On the nature of heptavalent technetium in concentrated nitric and perchloric acid - IN2P3 - Institut national de physique nucléaire et de physique des particules Access content directly
Journal Articles Inorganica Chimica Acta Year : 2013

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

F. Poineau
  • Function : Author
B.P. Burton-Pye
  • Function : Author
A. Maruk
  • Function : Author
G. Kirakosyan
  • Function : Author
D.B. Rego
  • Function : Author
E.V. Johnstone
  • Function : Author
A.P. Sattelberger
  • Function : Author
M. Fattahi
  • Function : Author
  • PersonId : 1178916
  • IdRef : 068954751
L.C. Francesconi
  • Function : Author
K.E. German
  • Function : Author
K.R. Czerwinski
  • Function : Author

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.

Domains

Radiochemistry

Dates and versions

in2p3-00869880 , version 1 (04-10-2013)

Identifiers

Cite

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, 2013, 398, pp.147-150. ⟨10.1016/j.ica.2012.12.028⟩. ⟨in2p3-00869880⟩
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