Page 31 - MODERN ELECTROCHEMISTRY

xxx CONTENTS

5.6.2.2. Results of Self-Diffusion Experiments .............. 648
5.6.3. Viscosity of Molten Salts .......................... 651
5.6.4. Validity of the Stokes–Einstein Relation in Ionic Liquids . ........ 654
5.6.5. Conductivity of Pure Liquid Electrolytes ................. 656
5.6.6. The Nernst–Einstein Relation in Ionic Liquids .............. 660
5.6.6.1. Degree of Applicability. ...................... 660
5.6.6.2. Possible Molecular Mechanisms for Nernst–Einstein Deviations. . . 662
5.6.7. Transport Numbers in Pure Liquid Electrolytes .............. 665
5.6.7.1. Transport Numbers in Fused Salts. ................ 665
5.6.7.2. Measurement of Transport Numbers in Liquid Electrolytes. . . . 668
5.6.7.3. Radiotracer Method of Calculating Transport Numbers in
Molten Salts............................... 671
Further Reading.................................... 673
5.7. Using a Hole Model to Understand Transport Processes in Simple
Ionic Liquids ............................. 674
5.7.1. A Simple Approach: Holes in Molten Salts and Transport Processes . . . 674
5.7.2. What Is the Mean Lifetime of Holes in the Molten Salt Model? ..... 676
5.7.3. Viscosity in Terms of the “Flow of Holes” ................. 677
5.7.4. The Diffusion Coefficient from the Hole Model .............. 678
5.7.5. Which Theoretical Representation of the Transport Process in Molten Salts
CanRationalizetheRelation .............. 680
5.7.6. An Attempt toRationalize ................ 681
5.7.7. How Consistent with Experimental Values Is the Hole Model for Simple
Molten Salts? ................................ 683
5.7.8. Ions May Jump into Holes to Transport Themselves: Can They Also
Shuffle About? ............................... 686
5.7.9. Swallin’s Model of Small Jumps ...................... 691
Further Reading ............................... 693
5.8. Mixtures of Simple Ionic Liquids: Complex Formation ...... 694
5.8.1. Nonideal Behavior of Mixtures . ...................... 694
5.8.2. Interactions Lead to Nonideal Behavior .................. 695
5.8.3. Complex Ions in Fused Salts ........................ 696
5.8.4. An Electrochemical Approach to Evaluating the Identity of Complex Ions
in Molten Salt Mixtures ........................... 697
5.8.5. Can One Determine the Lifetime of Complex Ions in Molten Salts? . . . 699

5.9. Spectroscopic Methods Applied to Molten Salts .......... 702
5.9.1. Raman Studies of Al Complexes in Low-Temperature “Molten” Systems 705
5.9.2. Other Raman Studies of Molten Salts ................... 706
5.9.3. Raman Spectra in Molten ................... 709
5.9.4. Nuclear Magnetic Resonance and Other Spectroscopic Methods Applied
to Molten Salts ............................... 709
Further Reading ............................... 713