Authors:S. Hasilkar, Keshav Chander, and S. Marathe
Attempts to carry out potentiometric determination of plutonium (by AgO-oxidation method) following the determination of thorium (by complexometric EDTA titration) gave positively biased irreproducible values of plutonium. In order to understand the factors leading to the erroneous values of plutonium, the effect of varying amounts of AgO and EDTA on redox [Fe(II)/K2Cr2O7] titration in the medium consisting of 1M H2SO4 and 0,4M HNO3 was studied. When AgO (up to 200 mg) was added in the titration medium and destroyed by sulfamic acid prior to the redox titration, the dichromate tittre value (amount of standard K2Cr2O7 solution equivalent to 1 g of Fe(II) solution) showed negative bias. The bias was found to decrease with increase in time interval between AgO destruction and the redox titration. The presence of EDTA (up to 15 mg) gave positive bias in the titre value. Results on the titre values obtained under different conditions of the aqueous medium indicated the possibility of formation of unstable Ag(II)-sulfamic acid compled, which is probably responsible for the irreproducible values of plutonium.
Authors:Keshav Chander, S. Hasilkar, and S. Marathe
A method for the sequential determination of thorium and plutonium has been developed. In the sample solution containing thorium and plutonium, thorium is first determined by complexometric titration with EDTA and then in the same solution plutonium is determined by redox titration employing potentiometry. Prior to the determination of plutonium, EDTA is destroyed by fuming with concentrated HClO4. Thorium is determined at 10 mg level and plutonium at 1 mg level with precision and accuracy of better than ±0.5%.
Effect of the presence of plutonium on the determination of uranium by potentiometric method has been studied. The presence of large quantities of plutonium does not appear to affect the determination of uranium present at 5 mg as well as 250 mg levels.
Authors:R. Manolkar, Keshav Chander, and S. Marathe
Liquid scintillation counting is useful and extensively employed for -activity measurement. However, quenching is observed and erroneous results are obtained when the size of the solution aliquot and its acidity exceed certain limits. A simple procedure has been developed to overcome the quenching effect of volume and acidity on -counting.
Authors:S. Hasilkar, N. Gopinath, Keshav Chander, S. Marathe, and H. Jain
A method based on the complexometric titration of thorium using ethylene diaminetetra-acetic acid (EDTA) as complexant has been developed for the determination of thorium in thorium-plutonium solution without resorting to prior separation of plutonium. Plutonium in the form of Pu(VI) does not affect the thorium determination when present up to 10% in thorium—plutonium solution. For oxidation of plutonium to Pu(VI), HClO4 or AgO was used. HClO4 is preferred. The thorium values obtained without prior separation of plutonium are compared with those obtained after separating plutonium by anion exchange technique. A precision of ±0.5% has been obtained for 5–10 mg of thorium in the aliquot.
Authors:V. Bhargava, V. Rao, S. Marathe, S. Sahakundu, and R. Iyer
A radiochemical method is described for the separation of heavier rare earths from the fission of uranium. The method is particularly
suitable for the separation of low yield (10−5%–10−7%), highly asymmetric rare earth fission products viz.179,177Lu,175Yb,173Tm,172,171Er,167Ho and161,160Tb in the neutron induced fission of natural and depleted uranium targets. Additional separation steps have been incorporated
for decontamination from239Np (an activation product) and93-90Y (a high fission-yield product) which show similar chemical behaviour to rare earths. Separation of individual rare earths
is achieved by a cation exchange method performed at 80°C by elution with α-hydroxyisobutyric acid (α-HIBA).
Authors:S. Sahakundu, S. Marathe, V. Rao, V. Bhargava, and R. Iyer
A new method for obtaining radiochemically pure67Cu from highly active fission product solutions is described. The method is based on the solvent extraction of the Cu(II)-diethyldithiocarbamate
complex in n-butyl acetate in the presence of hold-back carriers for Ni, Co, Mn, Mo, rare earths, Cd, Te and Sb, and subsequent
purification steps involving scavengings for Ag, Ba, Sr and Fe followed by an anion-exchange purification step for decontamination
from Te. Copper is finally extracted as the α-benzoin oxime complex in which form it is mounted and counted. The method has
several advantages over other methods in that decontamination is very high and it is sufficiently fast considering the stringent
radiochemical purity achieved. The67Cu separated by this procedure from a one-day-old mixture of fission products arising from 1010 fissions was found to be completely free of any contamination.
Authors:P. Nair, K. Lohithakshan, Mary Xavier, S. Marathe, and H. Jain
A method is described for the sequential determination of uranium and plutonium in plutonium bearing fuel materials. Uranium and plutonium are reduced to U(IV) and Pu(III) with titanous chloride and then titrated with dichromate to two end points which are detected amperometrically using two polarized platinum electrodes. Uranium-plutonium solutions of known concentrations containing plutonium in the proportions of 4, 30, 50, and 70% were analyzed with precisions better than 0.3%, maintaining the amounts of plutonium per aliquot in the range of 2–10 mg. No significant bias could be detected. Several samples of (U, Pu)O2 and (U, Pu)C were analyzed by this procedure. The effects of iron, fluoride, oxalic acid and mellitic acid on the method were also studied.
Authors:Mary Xavier, P. Nair, K. Lohithakshan, S. Marathe, and H. Jain
A method is described for the determination of uranium in the presence of iron and plutonium. Ti(III) is used as the reductant in a mixture of H2SO4 and HNO3. Fe(II) and Pu(III) are selectively oxidized by the nitrous acid generated in the reaction between Ti(III) and HNO3. The U(IV) is determined by titration with K2Cr2O7 using biamperometry to detect the end point. The method is applicable to a variety of nuclear materials encountered at different stages of the nuclear fuel cycle and has no bias. The precision of the method is evaluated at different levels from 100 microgram to 100 milligram. The method is simple, rapid and convenient.
Authors:P. Nair, M. Xavier, S. Marathe, and H. Jain
A biamperometric method for the determination of sulfate has been developed. Its application to the determination of sulfate content in rubidium uranium trisulfate is discussed. Sulfate is determined by titration with lead nitrate in aqueous ethanolic medium using ferrocyanide-ferricyanide redox system as biamperometric indicator. Initially, the method has been tested for standard. K2SO4 solutions. In case of Rb2 U(SO4)3, since uranium interferes, it is precipitated as ammonium diuranate and excess ammonia is removed prior to the titration. Precision of better than 0.3% was achieved with no significant bias.