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Title: Speciation of technetium peroxo complexes in sulfuric acid revisited

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 H2SO42SO44 - 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.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [1] ;  [5] ;  [2] ;  [6] ;  [3] ;  [7] ;  [1]
  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)
Publication Date:
OSTI Identifier:
1113042
Report Number(s):
SAND--2013-8259J
Journal ID: ISSN 0236-5731; PII: 3434
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Journal of Radioanalytical and Nuclear Chemistry
Additional Journal Information:
Journal Volume: 303; Journal Issue: 2; Journal ID: ISSN 0236-5731
Publisher:
Springer
Research Org:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY technetium; peroxo complexes; speciation; sulfuric acid