The disproportionation of Pu4+ in nitric acid solutions

The Pu4+ disproportionation equilibrium in nitric acid has been examined at ≤25deg C to extend our understanding and predictive ability with regard to species distribution under these conditions. Vis/UV absorption spectrophotometry has been used in a conventional manner to determine the concentrations of the various plutonium species. Values for the overall equilibrium quotient at 5, 15, and 25deg C were determined to be 0.098, 3.46, and 58.8, respectively, at zero ionic strength. From these values, the enthalpy of the reaction was found to be +52.7 kcal (220 kJ)/mol. The excellent reproducibility of the equilibrium quotients, even while parameters such as acid, nitrate ion and plutonium concentrations were changed, lend confidence to future predictive calculations regarding this reaction. (orig.)