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Keywords:

  • Technetium;
  • Sulfides;
  • Speciation;
  • X-ray absorption spectroscopy;
  • Density functional calculations

Abstract

The reaction between TcVII and H2S(g) in 12 M H2SO4 has been studied. This reaction produced a black solid and a brown supernate. The solid was analyzed by energy dispersive X-ray (EDX) and X-ray absorption fine structure (XAFS) spectroscopy and the results were consistent with the presence of Tc2S7. The speciation of technetium in the supernate was performed by UV/Visible and XAFS spectroscopy. Experiments showed that in 12 M H2SO4 an intermediate TcV sulfate complex was formed. Analysis indicated that the final complex present in solution was a polymeric species with a Tc–O–Tc core coordinated to sulfate ligands. Density Functional Theory (DFT) calculations showed that the proposed complexes were stable and that the theoretical structure was in good agreement with XAFS data.