A potentiometric titration method and a conductometric titration method were standardized for the determination of nitrate in thorium, uranium and plutonium solutions in the range of 2–10 mg, and 15–30 mg, respectively, with a precision and accuracy of 2% in both cases. The results were compared with those of other methods like Devarda's alloy reduction method and volumetric titration method. The procedures standardized have been recommended for the determination of nitrate in heavy element solutions used for the preparation of oxide and mixed oxide microspheres by the sol-gel technique.
Using radiotracer solutions of Hg (203Hg) and Os (185Os), techniques have been developed for sampling these elements presumably suitable for ion probe measurements. Mercury has been electrodeposited on the cross-sectional area (5 mm2) of an electrochemically pure Cu wire giving a recovery 25 to 30% at the tip. Similar efficiency is found for Hg distillate solutions. Osmium has been collected in a Ni–NiS bead after loading its thiourea complex solution on filter paper. The recovery in the bead is 80–90%. These methods should be of help for isotopic study of these elements by ion microprobe. The suitability of these samples for measurements remains unconfirmed.
Authors:Avinash Kumar, Deepak Kumar, K. Rao, J. Kumar, B. Singh, A. Sharma and P. Ravi
Prediction of downwind tritium air concentrations in the environment around Narora Atomic Power Station was studied on the
basis of Gaussian plume dispersion model. The tritium air concentrations by field measurement [measured tritium air concentrations
in the areas adjacent to NAPS] were compared with the theoretically calculated values (predicted) to validate the model. This
approach will be useful in evaluating environmental radiological impacts due to standard pressurised heavy water reactors.
Authors:Y. Gautam, S. Sharma, A. Sharma, V. Kumar, J. Kumar, A. Kumar, A. Hegde and P. Sarkar
Guidelines for the assessment of internal doses from monitoring suggest default measurement of uncertainties (i.e. lognormal
scattering factor, SF) to be used for different types of monitoring data. In this paper, SF values have been evaluated for
internal contamination due to 60Co in two cases using whole body counting data. SF values of 1.04 and 1.03 were obtained for case I and II, respectively while
SF value of 1.03 was obtained using bioassay data for case I. SF evaluated is in good agreement with the default values given
by IDEAS guidelines. The present study also presents the follow up study of a case I of 60Co internal contamination using whole body counting and bioassay analysis. The effect of medical intervention applied on the
subject is studied. Medical intervention of d-Penicillamine (250 mg × 4 daily) was orally administered from 13th day of initial exposure for about a fortnight, which showed
reduction of activity present by 33.4% through urine.
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− TheDCs 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 theDCs values at lower acidities.
Thermophysical properties of alternate PUREX/UREX extractant tri-iso-amyl phosphate (TiAP) in different diluents are not available
in literature. In this study, density, viscosity and refractive indices of 36% v/v TiAP solutions (~1.1 M) in C6–C16n-alkanes, benzene, toluene, carbon tetrachloride and iso-octane at 298.15 K and 0.1 MPa have been measured experimentally. In the case of n-alkanes, these properties were correlated by empirical functions of carbon number of diluents. In addition, for 36% TiAP
and 100% TiAP solutions, nitric acid extraction studies were also performed and acid uptakes as well as thermophysical properties
of equilibrated phases were also measured. Compositions of solvates in equilibrated organic phases were also proposed.
Study of runaway reaction between tri-n-butyl phosphate (TBP) and nitric acid resulting in red-oil formation (and related problems) in the process evaporators of
reprocessing plants has been a major safety concern since last 50 years. Thermal decomposition of nitrated TBP results in
rapid pressurization and in close-vent condition it may lead to failure of process vessel and containment. Thermal decomposition
of nitrated TBP is reported in the literature but corresponding studies for alternate PUREX/UREX solvent tri-iso-amyl phosphate (TiAP) are not available. In this work, comparative study of the thermal decomposition of nitrated solvents
(TBP as well as TiAP) under adiabatic conditions in a sealed autoclave is presented. Experimental results indicate much lesser
pressurization in the case of TiAP as compared to TBP.
This paper reports preparation of nanoparticles of oxides by the citrate–nitrate process and the effect of metal ions on the thermal decomposition characteristics of the corresponding citrate–nitrate gel precursors. In order to understand the effect of metal ions on the thermal decomposition characteristics of the precursors, we have prepared a series of single component oxides such as MO, where M = Zn, MO2, where M = Sn, Ce, Zr, and M2O3 where M = Al, Fe, Bi. In all the cases the citrate to nitrate ratio was fixed at 0.3. In order to ascertain the decomposition characteristics of the gel samples, TG/DTA studies were performed on the dried gel samples. After complete physico-chemical characterization of the precursors and the calcined products, it could be concluded that the nature of decomposition of the precursors depends largely on the nature of the metal ions. Finally, the advantages of the citrate–nitrate process such as its high degree of reproducibility, its potential for large-scale production of nano-crystalline ceramic oxide powders and its lower cost could be established based on a series of experiments and examples.
A precise, sensitive and rapid analytical technique has been developed for the simultaneous determination of Zr and Hf in
natural silicate matrices. The technique is based on radiochemical neutron activation analysis and employs a rapid fusion
dissolution of the sample and simultaneous precipitation of the Zr−Hf pair with p-hydroxybenzene arsonic acid in an acidic
medium. The indicator radionuclides,95Zr and181Hf, are counted with a pair of high resolution Ge(Li) detectors and the95Zr activity is corrected for the contribution from U fission. The chemical yields of the radiochemical separation are based
on Hf carrier, which quantitatively carries both Zr and Hf. The yield is determined by reactivation of the processed samples
and standards with a252Cf isotopic neutron source and by counting the 18.6 sec half-life179mHf. The sensitivity, precision and accuracy of the procedure are demonstrated by replicate analyses of several standard rocks,
meteorites and lunar samples which exhibit a wide range of Zr and Hf abundances.
Thermal decomposition of mono pyridine N-oxide complexe; of cobalt(II), nickel(II) and copper(II) propionates and mono quinoline N-oxide complex of copper(II) ben zoate has been studied by TG and DTA techniques. These dimeric complexes are stable upto 350–380 K and decompose in two stages: (i) successive elimination of the two ligand molecules (mostly endothermic); and (ii) decomposition of the resulting anhydrous metal(II) carboxylates by an exothermic multistep process in air.