Dans le cadre des études sur le stockage de colis de déchets nucléaires, l'effet de la température sur les propriétés de rétention de l'ion uranyle sur Zr2O(PO4)2 a été étudié en milieu NaClO4 0,1 M. Dans un premier temps, l'effet de la température sur les propriétés acido-basiques de la surface (point de charge nulle, constantes d'acidité) a été suivi. Des expériences en réacteurs fermés ont été effectuées à des températures allant de 25°C à 90°C : la sorption des ions uranyle est favorisée avec l'augmentation de la température indiquant un processus de sorption de nature endothermique. La caractérisation des complexes de surface a été effectuée à l'aide des techniques spectroscopiques SLRT et EXAFS. Les mesures SLRT montrent la présence de deux complexes de surface différents. La nature de ces complexes ne se modifie pas avec le pH (3-5) ni la température (25°C-90°C). Par ailleurs, la spectroscopie EXAFS a mis en évidence la formation de complexes de sphère interne, bidentates. L'information structurale a été ensuite utilisée pour la modélisation des sauts de sorption. Pour le calcul des constantes de sorption, un modèle à capacité constante a été utilisé. Les équilibres de sorption modélisés ont révélé la formation des complexes de sorption : (>ZrOH)2UO22+ et (>PO)2UO2. La dépendance en température des constante de sorption a été ensuite utilisée pour déterminer les grandeurs thermodynamiques associées (ΔH° et ΔS°) par l'application de l'équation de van't Hoff. La variation d'enthalpie de formation du complexe (>ZrOH)2UO22+ est nulle, alors que celle du complexe (>PO)2UO2 est positive (55 kJ/mol), confirmant le caractère endotermique de la réaction de sorption.

The Ph.D. project compiled in this thesis has focused on the role of the solvent in solid-liquid phase equilibria and in nucleation kinetics. Six organic substances have been selected as model compounds, viz. ortho-, meta- and para-hydroxybenzoic acid, salicylamide, meta- and para-aminobenzoic acid. The different types of crystal phases of these compounds have been explored, and their respective solid-state properties have been determined experimentally. The solubility of these crystal phases has been determined in various solvents between 10 and 50 oC. The kinetics of nucleation has been investigated for salicylamide by measuring the metastable zone width, in five different solvents under different experimental conditions. A total of 15 different crystal phases were identified among the six model compounds. Only one crystal form was found for the ortho-substituted compounds, whereas the meta-isomeric compounds crystallized as two unsolvated polymorphs. The para-substituted isomers crystallized as two unsolvated polymorphs and as several solvates in different solvents. It was discovered that the molar solubility of the different crystal phases was linked to the temperature dependence of solubility. In general, a greater molar solubility corresponds to a smaller temperature dependence of solubility. The generality of this relation for organic compounds was investigated using a test set of 41 organic solutes comprising a total of 115 solubility curves. A semi-empirical solubility model was developed based on how thermodynamic properties relate to concentration and temperature. The model was fitted to the 115 solubility curves and used to predict the temperature dependence of solubility. The model allows for entire solubility curves to be constructed in new solvents based on the melting properties of the solute and the solubility in that solvent at a single temperature. Based on the test set comprising the 115 solubility curves it was also found that the melting temperature of the solute can readily be predicted from solubility data in organic solvents. The activity of the solid phase (or ideal solubility) of four of the investigated crystal phases was determined within a rigorous thermodynamic framework, by combining experimental data at the melting temperature and solubility in different solvents and temperatures. The results show that the assumptions normally used in the literature to determine the activity of the solid phase may give rise to errors up to a factor of 12. An extensive variation in the metastable zone width of salicylamide was obtained during repeated experiments performed under identical experimental conditions. Only small or negligible effects on the onset of nucleation were observed by changing the saturation temperature or increasing the solution volume. The onset of nucleation was instead considerably influenced by different cooling rates and different solvents. A correlation was found between the supersaturation ratio at the average onset of nucleation and the viscosity of the solvent divided by the solubility of the solute. The trends suggest that an increased molecular mobility and a higher concentration of the solute reduce the metastable zone width of salicylamide. / QC 20100831