Author:
Poineau Frédéric,Fattahi Massoud,Montavon Gilles,Grambow Bernd
Abstract
Summary
The condensation mechanisms of tetravalent technetium in chloride media were studied in the pH range 0–1.5. A new dimer complex of Tc(IV) has thus been discovered, Tc2OCl10
4−. Spectroscopic and kinetics studies showed that the formation of this compound resulted from the condensation of TcCl5(H2O)−. An EXAFS study indicates that the dimer displays a [Tc-O-Tc]6+ structure. As the pH increases, UV-visible measurements showed a cyclization of [Tc-O-Tc]6+ into [Tc(μO)2Tc]4+ leading, in fine, to the precipitation of TcO2·x H2O. The aquation constant (K
aq) of TcCl6
2− into TcCl5(H2O)− and the dimerisation constant (logK
dim) of TcCl5(H2O)− into Tc2OCl10
4− were determined to be 2.20±0.26 and 4.68±0.09, respectively.
Subject
Physical and Theoretical Chemistry
Cited by
15 articles.
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