Formalization of the kinetics for autocatalytic dissolutions. Focus on the dissolution of uranium dioxide in nitric medium

Abstract

Uranium dioxide dissolution in nitric acid is a complex reaction. On the one hand, the dissolution produces nitrous oxides (NOX ), which makes it a triphasic reaction. On the other hand, one of the products accelerates the kinetic rate; the reaction is hence called autocatalytic. The kinetics for these kinds of reactions need to be formalized in order to optimize and design innovative dissolution reactors. In this work, the kinetics rates have been measured by optical microscopy using a single particle approach. The advantages of this analytical technique are an easier management of species transport in solution and a precise following of the dissolution rate. The global rate is well described by a mechanism considering two steps: a non-catalyzed reaction, where the catalyst concentration has no influence on the dissolution rate, and a catalyzed reaction. The mass transfer rate of the catalyst was quantified in order to discriminate when the reaction was influenced by catalyst accumulated in the boundary layer or uncatalyzed. This first approximation described well the sigmoid dissolution curve profile. Moreover, experiments showed that solutions filled with catalyst proved to lose reactivity over time. Results pointed out that the higher the liquid-gas exchanges, the faster the kinetic rate decreases with time. Thus, it was demonstrated, for the first time, that there is a link between catalyst and nitrous oxides. The outcome of this study leads to new ways for improving the design of dissolvers. Gas-liquid exchanges are indeed a lever to impact dissolution rates. Temperature and catalyst concentration can be optimized to reduce residence times in dissolvers.