Metal-Ammonia Solutions (eBook)

Front Cover 1
Metal—Ammonia Solutions 4
Copyright Page 5
Table of Contents 8
PREFACE 6
LIST OF PARTICIPANTS 7
CHAPTER 1. THE DILEMMA OF METAL-AMMONIA MODELS 10
NULL RESULTS 10
CATION-ELECTRON INTERACTIONS 11
ELECTRON-ELECTRON INTERACTIONS 12
NON-SPECIFIC CONCENTRATION EFFECTS 12
MODELS OF METAL-AMMONIA SOLUTIONS 13
CALCULATION OF EQUILIBRIUM CONSTANTS 14
CATION MOBILITY 19
ACTIVITY COEFFICIENTS 20
ENTHALPY OF SOLUTION 22
CONCLUSIONS 23
ACKNOWLEDGEMENT 24
REFERENCES 24
GENERAL DISCUSSION 25
CHAPTER 2. A MODEL FOR THE SOLVATED DIELECTRON IN DIELECTRIC MEDIA 28
THEORY 28
APPLICATION TO THE e2-CENTRE IN LIQUID AMMONIA 31
REFERENCES 34
GENERAL DISCUSSION 35
CHAPTER 3. STUDIES OF THE SPECIES 36
ELECTRONIC ENERGY TERMS 39
WAVEFUNCTIONS 40
DISCUSSION 46
ACKNOWLEDGEMENT 46
REFERENCES 46
GENERAL DISCUSSION 47
CHAPTER 4. METAL-AMMONIA SOLUTIONS VI—THE NATURE OF THE 1.5 µ BAND 50
CALCULATIONS 51
ACKNOWLEDGEMENTS 56
REFERENCES 56
DISCUSSION 56
CHAPTER 5. ELEMENTARY ELECTRONIC EXCITATIONS IN INSULATING LIQUIDS 58
I. INTRODUCTION 58
II. EXPERIMENTAL INFORMATION ON QUASI-FREE ELECTRON STATES IN NON-POLAR FLUIDS 60
III. ELECTRON-RARE GAS ATOM INTERACTIONS 61
IV. A CURSORY EXAMINATION OF 
65 
V. THE POLARIZATION POTENTIAL IN A NON-POLAR LIQUID 68
VI. WIGNER-SEITZ MODEL FOR THE QUASI-FREE ELECTRON STATE 70
VII. THE GROUND STATE ENERGY OF A QUASI-FREE ELECTRON 72
VIII. LOCALIZED EXCESS ELECTRON STATES IN NON-POLAR FLUIDS 75
IX. THE BUBBLE MODEL 78
X. THE ELECTRON BUBBLE IN LIQUID HELIUM 81
XI. A LOCALIZATION CRITERION FOR AN EXCESS ELECTRON IN A NON-POLAR FLUID 87
XII. ELECTRON LOCALIZATION IN SOLID HELIUM 88
XIII. POSITRONIUM BUBBLES IN NON-POLAR LIQUIDS 90
XIV. IMPLICATIONS FOR THE UNDERSTANDING OF 
92 
XV. ENERGETICS OF SOLVATED ELECTRONS 94
XVI. THE SIMPLE VERSION OF THE CONTINUUM MODEL 95
XVII. SPECULATIONS ON THE QUASI-FREE ELECTRON STATE IN POLAR LIQUIDS 98
XVIII. A MODIFIED CONTINUUM MODEL FOR THE SOLVATED ELECTRON 99
XIX. MEDIUM REARRANGEMENT ENERGY IN A POLAR SOLVENT 101
XX. CONFIGURATION DIAGRAMS FOR SOLVATED ELECTRONS 105
XXI. OPTICAL PROPERTIES 106
XXII. FUTURE TRENDS 109
ACKNOWLEDGEMENTS 110
REFERENCES 110
GENERAL DISCUSSION 112
CHAPTER 6. THE MAGNETIC PROPERTIES OF METAL-AMMONIA SOLUTIONS 114
MAGNETIC MEASUREMENTS 115
METAL-AMMONIA SOLUTIONS 119
CONCLUSIONS: THE STRUCTURE OF THE 
136 
ACKNOWLEDGEMENTS 138
REFERENCES 138
GENERAL DISCUSSION 139
CHAPTER 7. A PROTON RESONANCE STUDY OF METAL-AMMONIA SOLUTIONS 142
THEORY 143
EXPERIMENTAL 147
RESULTS AND DISCUSSION 149
ACKNOWLEDGEMENTS 152
REFERENCES 153
GENERAL DISCUSSION 153
CHAPTER 8. INTERMETALLIC SOLUTES IN LIQUID AMMONIA 154
EXPERIMENTAL RESULTS 154
KNIGHT SHIFTS 155
ESR ABSORPTIONS 157
CONCLUSIONS 157
ACKNOWLEDGEMENTS 157
REFERENCES 157
DISCUSSION 158
CHAPTER 9. MAGNETIC RESONANCE AND SUSCEPTIBILITY MEASUREMENTS ON SODIUM-HEXAMETHYLPHOSPHORAMIDE (HMPA) SOLUTIONS 160
RESULTS 160
DISCUSSION 162
ACKNOWLEDGEMENTS 165
REFERENCES 166
GENERAL DISCUSSION 166
CHAPTER 10. LITHIUM-7 KNIGHT SHIFTS FOR LITHIUM IN AMMONIA AND LITHIUM IN METHYLAMINE 168
EXPERIMENTAL 168
RESULTS 168
DISCUSSION 172
ACKNOWLEDGEMENTS 173
GENERAL REFERENCES 173
DISCUSSION 174
CHAPTER 11. REACTIONS OF METAL-AMMONIA SOLUTIONS 176
THE REACTION OF THE ELECTRON WITH 
177 
THE REACTION OF THE ELECTRON WITH PROTONIC ACIDS 179
ELECTRON-ADDITION REACTIONS 182
BOND-CLEAVAGE BY ELECTRONS 184
ACKNOWLEDGEMENT 186
REFERENCES 186
GENERAL DISCUSSION 187
CHAPTER 12. THE DECOMPOSITION OF DILUTE SOLUTIONS OF SODIUM AND POTASSIUM IN LIQUID AMMONIA AT -78°C: KINETICS AND MECHANISM 192
EXPERIMENTAL 193
RESULTS 193
DISCUSSION 196
REFERENCES 198
GENERAL DISCUSSION 199
CHAPTER 13. KINETICS OF THE REACTION OF SODIUM WITH ETHANOL IN LIQUID AMMONIA 202
EXPERIMENTAL SECTION 203
RESULTS AND DISCUSSION 203
ACKNOWLEDGEMENT 205
REFERENCES 205
GENERAL DISCUSSION 205
CHAPTER 14. PRESSURE EFFECTS IN METAL-AMMONIA SOLUTIONS 208
EXPERIMENTAL EQUIPMENT 210
EXPERIMENTAL RESULTS AND THEIR INTERPRETATION 214
REFERENCES 223
GENERAL DISCUSSION 224
CHAPTER 15. EFFECT OF PRESSURE AND METAL CONCENTRATION ON MAGNETIC PROPERTIES OF METAL-AMMONIA SOLUTIONS 228
(A) ESR MEASUREMENTS UNDER PRESSURE 228
(B) PRESSURE DEPENDENCE OF EQUILIBRIA 
229 
(C) EFFECT OF PRESSURE ON THE EQUILIBRIA 231
(D) THE PARA-HYDROGEN CONVERSION IN SODIUM-AMMONIA SOLUTIONS 232
REFERENCES 233
GENERAL DISCUSSION 233
CHAPTER 16. THE STRUCTURE OF Li(NH3)4 238
REFERENCES 241
GENERAL DISCUSSION 241
CHAPTER 17. THERMOELECTRIC POWER AND THOMSON COEFFICIENT IN THE INTERMEDIATE RANGE OF CONCENTRATIONS 242
(I) EQUIPMENT 242
(II) MEASUREMENTS AND TREATMENT OF DATA 244
(Ill) A TYPICAL RUN. EXPERIMENTAL RESULTS 246
DISCUSSION 250
COMMENTS ON THESE OBSERVATIONS 251
CONCLUSION 252
APPENDIX 252
REFERENCES 253
GENERAL DISCUSSION 253
CHAPTER 18. PROPERTIES OF CONCENTRATED METAL-AMMONIA SOLUTIONS 256
I. ANALYSIS OF EXPERIMENTAL RESULTS 256
II. RELATIONS BETWEEN PROPERTIES AND THEIR INTERPRETATION 281
REFERENCES 296
GENERAL DISCUSSION 298
CHAPTER 19. OPTICAL PROPERTIES OF CONCENTRATED METAL-AMMONIA SOLUTIONS 302
REFERENCES 306
GENERAL DISCUSSION 306
CHAPTER 20. MECANISME DE RELAXATION SPIN—RESEAU DES ELECTRONS SOLVATES 310
TEMPS DE CORRELATION EXPERIMENTAL 310
MECANISME DE LA RELAXATION 311
CALGUL DU TEMPS DE CORRELATION 312
REMARQUE 314
CONCLUSION 314
REFERENCES 315
GENERAL DISCUSSION 315
CHAPTER 21. ELECTRONS TRAPPED IN SOLIDS 318
ACKNOWLEDGEMENT 322
REFERENCES 322
GENERAL DISCUSSION 322
CHAPTER 22. ELECTRON AND NUCLEAR RESONANCE STUDIES OF LITHIUM-AMINE SOLUTIONS 326
RESULTS 326
DISCUSSION 329
ACKNOWLEDGEMENTS 333
REFERENCES 333
GENERAL DISCUSSION 333
CHAPTER 23. OPTICAL AND ELECTRON SPIN RESONANCE STUDIES OF SOLUTIONS OF POTASSIUMIN TETRAHYDROFURAN 338
EXPERIMENTAL 338
RESULTS 338
DISCUSSION 341
ACKNOWLEDGEMENTS 345
REFERENCES 345
GENERAL DISCUSSION 346
CHAPTER 24. THE METAL-NONMETAL TRANSITION AND PHASE SEPARATION 348
EXPERIMENTAL 352
REFERENCES 359
GENERAL DISCUSSION 360
CHAPTER 25. THE ACOUSTIC PROPERTIES OF METAL-AMMONIA SOLUTIONS 364
EXPERIMENTAL TECHNIQUES 364
DATA 366
CONCLUSIONS 372
REFERENCES 373
GENERAL DISCUSSION 373
CHAPTER 26. SOLID METAL-AMMONIA COMPOUNDS 376
ALKALINE EARTH METAL COMPOUNDS 378
LANTHANIDE METAL COMPOUNDS 381
REFERENCES 399
GENERAL DISCUSSION 400
CHAPTER 27. FIELD-DEPENDENT CONDUCTANCE IN SODIUM-LIQUID AMMONIA SOLUTIONS II—SEMI-CONDUCTOR BEHAVIOUR AT THE ELECTRODES 404
EXPERIMENTAL 404
RESULTS 406
DISCUSSION 411
REFERENCES 412
GENERAL DISCUSSION 412
CHAPTER 28. POSITRON ANNIHILATION IN CONCENTRATED METAL-AMMONIA SOLUTIONS 414
REFERENCES 419
GENERAL DISCUSSION 419
CHAPTER 29. SOME OPTICAL PROPERTIES OF THE HYDRATED ELECTRON 422
COMPARISON OF SPECTRA OF e-aq, e-NH3 AND F-CENTRES 424
ESR SPECTRUM OF e-aq 426
EFFECT OF TEMPERATURE ON ABSORPTION SPECTRUM OF e-aq 427
ELECTRON DENSITY CONTOURS 428
REFERENCES 431
GENERAL DISCUSSION 432
CHAPTER 30. ELECTRON SPIN RESONANCE STUDIES OF CONCENTRATED ALKALI METAL-AMMONIA SOLUTIONS 434
EXPERIMENTAL 435
INTERPRETATION OF SPECTRA 437
RESULTS 442
DISCUSSION 445
REFERENCES 446
DISCUSSION 447
CHAPTER 31. CONDUCTIVITY OF CONCENTRATED METAL-AMMONIA SOLUTIONS 448
ELECTRON SCATTERING MECHANISM 449
RESISTIVITY OF INDEPENDENT SCATTERERS 450
DISCUSSION 452
ACKNOWLEDGEMENT 453
REFERENCES 454
GENERAL DISCUSSION 454
CHAPTER 32. OPTICAL ABSORPTION SPECTRA OF ALKALIMETAL SOLUTIONS IN AMINES AND ETHERS 458
EXPERIMENTAL PROCEDURES 458
RESULTS AND CONCLUSIONS 469
DISCUSSION 481
ACKNOWLEDGEMENTS 486
REFERENCES 487
GENERAL DISCUSSION 487
CHAPTER 33. THE REACTION OF e- WITH Na+ IN ETHYLENEDIAMINE 492
REFERENCES 492
CHAPTER 34. SIMULTANEOUS OBSERVATION OF ABSORPTION AND ESR SPECTRA OF HMPA-POTASSIUM METAL SOLUTIONS 494
CHAPTER 35. CALCULATION OF THE EXCESS VOLUME IN DILUTE METAL-AMMONIA SOLUTIONS 498
REFERENCES 499
GENERAL DISCUSSION 499
CHAPTER 36. THE VOLUME EXPANSION OF SOLUTIONS OF LITHIUM IN METHYLAMINE AT -45°C 502
REFERENCES 503
GENERAL DISCUSSION 503
CHAPTER 37. PREPARATION OF DEUTEROAMMONIA 504
CHAPTER 38. THE CONDUCTANCE OF DILUTE METAL-AMMONIA AND METAL-AMINE SOLUTIONS 506
ACKNOWLEDGEMENT 509
REFERENCES 510
GENERAL DISCUSSION 510
CHAPTER 39. OPTICAL SPECTRA OF ALKALI METAL-AMMONIA SOLUTIONS 512
ACKNOWLEDGEMENT 520
REFERENCES 520
GENERAL DISCUSSION 520
INDEX 522