Transuranium Elements
A Half Century
L. R. Morss, EDITOR
Argonne National Laboratory
J. Fuger, EDITOR
Commission ofthe European Communities,
JRC, Institute for Transuranium Elements
Developed from a Symposium sponsored
by the Divisions of Nuclear Chemistry and Technology,
the History of Chemistry, and Inorganic Chemistry
of the American Chemical Society
American Chemical Society, Washington, DC 1992
Contents
Contributors
xv
Preface
xxiii
INTRODUCTION
1. Transuranium Elements: Their Impact on Science
and Technology
L. R. Morss and J. Fuger
2
HISTORICAL VIEWPOINTS
2. Transuranium Elements: A Half Century
Glenn T. Seaborg
10
3. Discovery of Neptunium
Philip H. Abelson
50
4. Chemistry of Plutonium Revealed
Robert E. Connick
56
5. The Transuranium Elements: Members of the 5f Series
Dieter M. Gruen
63
6. Early Days in the "Met Lab": Organization and Planning
in Scientific Research
Joseph J. Katz
7. Early Chemical Contributions in Los Alamos
Robert A. Penneman and Roger A. Meade
8. "Dry Chemistry" and Initiatory Thermodynamics
at the Metallurgical Laboratory
Edgar F. Westrum, Jr.
ix
78
86
93
NUCLEAR PHYSICS AND CHEMISTRY
9. Nuclear and Chemical Properties of Elements 103,
104, and 105
Darleane C. Hoffman
10. Production of Plutonium-237
J. Aaltonen, K. Aho, J. Bergman, and O. Solin
11.
104
116
Mass and Alpha Spectrometry for the Determination
of the Half-Life of 2 4 1 Pu
S. K. Aggarwal and H. C. Jain
121
12. Plutonium Determination by Isotope Dilution Technique
with Mass and Alpha Spectrometry
S. K. Aggarwal and H. C. Jain,
126
13.
Highly Enriched Isotope Samples of Uranium and
Transuranium Elements for Scientific Investigation
Stanislav P. Vesnovskii and Vladimir N. Polynov
131
SPECTROSCOPY, PHOTOPHYSICS, AND PHOTOCHEMISTRY
14. Unusual High-Temperature Behavior of Neptunium
and Plutonium Systems
Leo Brewer
138
15. Magnetic and Optical Properties of Np and Pu Ions
and Compounds
Norman M. Edelstein
145
16. Detection and Speciation of Trace Amounts of Neptunium
and Plutonium
N. Trautmann
159
17. Photochemical Removal of NpF 6 and PuF 6 from UF 6
Gas Streams
James V. Beitz and Clayton W. Williams
168
18. Vibronic Interaction and Crystal Structure Distortion
in Cm4+ in CeF 4
G. K. Liu, James V. Beitz, and W. T. Carnall
181
19. Ion—Ion Interaction and Energy Transfer of 4+
Transuranium Ions in Cerium Tetrafluoride
G. K. Liu and James V. Beitz
187
x
20. Investigation of Neptunium(V) Reduction to Neptunium(IV)
by Semiconductor Photocatalysis
Masanori Takahashi, Takashi Nishi, Takashi Ikeda,
and Hidetoshi Karasawa
195
CHEMISTRY
21. f-EIement Compound Synthesis Employing Powerful
Halogenating Agents
P. Gary Eller, Scott A. Kinkead, and Jon B. Nielsen
202
22. Cationic Speciation in Nonaqueous Media: Uranium,
Neptunium, and Plutonium in Oxidation States III and IV
Thomas A. O'Donnell
213
23. The Chemistry of Uranium(VI), Neptunium(VI), and
Plutonium(VI) in Aqueous Carbonate Solutions
Barbara E. Stout, Gregory R. Choppin, and James C. Sullivan
225
24. The Lanthanides and Actinides: Among Other Groups
of Elements in Mendeleev's System
N. B. Mikheev
233
25. Transuranium Organometallic Elements: The Next Generation
Bill D. Zwick, Alfred P. Sattelberger, and
Larry R. Avens
239
26. Gas-Phase Uranium Ion Reactions with 2,4,6-Tri-fbutylphenol and l,3,5-Tri-/-butylbenzene: Fourier Transform—
Ion Cyclotron Resonance Mass Spectrometry
Z. Liang, A. G. Marshall, A. Pires de Matos,
and J. C. Spirlet
247
27. Characterization of the Plutonium—Water Reaction: Reaction
Kinetics Between 200 and 350 ° C
f.
Jerry L Stakebake
251
SEPARATIONS AND THERMODYNAMICS
28. Reduction of Neptunium(VI) by Organic Compounds
Gregory R. Choppin and L. F. Rao
29. The Complexation Behavior of Neptunium and Plutonium
with Nitrilotriacetic Acid
Heino Nitsche and Kevin Becraft
XI
262
276
30. Catalyzed Electrolytic Plutonium Oxide Dissolution:
The Past 17 Years and Future Potential
Jack L. Ryan, Lane A. Bray, Earl J. Wheelwright,
and Garry H. Bryan
31. Aqueous Chemistry of Neptunium and Plutonium:
Studies in the USSR
A. S. Nikiforov and B. F. Myasoedov
32.
Recovery of Neptunium, Plutonium, and Americium
from Highly Active Waste: Trialkylphosphine Oxide Extraction
Yongjun Zhu and Chongli Song
33. 3-Phenyl-4-benzoyI-5-isoxazolone: A Novel Extractant
for Pu(IV) and Am(III)
Vijay K. Manchanda and Prasanta K. Mohapatra
288
305
318
331
MATERIALS PHYSICS
34. Metallic Covalency in Actinide Compounds
G. H. Lander
35. Nuclear Hyperfine Techniques in the Study
of Transuranium Materials
G. Michael Kalvius
36.
Surface Electronic Structure and Chemisorption
of Plutonium and Uranium
Bernard R. Cooper, Olle Eriksson, You-Gong Hao,
and Gayanath W. Fernando
37. Magnetization Measurements on Single Crystals
of Neptunium Monopnictides
K. Mattenberger, O. Vogt, J. Rebizant, and J. C. Spirlet
338
345
365
378
MATERIALS CHEMISTRY
38. High-Pressure Phases and Compressibility of Neptunium
and Plutonium Compounds
U. Benedict, S. Dabos-Seignon, S. Heathman,
J. P. Dancausse, M. Gensini, E. Gering,
and J. C. Spirlet
xn
396
39. Electronic, Structural, and Transport Properties
of (Almost) Rare-Earth-Like Actinide Hydrides
John W. Ward, Barbara Cort, Joyce A. Goldstone,
Andrew C. Lawson, Lawrence E. Cox, and Richard G. Haire
40. Hydrolysis of Plutonium: Plutonium—Oxygen Phase Diagram
John M. Haschke
41. The Pivotal Position of Plutonium in the Systematics
of Actinide Metals and Compounds
Richard G. Haire and J. K. Gibson
42. Defect Chemistry of Plutonium Oxides
Keiji Naito, Toshihide Tsuji, Tsuneo Matsui,
Takeo Fujino, Toshiyuki Yamashita, and Kinji Ohuchi
43. Formation of Lithium Plutonates by the Reaction of Lithium
Nitrate and Lithium Hydroxide with P u 0 2
Toshiyuki Yamashita, Kinji Ohuchi, K. Takahashi,
and T. Fujino
404
416
426
440
451
44. Mechanisms of the Rapid Dissolution of Plutonium Dioxide
in Acidic Media under Oxidizing or Reducing Conditions
C. Madie, P. Berger, and X. Machuron-Mandard
457
45. Complex Formation of the Lanthanides and Actinides
in Lower Oxidation States
N. B. Mikheev and A. N. Kamenskaya
469
46. Synthesis and Identification of (NH4)2PuCl6 and (NH4)2UCI6
and Preparation of PuCl3
Jon B. Nielsen, Scott A. Kinkead, and P. Gary Eller
481
47. Homogeneous Oxalate Precipitation of Pu(III)
Stephen L. Yarbro, Stephen B. Schreiber, Sharon L. Dünn,
and Clifford W. Mills
489
ANALYTICAL CHEMISTRY
48. Transuranium Reference Measurements
and Reference Materials
Werner Muller
496
49. Airborne Transuranium Elements: Progress
in Rapid Detection
M. Iwatschenko-Borho, E. Frenzel, and H. J. Kreiner
507
xiii
50.
Development of Neptunium and Plutonium Chemistry:
Contribution of Electrochemical Research
V. F. Peretrukhin and A. G. Maslennikov
515
51. A New Chemical Assay Standard for Plutonium
D. D. Sood, N. C. Jayadevan, K. D. Singh Mudher,
R. R. Khandekar, and K. Krishnan
524
Appendix: Papers Presented But Not Included in Book
533
INDEX
Index
536
xiv