Synthesis of Lanthanide and Actinide Compounds

376 Pages·1991·14.059 MB·English

by  John M. Haschke (auth.), G. Meyer, L. R. Morss (eds.)

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 lanthanide and aCt inide CO_poundS I edited by Gerd Me~er
and LeSTer R. Morss.
p. CI. -- lToplcs In f-elnent chnlSTry : II. 2)
Includes Inde ••
ISBN 978-94-010-5672-4 ISBN 987-94-011-37584 (eBook)
DOI 10.1007/978-94-011-37584
1. Lanthanul cOlpounds--SyntheSlS. 2. Actinlul cOlipoundS-
-SynThesis. I. Meyer. Gerd. II. Morss. Lester R. III. Series.
00191.L2S96 1990
546' .4112--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.
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 ele
ments, 30 elements altogether, are f elements, meaninj that their metallic
electronic configurations are typically 6s25d14f" and 7s 6d15f" 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 coor
dination 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 lan
thanides 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 Gerd Meyer and Lester R. Morss
July 1990
v
TABLE OF CONTENTS
PREFACE
Actinide Hydrides 1
J.M. Haschke (Golden, Colorado, U.S.A.)
1. INTRODUCTION 1
2. GENERAL PROCEDURES 2
2.1. Preparative Methods 2
2.2. Phase Equilibria 3
2.3. Procedures and Equipment 4
2.4. Product Variability 7
3. SAFETY 9
4. PRACTICAL CONSIDERATIONS 10
4.l. Experimental Limitations 10
4.2. Product Purity 11
5. KINETICS 12
5.l. General Observations 12
5.2. Kinetics of the U+H Reaction 14
2
5.2.1. The Reaction of Massive Uranium Metal.
General Observations. 14
5.2.2. The Reaction of Powdered Uranium Metal 32
'5.3. Kinetics of the Th+H Reaction 34
2
5.4. Kinetics of the Pu+H Reaction 35
2
5.4.1. The Reaction of Massive Plutonium Metal 35
5.4.2. The Reaction of Powdered Plutonium Metal 38
5.5. Hydrogen Isotope Effects 40
6. PRODUCT CHARACTERIZATION 40
6.1. Diffraction 40
6.2. Chemical Analysis 42
7. SPECIFIC PROCEDURES 43
7.l. Actinium Hydride 43
7.2. Thorium Hydrides 43
7.3. Protactinium Hydrides 44
7.4. Uranium Hydrides 44
7.5. Neptunium Hydrides 45
7.6. Plutonium Hydrides 45
7.7. Americium Hydrides 46
7.8. Curium Hydrides 47
7.9. Berkelium Hydrides 47
7.10. Californium Hydride 47
7.11. Transcalifornium Hydrides 47
8. DEHYDRIDING REACTIONS 48
9. CONCLUSIONS 49
10. REFERENCES 49
viii TABLE OF CONTENTS
Lanthanide Fluorides 55
B.G. Muller (Giessen, Germany)
1. INTRODUCTION 55
2. FLUORIDES WITH DIVALENT LANTHANIDES 55
2.1. Samarium Difluoride, SmF2 56
2.2. Europium Difluoride, EuF2 57
2.3. ytterbium Difluoride, YbF2 57
2.4. Thulium Difluoride, TmF 58
2
3. MIXED VALENCE FLUORIDES, MF2/MF3 58
3.1. The System SmF 2/SmF 3 58
3.2. The System EuF 2/EuF3 58
3.3. The System YbF2/YbF3 58
4. TERNARY FLUORIDES WITH DIVALENT LANTHANIDES 59
5. FLUORIDES WITH TETRAVALENT LANTHANIDES 59
5.1. Cerium Tetrafluoride, CeF. 60
5.2. Terbium Tetrafluoride, TbF. 60
5.3. praseodymium Tetrafluoride, PrF. 60
6. COMPLEX FLUORIDES WITH TETRAVALENT
LANTHANIDES 61
6.1. Complex Fluorides with Tetravalent Cerium 61
6.2. Complex Fluorides with Tetravalent Terbium 62
6.3. complex Fluorides with Tetravalent
praseodymium 62
6.4. Complex Fluorides with Tetravalent
Neodymium, Dysprosium (and Thulium) 63
7. FLUORIDES WITH TRIVALENT LANTHANIDES 64
7.1. Binary Lanthanide (III) Fluorides from
Aqueous solutions 64
7.2. Binary Lanthanide (III) Fluorides by
Solid-state/Gas Reactions 64
7.3. Complex Fluorides with Trivalent
Lanthanides 64
REFERENCES 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 ix
7.1. structural and Physical Properties 88
8. TETRAVALENT OXIDE FLUORIDES 89
9. PENTAVALENT ACTINIDE OXIDE FLUORIDES 89
10. HEXAVALENT OXIDE FLUORIDES 91
11. TRIVALENT FLUORO-COMPLEXES 94
12. TETRAVALENT FLUORIDES 104
13. PENTAVALENT FLUORO-COMPLEXES 107
14. HEXAVALENT FLUORO-COMPLEXES 111
15. OXIDE FLUORIDES COMPLEXES 116
16. PENTAVALENT OXIDE FLUORIDE COMPLEXES 116
17. HEXAVALENT OXIDE FLUORIDE COMPLEXES 117
REFERENCES 121
Binary Lanthanide (III) Halides, MX3 (X Cl, Br, I) 135
G. Meyer (Hannover, F.R.G.)
1. CHLORIDES AND BROMIDES 135
1.1. Introduction 135
1. 2. Conversion of Oxides to Chlorides:
Metathesis 135
1. 3. Conversion of Oxides to Chlorides:
Acid-base reactions 136
1.3.1. The Role of Ammonium Chloride 137
1.3.2. The Oxychloride Impurity Problem 138
1.3.3. Other Lanthanide Compounds as Starting
Materials 138
1.4. The Oxidation of Lanthanide Metals 140
2. IODIDES 140
2.1. Conversion of Oxides to Iodides 140
2.2. Direct Conversion of the Lanthanide
Metals to Triiodides 141
2.2.1. Mercuric Iodide for Synthesis 141
2.2.2. Elemental Iodine for Synthesis 141
REFERENCES 144
Complex Lanthanide (III) Chlorides, Bromides and
Iodides 145
G. Meyer (Hannover, F.R.G.)
1. INTRODUCTION 145
2. THERMOCHEMICAL CONSIDERATIONS 145
3. SYNTHETIC ROUTES 148
3.1. Route I: The Dry Route 149
3.2. Route II: The wet Route 150
3.3. Route III: The Ammonium Halide Decomposition
Route 151
3.4. Route IV: The Metallothermic Reduction Route 151
3.5. Route(s) V: Special Routes (to Iodides) 152
4. A SURVEY OF THE PRODUCTS 153
REFERENCES 157
x TABLE OF CONTENTS
Conproportionation Routes to Reduced Lanthanide
Halides 159
J.D. Corbett (Ames, Iowa, U.S.A.)
l. INTRODUCTION 159
2. REACTION PRINCIPLES 160
3. TECHNIQUES AND MATERIALS 162
3.l. containers 162
3.2. Reactants and Impurities 163
3.3. Characterization 164
4. DIHALIDES AND RELATED PHASES 165
5. SESQUIHALIDES 166
6. IMPURITY EFFECTS - PHASES CONTAINING
HETEROATOMS 167
6.l. Synthetic Aspects 170
6.2. Characteristics 171
REFERENCES 172
Action of Alkali Metals on Lanthanide (III) Halides:
an Alternative to the Conproportionation Route to
Reduced Lanthanide Halides 175
G. Meyer and T. Schleid (Hannover, F.R.G.)
l. INTRODUCTION 175
2. THE PROCEDURE 176
3. THE PRODUCTS 177
REFERENCES 184
The Binary Lanthanide Oxides: synthesis and
Identification 187
L. Eyring (Tempe, AZ, U.S.A.)
l. INTRODUCTION 187
2. THE BINARY LANTHANIDE OXIDE SYSTEMS 187
2.l. The Lower Oxides 187
2.2. The sesquioxides 188
2.3. The Higher Oxides 188
3. SOME GENERAL PREPARATIVE PROCEDURES 188
3.l. Vapor Species 188
3.2. The Lower Oxides 189
3.3. The Sesquioxides 189
3.3.l. Prepared from the metal 189
3.3.2. By the Decomposition of some Compound
Precursor 194
3.3.2.l. From the Hydroxide 194
3.3.2.2. From the Nitrates 194
3.3.2.3. From the Halides 197
3.3.2.4. From the Sulfates 197
3.3.2.5. From the Carbonates 197
TABLE OF CONTENTS xi
3.3.2.6. From the Oxalates 199
3.3.2.7. From the Formates, Acetates and citrates 199
3.3.2.8. Lattice Parameters of the Sesquioxides 199
3.4. The Higher Oxides 200
3.5. The Individual Oxides 202
3.5.1. Lanthanum Oxides 202
3.5.2. Cerium oxides 202
3.5.2.1. cerium (III) Oxide 202
3.5.2.2. Higher Oxides 202
3.5.3. Praseodymium Oxides 204
3.5.3.1. praseodymium (III) Oxides 205
3.5.3.2. Higher Oxides 205
3.5.4. Neodymium Oxides 208
3.5.4.1. Neodymium (II) Oxide 208
3.5.4.2. Neodymium (III) Oxides 209
3.5.5. Promethium Oxides 209
3.5.5.1. Promethium (II) Oxides 209
3.5.5.2. Promethium (III) Oxides 209
3.5.6. samarium oxides 209
3.5.6.1. samarium (II) Oxides 209
3.5.6.2. Samarium (III) Oxides 209
3.5.7. Europium Oxides 209
3.5.7.1. EuO 210
3.5.7.2. Eu,O. 211
3.5.7.3. Eu 0 212
2 3
3.5.8. Gadolinium oxide 212
3.5.9. Terbium Oxide 212
3.5.9.1. Terbium (III) Oxide 212
3.5.9.2. Higher Oxides 212
3.5.10. Dysprosium Oxide 215
3.5.11. Holmium Oxide 215
3.5.12. Erbium Oxide 215
3.5.13 • Thulium Oxide 215
3.5.14. ytterbium oxide 215
3.5.15. Lutetium Oxide 216
3.6. The preparation of Oxide single Crystals 216
3.6.1. The Lower Oxides 216
3.6.1.1. EuO 216
3.6.2. Lanthanide (III) Oxides 217
3.6.3. LnO, , Ln02_x 219
3.7. The oxygen-Deficient Sesquioxides 221
3.8. The oxygen-Excess Sesquioxides 221
3.9. Cerium Peroxides CeO, and CeO. 221
REFERENCES 221
Polynary Alkali-Metal Lanthanide Oxides 225
R. Hoppe and S. Voigt (Giessen, F.R.G.)
1. INTRODUCTION 225
2. THE APPLICATION OF ACTIVE LANTHANIDE OXIDES
AS STARTING MATERIALS 226