Description: Abstract: "The equilibrium quotients and the specific rate constants for the disproportionation of Pu(IV) have been measured as a function of hydrogen and plutonium ion concentrations in perchloric acid solutions of unit ionic strength at 25.00 +/- 0.02. Instead of obtaining the plutonium ion concentrations spectrophotometrically as has been done by previous workers, measurements of the mean oxidation number of the solutions were combined with electromotive force measurements of the Pu(III)-Pu(IV) 'couple and the total plutonium ion concentrations. From these data it is possible to calculate the concentrations of Pu(III), Pu(IV) and Pu(VI) present in the solutions at any time. The equilibrium quotient for the disproportionation reaction has been found to be directly dependent upon the fourth power of the hydrogen ion concentration, thus supporting the existence of the plutonyl ion, PuO2++, in these solutions. A weighted mean value of 0.0089 was found for the Pu(IV) disproportionation equilibrium quotient in perchloric acid solutions of unit ionic strength at 25. The rate of the forward (disproportionation) reaction has been found to exhibit an inverse third power hydrogen ion concentration dependence and the most probable rate determining step of this reaction is PuOH++++ + Pu(OH)2++ --> Pu+++ + PuO2+ + H2O + H+."
Creator: Rabideau, Sherman W.
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Partner: UNT Libraries Government Documents Department