A multiparametric study on the dissolution of synthetic brannerite

Brannerite, UTi2O6 is reported to occur in various uraniferous deposits worldwide. Natural brannerite specimens are found in the amorphous state and are usually considered to be refractory to dissolution due to the formation of TiO2 passivation layer. In the present work, brannerite was synthesized by wet chemistry route, then characterized prior the development of multiparametric dissolution experiments. The evolution of U and Ti concentrations was followed in 0.1–2 mol/L H2SO4 solutions, for temperatures ranging from 25 to 80 °C, in the presence (or not) of 2.8 g/L of dissolved Fe(III). The dissolution of synthetic brannerite was congruent in the whole experimental domain. The formation of Ti-enriched secondary phase at the surface of the brannerite grains was not evidenced. The dissolution rate constants, activation energies and partial orders of the overall dissolution reaction relative to proton activity were determined in the presence (or absence) of Fe(III). The introduction of Fe(III) in sulfuric acid solutions increased the dissolution rate constant by 5 orders of magnitude and induced significant modifications of the apparent activation energy (from 71 ± 4 to 91 ± 6 kJ/mol) and of the partial order relative to proton activity (from 0.42 ± 0.09 to 0.84 ± 0.08). This study suggested that the uncongruency of the brannerite dissolution and the changes usually observed in the rate-controlling step with temperature could be linked to the loss of the crystal structure in natural samples.