《the chemistry of the actinide elements P508》求取 ⇩

Ⅰ．INTRODUCTION1

Ⅱ．ACTINIUM5

1．Historical5

2．Isotopes5

3．Occurrence in Nature6

4．Preparation and Isolation7

4．1．Solvent extraction of thenoyltrifluoroacetone complex of actinium7

4．2．Isolation of actinium by ion exchange9

4．3．Purification of actinium by oxalate precipitation11

5．Actinium Metal11

6．Emission and Absorption Spectra of Actinium11

7．Chemical Properties and Compounds of Actinium12

Ⅲ．THORIUM16

1．Historical16

2．Isotopes17

3．Occurrence in Nature18

4．Extraction of Thorium from Monazite20

4．1．Sulphuric acid process20

4．2．Caustic digestion process22

4．3．Solvent extraction of thorium22

4．4．Solvent extraction of chelate complexes of thorium24

4．5．Ion exchange behaviour of thorium25

5．Thorium Metal26

5．1．Preparation27

5．2．Physical properties of thorium metal30

5．3．Thorium alloys and intermetallic compounds31

5．4．Chemical properties of thorium and its alloys33

6．Compounds of Thorium34

6．1．Hydrides35

6．2．Oxide38

6．3．Borides,carbides,and silicides39

6．4．Nitrides and phosphides42

6．5．Sulphides,selenides,and tellurides42

6．6．Halides46

6．7．Volatile Compounds of Thorium51

7．Thorium in Solution52

7．1．Oxidation potential52

7．2．Hydrolysis of Th+452

7．3．Complex ion formation56

7．4．Chelate compounds of thorium59

7．5．Water soluble salts of thorium60

7．6．Insoluble salts of thorium63

Ⅳ．PROTACTINIUM67

1．Historical67

2．Isotopes of Protactinium67

3．Occurrence and Isolation of Protactinium69

3．1．Coprecipitation of protactinium69

3．2．Solvent extraction of protactinium71

3．3．Ion-exchange behaviour of protactinium78

3．4．Isolation of protactinium by the method of Katzin,et al．81

3．5．Isolation according to Golden and Maddock81

3．6．Isolation according to Elson,et al．83

3．7．Isolation according to the method of Ha？ssinsky and Bouissièrres83

3．8．Isolation according to the method of Salutsky,et al．83

3．9．Isolation by volatilizing according to Malm and Fried85

4．The Element Protactinium and its Compounds86

4．1．Protactinium metal and hydride87

4．2．Protactinium oxides88

4．3．Protactinium halides88

4．4．Miscellaneous compounds89

5．Protactinium in Solution90

5．1．The lower oxidation state of protactinium in solution91

5．2．Absorption spectra of protactinium solutions93

Ⅴ．URANIUM94

1．Historical94

2．Isotopes95

3．Uranium in Nature96

3．1．Minerals98

Pitchblende99

Autunite99

Thucholite101

3．2．Economic deposits102

3．3．Important uranium reserves104

4．Extraction of Uranium106

4．1．Preconcentration107

4．2．Roasting and calcining108

4．3．Leaching or digestion109

Acid leaching109

Alkaline leaching111

4．4．Recovery of uranium from leach solutions113

Clarification114

Chemical precipitation114

Ion exchange116

Resin-in-pulp117

Solvent extraction117

Volatility procedures119

5．Uranium Metal120

5．1．Preparation121

5．2．Physical properties of uranium metal123

Crystal structure of metallic uranium125

Thermodynamic properties of uranium127

Magnetic susceptibility128

Electrical properties128

5．3．Uranium intermetallic compounds and alloys128

5．4．Chemical properties of uranium and its alloys131

5．5．Irradiation effects on uranium and its alloys132

6．Uranium Hydride,Deuteride,and Tritide133

6．1．Preparation and composition133

6．2．Physical properties．Dissociation pressure134

Thermodynamic relationships136

Crystal structure136

Magnetic properties137

6．3．Chemical properties of uranium hydride137

7．Uranium-oxygen System138

7．1．Nonstoichiometric systems139

7．2．Stoichiometric uranium oxides141

7．3．Phase relationships143

U-UO2．00143

UO2．00-UO2．25143

UO2．25-U3O8-x144

U3O8-x-U3O8144

7．4．Binary and tertiary oxide systems144

7．5．Uranates,polyuranates,and peruranates145

7．6．Preparation and chemical properties of uranium oxide145

8．Uranium Carbides,Borides,and Related Compounds148

8．1．Uranium-carbon system148

8．2．Uranium-boron system149

8．3．Uranium-nitrogen system151

8．4．Uranium-silicon system152

8．5．Uranium-sulphur,selenium,and tellurium systems152

9．Uranium Halides and Related Compounds153

9．1．Uranium fluorides153

Uranium trifluoride153

Uranium tetrafluoride153

Intermediate fluorides156

Uranium hexafluoride156

9．2．Uranium chlorides,bromides,and iodides161

Preparation161

Properties164

Volatility165

9．3．Uranium chelate compounds with 1,3 diketones166

9．4．Uranium alkoxides167

9．5．π-Cyclopentadienyl compounds of U(Ⅳ)170

9．6．Uranium(Ⅳ)borohydride170

9．7．Uranium(Ⅳ)amides and mercaptides171

10．Uranium Ions in Solution171

10．1．Hydrolytic behaviour of uranium ions172

Tripositive uranium,U+3174

Tetrapositive uranium,U+4175

Pentapositive uranium,UO？176

Hexapositive uranium,UO？+177

Hydrolytic reactions of UO？+178

10．2．Oxidation-reduction relationships179

Disproportionation reaction of UO+2180

Kinetics of oxidation-reduction reactions181

10．3．Complex ion formation183

Tetrapositive uranium183

Hexapositive uranium185

10．4．Important uranium salts191

10．5．Uranium in nonaqueous solvents194

Ⅵ．NEPTUNIUM204

1．Historical204

2．Isotopes205

3．Neptunium in Nature206

4．Preparation and Isolation of Neptunium206

4．1．Lanthanum fluoride oxidation-reduction cycle208

4．2．Solvent extraction of neptunium209

4．3．Extraction of neptunium as the thenoyltrifluoroacetone complex210

4．4．Ion exchange210

4．5．Volatility211

5．Neptunium Metal211

6．Neptunium Compounds213

6．1．X-ray crystal structure data214

6．2．Hydride214

6．3．Oxides and sulphides214

Neptunium dioxide216

Higher oxides216

Sulphides217

6．4．Carbides and silicides217

6．5．Nitride and phosphide217

6．6．Neptunium fluorides217

6．7．Neptunium chlorides,bromides,and iodide218

6．8．Neptunium compounds prepared from aqueous solution220

7．Neptunium Ions in Solution220

7．1．Oxidation potentials223

7．2．Hydrolytic reactions of neptunium ions225

7．3．Complex ions of neptunium226

7．4．Kinetics of oxidation-reduction and isotope exchange reactions of neptunium ions229

Disproportionation reactions229

Oxidation-reduction reactions of neptunium ions231

Kinetics of the oxidation of Np(Ⅳ)by Fe(Ⅲ)231

Kinetics of the Np(Ⅳ)-Np(Ⅵ)reaction233

The Np(Ⅳ)-Np(Ⅴ)isotope exchange234

The Np(Ⅴ)-Np(Ⅵ)isotope exchange236

Ⅶ．PLUTONIUM239

1．Historical239

2．Isotopes240

3．Plutonium in Nature241

4．Preparation and Purification of Plutonium244

4．1．Coprecipitation procedures247

Lanthanum fluoride cycle247

Bismuth phosphate cycle249

Bismuth phosphate process250

4．2．Solvent extraction procedures252

The Redox process254

Purex(TBP)process256

Chelation processes257

Solvent extraction by molten metals262

4．3．Ion exchange separations262

5．Plutonium Metal and Intermetallic Compounds264

5．1．Allotropic modifications,phase transformations,crystal structures and densities265

5．2．Linear expansion,electrical resistivity,and magnetic properties of plutonium metal268

5．3．Vapour pressure of liquid plutonium270

5．4．Chemical properties of plutonium270

5．5．Plutonium alloys and intermetallic compounds271

6．Compounds of Plutonium272

6．1．Plutonium hydrides and deuterides274

6．2．Plutonium carbides and silicides276

6．3．Plutonium nitride,phosphide,and arsenide277

6．4．Plutonium oxides,sulphides,and telluride278

6．5．Plutonium halides and oxyhalides281

Plutonium fluorides283

Trihalides of plutonium285

6．6．Plutonium hexafluoride285

Preparation286

Melting point,boiling point,and crystal structure286

Vapour pressure and related data286

Infra-red and visible absorption spectrum287

Magnetic susceptibility288

Radiation decomposition288

Chemical properties289

6．7．Plutonium compounds obtained from aqueous solution289

7．Plutonium Ions in Solution292

7．1．Absorption spectra of plutonium ions293

Fine structure of PuO？+ spectrum295

Infra-red spectrum of PuO？+296

Spectrophotometric analysis for oxidation states of plutonium297

7．2．Hydrolytic behaviour of plutonium ions297

Plutonium(Ⅲ)298

Plutonium(Ⅳ)299

Plutonium(Ⅳ)polymer300

Plutonium(Ⅴ)302

Plutonium(Ⅵ)303

7．3．Complex ions of plutonium304

Plutonium(Ⅲ)304

Plutonium(Ⅳ)305

Chloride ion305

Nitrate ion306

Fluoride ion306

Sulphate ion307

Oxalate ion308

Phosphate ion308

Hydrogen peroxide309

Other complexes310

Plutonium(Ⅴ)312

Plutonium(Ⅵ)313

Sulphate and carbonate313

7．4．Oxidation-reduction behaviour of the plutonium ions314

Oxidation potentials314

7．5．The plutonium(Ⅲ)-(Ⅳ)-(Ⅵ)equilibrium．The dispro-portionation of plutonium(Ⅳ)315

7．6．Disproportionation of plutonium(Ⅴ)．The plutonium (Ⅲ)-(Ⅳ)-(Ⅴ)-(Ⅵ)equilibrium321

7．7．Alpha reduction of plutonium(Ⅵ)325

7．8．Oxidation-reduction reactions of plutonium ions325

Ⅷ．AMERICIUM331

1．Historical331

2．Isotopes of Americium332

3．Preparation and Purification of Americium 241333

3．1．Precipitation or carrying procedures334

3．2．Ion exchange335

3．3．Solvent extraction340

3．4．Solvent extraction of the thenoyltrifluoroacetone(TTA)complex of americium342

3．5．The isolation of americium according to Hall and Herniman343

3．6．Purification of americium according to Los Alamos345

3．7．Extraction and purification of americium according to Berkeley346

4．Americium Metal347

5．Solid Compounds of Americium349

5．1．Americium hydrides349

5．2．Americium-oxygen system349

Americium sulphide351

5．3．Americium halides351

Americium tetrafluoride353

Americium trichloride354

Americium tribromide354

5．4．Americium(Ⅴ)and(Ⅵ)compounds355

6．Ions in solution357

6．1．Oxidation potentials of americium ions357

6．2．Americium(Ⅱ)359

6．3．Americium(Ⅲ)359

6．4．Americium(Ⅳ)364

6．5．Americium(Ⅴ)364

Absorption spectrum365

The americium(Ⅴ)ion,AmO？366

Disproportionation of americium(Ⅴ)366

Auto-reduction of americium(Ⅴ)solutions368

6．6．Americium(Ⅵ)369

Absorption spectrum of americium(Ⅵ)370

The americyl ion,AmO？+370

Auto-reduction of americium(Ⅵ)371

Isotopic exchange reactions of americium ions371

Some chemical properties of the AmO？+ ion371

Ⅸ．CURIUM373

1．Historical373

2．Isotopes373

3．Preparation and Isolation of Curium375

3．1．Isolation of curium by ion exchange376

3．2．Isolation of curium by solvent extraction377

3．3．Isolation and purification of curium according to Feay and Cunningham378

4．Curium Metal379

5．Anhydrous Curium Compounds379

6．Curium in Aqueous Solution．Possible Higher Oxidation States381

7．Absorption Spectra of Curium383

8．Magnetic Susceptibility of Curium385

Ⅹ．THE TRANSCURIUM ELEMENTS386

1．General386

2．Separation and Identification of the Transcurium Elements by Ion Exchange386

3．Berkelium392

3．1．Isotopes of berkelium392

3．2．Isolation of Bk243393

3．3．Chemical properties of berkelium394

4．Californium397

4．1．Isotopes of californium397

4．2．Chemical properties of californium399

5．Einsteinium400

5．1．Isotopes of einsteinium400

5．2．Chemical properties of einsteinium401

6．Fermium402

7．Mendelevium404

8．Nobelium405

Ⅺ．SUMMARY AND CORRELATION OF PROPERTIES406

1．General Considerations406

Sources of transuranium isotopes407

Atomic weights of transuranium isotopes410

2．Summary of Chemical and Physical Properties．The Metallic State411

2．1．Oxidation states413

2．2．Oxidation-reduction relationships418

2．3．Hydrolysis and complex ion formation421

2．4．Solid compounds432

2．5．Thermodynamic data432

2．6．Adsorption-elution behaviour433

3．Crystal Structure437

4．Absorption and Fluorescence Spectra439

4．1．Ultraviolet and visible absorption and fluorescence spectra439

4．2．Infra-red measurements442

5．Electronic Configuration from Magnetic Data444

5．1．Magnetic susceptibility studies445

5．2．Paramagnetic resonance studies452

6．Spectroscopic Data456

7．Electronic Structure463

8．Position in Periodic Table470

9．Future Elements472

APPENDIX ⅠAtomic Weights of Actinide Nuclides476

APPENDIX ⅡX-ray Energies of the Actinide Elements477

APPENDIX ⅢNuclear Spins of Actinide Nuclides480

NAME INDEX481

SUBJECT INDEX489

A Chart of Colours of Actinide Ions417