THE KINETICS OF THE DISPROPORTIONATION OF PLUTONIUM(V)

Journal Article · Fri Dec 20 04:00:00 EST 1957 · Journal of the American Chemical Society (U.S.)

DOI:https://doi.org/10.1021/ja01581a002· OSTI ID:4313898

Rabideau, S W

A study has been made of the kinetics of the disproportionation of plutonium(V) in perchlorate solutions of unit ionic strength in which the PuC/sub 2//sup +/ was prepared by the reduction of the plutonyl ion with iodide ion. With this method of preparation, the disproportionation of plutonium(V) was studied in the absence of significant quantities of plutonium(II) and (IV) in the initial phases of the experiments. The rate of disproportionation of plutonium(V) has been found to be directly proportional to the first power of the hydrogen ion concentration which suggests that the slow step is probably PuO/sub 2//sup +/+ Pu(O)OH/sup ++/ yields PuO/sub 2//sup ++/ Pu(O)OH/sup +/. An activation energy of 19.6 kcal. has been computed from the temperature dependence of the specific reaction rate constants for the slow step of the disproportiomation reaction. The disproportionation of plutonium(V) has also been studied in deuterium oxide to note the influence of a change in solvent upon the reaction rates. It appears from the kinetic results obtained that no evidence has been foumd which would support the hydrogen atom transfer mechanism in the plutonium(V) disproportionation reaction. Plutonium(V) also has been prepared from the plutonyl ion by the spontaneous alpha -reduction process. The kinetic data appear to be adequately described by a consideration of previously determined rate and equilibrium constants and the rate constant for the Pu(V)-- Pu(V reaction which was obtained from the experiments in which the plutonyl ion was reduced with iodide. (auth)

• Research Organization: Los Alamos Scientific Lab., N. Mex.
• Sponsoring Organization: USDOE
• NSA Number: NSA-12-004772
• OSTI ID: 4313898
• Journal Information: Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 79; ISSN JACSA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

CHEMICAL REACTIONS
CHEMISTRY
DEUTERIUM COMPOUNDS
DISPROPORTIONATION
HYDROGEN
IODIDES
IONS
MATHEMATICS
PERCHLORIC ACID
PLUTONIUM
PLUTONIUM COMPOUNDS
PRODUCTION
QUANTITY RATIO
REACTION KINETICS
REDUCTION
SOLVENTS
TEMPERATURE
THERMODYNAMICS