Solvation

• Gebundenes Buch

Produktbeschreibung

The book starts with an exposition of the relevant properties of ions and continues with a description of their solvation in the gas phase. The book contains a large amount of factual information in the form of extensive tables of critically examined data and illustrations of the points made throughout. It covers:

the relevant properties of prospective liquid solvents for the ions
the process of the transfer of ions from the gas phase into a liquid where they are solvated
various aspects of the solutions of the ions, such as structural and transport ones and the effects of the ions on the solvent dynamics and structure
what happens in cases where the solvent is a mixture selective solvation takes place
applications of the concepts expounded previously in fields such as electrochemistry, hydrometallurgy, separation chemistry, biophysics, and synthetic methods

Produktdetails

• Verlag: Wiley & Sons
• 1. Auflage
• Seitenzahl: 312
• Erscheinungstermin: 3. August 2015
• Englisch
• Abmessung: 240mm x 161mm x 21mm
• Gewicht: 633g
• ISBN-13: 9781118889145
• ISBN-10: 1118889142
• Artikelnr.: 42204616

Autorenporträt

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.

Inhaltsangabe

Preface ix 1 Introduction 1 1.1 The Significance and Phenomenology of Ions
in Solution 1 1.2 List of Symbols and Abbreviations 5 2 Ions and Their
Properties 10 2.1 Ions as Isolated Particles 10 2.1.1 Bare Ions 11 2.1.2
Ions in Clusters 26 2.2 Sizes of Ions 30 2.3 Ions in Solution 35 2.3.1
Thermodynamics of Ions in Aqueous Solutions 38 2.3.1.1 Heat Capacities of
Aqueous Ions 38 2.3.1.2 Entropies of Aqueous Ions 39 2.3.1.3 Enthalpies of
Formation of Aqueous Ions 43 2.3.1.4 Gibbs Energies of Formation of Aqueous
Ions 44 2.3.1.5 Ionic Molar Volumes in Aqueous Solutions 44 2.3.2 Other
Properties of Aqueous Ions 49 2.3.2.1 Ionic Conductivities in Aqueous
Solutions 49 2.3.2.2 Ionic Self?]Diffusion in Aqueous Solutions 50 2.3.2.3
Ionic Effects on the Viscosity 51 2.3.2.4 Ionic Effects on the Relaxation
of NMR Signals 55 2.3.2.5 Ionic Dielectric Decrements 55 2.3.2.6 Ionic
Effects on the Surface Tension 56 References 58 3 Solvents for Ions 63 3.1
Solvent Properties that Suit Ion Dissolution 63 3.2 Physical Properties of
Solvents 64 3.2.1 Volumetric Properties 64 3.2.2 Thermodynamic Properties
69 3.2.3 Electrical, Optical, and Magnetic Properties 70 3.2.4 Transport
Properties 75 3.3 Chemical Properties of Solvents 77 3.3.1 Structuredness
77 3.3.2 Solvent Properties Related to their Ion Solvating Ability 80
3.3.2.1 Polarity 81 3.3.2.2 Electron Pair Donicity and Ability to Accept a
Hydrogen Bond 83 3.3.2.3 Hydrogen Bond Donicity and Electron Pair
Acceptance 84 3.3.2.4 Softness 85 3.3.3 Solvents as Acids and Bases 86
3.3.4 Miscibility with and Solubility in Water 88 3.3.5 Spectroscopic and
Electrochemical Windows 90 3.4 Properties of Binary Aqueous Cosolvent
Mixtures 90 3.4.1 Physical Properties of Binary Aqueous Mixtures with
Cosolvents 90 3.4.1.1 Thermodynamic Properties of the Mixtures 92 3.4.1.2
Some Electrical, Optical, and Transport Properties of the Mixtures 98 3.4.2
Chemical Properties of Binary Aqueous Mixtures with Cosolvents 98 3.4.2.1
Structuredness 98 3.4.2.2 Properties Related to the Ion Solvating Ability
101 References 104 4 Ion Solvation in Neat Solvents 107 4.1 The Solvation
Process 107 4.2 Thermodynamics of Ion Hydration 109 4.2.1 Gibbs Energies of
Ion Hydration 109 4.2.1.1 Accommodation of the Ion in a Cavity 110 4.2.1.2
Electrostatic Interactions 110 4.2.2 Entropies of Ion Hydration 116 4.2.3
Enthalpies of Ion Hydration 116 4.3 Transfer Thermodynamics into Nonaqueous
Solvents 117 4.3.1 Selection of an Extra?]Thermodynamic Assumption 117
4.3.2 Thermodynamics of Transfer of Ions into Nonaqueous Solvents 118
4.3.2.1 Gibbs Energies of Transfer 118 4.3.2.2 Enthalpies of Transfer 126
4.3.2.3 Entropies of Transfer 130 4.3.2.4 Ionic Heat Capacities in
Nonaqueous Solvents 130 4.3.2.5 Ionic Volumes in Nonaqueous Solvents 133
4.4 The Structure of Solvated Ions 135 4.4.1 Hydration Numbers from
Diffraction Studies 138 4.4.2 Hydration Numbers from Computer Simulations
139 4.4.3 Hydration Numbers from Bulk Properties 141 4.4.4 Solvation
Numbers in Nonaqueous Solvents 147 4.5 The Dynamics of Solvated Ions 147
4.5.1 The Mobility of Ions in Solution 147 4.5.2 Rate of Solvent Exchange
Near Ions 150 4.6 Acid/Base Properties of Ions in Solution 151 References
153 5 Mutual Effects of Ions and Solvents 156 5.1 Ion Effects on the
Structure of Solvents 156 5.1.1 Experimental Studies of Ion Effects on the
Structure of Solvents 156 5.1.1.1 Self?]diffusion of Water Molecules 156
5.1.1.2 Viscosity B?]Coefficients 157 5.1.1.3 NMR Signal Relaxation 159
5.1.1.4 Dielectric Relaxation 159 5.1.1.5 Vibrational Spectroscopy 160
5.1.1.6 X?]Ray Absorption and Scattering 162 5.1.1.7 Structural Entropy 163
5.1.1.8 Transfer from Light to Heavy Water 165 5.1.1.9 Internal Pressure
168 5.1.1.10 Some Other Experimental Results 170 5.1.2 Computer Simulations
of Ion Effects on the Structure of Solvents 170 5.2 Ion Effects on the
Dynamics of the Solvent 171 5.2.1 Mean Residence Times of Solvent Molecules
Near Ions 171 5.2.2 Experimental Studies of Ion Effects on the Solvent
Orientation Dynamics 174 5.2.2.1 Ultrafast Infrared Spectroscopy 174
5.2.2.2 High?]frequency Dielectric Relaxation Spectroscopy 176 5.2.2.3 NMR
Relaxation Times 178 5.2.3 Computer Simulations of Reorientation Times 180
5.3 Solvent Effects on the Properties of Ions in Solution 180 5.3.1 Bulk
Properties 180 5.3.2 Molecular Properties 186 References 187 6 Ions in
Mixed Solvents 193 6.1 Ion Transfer into Solvent Mixtures 194 6.2
Properties of Ions in Solvent Mixtures 199 6.2.1 Thermodynamic Properties
of Ions in Mixed Solvents 199 6.2.2 Transport Properties of Ions in Mixed
Solvents 203 6.3 Preferential Solvation of Ions 205 6.3.1 Spectroscopic
Studies 207 6.3.2 Results from Thermodynamic Data 210 6.3.2.1 The QLQC
Method 211 6.3.2.2 The IKBI Method 213 6.3.2.3 Treatments Based on Stepwise
Solvent Replacements 215 References 216 7 Interactions of Ions with Other
Solutes 219 7.1 Ion-Ion Interactions 219 7.1.1 Activity Coefficients of
Electrolyte Solutions 220 7.1.2 Ion Hydration Related to Ion-Ion
Interactions 223 7.2 Ion Association 227 7.2.1 Electrostatic Theory of Ion
Association 230 7.2.1.1 Activity Coefficients of Neutral Ion Pairs 231
7.2.2 Methods for Studying Ion Association 232 7.2.3 Thermodynamic
Quantities Pertaining to Ion Association 234 7.2.4 Aggregation of Ions in
Solutions 237 7.3 Salting?]in and Salting?]out 239 7.3.1 Empirical
Setschenow Constant Data 240 7.3.2 Interpretation of Salting Phenomena 240
References 244 8 Applications of Solutions of Ions 247 8.1 Applications in
Electrochemistry 248 8.1.1 Batteries and Supercapacitors 248 8.1.2
Solvent?]Independent pH and Electrode Potential Scales 251 8.2 Applications
in Hydrometallurgy 257 8.3 Applications in Separation Chemistry 259 8.3.1
Solvent Extraction of Alkali Metal Cations 259 8.3.2 Solvation of Ionizable
Drug Molecules 262 8.4 Applications to Chemical Reaction Rates 264 8.5
Solvated Ions in Biophysical Chemistry 269 8.5.1 The Hofmeister Series 270
8.5.1.1 The Anion Hofmeister Series 270 8.5.1.2 The Cation Hofmeister
Series 271 8.5.1.3 Interpretation of the Hofmeister series 272 8.5.2 Water
Structure Effects of Ions 275 8.5.3 Some Aspects of Protein Hydration 277
References 279 Author Index 000 Subject Index 000