Experimental and Kinetic Simulations of Technetium-Catalyzed Hydrazine Oxidation in Nitric Acid Solution

The catalytic reaction of Tc plays a significant role in the chemical separation process during spent fuel reprocessing. However, few studies have been conducted on the chemical reaction mechanism between Tc and hydrazine. Moreover, the instability of Tc(V) and Tc(VI) makes their measurement difficult, rendering many aspects of the reaction process and mechanism unclear. This study investigates the catalytic reaction between Tc and hydrazine in a nitric acid solution. To this end, we obtained the kinetic laws of the reaction under various conditions of acidity, hydrazine concentration, and Tc concentration by monitoring the concentrations of hydrazine and Tc(VII) over time. The reaction kinetics model demonstrated that numerical simulations could effectively predict the reaction process. Results indicated that hydrazine promotes the reduction of Tc(VII) to Tc(IV), constituting the basis for establishing the Tc(IV, V, VI, VII) catalytic cycle. Among these, Tc(V) and Tc(VI) were important active intermediates and the main consumers of hydrazine. The research results may be useful for actinide separation processes based on valence control.