Crystal structures of Th(OH)PO4, U(OH)PO4 and Th2O(PO4)2.: Condensation mechanism of MIV(OH)PO4 (M = Th, U) into M2O(PO4)2

被引：38
|
作者：
Dacheux, Nicolas
Clavier, Nicolas
Wallez, Gilles
Quarton, Michel
机构：
[1] Univ Paris 06, CNRS, UMR 7574, F-75005 Paris, France
[2] Univ Paris 11, IPNO, Grp Radiochim, UMR 8608, F-91406 Orsay, France
来源：
SOLID STATE SCIENCES | 2007年 / 9卷 / 07期
关键词：
X-ray diffraction; Raman spectroscopy; crystal structure; radwaste matrix; actinide phosphate; condensation mechanism;
D O I：
10.1016/j.solidstatesciences.2007.04.015
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Three new crystal structures, isotypic with beta-Zr2OWO4)(2), have been resolved by the Rietveld method. All crystallize with an orthorhombic cell (S.G.: Cmca) with a = 7.1393(2) angstrom, b = 9.2641(2) angstrom, c = 12.5262(4) angstrom, V= 828.46(4) angstrom(3) and Z = 8 for Th(OH)PO4; a = 7.0100(2) angstrom, b=9.1200(2)angstrom, c=12.3665(3)angstrom, V=790.60(4)angstrom(3) and Z=8 for U(OH)PO4; a=7.1691(3)angstrom, b=9.2388(4)angstrom, c=12.8204(7)angstrom, V = 849.15(7) angstrom(3) and Z = 4 for Th2O(PO4)(2). By heating, the M(OH)PO4 (M = Th, U) compounds condense topotactically into M2O(PO4)(2), with a change of the environment of the tetravalent cation that lowers from 8 to 7 oxygen atoms. The lower stability of Th2O(PO4)(2) compared to that of U2O(PO4)(2) seems to result from this unusual environment for tetravalent thorium. (c) 2007 Elsevier Masson SAS. All rights reserved.
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页码：619 / 627
页数：9
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