Solubility Studies of Uranium(IV) by Laser-Induced Breakdown Detection (LIBD)

Uranium plays an important role in the long term safety assessment of nuclear waste repositories. It is therefore necessary to determine its correct thermodynamic data. However, the solubility of tetravalent uranium is not easily to measure because it shows a strong tendency to hydrolyse and to form hydroxides and hydrous oxides of low solubilities. Reported solubility products of U(IV) species are often too high due to the neglection of colloidal particles. Laser-induced breakdown detection (LIBD) provides an opportunity to detect such colloids down to a size of some nanometres at concentrations in the ppt range.
Solutions of U(VI)/HClO4/NaClO4 were reduced in an electrochemical cell under inert gas. The resulting U(IV) solutions were titrated coulometrically. Samples of the solution were pumped into a cuvette and investigated for the presence of colloids by LIBD. The pH of the onset of colloid formation and the U(IV) concentration were used to determine the solubility product of uranium(IV) hydroxide.