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AbstractAbstract
[en] The presented work describes the supramolecular structure of mixtures of a hydrophilic surfactant n-octyl-beta-glucoside (C8G1), and the hydrophobic metal ion extractant tributylphosphate (TBP) in n-dodecane/water as well as in the presence of salts. In the first part, basic solvent extraction system, composed of water, oil and extractant, will be introduced. The focus, however, lies on the extraction of multivalent metal ions from the aqueous phase. During this extraction process and in the following thermodynamic equilibrium, aggregation and phase transition in supramolecular assemblies occur, which are already described in literature. Notably, these reports rest on individual studies and specific conclusions, while a general concept is still missing. We therefore suggest the use of generalized phase diagrams to present the physico-chemical behaviour of (amphiphilic) extractant systems. These phase diagrams facilitated the development of a thermodynamic model based on molecular geometry and packing of the extractant molecules in the oil phase. As a result, we are now in the position to predict size and water content of extractant aggregates and, thus, verify the experimental results by calculation.Consequently, the second part presents a systematic study of the aqueous and organic phase of water/C8G1 and water/oil/TBP mixtures. The focus lies on understanding the interaction between metal ions and both amphiphilic molecules by means of small angle x-ray scattering (SAXS), dynamic light scattering (DLS) and UV-Vis spectroscopy. We confirmed the assumption that extraction of metal ions is driven by TBP, while C8G1 remains passive. In the third and last part, microemulsions of C8G1, TBP, water (and salt) and n-dodecane are characterized by small angle neutron scattering (SANS), and chemical analytics (Karl Fischer, total organic carbon, ICP-OES,...). The co-surfactant behaviour of TBP was highlighted by comparison to the classical n-alcohol (4≤n≤8) co-surfactants. The compositions of the C8G1/TBP and C8G1/n-hexanol interfacial mixed films obtained experimentally were confirmed by the prediction of a model based on the molecular geometrical parameters. We furthermore exploit the interfacial properties of these molecules to control the kinetics of liquid-liquid extraction and attempt a 'solvent free' ion separation using flotation. (author)
[fr]
Le but du travail est d'etudier la structure supramoleculaire de melanges de tensioactif hydrophile, n-octyl-beta-glucoside (C8G1), et d'un extractant d'ions metalliques hydrophobe, le tributyl-n-phosphate (TBP), en presence d'eau, d'huile et de sels. Les systemes classiques d'extraction ionique (composes d'une phase aqueuse, d'huile et d'extractant) dont le but est d'extraire un solute de la phase polaire sont passes en revue. L'aspect colloidal et les transitions de phases que l'on retrouve dans ces systemes sont souvent decrits singulierement. Nous avons transpose l'approche 'diagramme de phases' issue de la physico-chimie des systemes moleculaires organises a ces systemes d'extractant afin d'orienter globalement l'analyse de ces systemes complexes. La discussion est basee sur des considerations geometriques. Un modele thermodynamique a ete developpe en considerant les contraintes d'empilement de ces extractants dans le film moleculaire formant les micelles inverses d'extractant dans l'huile. Ce modele a permis de predire la solubilite de l'eau au sein de ces micelles inverses ainsi que leurs tailles obtenues experimentalement. Dans une deuxieme partie, le comportement physico-chimique des phases aqueuses et organiques composees respectivement d'eau/C8G1 et de TBP/huile/eau ont ete etudiees, en s'interessant particulierement aux effets de sels, par des techniques de diffusion de rayons X aux petits angles, diffusion dynamique de la lumiere et de spectroscopie UV-visible. Dans la derniere partie la description complete de la microemulsion en faisant varier la balance hydrophile-hydrophobe du melange C8G1 et TBP a ete obtenue en combinant des mesures de diffusion de neutrons aux petits angles et d'analyse chimique (Karl-Fischer, Carbone Organique Total, ICP-OES..). Le comportement co-surfactant du TBP a ete determine par comparaison aux co-surfactants classiques que sont les n-alcools (4≤n≤8). Les compositions de films moleculaires mixtes de C8G1/TBP et de C8G1/n-hexanol, obtenues experimentalement, ont ete confirmees par un modele base sur des parametres geometriques moleculaires. Nous avons tente d'exploiter les proprietes interfaciales de ces molecules pour le controle des cinetiques d'extraction liquide-liquide d'ion et la separation d'ions 'sans solvant' par flottationOriginal Title
Extractant d'ion metallique en microemulsion: de l'extraction par solvant a la science colloidale
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10 Jun 2011; 227 p; 232 refs.; Available from the INIS Liaison Officer for France, see the 'INIS contacts' section of the INIS-NKM website for current contact and E-mail addresses: http://www.iaea.org/INIS/contacts/; Chimie et Physicochimie des Materiaux
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