Synergism in a HDEHP/TOPO Liquid−Liquid Extraction System: An Intrinsic Ligands Property?

O Pecheur 1 Sandrine Dourdain 2, 3 D. Guillaumont 1 J. Rey 3 P Guilbaud 1 L. Berthon 1 M.C. Charbonnel 1 S Pellet-Rostaing 3 F Testard 4
1 DRCP - Département RadioChimie et Procédés
2 ICSM - UMR 5257 - Institut de Chimie Séparative de Marcoule
3 LTSM - Tri ionique par les Systèmes Moléculaires auto-assemblés
ICSM - UMR 5257 - Institut de Chimie Séparative de Marcoule
4 LIONS - Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire
NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)
Abstract : Among the proposed mechanisms to predict and understand synergism in solvent extraction, the possibility of a preorganization of the mixture of extractant molecules has never been considered. Whether involving synergistic aggregation as for solubilization enhancement with reverse micelles or favored molecular interaction between the extractant molecules, evaluation of this hypothesis requires characterization of the aggregates formed by the extractant molecules at different scales. We investigate here the HDEHP/ TOPO couple of extractant with methods ranging from vibrational spectroscopy and ESI-MS spectrometry to vapor pressure osmometry and neutron and X-ray scattering to cover both molecular and supramolecular scales. These experimental methods are subjected to DFT calculations and molecular dynamics calculations, allowing a rationalization of the results through the different scales. Performed in the absence of any cation, this original study allows a decorrelation of the mechanisms at the origin of synergy: it appears that no clear preorganization of the extractants can explain the synergy and therefore that the synergistic aggregation observed in the presence of cations is rather due to the chelation mechanisms than to intrinsic properties of the extractant molecules.
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Journal articles
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https://hal-cea.archives-ouvertes.fr/cea-01294523
Contributor : Serge Palacin <>
Submitted on : Tuesday, March 29, 2016 - 1:55:49 PM
Last modification on : Wednesday, August 28, 2019 - 10:52:02 AM

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O Pecheur, Sandrine Dourdain, D. Guillaumont, J. Rey, P Guilbaud, et al.. Synergism in a HDEHP/TOPO Liquid−Liquid Extraction System: An Intrinsic Ligands Property?. Journal of Physical Chemistry B, American Chemical Society, 2016, 120, pp.2814-2823. ⟨10.1021/acs.jpcb.5b11693⟩. ⟨cea-01294523⟩

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