内容

目次

1 Thermodynamics of Ion Hydration.- 1. The Thermodynamic Theory of Solvation.- 1.1. General Remarks.- 1.2. Resolution of Data into Solvation and Excess Properties.- 1.3. Standard States.- 1.4. Reference Solvents.- 1.5. Pair Interaction Coefficients.- 1.6. Temperature and Pressure.- 1.7. Single-Ion Properties.- 2. Molecular Interpretation.- 2.1. Introduction.- 2.2. The Born Model.- 2.3. The Debye—Pauling Model.- 2.4. Hamiltonian Models.- 2.5. A Chemical Model.- 3. Hydration of Gaseous Ions.- 3.1. Free Energies, Enthalpies, and Entropies of Hydration.- 3.2. Equations for Entropies of Aqueous Ions.- 3.3. The Chemical Model Interpretation of Ionic Entropies.- 3.4. Transition and Rare Earth Metal Ions at Infinite Dilution.- 4. Other Thermodynamic Properties of Ions at Infinite Dilution in Water.- 4.1. Partial Molar Volume of Solute X at infinite Dilution, VX(aq).- 4.2. Partial Molar Heat Capacity of Solute X at Infinite Dilution, CX(aq).- 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).- 4.4. Partial Molal Expansibility of Solute X at Infinite Dilution, EX(aq).- 4.5. Variation of Heat Capacity of Solute X at Infinite Dilution with Temperature, ?CX(aq)/?T.- 4.6. Variation of Partial Molal Isothermal Compressibility of Solute X at Infinite Dilution with Temperature, ?KTX(aq)/?T.- 4.7. Variation of Partial Molal Expansibility of Solute X at Infinite Dilution with Temperature, (?EX(aq)/?T)P.- 5. Solvent-Isotope Effect in Hydration.- 5.1. Introduction.- 5.2. Free Energies.- 5.3. Enthalpies.- 5.4. Entropies.- 5.5. Volumes.- 5.6. Heat Capacities.- 6. Reference Solvents.- 6.1. Free Energies in Nonaqueous Solvents.- 6.2. Entropies in Nonaqueous Solvents.- 6.3. Enthalpies in Nonaqueous Solvents.- 6.4. Heat Capacities in Nonaqueous Solvents.- 7. Ionic Hydration and Excess Properties.- 2 Thermodynamics of Aqueous Mixed Electrolytes.- 1. Introduction.- 2. Theoretical Framework.- 2.1. Symmetric, Common-Ion Mixtures.- 2.2. Symmetric, Multicomponent Mixtures.- 2.3. Nomenclature.- 3. Experimental Techniques.- 4. Experimental Results and Discussion.- 4.1. Concentration and Common-Ion Dependence.- 4.2. Young’s Sign Rule.- 4.3. Temperature Dependence of ?mHE.- 4.4. Tetraalkylammonium Electrolytes.- 3 Hydration Effects and Acid-Base Equilibria.- 1. Ionization of Liquid Water.- 1.1. Ionization of Water in Aqueous Electrolyte Solutions.- 1.2. Ionization of Water in Aqueous Organic Mixtures.- 2. Hydration of H+ and OH?.- 2.1. Gas-Phase Hydration of H+ and OH?.- 2.2. Hydration of H+ and OH? in Aqueous Solution.- 3. Organic Acids and Bases in Aqueous Solution.- 3.1. Thermodynamics of Ionization Reactions.- 3.2. Substituent Effects on Ionization of Organic Acids.- 3.3. Examples of Hydration Effects on Acid-Base Ionization Reactions.- 4 Ionic Transport in Water and Mixed Aqueous Solvents.- 1. Introduction.- 2. Measurement.- 3. Limiting Ionic Conductances in Binary Solutions.- 4. Mechanism of Ionic Conductance.- 4.1. Stokes’ Law.- 4.2. Solvent Dipole Relaxation Effect.- 4.3. Cosphere Effects.- 4.4. Temperature Coefficient.- 4.5. Pressure Coefficient.- 5. Limiting Ionic Conductance in Aqueous Solvent Mixtures.- 5 Infrared Spectroscopy of Aqueous Electrolyte Solutions.- 1. Introduction.- 2. Information on Aqueous Ionic Solutions Obtainable from Infrared Analysis.- 2.1. General.- 2.2. The Effects of Ions on the Structure of Water.- 2.3. Far Infrared.- 2.4. Fundamental Infrared.- 2.5. Near Infrared.- 3. Experimental Methods.- 3.1. General.- 3.2. Atmospheric Absorptions.- 3.3. Cells and Cell Path Lengths.- 3.4. Temperature Variation of Sample.- 3.5. Reflection Losses.- 3.6. Isotopically Dilute HDO as a Solvent.- 4. Critical Review of Available Infrared Data.- 4.1. Far Infrared.- 4.2. Fundamental Infrared.- 4.3. Near Infrared.- 4.4. Effect of Water on Infrared Spectra of Inorganic Ions.- 5. Conclusion.- 6 Raman Spectroscopy of Aqueous Electrolyte Solutions.- 1. Discussion.- 2. Raman Bands Arising from Solutes.- 3. Raman Bands Arising from the Solvent: Liquid Water.- 3.1. Intermolecular Region Vibrations.- 3.2. Intramolecular Bands of the Solvent.- 4. Addendum.- 7 Nuclear Magnetic Relaxation Spectroscopy.- 1. Introduction.- 2. Nuclear Magnetic Relaxation.- 2.1. Principles.- 2.2. Proton Relaxation Times and Correlation Times of Water in Paramagnetic Electrolyte Solutions.- 2.3. Oxygen-17 Relaxation in Aqueous Solutions of Paramagnetic Ions.- 2.4. Proton Relaxation Times and Correlation Times of Water in Diamagnetic Electrolyte Solutions.- 2.5. Quadrupolar Relaxation of Water in Diamagnetic Electrolyte Solutions.- 2.6. Relaxation Times of Ionic Nuclei Relaxing by Magnetic Dipole—Dipole Interaction.- 2.7. Self-Diffusion Coefficients in Electrolyte Solutions.- 2.8. Structural Interpretation of Microdynamic Data.- 8 Dielectric Properties.- 1. Basic Theory.- 1.1. Types of Dielectric Polarization and Its Decay.- 1.2. Dielectric Relaxation in a Model of Pure Water.- 1.3. Dielectric Relaxation in a Model of Aqueous Ionic Solutions.- 1.4. Comparison of the Molecular Rotational Correlation Times as Derived from Dielectric Relaxation and Proton Magnetic Resonance Relaxation.- 2. Experimental Methods.- 3. Characteristic Quantities Derived from Complex Permittivity Measurements.- 4. Information from the “Static” Permittivity.- 5. Information Obtainable from the Dielectric Relaxation Time with the Help of the Proton Magnetic Relaxation Rate.- 6. The Influence of Small Cations on the Dielectric Relaxation Time.- 6.1. Electrostatic Interaction Mechanisms Independent of the Water Structure.- 6.2. Mechanisms Depending on the Water Structure.- 7. Summary.- References.- Compound Index.- Formula Index.