Model for predicting hydroxylamine nitrate stability in plutonium process solutions

A mathematical model is described that may be used to determine the safety of hydroxylamine nitrate (HAN) solutions used in solvent extraction purification of plutonium. The most significant hazard associated with hydroxylamine use in processing plutonium is its rapid, autocatalytic reaction with nitric acid which can result in an explosion or pressurization of process vessels with radiological consequences to humans. In addition, heat is produced by the reaction that could potentially ignite process solvents. The HAN decomposition reaction can occur only under specific process conditions (temperature; HAN, plutonium and nitric acid concentrations) and the model is used to identify these conditions so that they can be avoided. A kinetics model has been developed using all of the known significant reactions that could occur in process solutions containing HAN and nitric acid as well as plutonium and iron. The reaction kinetics data (rate laws, rate constants, activation energies) used in the model were obtained from chemical literature sources. The model shows that the autocatalytic HAN reaction with nitric acid is very rapid and is catalyzed by Pu(III) and Fe(II) in process solutions. High temperatures and nitric acid concentrations also promote the reaction.

Research highlights
► We model stability of hydroxylamine nitrate in nitric acid solutions containing plutonium.
► The autocatalytic reaction of HAN with nitric acid produces significant heat and gas.
► Pu(III) and Fe(II) catalyze the autocatalytic reaction.
► High temperatures and high nitric acid concentrations promote the reaction.
► This presents the first accurate model available for making the stability prediction.