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Preparation and crystal structures of plutonium(IV) hexachloro complexes, Rb/sub 2/PuCl/sub 6/ and K/sub 2/PuCl/sub 6/

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

Rb/sub 2/PuCl/sub 6/ and K/sub 2/PuCl/sub 6/ were prepared by heating mixtures of anhydrous PuCl/sub 3/ and the respective alkali metal chlorides under high Cl/sub 2/ pressures. Their crystal structures were determined by powder X-ray crystallography. Rb/sub 2/PuCl/sub 6/: hexagonal, space group P6/sub 3/mc, a = 7.377 +- 0.002, c = 11.880 +- 0.007 A, Z = 2, V = 279.9 +- 0.3 A/sup 3/ (per formula), D/sub x/ = 3.69 gcm/sup 3/. K/sub 2/PuCl/sub 6/: monoclinic, space group P2m, a = 7.218 +- 0.005, b = 7.611 +- 0.006, c = 10.208 +- 0.007 A, ..beta.. = 91.59 +- 0.04/sup 0/, Z = 2, V = 280.3 +- 0.3 A/sup 3/ (per formula), D/sub x/ = 3.14 gcm/sup 3/. The variable atom parameters were obtained by means of electrostatic calculation to have the maximum Madelung constant. Raman spectra showed two lines corresponding to v/sub 1/(A/sub 1g/) and v/sub 5/(F/sub 2g) for both compounds. The difference of stability in M/sub 2/PuCl/sub 6/ (M = K, Rb, Cs) is discussed.

Research Organization:
Argonne National Lab., IL (USA)
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
7007062
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