Meyer, R E; Arnold, W D; Case, F I; O'Kelley, G D
Solubilities of Tc(IV) oxides have been determined in a number of solutions in the pH range 1 to 10. Technetium oxide was prepared by precipitation upon purified sand with a 30% excess of hydrazine and by electrodeposition. The oxide-covered sand was transferred to a small column, and the solutions to be studied were continuously cycled through the column. The electrodeposited oxide was formed on a platinum mesh electrode, and after careful rinsing, the solution to be studied was added to the electrolytic cell. The concentrations of total technetium and Tc(IV) species in the solutions were periodically determined by separating the oxidized and reduced technetium species using a solvent extraction procedure and counting the beta activity of the /sup 99/Tc with a liquid scintillation counter. In basic solutions, the concentrations of Tc(IV) species in equilibrium with the oxide were in the range of 10/sup /minus/8/ to 10/sup /minus/9/ mol/L and tended to increase slightly with pH. In acid solutions the concentrations were much higher and were consistent with literature data on the hydrolytic species of Tc(IV). Solubilities appeared to reach a minimum in the intermediate pH range, and they were generally a factor of three or four lower for oxides electrodeposited in basic solutions compared to those for oxides electrodeposited from acid solution. The oxides were hydrated, and assuming a formula of TcO/sub 2//center dot/nH/sub 2/O, the value of n was found to be 1.63 +- 0.28. These data can be used to estimate Tc(IV) solubilities for cases where solubility limits transport of technetium in reducing environments of high-level waste repositories. 22 refs., 7 figs., 9 tabs.