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Due to their amphiphilic properties, malonamide molecules in alkane are organized in reverse micelle type aggregates, composed of a polar core formed by the malonamide polar heads and the extracted solutes, and surrounded by a hydrophobic shell made up of the extractant alkyl chains. The aggregates interact with one another through an attractive potential, leading to the formation of a third phase. This occurs with the splitting of the organic phase into a light phase composed mostly of diluent, and a heavy third phase containing highly concentrated extractant and solutes. In this article, we show that the aggregation (monomer concentration, domain of stability, and attractive potential between micelles) greatly depends on the nature of the extracted solute, whereas the size of aggregate (aggregation number) is only slightly influenced by this. We describe the extraction of water, nitric acid, neodymium nitrate and uranyl nitrate. Strongly polarizable species induce consistently large attraction potentials and a small stability domain for the dispersion of nanodroplets in the solvent. Highly polarizable ions such as lanthanides or uranyl induce more long-range attractive interactions than do protons.

Three length scales have to be considered to describe microemulsions: persistence length, spontaneous radius of curvature of the surfactant film as intensive variables and finally the characteristic size imposed by the ratio of volume fraction to available specific area surface. The specific area per unit volume is an intensive variable linked to sizes and topologies that can be built without tearing the surfactant film. We show here that at least four types of bicontinuous microstructures have been detected so far, and that they can be distinguished by a simple experimental determination of the evolution of scattering peak position versus dilution. Besides the classical microstructures dominated by entropy or a priori considered as droplets, the other microstructures identified so far can be approximated as connected cylinders or randomly connected swollen bilayers. All these microstructures can be considered as “molten” precursors of the lyotropic liquid crystalline phases that are adjacent to microemulsions in phase diagrams.

We show that liquid–liquid extraction can be described as the equilibrium between two pseudophases of ions: the hydrated state in the water phase and the solvation state when the ions are adsorbed on an organized interface. The extractant is considered as a potential surface where the ions can adsorb. Unlike phenomenological binding “constants”, ion extraction/stripping can be seen as the sum of Langmuir isotherms. The number of aggregated extractants in one reverse micelle in the solvent is at least equal to or higher than the number of extracting molecules complexed at a given instant to the ion to be extracted. Considering extraction equilibrium as a sum of isotherms corresponding to the different states of aggregation of extractant molecule in the solvent, the resulting constant is representative of both the efficiency of the extraction and the structure of the solution. This is a first step toward the development of predictive models for the apparent distribution coefficients.

Key issues in radiochemistry, physical chemistry of separation and chemistry of materials needed for a sustainable nuclear energy production are described. These driving questions are at the origin of the creation of the Institute of Separation Chemistry at Marcoule. Each of the domains has been described extensively in recent reports for science and technology of the French academy of Science.