A description is given of observation by extraction and spectrophotometry on the oxidation of Pu(III) by aeration and also on the reduction of Pu(IV) with various concentrations of reducing agents and of nitric acid.
Observations were also made on the reduction of Pu(IV) and (VI) extracted in TBP and DBP phases with both nitrous acid and hydrogen peroxides. Further, the adaptability of these reagents to separation and purification of Pu from U and the correct amounts of the reagents required for adjusting the Pu valency were studied.
Oxidation of Pu(III) by aeration quite evident in low acid solution, but insignificant at concentrations above 2.0M nitric acid.
The most suitable concentrations of nitric acid for the reduction of Pu(VI) by nitrous acid (-0.5M) was below 0.2M. A percentage reduction in the range of 68-85% was observed on the Pu by nitrous acid in TBP phase after 5min, so that the method is quite promising for application to the purification of Pu.
A nitric acid concentration of 4.0M assured 100% conversion to Pu(IV) with an equimolor amount of hydrogen peroxide, while 100% of Pu(III) was obtained on the other hand with hydrogen peroxide added to an amount 10-20 times of the Pu.
In TBP phase the reduction percent of Pu by hydrogen peroxide was only in the range of 35-50% after 20min, which is significantly inferior to nitrous acid.
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