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Preparation and crystal structures of plutonium(III) pentachloro complexes, K/sub 2/PuCl/sub 5/ and Rb/sub 2/PuCl/sub 5/

Journal Article · · J. Solid State Chem.; (United States)

K/sub 2/PuCl/sub 5/ and Rb/sub 2/PuCl/sub 5/ were prepared by heating mixtures of anhydrous PuCl/sub 3/ and respective alkali metal chlorides in vacuum-sealed quartz ampoules at 400-500/sup 0/C. Their crystal structures are both orthorhombic with K/sub 2/PrCl/sub 5/-type structure (space group Pnma, Z = 4), determined by powder X-ray crystallography. K/sub 2/PuCl/sub 5/: lattice parameters a = 12,674 +/- 0.003, b = 8.727 +/- 0.002, c = 7.969 +/- 0.002 A; cell volume 220.4 +/- 0.2 A/sup 3/; X-ray density 3.726 +/- 0.004 g/cm/sup 3/. Rb/sub 2/PuCl/sub 5/: lattice parameters a = 13.093 +/- 0.008, b = 8.909 +/- 0.005, c = 8.178 +/- 0.005 A; cell volume 238.5 +/- 0.4 A/sup 3/; X-ray density 4.088 +/- 0.008 g/cm/sup 3/. Fourteen variable atom parameters of these complexes were obtained by electrostatic calculation with a program which maximizes the Madelung constant under the condition that the ion-ion separations in the crystal are all larger than respective critical distances. The measured Raman lines of Rb/sub 2/PuCl/sub 5/ are very close to those of hexachloride complexes. The bond lengths and stability of M/sub 2/PuCl/sub 5/ (M = K, Rb) are discussed.

Research Organization:
Argonne National Lab., IL (USA)
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
7257366
Journal Information:
J. Solid State Chem.; (United States), Journal Name: J. Solid State Chem.; (United States) Vol. 72:2; ISSN JSSCB
Country of Publication:
United States
Language:
English