Page 28 - MODERN ELECTROCHEMISTRY

CONTENTS xxvii

4.6.4. A Second Braking Effect of the Ionic Cloud on the Central Ion: The Electro-
phoretic Effect ............................... 509
4.6.5. The Net Drift Velocity of an Ion Interacting with Its Atmosphere .... 510
4.6.6. Electrophoretic Component of the Drift Velocity ............. 511
4.6.7. Procedure for Calculating the Relaxation Component of the Drift Velocity 512
4.6.8. Decay Time of an Ion Atmosphere ..................... 512
4.6.9. The Quantitative Measure of the Asymmetry of the Ionic Cloud around a
Moving Ion ................................. 514
4.6.10. Magnitude of the Relaxation Force and the Relaxation Component of the
Drift Velocity ................................ 514
4.6.11. Net Drift Velocity and Mobility of an Ion Subject to Ion–Ion Interactions 517
4.6.12. The Debye–Hückel–Onsager Equation .................. 518
4.6.13. Theoretical Predictions of the Debye–Hückel–Onsager Equation versus the
Observed Conductance Curves ....................... 520
4.6.14. Changes to the Debye–Hückel–Onsager Theory of Conductance . .... 522
4.7. Relaxation Processes in Electrolytic Solutions ........... 526
4.7.1. Definition of Relaxation Processes ..................... 526
4.7.2. Dissymmetry of the Ionic Atmosphere ................... 528
4.7.3. Dielectric Relaxation in Liquid Water ................... 530
4.7.4. Effects of Ions on the Relaxation Times of the Solvents in Their Solutions 532
Further Reading .................................... 533
4.8. Nonaqueous Solutions: A Possible New Frontier in Ionics ..... 534
4.8.1. Water Is the Most Plentiful Solvent .................... 534
4.8.2. Water Is Often Not an Ideal Solvent .................... 535
4.8.3. More Advantages and Disadvantages of Nonaqueous Electrolyte Solutions 536
4.8.4. The Debye–Hückel–Onsager Theory for Nonaqueous Solutions ..... 537
4.8.5. What Type of Empirical Data Are Available for Nonaqueous
Electrolytes? ................................ 538
4.8.5.1. Effect of Electrolyte Concentration on Solution Conductivity . . 538
4.8.5.2. Ionic Equilibria and Their Effect on the Permittivity of Electrolyte
Solutions .............................. 540
4.8.5.3. Ion–Ion Interactions in Nonaqueous Solutions Studied by
Vibrational Spectroscopy ..................... 540
4.8.5.4. Liquid Ammonia as a Preferred Nonaqueous Solvent ...... 543
4.8.5.5. Other Protonic Solvents and Ion Pairs ............... 544
4.8.6. The Solvent Effect on Mobility at Infinite Dilution ............ 544
4.8.7. Slope of the Curve as a Function of the Solvent ...... 545
4.8.8. Effect of the Solvent on the Concentration of Free Ions: Ion Association . 547
4.8.9. Effect of Ion Association on Conductivity ................. 548
4.8.10. Ion-Pair Formation and Non-Coulombic Forces .............. 551
4.8.11. Triple Ions and Higher Aggregates Formed in Nonaqueous Solutions . . 552
4.8.12. Some Conclusions about the Conductance of Nonaqueous Solutions of
True Electrolytes .............................. 553
Further Reading .................................... 554