The chapters making up this volume had originally been planned to form part of a single volume covering solid hydrates and aqueous solutions of simple molecules and ions. However, during the preparation of the manu- scripts it became apparent that such a volume would turn out to be very unwieldy and I reluctantly decided to recommend the publication of sepa- rate volumes. The most sensible way of dividing the subject matter seemed to lie in the separation of simple ionic solutions. The emphasis in the present volume is placed on ion-solvent effects, since a number of excellent texts cover the more general aspects of electrolyte solutions, based on the classical theories of Debye, Huckel, On sager, and Fuoss. It is interesting to speculate as to when a theory becomes "classical." Perhaps this occurs when it has become well known, well liked, and much adapted. The above-mentioned theories of ionic equilibria and transport certainly fulfill these criteria.
There comes a time when the refinements and modifications can no longer be related to physical significance and can no longer hide the fact that certain fundamental assumptions made in the development of the theory are untenable, especially in the light of information obtained from the application of sophisticated molecular and thermodynamic techniques.
The chapters making up this volume had originally been planned to form part of a single volume covering solid hydrates and aqueous solutions of simple molecules and ions. However, during the preparation of the manu- scripts it became apparent that such a volume would turn out to be very unwieldy and I reluctantly decided to recommend the publication of sepa- rate volumes. The most sensible way of dividing the subject matter seemed to lie in the separation of simple ionic solutions. The emphasis in the present volume is placed on ion-solvent effects, since a number of excellent texts cover the more general aspects of electrolyte solutions, based on the classical theories of Debye, Huckel, On sager, and Fuoss. It is interesting to speculate as to when a theory becomes "classical." Perhaps this occurs when it has become well known, well liked, and much adapted. The above-mentioned theories of ionic equilibria and transport certainly fulfill these criteria.
There comes a time when the refinements and modifications can no longer be related to physical significance and can no longer hide the fact that certain fundamental assumptions made in the development of the theory are untenable, especially in the light of information obtained from the application of sophisticated molecular and thermodynamic techniques.
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978-0-306-37183-7 (9780306371837)
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Schweitzer Klassifikation
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.
