Speciation of technetium peroxo complexes in sulfuric acid revisited

Journal Article · Sun Aug 24 00:00:00 EDT 2014 · Journal of Radioanalytical and Nuclear Chemistry

DOI:https://doi.org/10.1007/s10967-014-3434-1· OSTI ID:1113042

Poineau, Frederic ^[1]; German, Konstantin E. ^[2]; Burton-Pye, Benjamin P. ^[3]; Weck, Philippe F. ^[4]; Kim, Eunja ^[1]; Kriyzhovets, Olga ^[5]; Safonov, Aleksey ^[2]; Ilin, Viktor ^[6]; Francesconi, Lynn C. ^[3]; Sattelberger, Alfred P. ^[7]; Czerwinski, Kenneth R. ^[1]

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1. Univ. of Nevada, Las Vegas, NV (United States)
2. Russian Academy of Sciences (RAS), Moscow (Russian Federation)
3. Hunter College, New York, NY (United States)
4. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
5. Medical Inst. REAVIZ, Moscow (Russian Federation)
6. Russian Academy of Sciences (RAS), Moscow (Russian Federation); Medical Inst. REAVIZ, Moscow (Russian Federation)
7. Argonne National Lab. (ANL), Argonne, IL (United States)

We found that the reaction of Tc(+7) with H₂O₂ has been studied in H₂SO₄ and the speciation of technetium performed by UV–visible and 99-Tc NMR spectroscopy. UV–visible measurements show that for H₂SO₄ ≥ 9 M and H₂O₂ = 0.17 M, TcO₃(OH)(H₂O)₂ reacts immediately and blue solutions are obtained, while no reaction occurs for H₂SO₄< 9 M. The spectra of the blue solutions exhibit bands centered around 520 and 650 nm which are attributed to Tc(+7) peroxo species. Furthermore, our studies in 6 M H₂SO₄4 - begins to react for H₂O₂ = 2.12 M and red solutions are obtained. The UV–visible spectra of the red species are identical to the one obtained from the reaction of TcO₄ - with H₂O₂ in HNO₃ and consistent with the presence of TcO(O₂)₂(H₂O)(OH). The 99-Tc NMR spectrum of the red solution exhibits a broad signal centered at +5.5 ppm vs TcO₄ - and is consistent with the presence of a low symmetry Tc(+7) molecule.

• Research Organization: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
• Sponsoring Organization: USDOE National Nuclear Security Administration (NNSA)
• Grant/Contract Number: AC04-94AL85000
• OSTI ID: 1113042
• Report Number(s): SAND-2013-8259J; PII: 3434
• Journal Information: Journal of Radioanalytical and Nuclear Chemistry, Vol. 303, Issue 2; ISSN 0236-5731
• Publisher: Springer
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
technetium
peroxo complexes
speciation
sulfuric acid