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Abstract  

A method for the precipitation of plutonium(IV) oxalate from homogeneous solutions using diethyl oxalate is reported. The precipitate obtained is crystalline and easily filterable with yields in the range of 92–98% for precipitations involving a few mg to g quantities of plutonium. Decontamination factors for common impurities such as U(VI), Am(III) and Fe(III) were determined. TGA and chemical analysis of the compound indicate its composition as Pu(C2O4)2·6H2O. Data are obtained on the solubility of the oxalate in nitric acid and in mixtures of nitric acid and oxalic acid of varying concentrations. Green PuO2 obtained by calcination of the oxalate has specifications within the recommended values for trace foreign substances such as chlorine, fluorine, carbon and nitrogen.

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Abstract  

Mediated electrochemical oxidation is a promising technique for the destruction of organic compounds. Destruction of tributyl phosphate (TBP) in normal paraffin hydrocarbon (NPH) in nitric acid medium containing electro-generated Ag(II) was studied. Initially, the effect of uranium, presence of DBP along with uranium in the organic phase and direct electrochemical oxidation without catalyst (Ag) on the destruction of 30% TBP/NPH system was evaluated. For a comparison, the rate of destruction of NPH alone was studied. Further, radioactive laboratory waste solution was tested for the destruction of organic waste under similar experimental conditions. The electrolyte used in the system was 0.5 M AgNO3 in 8 M HNO3 at 333 K. The uniqueness in all these experiments is the use of a double end open porcelain diaphragm for the isolation of electrodes. Though there would be a slight reduction in the efficiency, two major hurdles viz., reduction in the concentration of nitric acid and reduction in the volume of catholyte resulting in an increase in cell voltage were avoided. The problem of the migration of Ag+/Ag2+ and accumulating at the cathode site was overcome by using double end open diaphragm and thorough mixing. The results revealed that the rate of destruction of organics is favoured in the presence of uranium in organic phase and with increase in temperature.

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Journal of Radioanalytical and Nuclear Chemistry
Authors: A. Palamalai, S. Mohan, M. Sampath, R. Srinivasan, P. Govindan, A. Chinnusamy, V. Raman, and G. Balasubramanian

Abstract  

Some batches of233U oxide product obtained from the reprocessing treatment of irradiated thorium rods, called J-rods in our plant, have been found to contain thorium as much as 85% and iron above 5% as impurities. This product has to be purified before sending for fabrication of the fuel. The present purification method consists of the following three steps: (1) preferential dissolution of U3O8 as compared to thoria, (2) a novel solvent extraction process, and (3) preferential precipitation of Th as oxalate leaving behind the entire U in the filtrate. Development and application of the present purification method to the above233U oxide proxduct are presented in this paper.

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