Actinides in Perspective (eBook)

Front Cover 1
Actinides in Perspective 4
Copyright Page 5
Table of Contents 8
ACTINIDES — 1981 6
PREFACE 7
CHAPTER 1. THE PLUTONIUM STORY 12
ABSTRACT 12
KEYWORDS 12
INTRODUCTION 12
HISTORICAL BACKGROUND 13
DISCOVERY OF PLUTONIUM 13
CHEMICAL INVESTIGATIONS AT BERKELEY 15
DEMONSTRATION OF FISSIONABILITY OF 
17 
PRODUCTION OF 239Pu 20
ULTRAMICROCHEMICAL INVESTIGATIONS 23
CHEMICAL PROPERTIES AND ELECTRONIC STRUCTURE 27
PRESENCE IN NATURE 31
REFERENCES 31
CHAPTER 2. A HISTORY OF THE DISCOVERY OF THE TRANSPLUTONIUM ELEMENTS 34
ABSTRACT 34
KEY WORDS 34
AMERICIUM AND CURIUM (ELEMENTS 95 AND 96) 35
BERKELIUM AND CALIFORNIUM (ELEMENTS 97 AND 98) 37
EINSTEINIUM AND FERMIUM (ELEMENTS 99 AND 100) 38
MENDELEVIUM, Md (ELEMENT 101) 39
NOBELIUM, No (ELEMENT 102): THE FIRST OF THE "CONTROVERSIAL" ELEMENTS 41
LAWRENCIUM, Lr (ELEMENT 103) 48
ELEMENT 104—RUTHERFORDIUM (Rf) 49
HAHNIUM (Ha)—ELEMENT 105 57
ELEMENT 106 60
ELEMENT 107 63
EVEN HEAVIER ELEMENTS? 64
REFERENCES 65
CHAPTER 3. THE ROLE OF W. H. ZACHARIASEN IN ACTINIDE RESEARCH 68
ABSTRACT 68
INTRODUCTION 69
THE UNIVERSITY OF CHICAGO 72
THE METALLURGICAL LAB, UNIVERSITY OF CHICAGO 72
PLUTONIUM METAL 81
CHAPTER 4. PHOTOEMISSION TECHNIQUES 92
ABSTRACT 92
KEYWORDS 92
INTRODUCTION 92
REVIEW OF THE ELECTRON SPECTROSCOPIES 93
IDENTIFICATION OF THE 5f STATES 98
LOCALIZATION VERSUS ITINERANCY 103
ELECTRON SPIN POLARIZATION 108
CORE LEVEL SPECTROSCOPIES 110
CONCLUSION AND OUTLOOK 114
REFERENCES 115
CHAPTER 5. NEUTRON SCATTERING STUDIES OF THE ACTINIDES 118
ABSTRACT 118
KEYWORDS 118
NUCLEAR ELASTIC SCATTERING 118
MAGNETIC ELASTIC SCATTERING 122
NEUTRON INELASTIC SCATTERING 127
CONCLUSIONS 131
ACKNOWLEDGEMENTS 132
REFERENCES 132
CHAPTER 6. FIRST PRINCIPLES CALCULATIONS ON ACTINIDE COMPOUNDS 134
ABSTRACT 134
KEYWORDS 134
I. INTRODUCTION 135
II. THEORETICAL METHODS 135
III. SELECTED RESULTS 140
ACKNOWLEDGEMENTS 152
REFERENCES 153
CHAPTER 7. BAND STRUCTURE STUDIES 156
ABSTRACT 156
KEYWORDS 156
1. INTRODUCTION 156
2. RELATIVISTIC HARTREE-FOCK-AND HARTREE-FOCK-SLATER EQUATIONS 156
3. RELATIVISTIC MODEL HAMILTONIANS 158
4. BAND THEORY OF STOICHIOMETRIC PHASES 161
5. RELATIVISTIC SCATTERING THEORY 161
6. THE SELFCONSISTENT RELATIVISTIC KKR-METHOD 164
7. IMPURITIES 165
8. ELECTRONIC STRUCTURE OF CONCENTRATED ALLOYS: THE COHERENT 
166 
9. DENSITY OF STATES, LOCAL DENSITY OF STATES 167
10. PHYSICAL PROPERTIES RELATED TO THE ELECTRONIC STRUCTURE 169
11. SINGLE SITE SCATTERING 170
12. SUMMARY TO RELATIVISTIC SCATTERING 171
13. APPLICATIONS OF SINGLE SITE SCATTERING AND CLUSTER METHODS 172
14. SELF CONSISTENT RELATIVISTIC BAND STRUCTURES FOR 
175 
15. IMPURITIES AND ALLOYS 178
16. MIXED CRYSTALS [34] 180
17. SPECIAL APPLICATIONS OF RELATIVISTIC SCATTERING THEORY 182
18. CONCLUSION 183
ACKNOWLEDGEMENT 184
REFERENCES 184
CHAPTER 8. DEFECT STRUCTURES IN ACTINIDE COMPOUNDS 186
ABSTRACT 186
KEYWORDS 186
INTRODUCTION 186
GENERAL PROPERTIES OF POINT DEFECTS IN COMPOUNDS 187
DEFECT STRUCTURES IN ACTINIDE MONOCARBIDES 190
CONCLUSION 209
ACKNOWLEDGEMENT 209
REFERENCES 209
CHAPTER 9. NEW ELEMENTS IN THE TRANSFERMIUM REGION 214
ABSTRACT 214
KEYWORDS 214
INTRODUCTION 214
SYNTHESIS REACTIONS 216
RADIOACTIVE PROPERTIES OF NUCLEI IN THE TRANSFERMIUM REGION 222
PERSPECTIVES 228
ACKNOWLEDGEMENT 229
REFERENCES 229
CHAPTER 10. ISOTOPE IDENTIFICATION IN THE TRANSFERMIUM REGION BY a-a 
234 
ABSTRACT 234
KEYWORDS 234
INTRODUCTION 235
KINEMATIC SEPARATION 236
IDENTIFICATION TECHNIQUE 237
EXPERIMENTAL RESULTS 241
DISCUSSION 251
ACKNOWLEDGEMENT 253
REFERENCES 253
CHAPTER 11. FISSION PROPERTIES OF THE ACTINIDES 256
ABSTRACT 256
KEYWORDS 256
INTRODUCTION 256
SADDLE POINT PROPERTIES 257
SCISSION PROPERTIES 267
SUMMARY 273
ACKNOWLEDGEMENTS 274
REFERENCES 274
CHAPTER 12. STATUS OF SUPERHEAVY ELEMENT RESEARCH 278
ABSTRACT 278
KEYWORDS 278
INTRODUCTION 278
PREDICTED NUCLEAR AND CHEMICAL PROPERTIES 279
SEARCH FOR SUPERHEAVY ELEMENTS IN NATURE 281
PRODUCTION OF SUPERHEAVY ELEMENTS WITH HEAVY IONS 284
CONCLUSIONS 296
REFERENCES 297
CHAPTER 13. SINGLE CRYSTAL PREPARATION OF ACTINIDES AND ACTINIDE 
300 
ABSTRACT 300
KEYWORDS 300
INTRODUCTION 300
CRYSTALS OF ACTINIDES AND THEIR COMPOUNDS 306
CRYSTAL-GROWING TECHNIQUES 307
CONCLUSIONS 318
ACKNOWLEDGEMENTS 318
REFERENCES 318
CHAPTER 14. PREPARATION OF TRANSPLUTONIUM METALS AND COMPOUNDS 320
ABSTRACT 320
KEY WORDS 320
INTRODUCTION 320
SAMPLE CONSTRAINTS AND ISOTOPE SELECTION 321
SAMPLE PURITY 322
PREPARATION – 
324 
PREPARATION OF TRANSPLUTONIUM OXIDES 327
ANHYDROUS HALIDES 331
OTHER COMPOUNDS 336
PREPARATION OF THE TRANSPLUTONIUM METALS 339
CONCLUDING REMARKS 347
REFERENCES 348
CHAPTER 15. THE PREPARATION OF PROTACTINIUM METAL AND COMPOUNDS 354
ABSTRACT 354
KEYWORDS 354
INTRODUCTION 354
PROTACTINIUM METAL 355
INTERMETALLIC COMPOUNDS 355
HALIDES 356
OXIDE HALIDES 358
HALOGENO-COMPLEXES 360
HALIDE COMPLEXES WITH DONOR LIGANDS 361
EXCHANGE REACTIONS OF PROTACTINIUM HALIDES AND HALOGENO-COMPLEXES 362
OXIDES AND PEROXIDES 364
SULPHIDES, SULPHATES AND SELENATES 365
NITRIDE, NITRATES AND PHOSPHATES 366
PROTACTINIUM CARBIDE 366
PROTACTINIUM HYDRIDE 366
MISCELLANEOUS COMPOUNDS 367
REFERENCES 367
CHAPTER 16. PREPARATION OF THE ACTINIDE METALS 372
ABSTRACT 372
KEYWORDS 372
1. INTRODUCTION 373
2. PREPARATION OF THE ACTINIDE METAL SAMPLES 373
3. PREPARATION OF THE METALS 374
4. REFINING OF ACTINIDE METALS 379
5. CRYSTAL GROWTH OF THE ACTINIDE METALS 387
6. CHARACTERIZATION 389
7. CONCLUSION 389
REFERENCES 390
CHAPTER 17. COMPLEX OXIDE SYSTEMS OF THE ACTINIDES 392
ABSTRACT 392
KEYWORDS 392
INTRODUCTION 392
COMPARISON OF BINARY AND COMPLEX ACTINIDE OXIDES 393
COORDINATION GEOMETRY AND STABILITY OF COMPLEX OXIDES 394
THERMODYNAMIC PROPERTIES 403
MAGNETIC PROPERTIES 406
PHOTOELECTRON AND MÖSSBAUER SPECTROSCOPY 407
VIBRATIONAL AND VISIBLE SPECTROSCOPY 408
SYNTHESIS OF COMPLEX OXIDES 408
CONCLUSIONS 410
REFERENCES 411
CHAPTER 18. THERMODYNAMIC PROPERTIES OF THE ACTINIDES :CURRENT PERSPECTIVES 420
ABSTRACT 420
KEYWORDS 420
INTRODUCTION 420
THE OXIDES 421
THE AQUEOUS IONS 424
REFERENCES 438
CHAPTER 19. CHEMICAL AND PHYSICOCHEMICAL PROPERTIES OF ACTINIDE ORGANOMETALLIC COMPOUNDS. CATALYTIC AND STOICHIOMETRIC 
444 
ABSTRACT 444
KEYWORDS 444
INTRODUCTION 444
PREPARATION OF BIS(PENTAMETHYLCYCLOPENTADIENYL) THORIUM AND 
445 
REACTIONS OF ACTINIDE-TO-CARBON BONDS WITH KETONES, ALCOHOLS, 
448 
REACTION OF ACTINIDE-TO-CARBON BONDS WITH CARBON MONOXIDE. 
449 
REACTION OF ACTINIDE-TO-CARBON BONDS WITH HYDROGEN. ORGANOACTINIDE 
455 
CATALYSIS WITH ORGANOACTINIDE HYDRIDES 458
CONCLUSIONS AND PROSPECTS 461
ACKNOWLEDGMENTS 461
REFERENCES 461
CHAPTER 20. CHEMICAL PROPERTIES OF THE 
464 
ABSTRACT 464
KEYWORDS 464
INTRODUCTION 465
EINSTEINIUM 465
FERMIUM 477
MENDELEVIUM 480
NOBELIUM 485
LAWRENCIUM 490
ACTINIDE SUMMARY 491
TRANSACTINIDES 492
ACKNOWLEDGMENT 496
REFERENCES 496
CHAPTER 21. SPECIFIC SEQUESTERING AGENTS FOR ACTINIDE IONS 502
ABSTRACT 502
KEYWORDS 502
INTRODUCTION 503
ACKNOWLEDGMENT 516
REFERENCES 516
CHAPTER 22. SOLUTION CHEMISTRY OF THE TRANSPLUTONIUM 
520 
ABSTRACT 520
KEYWORDS 520
INTRODUCTION 520
CHEMISTRY OF TPE IN THE LOWEST OXIDATION STATES 540
USE OF THE UNUSUAL OXIDATION STATES OF TPE FOR ISOLATION AND DETERMINATION OF THESE 
543 
CONCLUSIONS 546
REFERENCES 547
CHAPTER 23. CHEMICAL PROBLEMS ASSOCIATED WITH REPROCESSING 552
ABSTRACT 552
KEYWORDS 552
INTRODUCTION 552
PUREX PROCESS APPLIED TO OXIDE FUELS 553
FUEL DISSOLUTION 555
IODINE TRAPPING 556
BEHAVIOR OF RUTHENIUM 556
U-Pu PARTITION AND Pu PURIFICATION CYCLES 557
BEHAVIOR OF NEPTUNIUM 559
BEHAVIOR OF Te AND Pd 560
TECHNETIUM 560
PALLADIUM 560
TREATMENT OF MEDIUM ACTIVITY WASTES 561
CONCLUSION 562
REFERENCES 562
CHAPTER 24. SOLUBILITIES OF ACTINIDES IN NEUTRAL OR BASIC SOLUTIONS 564
ABSTRACT 564
KEYWORDS 564
INTRODUCTION 564
ACTINIDE COMPLEXES WITH INORGANIC LIGANDS 565
ESTIMATED ACTINIDE SOLUBILITIES FOR DISCRETE OXIDATION STATES 572
FORMATION OF COLLOIDS AND SORPTION PHENOMENA 584
CONCLUSIONS 586
ACKNOWLEDGEMENTS 588
REFERENCES 588
Summary: Nuclear Science 592
Summary: Electronic Structure 596
Summary: Thermodynamics 598
Summary: Optical Spectroscopy 601
Summary: Preparative Chemistry 603
Summary: Solution Chemistry 604
List of Attendees 606
Subject Index 616