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Title: Composition and structure of complexes formed in the reaction of uranyl di(2-ethylhexyl)phosphate and tributyl phosphate or di-n-octyl sulfoxide in benzene solutions

Journal Article · · Journal of Structural Chemistry
OSTI ID:387432

This paper reports on {sup 31}P NMR and IR studies of the interaction of tributyl phosphate (TBP) and di-n-octyl sulfoxide (DOSO) with polymer molecules of uranyl di-2-ethylhexyl phosphate (UO{sub 2}X{sub 2})p (I) in C{sub 6}H{sub 6} solutions. Detailed interpretations of the {sup 31}P NMR spectra and the v{sub as}(POO) IR bands and determination of the fraction of nonequivalent phosphorus atoms of X{sup -} anions and uranium (VI) atoms as well as the concentration of U(VI)-bonded TBP in I have shown that only a single TBP or DOSO molecule is coordinated to the uranium atoms of polymer I at C{sub TBP} = 0.1-2 M or C{sub DOSO}=0.1-0.5 M. In the case of 100% TBP, two TBP molecules are coordinated to some U(VI) atoms. Distribution of TBP (DOSO) molecules along the polymer chain agrees with the mean statistical value. The portion of terminal chelate POO-groups of X{sup -} anions is determined. The dependence of the degree of (UO{sub 2}X{sub 2})p{center_dot}nL (L = TBP, DOSO) polymerization on C{sub L} is obtained. Saturation of solutions with water only slightly affects the terminal POO-groups and has no effect on the distribution of L along the polymer chain of I.

OSTI ID:
387432
Journal Information:
Journal of Structural Chemistry, Vol. 35, Issue 6; Other Information: PBD: May 1995; TN: Translated from Zhurnal Strukturnoi Khimii; 35: No. 6, 66-73(Nov-Dec 1994)
Country of Publication:
United States
Language:
English