Molecular Hydrogen Yields from the α-Self-Radiolysis of Nitric Acid Solutions Containing Plutonium or Americium.

Abstract

The yield of molecular hydrogen, as a function of nitric acid concentration, from the α-radiolysis of aerated nitric acid and its mixtures with sulfuric acid containing plutonium or americium has been investigated. Comparison of experimental measurements with predictions of a Monte Carlo radiation track chemistry model shows that, in addition to scavenging of the hydrated electron, its precursor, and the hydrogen atom, the quenching of excited state water is important in controlling the yield of molecular hydrogen. In addition, increases in solution acidity cause a significant change in the track reactions, which can be explained as resulting from scavenging of eaq- by Haq+ to form H•. Although plutonium has been shown to be an effective scavenger of precursors of molecular hydrogen below 0.1 mol dm-3 nitrate, previously reported effects of plutonium on G(H2)α between 1 and 10 mol dm-3 nitric acid were not reproduced. Modeling results suggest that plutonium is unlikely to effectively compete with nitrate ions in scavenging the precursors of molecular hydrogen at higher nitric acid concentrations, and this was confirmed by comparing molecular hydrogen yields from plutonium solutions with those from americium solutions. Finally, comparison between radionuclide, ion accelerator experiments, and model predictions leads to the conclusion that the high dose rate of accelerator studies does not significantly affect the measured molecular hydrogen yield. These reactions provide insight into the important processes for liquors common in the reprocessing of spent nuclear fuel and the storage of highly radioactive liquid waste prior to vitrification.