Page 20 - MODERN ELECTROCHEMISTRY

CONTENTS xix

2.6.2. How Does One Obtain Individual Ionic Volume from the Partial Molar
Volume of Electrolytes? .......................... 56
2.6.3. Conway’s Successful Extrapolation .................... 57

2.7. Compressibility and Vibration Potential Approach to Solvation
Numbers of Electrolytes ....................... 58
2.7.1. Relation of Compressibility to Solvation .................. 58
2.7.2. Measuring Compressibility: How It Is Done ................ 60
2.8. Total Solvation Numbers of Ions in Electrolytes .......... 61
2.8.1. Ionic Vibration Potentials: Their Use in Obtaining the Difference of the
Solvation Numbers of Two Ions in a Salt ................. 63
2.9. Solvation Numbers at High Concentrations ............. 68
2.9.1. Hydration Numbers from Activity Coefficients .............. 68
2.10. Transport.................................. 70
2.10.1. The Mobility Method ................................. 70
2.11. Spectroscopic Approaches to Obtaining Information on Structures
near an Ion .............................. 72
2.11.1. General ................................... 72
2.11.2. IR Spectra ................................... 73
2.11.3. The Neutron Diffraction Approach to Solvation .............. 77
2.11.4. To What Extent Do Raman Spectra Contribute to Knowledge of the
Solvation Shell? ................................. 83
2.11.5. Raman Spectra and Solution Structure ................... 84
2.11.6. Information on Solvation from Spectra Arising from Resonance in the
Nucleus....................................... 85
Further Reading ................................... 86
2.12. Dielectric Effects ............................ 87
2.12.1. Dielectric Constant of Solutions ...................... 87
2.12.2. How Does One Measure the Dielectric Constant of Ionic Solutions? . . . 92
2.12.3. Conclusion. . . ................................. 93
Further Reading ............................... 93
2.13. Ionic Hydration in the Gas Phase .................. 94
2.14. Individual Ionic Properties ............................. 98
2.14.1. Introduction..................................... 98
2.14.2. A General Approach to Individual Ionic Properties: Extrapolation to Make
the Effects of One Ion Negligible........................ 99
2.15. Individual Heat of Hydration of the Proton ............. 99
2.15.1. Introduction. ... ................................. 99
2.15.2. Relative Heats of Solvation of Ions in the Hydrogen Scale ........ 100