Effect of complexing agents (DTPA and oxalic acid) on the extraction behavior of technetium in the TBP-N2H5NO3-HNO3 system

Melent’ev, A. B.; Mashkin, A. N.; Tugarina, O. V.; Kolupaev, D. N.; German, K. É.; Тананаев, И. Г.

doi:10.1134/s106636221102010x

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“…During this step, the behavior of Tc is poorly understood. In nitric acid, the heptavalent Tc may be reduced to lower valences (most likely IV) by various reducing agents. – Previous studies have shown that Tc(IV) species are not extractable by TBP, but Tc(IV) can form kinetically stable complexes with DBP that can be extracted . Solvent extraction studies have shown that a TcO 2+ oxocation complex with the formula TcO(DBP·HDBP) 2 was extracted, but no structural data were reported.…”

Section: Introductionmentioning

confidence: 99%

Structural Investigation of Technetium Dibutylphosphate Species Using X-ray Absorption Fine Structure Spectroscopy

George,

Salcedo,

Greenberg

et al. 2023

Inorg. Chem.

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Section: Introductionmentioning

confidence: 99%

Structural Investigation of Technetium Dibutylphosphate Species Using X-ray Absorption Fine Structure Spectroscopy

George,

Salcedo,

Greenberg

et al. 2023

Inorg. Chem.

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Experimental and Kinetic Simulations of Technetium-Catalyzed Hydrazine Oxidation in Nitric Acid Solution

Yu,

Zhang,

Ning

et al. 2024

Processes

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The catalytic reaction of Tc plays a significant role in the chemical separation process during spent fuel reprocessing. However, few studies have been conducted on the chemical reaction mechanism between Tc and hydrazine. Moreover, the instability of Tc(V) and Tc(VI) makes their measurement difficult, rendering many aspects of the reaction process and mechanism unclear. This study investigates the catalytic reaction between Tc and hydrazine in a nitric acid solution. To this end, we obtained the kinetic laws of the reaction under various conditions of acidity, hydrazine concentration, and Tc concentration by monitoring the concentrations of hydrazine and Tc(VII) over time. The reaction kinetics model demonstrated that numerical simulations could effectively predict the reaction process. Results indicated that hydrazine promotes the reduction of Tc(VII) to Tc(IV), constituting the basis for establishing the Tc(IV, V, VI, VII) catalytic cycle. Among these, Tc(V) and Tc(VI) were important active intermediates and the main consumers of hydrazine. The research results may be useful for actinide separation processes based on valence control.

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Effect of complexing agents (DTPA and oxalic acid) on the extraction behavior of technetium in the TBP-N2H5NO3-HNO3 system

Cited by 2 publications

References 5 publications

Structural Investigation of Technetium Dibutylphosphate Species Using X-ray Absorption Fine Structure Spectroscopy

Structural Investigation of Technetium Dibutylphosphate Species Using X-ray Absorption Fine Structure Spectroscopy

Experimental and Kinetic Simulations of Technetium-Catalyzed Hydrazine Oxidation in Nitric Acid Solution

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