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 2

L. R. Morss and J. Fuger

HISTORICAL VIEWPOINTS

2. Transuranium Elements: A Half Century 10 Glenn T. Seaborg

3. Discovery of Neptunium 50 Philip H. Abelson

4. Chemistry of Plutonium Revealed 56 Robert E. Connick

5. The Transuranium Elements: Members of the 5f Series 63 Dieter M. Gruen

6. Early Days in the "Met Lab": Organization and Planning in Scientific Research 78

Joseph J. Katz

7. Early Chemical Contributions in Los Alamos 86 Robert A. Penneman and Roger A. Meade

8. "Dry Chemistry" and Initiatory Thermodynamics at the Metallurgical Laboratory 93

Edgar F. Westrum, Jr.

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NUCLEAR PHYSICS AND CHEMISTRY

9. Nuclear and Chemical Properties of Elements 103, 104, and 105 104

Darleane C. Hoffman

10. Production of Plutonium-237 116 J. Aaltonen, K. Aho, J. Bergman, and O. Solin

11. Mass and Alpha Spectrometry for the Determination of the Half-Life of 241Pu 121

S. K. Aggarwal and H. C. Jain

12. Plutonium Determination by Isotope Dilution Technique with Mass and Alpha Spectrometry 126

S. K. Aggarwal and H. C. Jain,

13. Highly Enriched Isotope Samples of Uranium and Transuranium Elements for Scientific Investigation 131

Stanislav P. Vesnovskii and Vladimir N. Polynov

SPECTROSCOPY, PHOTOPHYSICS, AND PHOTOCHEMISTRY

14. Unusual High-Temperature Behavior of Neptunium and Plutonium Systems 138

Leo Brewer

15. Magnetic and Optical Properties of Np and Pu Ions and Compounds 145

Norman M. Edelstein

16. Detection and Speciation of Trace Amounts of Neptunium and Plutonium 159

N. Trautmann

17. Photochemical Removal of NpF6 and PuF6 from UF6

Gas Streams 168 James V. Beitz and Clayton W. Williams

18. Vibronic Interaction and Crystal Structure Distortion in Cm4+ in CeF4 181

G. K. Liu, James V. Beitz, and W. T. Carnall

19. Ion—Ion Interaction and Energy Transfer of 4+ Transuranium Ions in Cerium Tetrafluoride 187

G. K. Liu and James V. Beitz

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20. Investigation of Neptunium(V) Reduction to Neptunium(IV) by Semiconductor Photocatalysis 195

Masanori Takahashi, Takashi Nishi, Takashi Ikeda, and Hidetoshi Karasawa

CHEMISTRY

21. f-EIement Compound Synthesis Employing Powerful Halogenating Agents 202

P. Gary Eller, Scott A. Kinkead, and Jon B. Nielsen

22. Cationic Speciation in Nonaqueous Media: Uranium, Neptunium, and Plutonium in Oxidation States III and IV 213

Thomas A. O'Donnell

23. The Chemistry of Uranium(VI), Neptunium(VI), and Plutonium(VI) in Aqueous Carbonate Solutions 225

Barbara E. Stout, Gregory R. Choppin, and James C. Sullivan

24. The Lanthanides and Actinides: Among Other Groups of Elements in Mendeleev's System 233

N. B. Mikheev

25. Transuranium Organometallic Elements: The Next Generation 239 Bill D. Zwick, Alfred P. Sattelberger, and Larry R. Avens

26. Gas-Phase Uranium Ion Reactions with 2,4,6-Tri-f-butylphenol and l,3,5-Tri-/-butylbenzene: Fourier Transform— Ion Cyclotron Resonance Mass Spectrometry 247

Z. Liang, A. G. Marshall, A. Pires de Matos, and J. C. Spirlet

27. Characterization of the Plutonium—Water Reaction: Reaction Kinetics Between 200 and 350 ° C f. 251

Jerry L Stakebake

SEPARATIONS AND THERMODYNAMICS

28. Reduction of Neptunium(VI) by Organic Compounds 262 Gregory R. Choppin and L. F. Rao

29. The Complexation Behavior of Neptunium and Plutonium with Nitrilotriacetic Acid 276

Heino Nitsche and Kevin Becraft

XI

30. Catalyzed Electrolytic Plutonium Oxide Dissolution: The Past 17 Years and Future Potential 288

Jack L. Ryan, Lane A. Bray, Earl J. Wheelwright, and Garry H. Bryan

31. Aqueous Chemistry of Neptunium and Plutonium: Studies in the USSR 305

A. S. Nikiforov and B. F. Myasoedov

32. Recovery of Neptunium, Plutonium, and Americium from Highly Active Waste: Trialkylphosphine Oxide Extraction 318

Yongjun Zhu and Chongli Song

33. 3-Phenyl-4-benzoyI-5-isoxazolone: A Novel Extractant for Pu(IV) and Am(III) 331

Vijay K. Manchanda and Prasanta K. Mohapatra

MATERIALS PHYSICS

34. Metallic Covalency in Actinide Compounds 338 G. H. Lander

35. Nuclear Hyperfine Techniques in the Study of Transuranium Materials 345

G. Michael Kalvius

36. Surface Electronic Structure and Chemisorption of Plutonium and Uranium 365

Bernard R. Cooper, Olle Eriksson, You-Gong Hao, and Gayanath W. Fernando

37. Magnetization Measurements on Single Crystals of Neptunium Monopnictides 378

K. Mattenberger, O. Vogt, J. Rebizant, and J. C. Spirlet

MATERIALS CHEMISTRY

38. High-Pressure Phases and Compressibility of Neptunium and Plutonium Compounds 396

U. Benedict, S. Dabos-Seignon, S. Heathman, J. P. Dancausse, M. Gensini, E. Gering, and J. C. Spirlet

xn

39. Electronic, Structural, and Transport Properties of (Almost) Rare-Earth-Like Actinide Hydrides 404

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 416 John M. Haschke

41. The Pivotal Position of Plutonium in the Systematics of Actinide Metals and Compounds 426

Richard G. Haire and J. K. Gibson

42. Defect Chemistry of Plutonium Oxides 440 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 Pu0 2 451

Toshiyuki Yamashita, Kinji Ohuchi, K. Takahashi, and T. Fujino

44. Mechanisms of the Rapid Dissolution of Plutonium Dioxide in Acidic Media under Oxidizing or Reducing Conditions 457

C. Madie, P. Berger, and X. Machuron-Mandard

45. Complex Formation of the Lanthanides and Actinides in Lower Oxidation States 469

N. B. Mikheev and A. N. Kamenskaya

46. Synthesis and Identification of (NH4)2PuCl6 and (NH4)2UCI6

and Preparation of PuCl3 481 Jon B. Nielsen, Scott A. Kinkead, and P. Gary Eller

47. Homogeneous Oxalate Precipitation of Pu(III) 489 Stephen L. Yarbro, Stephen B. Schreiber, Sharon L. Dünn, and Clifford W. Mills

ANALYTICAL CHEMISTRY

48. Transuranium Reference Measurements and Reference Materials 496

Werner Muller

49. Airborne Transuranium Elements: Progress in Rapid Detection 507

M. Iwatschenko-Borho, E. Frenzel, and H. J. Kreiner

xiii

50. Development of Neptunium and Plutonium Chemistry: Contribution of Electrochemical Research 515

V. F. Peretrukhin and A. G. Maslennikov

51. A New Chemical Assay Standard for Plutonium 524 D. D. Sood, N. C. Jayadevan, K. D. Singh Mudher, R. R. Khandekar, and K. Krishnan

Appendix: Papers Presented But Not Included in Book 533

INDEX

Index 536

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