the chemistry of the actinide elementsPDF电子书下载

Ⅰ．INTRODUCTION 1

Ⅱ．ACTINIUM 5

1．Historical 5

2．Isotopes 5

3．Occurrence in Nature 6

4．Preparation and Isolation 7

4．1．Solvent extraction of thenoyltrifluoroacetone complex of actinium 7

4．2．Isolation of actinium by ion exchange 9

4．3．Purification of actinium by oxalate precipitation 11

5．Actinium Metal 11

6．Emission and Absorption Spectra of Actinium 11

7．Chemical Properties and Compounds of Actinium 12

Ⅲ．THORIUM 16

1．Historical 16

2．Isotopes 17

3．Occurrence in Nature 18

4．Extraction of Thorium from Monazite 20

4．1．Sulphuric acid process 20

4．2．Caustic digestion process 22

4．3．Solvent extraction of thorium 22

4．4．Solvent extraction of chelate complexes of thorium 24

4．5．Ion exchange behaviour of thorium 25

5．Thorium Metal 26

5．1．Preparation 27

5．2．Physical properties of thorium metal 30

5．3．Thorium alloys and intermetallic compounds 31

5．4．Chemical properties of thorium and its alloys 33

6．Compounds of Thorium 34

6．1．Hydrides 35

6．2．Oxide 38

6．3．Borides,carbides,and silicides 39

6．4．Nitrides and phosphides 42

6．5．Sulphides,selenides,and tellurides 42

6．6．Halides 46

6．7．Volatile Compounds of Thorium 51

7．Thorium in Solution 52

7．1．Oxidation potential 52

7．2．Hydrolysis of Th+4 52

7．3．Complex ion formation 56

7．4．Chelate compounds of thorium 59

7．5．Water soluble salts of thorium 60

7．6．Insoluble salts of thorium 63

Ⅳ．PROTACTINIUM 67

1．Historical 67

2．Isotopes of Protactinium 67

3．Occurrence and Isolation of Protactinium 69

3．1．Coprecipitation of protactinium 69

3．2．Solvent extraction of protactinium 71

3．3．Ion-exchange behaviour of protactinium 78

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

3．5．Isolation according to Golden and Maddock 81

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

3．7．Isolation according to the method of Ha？ssinsky and Bouissièrres 83

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

3．9．Isolation by volatilizing according to Malm and Fried 85

4．The Element Protactinium and its Compounds 86

4．1．Protactinium metal and hydride 87

4．2．Protactinium oxides 88

4．3．Protactinium halides 88

4．4．Miscellaneous compounds 89

5．Protactinium in Solution 90

5．1．The lower oxidation state of protactinium in solution 91

5．2．Absorption spectra of protactinium solutions 93

Ⅴ．URANIUM 94

1．Historical 94

2．Isotopes 95

3．Uranium in Nature 96

3．1．Minerals 98

Pitchblende 99

Autunite 99

Thucholite 101

3．2．Economic deposits 102

3．3．Important uranium reserves 104

4．Extraction of Uranium 106

4．1．Preconcentration 107

4．2．Roasting and calcining 108

4．3．Leaching or digestion 109

Acid leaching 109

Alkaline leaching 111

4．4．Recovery of uranium from leach solutions 113

Clarification 114

Chemical precipitation 114

Ion exchange 116

Resin-in-pulp 117

Solvent extraction 117

Volatility procedures 119

5．Uranium Metal 120

5．1．Preparation 121

5．2．Physical properties of uranium metal 123

Crystal structure of metallic uranium 125

Thermodynamic properties of uranium 127

Magnetic susceptibility 128

Electrical properties 128

5．3．Uranium intermetallic compounds and alloys 128

5．4．Chemical properties of uranium and its alloys 131

5．5．Irradiation effects on uranium and its alloys 132

6．Uranium Hydride,Deuteride,and Tritide 133

6．1．Preparation and composition 133

6．2．Physical properties．Dissociation pressure 134

Thermodynamic relationships 136

Crystal structure 136

Magnetic properties 137

6．3．Chemical properties of uranium hydride 137

7．Uranium-oxygen System 138

7．1．Nonstoichiometric systems 139

7．2．Stoichiometric uranium oxides 141

7．3．Phase relationships 143

U-UO2．00 143

UO2．00-UO2．25 143

UO2．25-U3O8-x 144

U3O8-x-U3O8 144

7．4．Binary and tertiary oxide systems 144

7．5．Uranates,polyuranates,and peruranates 145

7．6．Preparation and chemical properties of uranium oxide 145

8．Uranium Carbides,Borides,and Related Compounds 148

8．1．Uranium-carbon system 148

8．2．Uranium-boron system 149

8．3．Uranium-nitrogen system 151

8．4．Uranium-silicon system 152

8．5．Uranium-sulphur,selenium,and tellurium systems 152

9．Uranium Halides and Related Compounds 153

9．1．Uranium fluorides 153

Uranium trifluoride 153

Uranium tetrafluoride 153

Intermediate fluorides 156

Uranium hexafluoride 156

9．2．Uranium chlorides,bromides,and iodides 161

Preparation 161

Properties 164

Volatility 165

9．3．Uranium chelate compounds with 1,3 diketones 166

9．4．Uranium alkoxides 167

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

9．6．Uranium(Ⅳ)borohydride 170

9．7．Uranium(Ⅳ)amides and mercaptides 171

10．Uranium Ions in Solution 171

10．1．Hydrolytic behaviour of uranium ions 172

Tripositive uranium,U+3 174

Tetrapositive uranium,U+4 175

Pentapositive uranium,UO？ 176

Hexapositive uranium,UO？+ 177

Hydrolytic reactions of UO？+ 178

10．2．Oxidation-reduction relationships 179

Disproportionation reaction of UO+2 180

Kinetics of oxidation-reduction reactions 181

10．3．Complex ion formation 183

Tetrapositive uranium 183

Hexapositive uranium 185

10．4．Important uranium salts 191

10．5．Uranium in nonaqueous solvents 194

Ⅵ．NEPTUNIUM 204

1．Historical 204

2．Isotopes 205

3．Neptunium in Nature 206

4．Preparation and Isolation of Neptunium 206

4．1．Lanthanum fluoride oxidation-reduction cycle 208

4．2．Solvent extraction of neptunium 209

4．3．Extraction of neptunium as the thenoyltrifluoroacetone complex 210

4．4．Ion exchange 210

4．5．Volatility 211

5．Neptunium Metal 211

6．Neptunium Compounds 213

6．1．X-ray crystal structure data 214

6．2．Hydride 214

6．3．Oxides and sulphides 214

Neptunium dioxide 216

Higher oxides 216

Sulphides 217

6．4．Carbides and silicides 217

6．5．Nitride and phosphide 217

6．6．Neptunium fluorides 217

6．7．Neptunium chlorides,bromides,and iodide 218

6．8．Neptunium compounds prepared from aqueous solution 220

7．Neptunium Ions in Solution 220

7．1．Oxidation potentials 223

7．2．Hydrolytic reactions of neptunium ions 225

7．3．Complex ions of neptunium 226

7．4．Kinetics of oxidation-reduction and isotope exchange reactions of neptunium ions 229

Disproportionation reactions 229

Oxidation-reduction reactions of neptunium ions 231

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

Kinetics of the Np(Ⅳ)-Np(Ⅵ)reaction 233

The Np(Ⅳ)-Np(Ⅴ)isotope exchange 234

The Np(Ⅴ)-Np(Ⅵ)isotope exchange 236

Ⅶ．PLUTONIUM 239

1．Historical 239

2．Isotopes 240

3．Plutonium in Nature 241

4．Preparation and Purification of Plutonium 244

4．1．Coprecipitation procedures 247

Lanthanum fluoride cycle 247

Bismuth phosphate cycle 249

Bismuth phosphate process 250

4．2．Solvent extraction procedures 252

The Redox process 254

Purex(TBP)process 256

Chelation processes 257

Solvent extraction by molten metals 262

4．3．Ion exchange separations 262

5．Plutonium Metal and Intermetallic Compounds 264

5．1．Allotropic modifications,phase transformations,crystal structures and densities 265

5．2．Linear expansion,electrical resistivity,and magnetic properties of plutonium metal 268

5．3．Vapour pressure of liquid plutonium 270

5．4．Chemical properties of plutonium 270

5．5．Plutonium alloys and intermetallic compounds 271

6．Compounds of Plutonium 272

6．1．Plutonium hydrides and deuterides 274

6．2．Plutonium carbides and silicides 276

6．3．Plutonium nitride,phosphide,and arsenide 277

6．4．Plutonium oxides,sulphides,and telluride 278

6．5．Plutonium halides and oxyhalides 281

Plutonium fluorides 283

Trihalides of plutonium 285

6．6．Plutonium hexafluoride 285

Preparation 286

Melting point,boiling point,and crystal structure 286

Vapour pressure and related data 286

Infra-red and visible absorption spectrum 287

Magnetic susceptibility 288

Radiation decomposition 288

Chemical properties 289

6．7．Plutonium compounds obtained from aqueous solution 289

7．Plutonium Ions in Solution 292

7．1．Absorption spectra of plutonium ions 293

Fine structure of PuO？+ spectrum 295

Infra-red spectrum of PuO？+ 296

Spectrophotometric analysis for oxidation states of plutonium 297

7．2．Hydrolytic behaviour of plutonium ions 297

Plutonium(Ⅲ) 298

Plutonium(Ⅳ) 299

Plutonium(Ⅳ)polymer 300

Plutonium(Ⅴ) 302

Plutonium(Ⅵ) 303

7．3．Complex ions of plutonium 304

Plutonium(Ⅲ) 304

Plutonium(Ⅳ) 305

Chloride ion 305

Nitrate ion 306

Fluoride ion 306

Sulphate ion 307

Oxalate ion 308

Phosphate ion 308

Hydrogen peroxide 309

Other complexes 310

Plutonium(Ⅴ) 312

Plutonium(Ⅵ) 313

Sulphate and carbonate 313

7．4．Oxidation-reduction behaviour of the plutonium ions 314

Oxidation potentials 314

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)equilibrium 321

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

7．8．Oxidation-reduction reactions of plutonium ions 325

Ⅷ．AMERICIUM 331

1．Historical 331

2．Isotopes of Americium 332

3．Preparation and Purification of Americium 241 333

3．1．Precipitation or carrying procedures 334

3．2．Ion exchange 335

3．3．Solvent extraction 340

3．4．Solvent extraction of the thenoyltrifluoroacetone(TTA)complex of americium 342

3．5．The isolation of americium according to Hall and Herniman 343

3．6．Purification of americium according to Los Alamos 345

3．7．Extraction and purification of americium according to Berkeley 346

4．Americium Metal 347

5．Solid Compounds of Americium 349

5．1．Americium hydrides 349

5．2．Americium-oxygen system 349

Americium sulphide 351

5．3．Americium halides 351

Americium tetrafluoride 353

Americium trichloride 354

Americium tribromide 354

5．4．Americium(Ⅴ)and(Ⅵ)compounds 355

6．Ions in solution 357

6．1．Oxidation potentials of americium ions 357

6．2．Americium(Ⅱ) 359

6．3．Americium(Ⅲ) 359

6．4．Americium(Ⅳ) 364

6．5．Americium(Ⅴ) 364

Absorption spectrum 365

The americium(Ⅴ)ion,AmO？ 366

Disproportionation of americium(Ⅴ) 366

Auto-reduction of americium(Ⅴ)solutions 368

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 ions 371

Some chemical properties of the AmO？+ ion 371

Ⅸ．CURIUM 373

1．Historical 373

2．Isotopes 373

3．Preparation and Isolation of Curium 375

3．1．Isolation of curium by ion exchange 376

3．2．Isolation of curium by solvent extraction 377

3．3．Isolation and purification of curium according to Feay and Cunningham 378

4．Curium Metal 379

5．Anhydrous Curium Compounds 379

6．Curium in Aqueous Solution．Possible Higher Oxidation States 381

7．Absorption Spectra of Curium 383

8．Magnetic Susceptibility of Curium 385

Ⅹ．THE TRANSCURIUM ELEMENTS 386

1．General 386

2．Separation and Identification of the Transcurium Elements by Ion Exchange 386

3．Berkelium 392

3．1．Isotopes of berkelium 392

3．2．Isolation of Bk243 393

3．3．Chemical properties of berkelium 394

4．Californium 397

4．1．Isotopes of californium 397

4．2．Chemical properties of californium 399

5．Einsteinium 400

5．1．Isotopes of einsteinium 400

5．2．Chemical properties of einsteinium 401

6．Fermium 402

7．Mendelevium 404

8．Nobelium 405

Ⅺ．SUMMARY AND CORRELATION OF PROPERTIES 406

1．General Considerations 406

Sources of transuranium isotopes 407

Atomic weights of transuranium isotopes 410

2．Summary of Chemical and Physical Properties．The Metallic State 411

2．1．Oxidation states 413

2．2．Oxidation-reduction relationships 418

2．3．Hydrolysis and complex ion formation 421

2．4．Solid compounds 432

2．5．Thermodynamic data 432

2．6．Adsorption-elution behaviour 433

3．Crystal Structure 437

4．Absorption and Fluorescence Spectra 439

4．1．Ultraviolet and visible absorption and fluorescence spectra 439

4．2．Infra-red measurements 442

5．Electronic Configuration from Magnetic Data 444

5．1．Magnetic susceptibility studies 445

5．2．Paramagnetic resonance studies 452

6．Spectroscopic Data 456

7．Electronic Structure 463

8．Position in Periodic Table 470

9．Future Elements 472

APPENDIX Ⅰ Atomic Weights of Actinide Nuclides 476

APPENDIX Ⅱ X-ray Energies of the Actinide Elements 477

APPENDIX Ⅲ Nuclear Spins of Actinide Nuclides 480

NAME INDEX 481

SUBJECT INDEX 489

A Chart of Colours of Actinide Ions 417