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On the nature of heptavalent technetium in concentrated nitric and perchloric acid

Abstract : The speciation of Tc(+7) was performed in HClO4 and HNO3 by 99-Tc NMR, UV-Vis and XAFS spectroscopy. The speciation of Tc(+7) depends on the concentration and strength of the acid. Pertechnetic acid, HTcO4, forms above 8 M HClO4 while in concentrated HNO3, [TcO4]− is still the predominant species. EXAFS spectroscopy shows that the structure of HTcO4 in HClO4 is similar to the one in H2SO4. The reactivity of Tc(+7) was analyzed in the frame of the partial charge model. The partial charge calculated on the Tc atoms (ΔTc) indicates that HTcO4 (ΔTc = +057) is more electrophilic than [TcO4]− (ΔTc = +0.52). The difference in the oxidizing properties between [TcO4]− and HTcO4 is given from the reaction of these species with 12 M HCl(aq). In 13 M sulfuric acid HTcO4 is reduced to Tc(+5) while [TcO4]− is not reduced in 6 M H2SO4.
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http://hal.in2p3.fr/in2p3-00869880
Contributor : Dominique Girod <>
Submitted on : Friday, October 4, 2013 - 1:16:10 PM
Last modification on : Thursday, February 7, 2019 - 4:21:19 PM

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F. Poineau, B.P. Burton-Pye, A. Maruk, G. Kirakosyan, I. Denden, et al.. On the nature of heptavalent technetium in concentrated nitric and perchloric acid. Inorganica Chimica Acta, Elsevier, 2013, 398, pp.147-150. ⟨10.1016/j.ica.2012.12.028⟩. ⟨in2p3-00869880⟩

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