modern electrochemistry 2ed 2002 vol 1 ionics - bockris, reddy & amulya

[...]... 2 .15 .13 .3 2 .15 .13 .4 2 .15 .13 .5 2 .15 .13 .6 (Model A) 2 .15 .13 .7 (Model C) Is There a Connection between the Entropy of Solvation and the Heats of Hydration? Krestov’s Separation of Ion and Solvent Effects in Ion Hydration 10 1 10 2 10 3 10 6 10 7 11 0 11 4 11 4 11 7 11 9 12 0 12 1 12 1 12 1 12 2 12 2 12 4 12 4 12 6 12 6 12 7 12 7 12 7 13 0 13 2 13 3 13 4 13 8 13 9 More... Relative Heats of Solvation of Ions in the Hydrogen Scale 99 99 10 0 2 .15 2 .15 .1 2 .15 .2 99 xx CONTENTS 2 .15 .3 2 .15 .4 2 .15 .5 2 .15 .6 2 .15 .7 2 .15 .8 2 .15 .9 2 .15 .10 2 .15 .11 2 .15 .12 2 .15 .13 2 .15 .14 2 .15 .15 2 .16 2 .16 .1 2 .16 .2 2 .16 .3 2 .16 .4 2 .17 2 .17 .1 2 .17 .2 2 .17 .3 2 .17 .4 Do Oppositely Charged Ions of Equal Radii Have Equal Heats of Solvation? The Water Molecule as... 2 .15 .11 .1 2 .15 .11 .2 2 .15 .11 .3 2 .15 .11 .4 (Model A) 2 .15 .11 .5 (Model B) 2 .15 .11 .6 (Model C) 2 .15 .11 .7 2 .15 .11 .8 2 .15 .11 .9 Numerical Evaluation of Entropy of Hydration: Some Possible Models Entropy Changes Accompanying Hydration 2 .15 .13 .1 2 .15 .13 .2 2 .15 .13 .3 2 .15 .13 .4... 1. 5.2.5 Electrochemistry as an Interdisciplinary Field, Distinct from Chemistry 12 12 13 13 13 15 15 15 15 1. 6 The Frontier in Ionics: Nonaqueous Solutions 16 1. 4.3 1. 5 1. 5 .1 1.5.2 xvii 6 8 9 xviii CONTENTS 1. 7 A New World of Rich Variety: Room-Temperature Molten Salts 19 1. 8 Electrochemical Determination of Radical Intermediates by Means of Infrared Spectroscopy 20 1. 9... 363 367 370 372 374 378 380 382 385 386 390 396 4 01 405 411 412 413 414 415 418 420 4 21 4 21 424 426 427 428 429 432 434 438 439 xxvi CONTENTS 4.4 4.4 .1 4.4.2 4.4.3 4.4.4 4.4.5 4.4.6 4.4.7 4.4.8 4.4.9 4.4 .10 4.4 .11 4.4 .12 4.4 .13 4.4 .14 4.4 .15 4.5 4.5 .1 4.5.2 4.5.3 4.5.4 4.5.5 4.5.6 4.5.7 4.5.8 4.5.9 4.5 .10 4.6 4.6 .1 4.6.2 4.6.3 A Simple Atomistic Picture of Ionic Migration ... 2.8 2.8 .1 2 .11 .1 2 .11 .2 2 .11 .3 2 .11 .4 2 .11 .5 2 .11 .6 63 68 70 72 72 73 77 83 84 85 86 2 .12 2 .12 .1 2 .12 .2 2 .12 .3 Dielectric Effects Dielectric Constant of Solutions How Does One Measure the Dielectric Constant of Ionic Solutions? Conclusion Further Reading 87 87 92 93 93 2 .13 Ionic Hydration... Slags Further Reading 726 726 Appendix 5 .1 The Effective Mass of a Hole 754 Appendix 5.2 Some Properties of the Gamma Function 755 Appendix 5.3 The Kinetic Theory Expression for the Viscosity of a Fluid 756 5 .10 .1 5 .10 .2 5 .13 .3 5 .13 .4 5 .13 .5 5 .13 .6 5 .13 .7 5 .13 .8 5 .13 .9 5 .13 .10 5 .13 .11 5 .13 .12 5 .13 .13 Supplemental References Index 722... Further Reading 714 714 715 717 5 .11 Molten Salts as Reaction Media Further Reading 717 719 5 .12 5 .12 .1 5 .12 .2 5 .12 .3 5 .12 .4 5 .12 .5 The New Room-Temperature Liquid Electrolytes Reaction Equilibria in Low-Melting-Point Liquid Electrolytes Electrochemical Windows in Low-Temperature Liquid Electrolytes Organic... Coefficients 347 CHAPTER 4 ION TRANSPORT IN SOLUTIONS 4 .1 Introduction 3 61 4.2 Ionic Drift under a Chemical-Potential Gradient: Diffusion 363 CONTENTS xxv 4.2 .1 4.2.2 4.2.3 4.2.4 4.2.5 4.2.6 4.2.7 4.2.8 4.2.9 4.2 .10 4.2 .11 4.2 .12 4.2 .13 4.2 .14 4.2 .15 4.2 .16 4.2 .17 4.2 .18 4.2 .19 4.2.20 4.3 4.3 .1 4.3.2 4.3.3 4.3.4 4.3.5 4.3.6 4.3.7 4.3.8 4.3.9 4.3 .10 The Driving Force for Diffusion ... Mobility: The Conway, Bockris, and Linton (CBL) Theory How Well Does the Field-Induced Water Reorientation Theory Conform with the Experimental Facts? Proton Mobility in Ice Further Reading 565 565 567 569 4.9 4.9 .1 4.9.2 4.9.3 4 .11 .5 4 .11 .6 4 .11 .7 4 .11 .8 559 559 559 560 560 5 61 5 71 575 576 580 5 81 5 81 Appendix 4 .1 The Mean Square Distance . xix 2.6.2. 2.6.3. 2.7. 2.7 .1. 2.7.2. 2.8. 2.8 .1. 2.9. 2.9 .1. 2 .10 . 2 .10 .1. 2 .11 . 2 .11 .1. 2 .11 .2. 2 .11 .3. 2 .11 .4. 2 .11 .5. 2 .11 .6. 2 .12 . 2 .12 .1. 2 .12 .2. 2 .12 .3. 2 .13 . 2 .14 . 2 .14 .1. 2 .14 .2. 2 .15 . 2 .15 .1. 2 .15 .2. How Does One Obtain Individual Ionic Volume from the Partial Molar Volume. London University). xv 7KLVSDJHLQWHQWLRQDOOOHIWEODQN CONTENTS Nomenclature xxxiii CHAPTER 1 ELECTROCHEMISTRY 1. 1. 1. 2. 1. 3. 1. 4. 1. 4 .1. 1. 4.2. 1. 4.3. 1. 5. 1. 5 .1. 1. 5.2. 1. 5.3. 1. 6. A State of Excitement Two Kinds of Electrochemistry Some Characteristics. Frontier in Ionics: Nonaqueous Solutions xvii xviii CONTENTS 1. 7. 1. 8. 1. 9. 1. 10. 1. 11. 1. 12. 1. 12 .1. 1. 12.2. A New World of Rich Variety: Room-Temperature Molten Salts . Electrochemical Determination