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Mechanism for Solvent Extraction of Lanthanides from Chloride Media by Basic Extractants

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The solvent extraction of lanthanides from chloride media to an organic phase containing an anion exchanger in the chloride form is known to show low extraction percentages and small separation factors. The coordination chemistry of the lanthanides in combination with this kind of extractant is poorly understood. Previous work has mainly used solvent extraction based techniques (slope analysis, fittings of the extraction curves) to derive the extraction mechanism of lanthanides from chloride media. In this paper, EXAFS spectra, luminescence lifetimes, excitation and emission spectra, and organic phase loadings of lanthanides in dry, water-saturated and diluted Aliquat 336 chloride or Cyphos IL 101 have been measured. The data show the formation of the hydrated lanthanide ion [Ln(H2O)8–9]3+ in undiluted and diluted Aliquat 336 and the complex [LnCl6]3− in dry Aliquat 336. The presence of the same species [Ln(H2O)8–9]3+ in the aqueous and in the organic phase explains the small separation factors and the poor selectivities for the separation of mixtures of lanthanides. Changes in separation factors with increasing chloride concentrations can be explained by changes in stability of the lanthanide chloro complexes in the aqueous phase, in combination with the extraction of the hydrated lanthanide ion to the organic phase. Finally, it is shown that the organic phase can be loaded with 107 g·L−1 of Nd(III) under the optimal conditions.

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Acknowledgements

The authors thank the KU Leuven (Projects GOA/13/008 and IOF-KP RARE3), the FWO Flanders (postdoctoral fellowship to TVDH), VLAIO Flanders (Ph.D. fellowship to BO) and the Brazilian Science without Border program from CNPq (postdoctoral fellowship to ERS).

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  1. Department of Chemistry, KU Leuven, Celestijnenlaan 200F, P.O. Box 2404, 3001, Heverlee, Belgium

    Tom Vander Hoogerstraete, Ernesto Rezende Souza, Bieke Onghena, Dipanjan Banerjee & Koen Binnemans

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Vander Hoogerstraete, T., Souza, E.R., Onghena, B. et al. Mechanism for Solvent Extraction of Lanthanides from Chloride Media by Basic Extractants. J Solution Chem 47, 1351–1372 (2018). https://doi.org/10.1007/s10953-018-0782-4

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