Page 22 - MODERN ELECTROCHEMISTRY

CONTENTS xxi

2.18. Computation of Ion–Water Clusters in the Gas Phase ....... 157
2.19. Solvent Dynamic Simulations for Aqueous Solutions ....... 163
Further Reading . ................................... 166

2.20. Interactions of Ions with Nonelectrolytes in Solution ........ 166
2.20.1. The Problem ................................. 166
2.20.2. Change in Solubility of a Nonelectrolyte Due to Primary Solvation ...... 167
2.20.3. Change in Solubility Due to Secondary Solvation .............. 168
2.20.4. Net Effect on Solubility of Influences from Primary and Secondary
Solvation . .................................. 171
2.20.5. Cause of Anomalous Salting In ....................... 173
2.20.6. Hydrophobic Effect in Solvation ....................... 175
Further Reading .................................... 178
2.21. Dielectric Breakdown of Water .................... 179
2.21.1. Phenomenology ................................ 179
2.21.2. Mechanistic Thoughts ............................ 181
2.22. Electrostriction ............................ 185
2.22.1. Electrostrictive Pressure near an Ion in Solution ............... 185
2.22.2. Maximum Electrostrictive Decrease in the Volume of Water in the First
Hydration Shell ..................... ................ 187
2.22.3. Dependence of Compressibility on Pressure ................. 187
2.22.4. Volume Change and Where It Occurs in Electrostriction .......... 189
2.22.5. Electrostriction in Other Systems........................... 190
Further Reading ........................................ 190
2.23. Hydration of Polyions ......................... 190
2.23.1. Introduction .................................. 190
2.23.2. Volume of Individual Polyions ........................ 191
2.23.3. Hydration of Cross-Linked Polymers (e.g., Polystyrene Sulfonate) . . . 191
2.23.4. Effect of Macroions on the Solvent ..................... 192
2.24. Hydration in Biophysics . ...................... 192
2.24.1. A Model for Hydration and Diffusion of Polyions .............. 193
2.24.2. Molecular Dynamics Approach to Protein Hydration ............ 194
2.24.3. Protein Dynamics as a Function of Hydration ................ 194
2.24.4. Dielectric Behavior of DNA ......................... 195
2.24.5. Solvation Effects and the Transition ............ 197
2.25. Water in Biological Systems . . ............... .... 197
2.25.1. Does Water in Biological Systems Have a Different Structure from Water
In Vitro? . . . ..................... ............... 197
2.25.2. Spectroscopic Studies of Hydration of Biological Systems ......... 198
2.25.3. Molecular Dynamic Simulations of Biowater ................ 198