Speciation of Technetium Dibutylphosphate in the Third Phase Formed in the TBP/HNO 3 Solvent Extraction System

The speciation of technetium in the nitric acid/dibutylphosphoric acid (HDBP)- -dodecane system was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy and theoretical methods. Tetravalent technetium, produced by the hydrazine reduction of TcO in 3 M HNO , was extracted by HDBP...

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Published in:ACS omega 2024-04, Vol.9 (13), p.15527-15534
Main Authors: George, Jonathan, Salcedo, Ramsey, Greenberg, Rachel, Elshendidi, Hossam, McGregor, Donna, Burton-Pye, Benjamin, Francesconi, Lynn C, Paulenova, Alena, Gelis, Artem V, Poineau, Frederic
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Language:English
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Summary:The speciation of technetium in the nitric acid/dibutylphosphoric acid (HDBP)- -dodecane system was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy and theoretical methods. Tetravalent technetium, produced by the hydrazine reduction of TcO in 3 M HNO , was extracted by HDBP in -dodecane (30% by volume). During extraction, the splitting of the organic phase into a heavy phase and a light phase was observed. EXAFS analysis is consistent with the presence of Tc(NO ) (DBP)(HDBP) in the light phase and Tc(NO ) (DBP) (HDBP) in the heavy phase. Density functional theory calculations at the B3LYP/6-31G* level confirm the stability of the proposed species and indicate that stereoisomers -mer- and fac-Tc(NO ) (DBP)(HDBP) for the light phase and cis- and trans-Tc(NO ) (DBP) (HDBP) for the heavy phase] could coexist in the system (in the -dodecane solution). Mechanisms of formation of Tc(NO ) (DBP)(HDBP) and Tc(NO ) (DBP) (HDBP) are proposed.
ISSN:2470-1343
2470-1343
DOI:10.1021/acsomega.4c00393