15
Synthesis of Lanthanide and Actinide Compounds
Synthesis of Lanthanide and Actinide Compounds
TOPICS IN f-ELEMENT CHEMISTRY
VOLUME 2
Editor
SHYAMA P. SINHA, University of Dayton, US.A.
Editorial Advisory Board
J.L. ATWOOD, University of Alabama, US.A.
W.J. EVANS, University of California, Irvine, US.A.
M.F. LAPPERT, University of Sussex, Brighton, UK.
J.D. NAVRATIL, Rockwell International, Golden, Colorado, US.A.
A.A. PINKERTON, University of Toledo, Ohio, US.A.
H. SCHUMANN, Technische Universitat Berlin, Berlin, Germany
The titles {Jublished in this series are listed at the end of this volume.
Synthesis of Lanthanide and Actinide Compounds
Edited by
G. MEYER
Ins/i/ul fUr Anorganische Chomia, Universitilt Hannover, Hannover, F.R.G.
and
L. R. MORSS Chemistry Division, Argonne National Laboratory, Algonna, Illinois, US.A.
~.
" SPRINGER SCIENCE+BUSINESS MEDIA, BV.
Library of Congress CataJoging-in-Publication Data
S~nThesls of lanthan ide and aC t inide CO _poundS I edited by Gerd Me~er and LeSTer R . Morss.
p. CI. -- lToplcs In f-elnen t chnlSTry : II. 2) I nclud es Inde • • ISBN ISBN 987-94-011-37584 (eBook)
1. Lan t hanu l cO l pounds--Syn t heSlS . 2 . Act inlul cOlipoundS--SynThesis. I. Meyer . Gerd. II. Morss. Lester R. I I I. Ser ies. 00191 . L2S96 1990 546' . 41 12--dc20 90-49532
ISBN 978-94-010-5672-4
Printed on acid-free paper
All Rights Reserved @ 1991 Springer Science+Business Media Oordrecht Originally published byKluwer Academic Publishers in 1991 Softcover reprint of the hardcover 1st edition 1991 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system. without written permission from the copyright owner.
978-94-010-5672-4 DOI 10.1007/978-94-011-37584
PREFACE
The history of the rare earths has entered its third century; trans uranium elements are now a half century old. Both the lanthanide and actinide elements, 30 elements altogether, are f elements, meaninj that their metallic electronic configurations are typically 6s 2 5d 14f" and 7s 6d 15f" respectively. To an elementary approximation as summarized in the 'average inorganic chemistry textbook, these configurations cause their chemistry to be described by the trivalent state accompanied by less interesting effects such as the lanthanide contraction. However, the discovery of divalent and tetravalent lanthanides and di- to seven-valent actinides hinted at the existence of more interesting although still classic solid-state and coordination chemistry. Metallic halides and chalcogenides and electron-poor cluster compounds have been the outgrowth of many synthetic efforts during the past 25 years or so. These days, one can say that the lanthanides and actinides are not at all boring; the fascination arises from every element being an individual, having its own chemistry.
This book contains a collection of invited reviews on the optimum synthesis of lanthanide and actinide compounds. Since each article was written by one ore two specialists, we have imposed only minimal editorial constraints on the authors as long as synthesis was emphasized, rather than structures and properties. Thereby, short and long articles have emerged. One may note that important classes of compounds such as lanthanide hydrides or actinide halides (other than fluorides) are not covered. Our plan is to incorporate these and other subjects in a second volume. Still we hope that the reader will find something interesting in this (first) volume. We are grateful to our authors for taking the burden to write an article and for the patience that some have shown while waiting for their article to be published. G. M. thanks Sabine Stager who has technically edited quite a number of papers, not only his own.
Hannover and Argonne July 1990
v
Gerd Meyer and Lester R. Morss
TABLE OF CONTENTS
PREFACE
Actinide Hydrides J.M. Haschke (Golden, Colorado, U.S.A.)
1. 2. 2.1. 2.2. 2.3. 2.4. 3. 4. 4.l. 4.2. 5. 5.l. 5.2. 5.2.1.
5.2.2. '5.3. 5.4. 5.4.1. 5.4.2. 5.5. 6. 6.1. 6.2. 7. 7.l. 7.2. 7.3. 7.4. 7.5. 7.6. 7.7. 7.8. 7.9. 7.10. 7.11. 8. 9. 10.
INTRODUCTION GENERAL PROCEDURES Preparative Methods Phase Equilibria Procedures and Equipment Product Variability SAFETY PRACTICAL CONSIDERATIONS Experimental Limitations Product Purity KINETICS General Observations Kinetics of the U+H2 Reaction The Reaction of Massive Uranium Metal. General Observations. The Reaction of Powdered Uranium Metal Kinetics of the Th+H2 Reaction Kinetics of the Pu+H2 Reaction The Reaction of Massive Plutonium Metal The Reaction of Powdered Plutonium Metal Hydrogen Isotope Effects PRODUCT CHARACTERIZATION Diffraction Chemical Analysis SPECIFIC PROCEDURES Actinium Hydride Thorium Hydrides Protactinium Hydrides Uranium Hydrides Neptunium Hydrides Plutonium Hydrides Americium Hydrides Curium Hydrides Berkelium Hydrides Californium Hydride Transcalifornium Hydrides DEHYDRIDING REACTIONS CONCLUSIONS REFERENCES
1
1 2 2 3 4 7 9
10 10 11 12 12 14
14 32 34 35 35 38 40 40 40 42 43 43 43 44 44 45 45 46 47 47 47 47 48 49 49
viii TABLE OF CONTENTS
Lanthanide Fluorides B.G. Muller (Giessen, Germany)
1. 2. 2.1. 2.2. 2.3. 2.4. 3. 3.1. 3.2. 3.3. 4. 5. 5.1. 5.2. 5.3. 6.
6.1. 6.2. 6.3.
6.4.
7. 7.1.
7.2.
7.3.
INTRODUCTION FLUORIDES WITH DIVALENT LANTHANIDES Samarium Difluoride, SmF2 Europium Difluoride, EuF2 ytterbium Difluoride, YbF2 Thulium Difluoride, TmF2
MIXED VALENCE FLUORIDES, MF2/MF3 The System SmF 2/SmF 3 The System EuF 2/EuF 3 The System YbF2/YbF3 TERNARY FLUORIDES WITH DIVALENT LANTHANIDES FLUORIDES WITH TETRAVALENT LANTHANIDES Cerium Tetrafluoride, CeF. Terbium Tetrafluoride, TbF. praseodymium Tetrafluoride, PrF. COMPLEX FLUORIDES WITH TETRAVALENT LANTHANIDES Complex Fluorides with Tetravalent Cerium Complex Fluorides with Tetravalent Terbium complex Fluorides with Tetravalent praseodymium Complex Fluorides with Tetravalent Neodymium, Dysprosium (and Thulium) FLUORIDES WITH TRIVALENT LANTHANIDES Binary Lanthanide (III) Fluorides from Aqueous solutions Binary Lanthanide (III) Fluorides by Solid-state/Gas Reactions Complex Fluorides with Trivalent Lanthanides REFERENCES
55
55 55 56 57 57 58 58 58 58 58 59 59 60 60 60
61 61 62
62
63 64
64
64
64 65
Actinide Fluorides 67 N.P. Freestone (Northampton, England) and J. H. Hol-loway (Leicester, England) 1. INTRODUCTION 67 2. ACTINIDE TRIFLUORIDES 68 2.1. Introduction 68 2.2. Preparation 68 2.3. Physical and Structural Properties 70 3. ACTINIDE TETRAFLUORIDES 71 3.1. Introduction 71 3.2. Preparation 71 4. INTERMEDIATE FLUORIDES 75 5. PENTAFLUORIDES 77 6. ACTINIDE HEXAFLUORIDES 80 7. TRIVALENT OXIDE FLUORIDES 87
TABLE OF CONTENTS
7.1. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17.
structural and Physical Properties TETRAVALENT OXIDE FLUORIDES PENTAVALENT ACTINIDE OXIDE FLUORIDES HEXAVALENT OXIDE FLUORIDES TRIVALENT FLUORO-COMPLEXES TETRAVALENT FLUORIDES PENTAVALENT FLUORO-COMPLEXES HEXAVALENT FLUORO-COMPLEXES OXIDE FLUORIDES COMPLEXES PENTAVALENT OXIDE FLUORIDE COMPLEXES HEXAVALENT OXIDE FLUORIDE COMPLEXES REFERENCES
Binary Lanthanide (III) Halides, MX3 (X G. Meyer (Hannover, F.R.G.)
Cl, Br, I)
1. 1.1. 1. 2.
1. 3.
1.3.1. 1.3.2. 1.3.3.
1.4. 2. 2.1. 2.2.
2.2.1. 2.2.2.
CHLORIDES AND BROMIDES Introduction Conversion of Oxides to Chlorides: Metathesis Conversion of Oxides to Chlorides: Acid-base reactions The Role of Ammonium Chloride The Oxychloride Impurity Problem Other Lanthanide Compounds as Starting Materials The Oxidation of Lanthanide Metals IODIDES Conversion of Oxides to Iodides Direct Conversion of the Lanthanide Metals to Triiodides Mercuric Iodide for Synthesis Elemental Iodine for Synthesis REFERENCES
Complex Lanthanide (III) Chlorides, Bromides and
ix
88 89 89 91 94
104 107 111 116 116 117 121
135
135 135
135
136 137 138
138 140 140 140
141 141 141 144
Iodides 145 G. Meyer (Hannover, F.R.G.)
1. 2. 3. 3.1. 3.2. 3.3.
3.4. 3.5. 4.
INTRODUCTION THERMOCHEMICAL CONSIDERATIONS SYNTHETIC ROUTES Route I: The Dry Route Route II: The wet Route Route III: The Ammonium Halide Decomposition Route Route IV: The Metallothermic Reduction Route Route(s) V: Special Routes (to Iodides) A SURVEY OF THE PRODUCTS REFERENCES
145 145 148 149 150
151 151 152 153 157
x TABLE OF CONTENTS
Conproportionation Routes to Reduced Lanthanide Halides J.D. Corbett (Ames, Iowa, U.S.A.)
l. 2. 3. 3.l. 3.2. 3.3. 4. 5. 6.
6.l. 6.2.
INTRODUCTION REACTION PRINCIPLES TECHNIQUES AND MATERIALS containers Reactants and Impurities Characterization DIHALIDES AND RELATED PHASES SESQUIHALIDES IMPURITY EFFECTS - PHASES CONTAINING HETEROATOMS Synthetic Aspects Characteristics REFERENCES
Action of Alkali Metals on Lanthanide (III) Halides: an Alternative to the Conproportionation Route to
159
159 160 162 162 163 164 165 166
167 170 171 172
Reduced Lanthanide Halides 175 G. Meyer and T. Schleid (Hannover, F.R.G.)
l. 2. 3.
INTRODUCTION THE PROCEDURE THE PRODUCTS REFERENCES
The Binary Lanthanide Oxides: synthesis and Identification L. Eyring (Tempe, AZ, U.S.A.)
l. 2. 2.l. 2.2. 2.3. 3. 3.l. 3.2. 3.3. 3.3.l. 3.3.2.
3.3.2.l. 3.3.2.2. 3.3.2.3. 3.3.2.4. 3.3.2.5.
INTRODUCTION THE BINARY LANTHANIDE OXIDE SYSTEMS The Lower Oxides The sesquioxides The Higher Oxides SOME GENERAL PREPARATIVE PROCEDURES Vapor Species The Lower Oxides The Sesquioxides Prepared from the metal By the Decomposition of some Compound Precursor From the Hydroxide From the Nitrates From the Halides From the Sulfates From the Carbonates
175 176 177 184
187
187 187 187 188 188 188 188 189 189 189
194 194 194 197 197 197
TABLE OF CONTENTS
3.3.2.6. 3.3.2.7. 3.3.2.8. 3.4. 3.5. 3.5.1. 3.5.2. 3.5.2.1. 3.5.2.2. 3.5.3. 3.5.3.1. 3.5.3.2. 3.5.4. 3.5.4.1. 3.5.4.2. 3.5.5. 3.5.5.1. 3.5.5.2. 3.5.6. 3.5.6.1. 3.5.6.2. 3.5.7. 3.5.7.1. 3.5.7.2. 3.5.7.3. 3.5.8. 3.5.9. 3.5.9.1. 3.5.9.2. 3.5.10. 3.5.11. 3.5.12. 3.5.13 • 3.5.14. 3.5.15. 3.6. 3.6.1. 3.6.1.1. 3.6.2. 3.6.3. 3.7. 3.8. 3.9.
From the Oxalates From the Formates, Acetates and citrates Lattice Parameters of the Sesquioxides The Higher Oxides The Individual Oxides Lanthanum Oxides Cerium oxides cerium (III) Oxide Higher Oxides Praseodymium Oxides praseodymium (III) Oxides Higher Oxides Neodymium Oxides Neodymium (II) Oxide Neodymium (III) Oxides Promethium Oxides Promethium (II) Oxides Promethium (III) Oxides samarium oxides samarium (II) Oxides Samarium (III) Oxides Europium Oxides EuO Eu,O. Eu2 0 3
Gadolinium oxide Terbium Oxide Terbium (III) Oxide Higher Oxides Dysprosium Oxide Holmium Oxide Erbium Oxide Thulium Oxide ytterbium oxide Lutetium Oxide The preparation of Oxide single Crystals The Lower Oxides EuO Lanthanide (III) Oxides LnO, , Ln02 _ x
The oxygen-Deficient Sesquioxides The oxygen-Excess Sesquioxides Cerium Peroxides CeO, and CeO. REFERENCES
Polynary Alkali-Metal Lanthanide Oxides R. Hoppe and S. Voigt (Giessen, F.R.G.)
1. 2.
INTRODUCTION THE APPLICATION OF ACTIVE LANTHANIDE OXIDES AS STARTING MATERIALS
xi
199 199 199 200 202 202 202 202 202 204 205 205 208 208 209 209 209 209 209 209 209 209 210 211 212 212 212 212 212 215 215 215 215 215 216 216 216 216 217 219 221 221 221 221
225
225
226
xii TABLE OF CONTENTS
3. 3.1.
3.2. 3.3. 3.4. 3.5. 3.6. 4.
AN OVERVIEW OF SUCCESSFUL SYNTHESIS The Synthesis of LiM02 and NaM02 Type Oxides The Synthesis of Li.M06 Type Oxides LiEu30. and Derivatives Oxides AM02 A~03 Type Oxides A2Li'4 [M30 ,4 ] Type and Related Oxides FUTURE POSSIBILITIES FOR THE SYNTHESIS OF POLY NARY LANTHANIDE OXIDES ACKNOWLEDGEMENTS REFERENCES
Synthesis of Actinide Oxides L.R. Morss (Argonne, Illinois, U.S.A.)
1. 1.1. 1. 2. 2. 2.1.
2.2. 2.3.
3. 3.1. 3.2.
3.3.
3.4.
3.5. 4. 4.1. 4.2. 4.3. 5. 5.1. 5.2. 5.3. 6.
6.1. 6.2.
7. 8. 8.1.
MONOXIDES Thin Films(surface layers) Bulk Samples SESQUIOXIDES Conventional and Microsyntheses: Ac2 0 31 (Am-Es )203 Ultramicrosynthetic Techniques Sesquioxides Requiring Strongly Reducing Condi tions : U01.66 I PU20 3 DIOXIDES Th02
Pa02 and U02 (Dioxides Requiring Reducing Conditions) Other Air-Stable Dioxides: Np021 PU021
Am02 I and Bk02 Cm02 and Cf02 (Dioxide Requiring oxidizing Conditions) Mixed Oxides with Fluorite-Type Structure "PENTOXIDES" Pa20 5 and its "Hydrates" U 2 0 5
NP20 5
TRIOXIDES AND THEIR "HYDRATES" Polymorphs of U03 (U I Np I Pu) O2 ( OH) 2 Other "Hydrates" NON STOICHIOMETRIC AND MIXED-VALENCE ACTINIDE OXIDES Hypostoichiometric Th02_x and U02_X
Transuranium Oxide Systems between An01.5 and An02
ACTINIDE PEROXIDES COMPLEX ACTINIDE OXIDES Synthesis from Binary Oxides
227
227 227 230 230 230 233
233 234 234
237
237 237 238 238
23b 239
240 240 240
241
242
242 243 243 243 243 243 244 244 245 245
246 246
246 247 247 247
TABLE OF CONTENTS
8.2.
8.3. 8.4. 8.5.
Synthesis by Grinding and Heating other Solid Compounds Synthesis from Precursor Materials Hydrothermal and Molten Salt Synthesis High-Pressure, Sealed-Tube, and Ion-Exchange synthesis ACKNOWLEDGEMENTS REFERENCES
Chemical (Vapour Phase) Transport in Lanthanide and Actinide Oxide and Oxychloride Chemistry U. Schaffrath and R Gruehn (Giessen, F.R.G.) , I. Tantalates, Oxychlorotantalates and Niobates
1. 2. 2.1.
2.1.1. 2.1.2. 2.1. 3. 2.1.4. 2.1.5. 2.2. 3. 3.1.
3.1.1.
3.1. 2.
3.1. 3.
3.2.
INTRODUCTION OXYCHLOROTANTALATES AND -NIOBATES Microcrystalline Powders by Isothermal Preparative Routes Ln, Ta (Nb) 05XCl, ' Ln2 '+Ln4+Ta06 C1 3
Ln 3 TaO.C1 6
Ln2 MO.C1 3
Ln2 Ta 2 0 7 Cl 2
Transport in a Temperature Gradient TERNARY OXIDES Preparative Routes to Powder Samples of Monophasic Ternary Oxides in Systems Ln2 0 3 /M2 0 5
Usual Preparation by Solid State Interaction of Binary Oxides Preparation by Solid State Interaction of Oxides and Oxyhalides Preparation by Isothermal Reaction Using a Mineralizer Chemical Transport Reactions ACKNOWLEDGEMENTS REFERENCES
II. Thorium Tantalates and Niobates
1. 1.1. 1.2. 1.2.1. 1.2.2. 1. 3. 1. 4. 1.4.1. 1.5. 1.5.1.
THORIUM TANTALATES Introduction Th 2 Ta 2 0 9
Preparation and Crystal Structure Transport in a Temperature Gradient ThTa2 0 7
ThTa.O'2
Preparation and Chemical Transport ThTa6 0 '7
Preparation
xiii
248 249 249
249 250 250
259
259 260
260 260 260 261 261 261 261 263
263
263
263
265 265 267 267
269
269 269 269 269 271 271 272
274 274
xiv TABLE OF CONTENTS
2. 2.1. 2.2. 2.2.1. 2.3. 2.3.1. 2.4. 2.5. 2.5.1.
THORIUM NIOBATES Introduction Th2 Nb2 0 g
Preparation and Transport Reaction ThNb2 0 7
preparation and Crystal structure ThNb.012
ThNb.022
Preparation ACKNOWLEDGEMENTS REFERENCES
synthesis of Phosphates, Carbonates, Titanates and
274 274 275 275 276 276 276 276 276 277 277
other Lanthanide and Actinide Elements 279 C. E. Bamberger (Oak Ridge, TN, U.S.A.)
1. 2. 2.1. 2.2.
2.2.1.
2.2.2.
2.2.3. 2.2.4. 2.2.5. 3. 3.1.
3.1.1. 3.1.2. 3.1.3. 3.1.4. 3.2.
3.3. 4. 5. 6.
7.
INTRODUCTION SYNTHESIS OF PHOSPHATES preparation from Aqueous Solution High Temperature Synthesis Involving One or More Solid Phases Reactions with H3 PO. or its Condensation Products Reaction with Phosphates of Monovalent cations Reactions with BPO. Miscellaneous Methods Conclusions SYNTHESIS OF CARBONATES Precipitation Reactions from Aqueous Solution Hexavalent Elements, Actinyl(VI) Species Pentavalent Elements, Actinvl(V) Species Tetravalent Elements Trivalent Elements (and Eu 2 +) Thermal Decomposition of Salts of Organic Acids Conclusions SYNTHESIS OF TITANATES SYNTHESIS OF ZIRCONATES SYNTHESIS OF VANADATES, NIOBATES, TANTALATES AND OTHER METALLATES CONCLUDING REMARKS REFERENCES
279 281 281
285
286
287 291 292 293 293
294 294 296 298 298
301 302 302 305
305 309 310
Preparation of Rare Earth Sulfides and Selenides 321 M. Guittard and J. Flahaut (Paris, France)
1. INTRODUCTION 321
TABLE OF CONTENTS
2. 2.2.
2.1.1. 2.1.2. 2.1.3. 2.1.4.
2.1.5.
2.2. 2.2.1.
2.2.2.
2.2.3. 2.2.4. 2.2.5. 3. 3.1.
3.1.1. 3.1.2. 3.1.3.
3.1.4. 3.1.5. 3.1.6. 3.2. 3.2.1. 3.2.2. 3.2.3. 4.
4.1. 4.1.1. 4.1.2. 4.1.3. 4.1.4. 4.1.5. 4.2.
5. 5.1. 5.1.1. 5.1.2. 5.1.3. 5.1.4. 5.2. 5.2.1. 5.2.2.
RARE EARTH SESQUISULFIDES, R2 S3 Preparation of the R2 S3 Sulfides as Powders or in Microcrystalline Form Direct Combination of the Elements Action of Hydrogen Sulfide on the Oxides Action of Carbon Sulfide on Oxides Action of Hydrogen Sulfide on various R.E. Salts R2 S3 Sulfides by Thermal Dissociation of Polysulfides Growth of Single Crystals of R2 S3 Sulfides Direct Synthesis from the Elements using an RI3 Flux Crystal Growth using a Gel as a Reaction Medium Iodine Vapour Phase Transport Melt Techniques Flux Methods RARE EARTH MONOSULFIDES, RS Preparation of the Monosulfides in Powdered or Microcrystalline Form Direct Combination of the Elements Thermal Dissociation of R2 S3 Sulfides Action of a Reducing Element on R2 S3 Sulfides Action of the R.E. Metals on R2 S3 Sulfides Action of PbS on R.E. Metals The Special Case of EuS preparation of RS Single Crystals Melt Methods Sublimation Iodine Vapour Transport INTERMEDIATE COMPOSITIONS BETWEEN RS1.5 AND RS preparation of Powder Samples Direct Combination of the Elements Reduction of R2 S3 Sulfides by a Metal Thermal Dissociation of R2 S3 Sulfides Combination of RS and R2 S3 Sulfides The Special Case of Eu3S. Growth of Single Crystals POLYSULFIDES preparation of Polysulfides Powders Direct Combination of the Constituents Action of Sulfer on R2 S3 Sulfides The Action of H2 S on R2 0 3 Oxides The Action of H2 S on R.E. Salts single Crystals of Polysulfides Flux Methods Direct Combination of the Elements by Vapour-Phase Transport Reactions
xv
322
324 324 325 329
331
331 331
331
332 332 332 334 334
334 334 335
335 335 336 336 336 336 337 337
337 337 337 338 338 338 338 338 338 339 339 339 340 340 340 340
340
xvi
5.2.3. 5.2.4. 6. 6.l. 6.2. 6.3. 7.
7.l. 7.2. 7.3. 8. 9. 9.l. 9.2.
TABLE OF CONTENTS
The Action of Thiocyanate on R.E. Carbonates 340 High Pressure Methods 340 RARE EARTH SESQUISELENIDES, R2 Se3 341 Direct Combination of the Elements 341 Action of Hydrogen Selenide on Oxides 342 Other Methods 343 MONOSELENIDES RSe AND THEIR HOMOGENEITY RANGES 343 Direct Combination of the Elements 343 Other Methods 344 The Special Case of EuSe 344 INTERMEDIATE SELENIDES BETWEEN R2 Se3 AND RSe 344 POLYSELENIDES 345 Direct Combination of the Elements 346 Other Methods 346 REFERENCES 347
synthesis of f-Element Pnictides J.e. Spirlet (Karlsruhe, F.R.G.)
353
l. 2. 3. 4.
4.l. 4.2.
4.3.
4.4.
4.5. 5.
INTRODUCTION PHASE OCCURRENCE AND PHASE DIAGRAM PREPARATION SINGLE CRYSTAL GROWTH OF THE LANTHANIDE AND ACTINIDE PNICTIDES Introduction Single Crystal Growth of Lanthanide and Actinide Pnictides from the Melt Single Crystal Growth of Lanthanide and Actinide Pnictides from the Vapour single Crystal Growth of Lanthanide and Actinide Pnictides from the Solution single Crystal Growth from the Solid State CONCLUSION REFERENCES
353 353 357
358 358
359
359
363 364 365 366
