Reduction Rates for Higher Americium Oxidation States in Nitric Acid

Grimes, Travis Shane¹  Mincher, Bruce Jay¹  Schmitt, Nicholas C¹ 

[1]Idaho National Lab. (INL), Idaho Falls, ID (United States)

关键词: AMERICIUM;    NITRIC ACID;    REDUCTION;    CONCENTRATION RATIO;    DODECANE;    SODIUM COMPOUNDS;    CERIUM IONS;    OXIDATION;    PERCHLORIC ACID;    ABUNDANCE;    COMPARATIVE EVALUATIONS;    VALENCE;    SEPARATION PROCESSES;    CHEMICAL REACTION KINETICS;    BISMUTH COMPOUNDS;    OXYGEN COMPOUNDS;    STABILITY americium reduction nitric acid;    Americium reduction kinetics;    Americium VI oxidation;   

DOI  :  10.2172/1244636
RP-ID  :  INL/EXT--15-36767
PID  :  OSTI ID: 1244636
Others  :  TRN: US1601059

学科分类：化学（综合）

美国|英语

来源: SciTech Connect

【 摘 要 】

The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.