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  • Author or Editor: P. Mohapatra x
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Abstract  

The role of temperature on the distribution of Am3+ and UO2 2+ was investigated in the extraction systems involving TBP and DOSO as the neutral oxodonors and picrate as the organophilic counter anion. The inner-sphere water molecules and their substitution by the oxodonor molecules appeared to influence the extraction constants of these metal ions. The conditional extraction constants for Am3+ were found to be larger (about 3 order of magnitude) than those for UO2 2+. From the thermodynamics data it appeared that both TBP as well as DOSO bind Am3+ ion through outer-sphere coordination. In presence of 1M NaCl, though the interaction with TBP remains unaltered DOSO tend to form an inner-sphere complex. On the other hand, UO2 2+ forms inner-sphere complexes with DOSO and outer-sphere complex with TBP in the absence of salt. In the presence of 1M NaCl, both TBP and DOSO form inner-sphere complexes. The effect of ionic strength on metal ion extraction was also investigated.

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Abstract  

The extraction behavior of Am3+ and UO2 2+ is investigated employing chloroform solution of 18-crown-6 as the organic phase and picrate solution at pH 3.0 as the aqueous phase. In contrast to the commonly observed behavior, the extraction of Am3+ is preferred to that of UO2 2+. This unusual separation behavior is investigated as a function of several variable parameters such as crown ether concentration, picric acid concentration, inert electrolyte concentration, nature of diluent etc. Thermodynamic parameters are also evaluated.

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Abstract  

With increasing global nuclear activities, there is a growing interest in understanding the migration behavior of transuranic elements in the terrestrial environment. The laboratory investigations on the adsorption behavior of AM(III) (10–7M) in aqueous solutions showed that there was not adsorption of Am(III) on glass or polyethylene vials from aqueous solutions at pH<3. The rate of adsorption was found to be inversely related to the (H+) in the pH range 4–7. It was also found to be strongly influenced by stirring/shaking as well as by the presence of particulate matter in the aqueous phase. The presence of particulate matter (>0.6 m) in the aqueous solutions significantly inhibits the adsorption rate. Attempts to fit the kinetic data (collected on filtered [particle size >0.6 m] or unfiltered distilled water at pH 6) to the reversible or irreversible first order rate equation did not successfully indicate the complexity of the adsorption process. The presence of 20mg/liter of humic acid at pH 6.3 completely inhibits the adsorption of Am on glass surfaces.

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Abstract  

The extraction behavior of several metal ions viz., Am3+, Eu3+, UO2 2+, Th4+, Sr2+ and Cs+ was investigated from sulphate medium employing phosphotungstic acid (PTA) and polyethylene glycol (PEG). The influence of various parameters such as pH, PTA concentration, PEG concentration and salt concentration was studied. The order of extraction followed the trend: Am3+>Eu3+>>Th4+>UO2 2+>Sr2+>Cs+ which deviate significantly from the reported order with conventional solvents. The relatively poor extraction of UO2 2+, Sr2+ and Cs+ was ascribed to their lack of interaction with the phosphotungstate anion. The separation behaviour of Am3+ vis-a-vis Eu3+ was also investigated under different experimental conditions.

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Abstract  

Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) is a challenging task in the nuclear fuel cycle due to their similar charge and chemical behaviour. Some soft donor ligands show selectivity for An(III) over Ln(III) due to the formation of stronger covalent bonds with the former. The extraction behaviour of Am(III) and Eu(III) is studied in the present work with a mixture of Cyanex-301 (bis(2,4,4-trimethylpentyl)di-thiophosphinic acid) with several various ‘N’, ‘O’ or ‘S’ donor neutral ligands. Comparison of the data was done with that of the oxygen donor analogue of Cyanex-301, i.e. Cyanex-272 (bis(2,4,4-trimethylpentyl)phosphinic acid). Effect of the organic diluent on the extraction behaviour of Am(III) using Cyanex-301 in presence of ‘N’ donor synergists was also studied. Ab initio molecular orbital calculations were carried out using GAMESS software and charges on the donor atoms were calculated which helped in understanding the co-ordination chemistry of the ligands and explained the separation behaviour.

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Abstract  

The extraction behavior of Th(IV) from dilute nitric as well as perchloric acid medium using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and its mixture with tri-n-octyl phosphine oxide (TOPO) was investigated. The species of the type Th(X)(PMBP)3·(HPMBP) and Th(X)(PMBP)3·(TOPO) were extracted for the binary and ternary extraction systems, respectively, where X=NO3− or ClO4−. The presence of 1.25·10−5M Th carrier in the aqueous phase resulted in the extracted species of the type of Th(PMBP)4 and Th(PMBP)4·(TOPO), respectively. The extraction constant (logk ex) for the binary species Th(PMBP)4 was found to be 6.89±0.01 while the overall extraction constant (logK) for the ternary species Th(PMBP)4·(TOPO) was calculated to be 13.17±0.06.

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Abstract  

Extraction behavior of137Cs was studied from nitric acid medium using dibenzo 18 crown 6 (DB18C6), 4,4'(5')di-acetylbenzo 18 crown 6 (DAB18C6), 4, 4'(5')di-hexanoylbenzo 18 crown 6 (DHB18C6), 4,4'(5')di-nonanoylbenzo 18 crown 6 (DNB18C6) and 4,4'(5')di-t-butylbenzo 18 crown 6 (DTBB18C6) in nitrobenzene medium. The stoichiometry of the species extracted with dibenzo 18 crown 6 (L) conformed to ML+. NO3 TheD Cs values were found not to be affected by the presence of aluminium nitrate in the aqueous phase. The separation behavior of fission products obtained from an irradiated natural uranium target was also studied. Presence of 0.004M phosphotungstic acid found to enhance theD Cs values at lower acidities.

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Abstract  

Three different resins containing ammonium molybdophosphate (AMP), viz. PMMA (polymethylmethacrylate) resin, composite AMP resin and ALIX (a bisphenol based resin), were evaluated for their irradiation stability. The studies included batch as well as column studies and were carried out for cesium uptake behaviour at 3 M acidity. The resin beads were irradiated to varying dose viz., 0 MRad, 10 MRad, 20 MRad, 50 MRad and 100 MRad. The time taken to attain equilibrium was rather long and about 2–5 h were found to be required for attaining equilibrium in batch studies. Batch Cs(I) uptake studies revealed no significant effect on the K d values in case of the PMMA resin while in case of the composite resin and ALIX resin, a decrease in the K d was observed as a function of irradiation dose. The resin capacity indicated contrasting behaviour with irradiation dose for the resins. Column runs have been carried out for the uptake of radio cesium using both unirradiated and irradiated resins using feed solutions containing 3 MHNO3. The loading capacities of the resins were found to be proportional to their Cs loading capacities observed in batch studies. Study revealed that the composite AMP had the maximum and PMMA has the least loading capacity. Results of these studies show that these AMP based resins can be used for cesium separation from acidic nuclear waste.

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Abstract  

Extraction of uranium from tissue paper, synthetic soil, and from its oxides (UO2, UO3 and U3O8) was carried out using supercritical carbon dioxide modified with methanol solutions of extractants such as tri-n-butyl phosphate (TBP) or N,N-dihexyl octanamide (DHOA). The effects of temperature, pressure, extractant/nitric acid (nitrate) concentration, and of hydrogen peroxide on uranium extraction were investigated. The dissolution and extraction of uranium in supercritical CO2 modified with TBP, from oxide samples followed the order: UO3 ≫ UO2 > U3O8. Addition of hydrogen peroxide in the modifier solution enhanced the dissolution/extraction of uranium in dynamic mode. DHOA appeared better than TBP for recovery of uranium from different oxide samples. Similar enhancement in uranium extraction was observed in static mode experiments in the presence of hydrogen peroxide. Uranium estimation in the extracted fraction was carried out by spectrophotometry employing 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP) as the chromophore.

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