Behavior of Heptavalent Technetium in Sulfuric Acid under α‑Irradiation: Structural Determination of Technetium Sulfate Complexes by X‑ray Absorption Spectroscopy and First Principles Calculations

The effect of α-radiolysis on the behavior of heptavalent technetium has been investigated in 13 and 18 M H2SO4. Irradiation experiments were performed using α-particles (4He2+, E = 68 MeV) generated by the ARRONAX cyclotron. UV–visible and X-ray absorption fine structure spectroscopic studies indic...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2014-03, Vol.118 (9), p.1568-1575
Main Authors: Denden, I, Poineau, F, Schlegel, M. L, Roques, J, Solari, P. Lorenzo, Blain, G, Czerwinski, K. R, Essehli, R, Barbet, J, Fattahi, M
Format: Article
Language:English
Subjects:
Absorption spectroscopy
Alpha Particles
Density
Fine structure
Mathematical analysis
Molecular Structure
Quantum Theory
Spectroscopy
Sulfates
Sulfates - chemistry
Sulfuric Acids - chemistry
Technetium
Technetium - chemistry
X-Ray Absorption Spectroscopy
X-rays
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Summary:The effect of α-radiolysis on the behavior of heptavalent technetium has been investigated in 13 and 18 M H2SO4. Irradiation experiments were performed using α-particles (4He2+, E = 68 MeV) generated by the ARRONAX cyclotron. UV–visible and X-ray absorption fine structure spectroscopic studies indicate that Tc(VII) is reduced to Tc(V) under α-irradiation. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements are consistent with the presence of mononuclear technetium sulfate complexes. Experimental results and density functional calculations show the formation of [TcO(HSO4)3(H2O)(OH)]− and/or [TcO(HSO4)3(H2O)2] and [Tc(HSO4)3(SO4)(H2O)] and/or [Tc(HSO4)3(SO4)(OH)]− for 13 and 18 M H2SO4, respectively.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp404967f