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Gaillard DC, Boltoeva M, Billard I, et al. Insights into the mechanism of extraction of uranium (VI) from nitric acid solution into an ionic liquid by using tri-n-butyl phosphate. Chemphyschem. 2015;16(12):2653-62doi: 10.1002/cphc.201500283.
Gaillard, D. C., Boltoeva, M., Billard, I., Georg, S., Mazan, V., Ouadi, A., Ternova, D., & Hennig, C. (2015). Insights into the mechanism of extraction of uranium (VI) from nitric acid solution into an ionic liquid by using tri-n-butyl phosphate. Chemphyschem : a European journal of chemical physics and physical chemistry, 16(12), 2653-62. https://doi.org/10.1002/cphc.201500283
Gaillard, Dr Clotilde, et al. "Insights into the mechanism of extraction of uranium (VI) from nitric acid solution into an ionic liquid by using tri-n-butyl phosphate." Chemphyschem : a European journal of chemical physics and physical chemistry vol. 16,12 (2015): 2653-62. doi: https://doi.org/10.1002/cphc.201500283
Gaillard DC, Boltoeva M, Billard I, Georg S, Mazan V, Ouadi A, Ternova D, Hennig C. Insights into the mechanism of extraction of uranium (VI) from nitric acid solution into an ionic liquid by using tri-n-butyl phosphate. Chemphyschem. 2015 Aug 24;16(12):2653-62. doi: 10.1002/cphc.201500283. Epub 2015 Jul 06. PMID: 26149535.
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Chemphyschem. 2015 Aug 24;16(12):2653-62. doi: 10.1002/cphc.201500283. Epub 2015 Jul 06.

Insights into the mechanism of extraction of uranium (VI) from nitric acid solution into an ionic liquid by using tri-n-butyl phosphate.

Chemphyschem : a European journal of chemical physics and physical chemistry

Dr Clotilde Gaillard, Maria Boltoeva, Isabelle Billard, Sylvia Georg, Valérie Mazan, Ali Ouadi, Dariia Ternova, Christoph Hennig

Affiliations

  1. Institut de Physique Nucléaire de Lyon, Université de Lyon, CNRS-IN2P3, 69622 Villeurbanne cedex (France). [email protected].
  2. Université de Strasbourg, IPHC, 23 rue du Lœss, 67037 Strasbourg (France).
  3. CNRS, UMR 7178, 67037 Strasbourg (France).
  4. Univ. Grenoble Alpes, LEPMI, F-38000 Grenoble (France).
  5. CNRS, LEPMI, F-38000 Grenoble (France) (present address).
  6. Institute of Organic Chemistry, NASU, Kyiv (Ukraine).
  7. Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, P.O. Box 510119, 01314 Dresden (Germany).

PMID: 26149535 DOI: 10.1002/cphc.201500283

Abstract

We present new results on the liquid-liquid extraction of uranium (VI) from a nitric acid aqueous phase into a tri-n-butyl phosphate/1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (TBP/[C4 mim][Tf2 N]) phase. The individual solubilities of the ionic-liquid ions in the upper part of the biphasic system are measured over the whole acidic range and as a function of the TBP concentration. New insights into the extraction mechanism are obtained through the in situ characterization of the extracted uranyl complexes by coupling UV/Vis and extended X-ray absorption fine structure (EXAFS) spectroscopy. We propose a chemical model to explain uranium (VI) extraction that describes the data through a fit of the uranyl distribution ratio DU . In this model, at low acid concentrations uranium (VI) is extracted as the cationic complex [UO2 (TBP)2 ](2+) , by an exchange with one proton and one C4 mim(+) . At high acid concentrations, the extraction proceeds through a cationic exchange between [UO2 (NO3 )(HNO3 )(TBP)2 ](+) and one C4 mim(+) . As a consequence of this mechanism, the variation of DU as a function of TBP concentration depends on the C4 mim(+) concentration in the aqueous phase. This explains why noninteger values are often derived by analysis of DU versus [TBP] plots to determine the number of TBP molecules involved in the extraction of uranyl in an ionic-liquid phase.

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: ionic liquids; solvent extraction; tri-n-butyl phosphate; uranium

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