Skip to main content
SpringerLink
Log in

Speciation of technetium peroxo complexes in sulfuric acid revisited

  • Published:
Journal of Radioanalytical and Nuclear Chemistry Aims and scope Submit manuscript

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

Notes

  1. The time required between the preparation and EXAFS measurement of the samples (~3 days) is longer than the life-time of the samples.

References

  1. Matsumoto S, Uchiyama G, Ozawa M, Kobayashi Y, Shirato K (2003) Radiochemistry 45:219–224

    Article  CAS  Google Scholar 

  2. Nagaishi R (2001) Radiat Phys Chem 60:369–375

    Article  CAS  Google Scholar 

  3. Fujine S, Uchiyama G, Maeda M (1994). Proceeding of actinide and fission product partitioning and transmutation. Cadarache, France, 12–14 Dec 1994. http://www.oecd-nea.org/pt/docs/iem/cadarache94/Cadarache.html. Accessed 2014

  4. Poineau F, Weck PF, Burton-Pye BP, Kim E, Francesconi LC, Sattelberger AP, German KE, Czerwinski KR (2013) Eur J Inorg Chem 26:4595–4600

    Article  Google Scholar 

  5. Tumanova DN, German KE, Peretrukhin VF, Tsivadze AY (2008) Dokl Phys Chem 420:114–117

    Article  CAS  Google Scholar 

  6. Poineau F, Weck PF, German KE, Maruk A, Kirakosyan G, Lukens WW, Rego DB, Sattelberger AP, Czerwinski KR (2010) Dalton Trans 39:8616–8619

    Article  CAS  Google Scholar 

  7. Poineau F, Weck PF, Burton-Pye BP, Denden I, Kim E, Kerlin W, German KE, Fattahi M, Francesconi LC, Sattelberger AP, Czerwinski KR (2013) Dalton Trans 42:4348–4352

    Article  CAS  Google Scholar 

  8. Poineau F, Burton-Pye BP, Maruk A, Kirakosyan G, Denden I, Rego DB, Johnstone EV, Sattelberger AP, Fattahi M, Francesconi LC, German KE, Czerwinski KR (2013) Inorg Chim Acta 398:147–150

    Article  CAS  Google Scholar 

  9. Herrmann WA, Correia JDG, Kuhn FE, Artus GRJ, Romao CC (1996) Chem Eur J 2:168–173

    Article  CAS  Google Scholar 

  10. Monger JM, Redlich O (1956) J Phys Chem 60:797–799

    Article  CAS  Google Scholar 

  11. Mikhalev VA (2005) Radiochemistry 47:319–333

    Article  CAS  Google Scholar 

Download references

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.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Nevada Las Vegas, Las Vegas, NV, USA

    Frederic Poineau & Kenneth R. Czerwinski

  2. A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russian Federation

    Konstantin E. German, Aleksey Safonov & Viktor Ilin

  3. Department of Chemistry, Hunter College, New-York, NY, USA

    Benjamin P. Burton-Pye & Lynn C. Francesconi

  4. Sandia National Laboratories, Albuquerque, NM, USA

    Philippe F. Weck

  5. Department of Physics and Astronomy, University of Nevada Las Vegas, Las Vegas, NV, USA

    Eunja Kim

  6. Medical Institute REAVIZ, Moscow Branch, Moscow, Russian Federation

    Olga Kriyzhovets & Viktor Ilin

  7. Energy Engineering and Systems Analysis Directorate, Argonne National Laboratory, Lemont, IL, USA

    Alfred P. Sattelberger

Authors
  1. Frederic Poineau
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Konstantin E. German
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Benjamin P. Burton-Pye
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Philippe F. Weck
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Eunja Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Olga Kriyzhovets
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Aleksey Safonov
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Viktor Ilin
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Lynn C. Francesconi
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Alfred P. Sattelberger
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Kenneth R. Czerwinski
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Frederic Poineau.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Poineau, F., German, K.E., Burton-Pye, B.P. et al. Speciation of technetium peroxo complexes in sulfuric acid revisited. J Radioanal Nucl Chem 303, 1163–1167 (2015). https://doi.org/10.1007/s10967-014-3434-1

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10967-014-3434-1

Keywords

Search

Navigation