Search Results

You are looking at 1 - 10 of 12 items for

  • Author or Editor: S. Godbole x
  • Refine by Access: All Content x
Clear All Modify Search

Abstract  

Due to the scarcity of good quality uranium resources, the growth of nuclear technology in India is dependent on the utilization of the vast thorium resources. Therefore, Advance Heavy Water Reactor is going to acquire significant role in the scenario of Indian nuclear technology, where (Th, Pu)O2 will be utilized as fuel in the outermost ring of the reactor core. This will lead to a complex matrix containing thorium as well as americium, which is formed due to β- decay of plutonium. The amount of americium is dependent on the burn up and the storage time of the Pu based fuels. In the present case, attempt was made to develop a method for the determination of americium as well as thorium by ICP-AES. Two emission lines of americium were identified and calibration curves were established for determination of americium. Though the detection limit of 283.236 nm line (5 ng mL−1) of americium was found to be better than that of 408.930 nm (11 ng mL−1), the former line is significantly interfered by large amount of thorium. Three analytical lines (i.e. 283.242, 283.730 and 401.913 nm) of thorium were identified and calibration curves were established along with their detection limits. It was observed that 283.242 and 401.913 nm line are having similar detection limits (18 and 13 ng mL−1, respectively) which are better than that of 283.730 nm (60 ng mL−1). This can be attributed to the high background of 283.273 nm channel of thorium. The spectral interference study revealed that even small amount of americium has significant contribution on 283.242 nm channel of thorium while the other two channels remain practically unaffected. Considering both these facts, spectral interference and analytical performance (detection limits and sensitivity), it was concluded that 401.913 nm line is the best analytical line out of the three lines for determination of thorium in presence of americium.

Restricted access

Abstract  

Synergistic extraction studies on Np(VI) and Pu(VI) have been carried out as a part of the programme on the synergistic extraction of hexavalent actinides. Extraction of Np(VI) and Pu(VI) were carried out by mixtures of HTTA and TBP in benzene from aqueous perchlorate and nitrate media. Equilibrium constant values for the various reaction equilibria involved were calculated from the data obtained by using slope-ratio as well as Job’s method. The extraction of Np(VI) by the synergistic mixture from 1M nitric acid indicated that the species NpO2 (TTA) (NO3). TBP was not involved in the extraction. The log values of KA, KAB and βAB were −1.5, 2.92 and 4.43, respectively for Np(VI) and −1.63, 2.50 and 4.13 respectively for Pu(VI).

Restricted access

Abstract  

DHOA (Di-n-hexyl-octanamide) is one of the alternative extractants to TBP (tri-n-butyl phosphate) known for the extraction of uranium from moderate nitric acid medium without significant extraction of the fission products. Analytical application of DHOA was explored to develop a methodology for determination of trace metallic constituents in uranium based nuclear materials. This involved the separation of uranium matrix by 1.1 M DHOA-dodecane followed by the analysis of the raffinate for trace constituents by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). A systematic study showed that four contacts of 1.1 M DHOA-dodecane were required for quantitative extraction of U from 4 M HNO3 feed for the sample size of 1 g in 10 mL. The feasibility of using DHOA for extraction of U from trace metallic constituents in U based fuel materials without losing trace quantities of analytes of interest was studied by using synthetic samples after appropriate spiking of common impurities and critical elements at their required specification limits (common elements—5 ppm, critical elements—1 ppm). A systematic study was carried out to compare the analytical performance of DHOA with TBP, which revealed that DHOA could successfully be employed for the determination of 19 trace constituents with lower estimation limits of 5 ppm for common impurities and 1 ppm for critical elements.

Restricted access

Abstract  

Extraction of U/VI/ by mixtures of 8-hydroxy quinoline /Oxine/ and neutral donors was studied from 0.1M NaCl at a pH 4.5. The presence of a neutral donor enhanced the extraction of U/VI/ and the species responsible for synergism was established to be 11 adduct UO2Ox2S. From the data, the equilibrium constants for the adduct formation reaction were calculated and was found to be the lowest with TBP and the highest with TOPO.

Restricted access

Abstract  

Crown-ethers extract uranium/VI/, neptunium/IV/ and americium/III/ into MIBK from aqueous thiocyanate solutions. The synergic extraction of U/VI/with crown-ethers and HTTA is also possible.

Restricted access

Abstract  

This paper describes the development of a separation method for americium from the effluents emanating from anion exchange column, used for the recovery of plutonium from analytical waste solutions. The waste contained uranium, sodium, calcium and iron as the major impurities as estimated by ICP-AES method. ~99% pure americium was obtained by three separation steps using solvent extraction and extraction chromatography techniques. In the first step, uranium was quantitatively separated by giving five contacts of equal volumes of 30% TBP in n-dodecane. Fe and Na were separated in the next step using 0.1 M TODGA + 0.5 M DHOA as the extractant. In the last step, Am was separated from the co-extracted Ca (about 76%) using CMPO loaded extraction chromatographic column. The overall recovery was >80% with decontamination factor (D.F.) from the impurities being >3000 while the purity of the product was 99%.

Restricted access

Abstract  

Double sulfates of thallium and lanthanides form an interesting series of compounds with first fractional crystallization leading to the formation of tetrahydrated double sulfates. The radiation induced defects including changes in the oxidation states were studied by carrying out EPR investigations of -irradiated Tl (I) Ln (III) (SO4)2.4H2O (Ln=Sm, Eu and Nd) compounds. The important finding of these investigations is the formation of a radiation-induced paramagnetic center Tl2+ simultaneously with that of Eu2+, revealing their intrinsic association. Similar formation of Tl2+ was not observed in other rare earth salts, implying that the stability of the half-filled electronic configuration of Eu2+ may be responsible for the stabilization of Tl2+. Their relaxation back to Eu3+ and Tl+ simultaneously at 255 K gives further confirmation of their association and suggests that the matrix intrinsically does not favor the stabilization of Eu2+ as reported in a number of other matrices. The hyperfine coupling constant for Tl2+ was calculated using the Breit-Rabi equation and was found to be 80 GHz.

Restricted access

Abstract  

Trace metallic impurity analysis by spectroscopic techniques is one of the important steps of chemical quality control of nuclear fuel materials. Depending on the burn-up and the storage time of the fuel, there is an accumulation of 241Am in plutonium based fuel materials due to β decay of 241Pu. In this paper, attempts were made to develop a method for separation of 241Am from 1.2 kg of analytical solid waste containing 70% U, 23% Pu, 5% Ag and 1–2% C as major constituents along with other minor constituents generated during trace metal assay of plutonium based fuel samples by d. c. arc carrier distillation atomic emission spectrometry. A combination of ion exchange, solvent extraction and precipitation methods were carried out to separate ~45 mg of 241Am as Am(NO3)3 from 15 L of the analytical waste solution. Dowex 1×4 ion exchange chromatographic method was used for separation of Pu whereas 30% TBP–kerosene was utilized for separation of U. Am was separated from other impurities by fluoride precipitation followed by conversion to nitrate. The recovery of Pu from ion exchange chromatographic separation step was ~93% while the cumulative recovery of Am after separation process was found to be ~90%.

Restricted access

Abstract  

During the simultaneous extraction of plutonium and uranium using anion exchange chromatographic technique from analytical waste in hydrochloric acid medium, 241Am which is invariably present in the plutonium bearing fuel samples remains in the effluent. A two step separation scheme was developed for the recovery and purification of Am from the assorted waste to facilitate the disposal of large volume of aqueous waste and the purified Am solution was utilized for spectroscopic investigation. The separation scheme involved solvent extraction using 0.1 M TODGA + 0.5 M DHOA for separation of americium from Fe, Pb, Ni and Na followed by extraction chromatographic technique using CMPO on inert support as stationary phase for separation of Ca from Am. A systematic study on the extraction behavior of Am from hydrochloric acid medium revealed that out of four extraction systems well known for actinide partitioning namely 0.1 M TODGA + 0.5 M DHOA, 1 M DMDBTDMA, 0.2 M CMPO + 1.2 M TBP and 30% TRPO, only 0.1 M TODGA + 0.5 M DHOA extracts americium from 7.5 M HCl feed acidity. A comparative study involving CMPO solvent extraction and column chromatographic technique revealed that elution of Am from column is satisfactory as compared to inefficient stripping of Am from organic phase in solvent extraction technique using 0.1 M HNO3. The purity of the final solution was checked for 17 elements of interest and was found to be 98% pure, while the overall recovery of this two step separation scheme was found to be 95%.

Restricted access

Abstract  

Energy dispersive X-ray fluorescence (EDXRF) spectrometric methods have been developed for the determination of some common metallic impurities in ThO2 matrix. A series of ThO2 standards containing the analyte impurities in the range 10–100 (or 100–500) μg/g was prepared synthetically. The spectrometer conditions were optimized to obtain calibration plots for the various analytes. The accuracy and precision of the developed methodology for regular assay of ThO2 was evaluated by analyzing three synthetic samples. Further three secondary ThO2 standards were analyzed by EDRXF to check the developed methods. The determined concentrations of Ca, Cr, Fe, Ni and Cu were in good agreement with the certified values of the secondary standards.

Restricted access