Correlation between aggregation and extracting properties in solvent extraction systems: extraction of actinides (III) and lanthanides (III) by a malonamide in non acidic media

The organic phases of the DIAMEX (Diamide Extraction) process, allowing the co-extraction of actinides(III) and lanthanides(III) from high level radioactive wastes using a malonamide extractant molecule (DMDOHEMA) diluted in alkanes, are investigated. The aim of this study is to establish a link between different structures/organizations of diamide extractants and their extracting properties towards An(III) and Ln(III) cations. It is demonstrated that diamide, which are amphiphilic molecules, are organized in different structures (monomers, reverse micelles, lamellar phases..). This study deals with the effect of the composition of the extracting system on the extracting and aggregation properties of the DMDOHEMA solutions. The effects of the extractant (DMDOHEMA diluted in n-heptane) and metal concentrations (for a given extractant concentration) from a LiNO3 aqueous phase are investigated at two scales: at the supra-molecular scale by characterizing the aggregation by vapor-pressure osmometry (VPO) and small angle neutron and X-ray scattering (SANS and SAXS) experiments, and at the molecular scale by quantifying the extracted solutes (metal nitrate and water) and by determining the stoichiometries of the extracted complexes by electro-spray mass spectrometry (ESI-MS). The extraction equilibria can then be modeled by two approaches: a classical approach in solvent extraction based on mass action laws to determine extraction equilibria and their associated thermodynamic constants, and a physical chemical approach which consists in considering the extracted ions as adsorbed on a specific available surface of the extractant molecule. Thus, the extraction equilibrium can be considered as a sum of Langmuir isotherms corresponding to the different states of aggregation. The resulting constants are representative of both extraction efficiency and organic phase structure. (authors)