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Journal of Radioanalytical and Nuclear Chemistry

, Volume 303, Issue 2, pp 1163–1167 | Cite as

Speciation of technetium peroxo complexes in sulfuric acid revisited

  • Frederic PoineauEmail author
  • Konstantin E. German
  • Benjamin P. Burton-Pye
  • Philippe F. Weck
  • Eunja Kim
  • Olga Kriyzhovets
  • Aleksey Safonov
  • Viktor Ilin
  • Lynn C. Francesconi
  • Alfred P. Sattelberger
  • Kenneth R. Czerwinski
Article

Abstract

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. Studies in 6 M H2SO4 show that TcO4 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.

Keywords

Technetium Peroxo complexes Speciation Sulfuric acid 

Notes

Acknowledgments

Funding for this research was provided by the U.S. Department of Energy, Office of Nuclear Energy, NEUP grant through INL/BEA, 321 LLC, 00129169, agreement number DE-AC07-05ID14517. Further supports were provided by the National Science Foundation (Grant NSF-CHE 0750118 and Grant NSF-CHE-0959617 for purchase of the 400 MHz NMR spectrometer at Hunter College) and the U. S Department of Energy, Grant DE-FG02- 09ER16097 (Heavy Element Chemistry, Office of Science) and Grant DE-SC0002456 (Biological and Environmental Research, Office of Science). Infrastructure at Hunter College is partially supported by Grant RR003037 from the National Center for Research Resources (NCRR), a component of the National Institutes of Health (NIH). Sandia National Laboratories is a multiprogram laboratory operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under Contract DE-AC04-94AL85000. The authors thank Trevor Low and Julie Bertoia for outstanding health physics support.

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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2014

Authors and Affiliations

  • Frederic Poineau
    • 1
    Email author
  • Konstantin E. German
    • 2
  • Benjamin P. Burton-Pye
    • 3
  • Philippe F. Weck
    • 4
  • Eunja Kim
    • 5
  • Olga Kriyzhovets
    • 6
  • Aleksey Safonov
    • 2
  • Viktor Ilin
    • 2
    • 6
  • Lynn C. Francesconi
    • 3
  • Alfred P. Sattelberger
    • 7
  • Kenneth R. Czerwinski
    • 1
  1. 1.Department of ChemistryUniversity of Nevada Las VegasLas VegasUSA
  2. 2.A. N. Frumkin Institute of Physical Chemistry and ElectrochemistryRussian Academy of SciencesMoscowRussian Federation
  3. 3.Department of ChemistryHunter CollegeNew-YorkUSA
  4. 4.Sandia National LaboratoriesAlbuquerqueUSA
  5. 5.Department of Physics and AstronomyUniversity of Nevada Las VegasLas VegasUSA
  6. 6.Medical Institute REAVIZMoscowRussian Federation
  7. 7.Energy Engineering and Systems Analysis DirectorateArgonne National LaboratoryLemontUSA

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