Simulations of electrolytes at the liquid-liquid interface and of lanthanide cations complexes in gas phase

Two processes related to liquid/liquid extraction of ions by extractant molecules were studied: the ion approach at the interface and the ion complexation by ligands. In the first part, the behaviour of salts at the chloroform/water interface was simulated by molecular dynamics. The aim was to understand the way these salts ions approach the interface in order to be extracted. Some ions are repelled by the interface (K+, Cl-, UO22+, Na+, NO3-) whereas others adsorb (amphiphilic molecules and also ClO4-, SCN-, guanidinium Gu+ and picrate Pic-). The surface-active counter-ions make the ion approach at the interface easier. In a perfectly homogeneous mixture of the two solvents (water and chloroform) de-mixing, the ions seem to influence the phases separation rate. Nitric acid which is known to favour liquid/liquid extraction reveals strong adsorption at the interface in its neutral form and a smaller one in its ionic form (H3O+/NO3-). HNO3 and H3O+ display particular orientations at the interface: hydrogen atoms are pointing in the direction of the water slab. The nature of the organic phase can also influence the ion approach at the interface. For example, Gu+ and Pic- adsorb much less at the supercritical CO2/water interface than at the chloroform/water interface. In the second part, complexes of La3+, Eu3+ and Yb3+ with ligands such as amide, urea, thio-amide, thiourea were studied by quantum mechanics. Our calculations show that cation-ligand interactions depend on the nature of substituents on ligands, on the presence of counter-ions or on the number of ligands in the complex. Sulfur compounds seem to less interact with cations than oxygen compounds. Ureas interact as much as amides and are potentially good ligands. (author)