Direct spectrophotometric analysis of low level Pu (III) in Pu(IV) nitrate solution

Among the various methods demonstrated for the conversion of plutonium nitrate to its oxide, the oxalate precipitation process either as Pu (III) or Pu (IV) oxalate gained wide acceptance. Since uranous nitrate is the most successful partitioning agent used in the PUREX process for the separation of Pu from the bulk amount of U, the Pu (III) oxalate precipitation of the purified nitrate solution will not give required decontamination from U. Hence Pu IV oxalate precipitation process is a better option to achieve the end user's specified PuO2 product. Prior to the precipitation process, ensuring of the Pu (IV) oxidation state is essential. Hence monitoring of the level of Pu oxidation state either Pu (III) or Pu (IV) in the feed solution plays a significant role to establish complete conversion of Pu (III). The method in vogue to estimate Pu(lV) content is extractive radiometry using Theonyl Trifluoro Acetone (TTA). As the the method warrants a sample preparation with respect to acidity, a precise measurement of Pu (IV) without affecting the Pu(III) level in the feed sample is difficult. Present study is focused on the exploration of direct spectrophotometry using an optic fiber probe of path length of 40mm to monitor the low level of Pu(III) after removing the bulk Pu(lV) which interfere in the Pu(III) absorption spectrum, using TTA-TBP synergistic mixture without changing the sample acidity