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- Author or Editor: P. Naik x
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Abstract
Reaction rate constants for the reactions of 3-pyridinol with oxidizing radicals viz. OH, N3, Br 2 – , Cl 2 – , SO 4 – and O– have been determined in aqueous solutions at different, pH's. Absorption spectra of the product transient species have been recorded in the 320–600 nm region. In the alkaline region (pH 13) the N3 reaction product decays in two steps and O– does not bring about one-electron oxidation. Similarly, at neutral pH, SO 4 – does not cause selective one-electron oxidation of 3-pyridinol.
Abstract
The complexes of cobalt(II) with dothiepin (DOT) hydrochloride have been studied for kinetics of thermal degradation by thermogravimetric analysis (TG) and derivative thermogravimetric studies (DTG) in a static nitrogen atmosphere at a heating rate of 10 C min−1. A general mechanism of thermal decomposition is advanced involving dehydration and decomposition process for both organic and inorganic ligands. The thermal degradation reactions were found to proceed in three steps having an activation energy in the range 6.75–170 kJ mol−1. Thermal decomposition kinetics parameters were computed on the basis of thermal decomposition data.
Abstract
Rate constants for the reaction of the primary species of water radiolysis, viz. e
aq'
–
, H and OH, with picolinic acid have been determined at various pHs. The semi-reduced species exhibits 
max at 305 and 350 nm. It is a strong reductant and has two pKa values of 1 and 5.7. The OH adduct of this compound also exhibits two pKa s at 2.1 and 5.2. H-atom reaction with picolinic acid gives rise to a mixture of species.
Summary
Single neutron transfer reactions on 197Au induced by 12C and 16O at near Coulomb barrier energies have been studied using radiochemical and off-line gamma-ray spectrometric techniques. High spin yield fraction (HSF = σm/(σm+σg)) for 196m,gAu and formation cross section ratio (σ198/σ196) of 198Au and 196Au have been determined for both 197Au+12C and 197Au+16O reactions at different excitation energies near the Coulomb barrier. The HSF of 196m,gAu and σ198/σ196 values in both reactions are seen to sharply increase with increasing excitation energy near the Coulomb barrier and then slowly increase reaching a constant value at high projectile energy. These observations have been analyzed in terms of nuclear structural and kinematic parameters. A comparison the effects of Coulomb excitation and nucleon transfer process during heavy-ion interactions indicates a predominant effect of the latter process in the background of the Coulomb excitation. Observed reaction systematics seem to follow the quasi-elastic transfer process.
Abstract
Silica-gel has been used as an inert support for the extraction chromatographic separation of actinides and lanthanides from HNO3 and synthetic high level waste (HLW) solutions. Silica-gel was impregnated with tri-butyl phosphate (TBP), to yield STBP; 2-ethylhexyl phosphonic acid, mono 2-ethylhexyl ester (KSM-17, equivalent to PC-88A), SKSM; octyl(phenyl)-N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO), SCMPO; and trialkylphosphine oxide (Cyanex-923), SCYN and sorption of Pu(IV), Am(III) and Eu(III) from HNO3 solutions was studied batchwise. Several parameters, like time of equilibration, HNO3 and Pu(IV) concentrations were varied. The uptake of Pu(IV) from 3.0M HNO3 followed the order SCMPO>SCYN>SKSM>STBP. With increasing HNO3 concentration, D Pu increased up to 3.0M of HNO3 for STBP, SKSM and SCMPO and then decreased. In the case of Am and Eu with SCMPO, the D values initially increased between 0.5 to 1.0M of HNO3, remained constant up to 5.0M and then slightly decreased at 7.5M. Also, the effects of NaNO3, Nd(III) and U(VI) concentrations on the uptake of Am(III) from HNO3 solutions were evaluated. With increasing NaNO3 concentration up to 3.0M, D Am remained almost constant while it was observed that it decreases drastically by adding Nd(III) or U(VI). The uptake of Pu and Am from synthetic pressurized heavy water reactor high level waste (PHWR-HLW) in presence of high concentrations of uranium and after depleting the uranium content, and finally extraction chromatographic column separation of Pu and Am from U-depleted synthetic PHWR-HLW have been carried out. Using SCMPO, high sorption of Pu, Am and U was obtained from the U-depleted HLW solution. These metal ions were subsequently eluted using various reagents. The sorption results of the metal ions on silica-gel impregnated with several phosphorus based extractants have been compared. The uptake of Am, Pu and rare earths by SCMPO has been compared with those where CMPO was sorbed on Chromosorb-102, Amberchrom CG-71 and styrene divinylbenzene copolymer immobilized in porous silica particles.
Abstract
The improvement and the refinement of non-viable Rhizopus arrhizus biomass were investigated via immobilization. Immobilization was carried out by using sodium alginate/CaCl2 solution and formaldehyde/HCl cross-linking with dead Rhizopus arrhizus biomass and were used for the sorption of radionuclides from low level effluent wastes. The sodium alginate/CaCl2 immobilized biomass (ratio 1:2) showed about 86% sorption for 241Am activity but due to its soft nature and tendency to undergo distortion in shape, is unsuitable for practical applications. The biomass cross-linked with 15% formaldehyde/0.1 M HCl solution has a relatively high mechanical strength and rigidity. It was showing a sorption of >99% for 241Am activity and has the sorption capacity of ~65 mg/g for americium and uranium. Hence, it can be utilized for the removal of radionuclides from radioactive waste effluents.
Abstract
A single reagent radioimmunoassay for thyroxine in blood samples absorbed on filter paper for the mass screening of neonatal hypothyroidism is described. Blood samples were collected by pricking the heel of newborn babies (3 days old) and pressing Whatman 3 filter paper against the wound. 6 mm diameter blood spots were punched out at the time of assay and incubated with 0.4 ml of a preincubated antigen-antibody complex for six hours at 37 °C. 1 ml of 22% polyethylene glycol is used for the precipitation of antigen-antibody complex. The assay has a sensitivity of 2.2 ng/ml. 500 samples collected from newborns were analyzed in the assay and gave a mean of 117.6±31.9 ng/ml.
Abstract
GEL combustion technique was applied to obtain oxides of thorium and cerium from their respective nitrate solutions using citric acid as the gelating agent. The dried samples were characterized by IR and TG studies. Intermediate and final products during TG studies have been isolated and characterized by XRD studies. All the TG runs during heating of thorium and cerium nitrate with citric acid dried Gels showed a two step process. The weight loss at each step and the X-ray data of the product at each step, helped in suggesting a possible mechanism. Kinetic study was carried out independently for each step. The reaction mechanism as observed during interactive procedure was found to be diffusion controlled. The kinetic parameters (activation energy and pre-exponential factor) for each step in all reactions have been calculated. Observations from XRD studies show that with increase in cerium concentration in the oxides, the lattice parameter values have shown a decreasing trend for all the five compositions studied. It was observed that in TG studies with increase in cerium concentration, the final temperature of the reactions have shown a decreasing trend. SEM studies of the powders reveal that synthesized oxides have a tendency to form agglomerate of varying size ranging from 50 to 100 μm in case of mixed oxides but the size of thorium oxide powder so synthesized have pore size 10–100 μm. SEM images shows that GEL combustion may result in agglomeration, if the temperature is not properly controlled to the desired value. SEM studies also reveal that each agglomerate contains approximately 10–100 individual particles. Surface area of the mixed oxide powders were determined using Gas adsorption technique. The surface area was found to be in the range of 3–17 m2/g in all cases. Specific surface area of thorium oxide was found to be lesser than cerium oxide but in case of mixed oxides surface area decreases with increase in cerium content. Majority of pores, indicating the particle size are in the range of 0.01–0.04 cm3/g.
Abstract
The 100Mo(γ, n) reaction cross-section was experimentally determined at end point bremsstrahlung energy of 10 and 12.5 MeV using off-line γ-ray spectrometric technique. It was also found that 100Mo(γ, n) reaction cross-section increases sharply from the end point bremsstrahlung energy of 10 MeV to 12.5 MeV, which may be because of GDR around the energy region of 12–16 MeV. The 100Mo(γ, n) reaction cross-section as a function of photon energy was calculated theoretically using TALYS 1.2 computer code. The flux-weighted average values of 100Mo(γ, n) reaction cross-section for bremsstrahlung having end point energy of 10 and 12.5 MeV were also calculated using the experimental and theoretical data of mono-energetic photon. The present experimental 100Mo(γ, n) reaction cross-sections were compared with the bremsstrahlung flux-weighted average values of experimental and theoretical data and found to be in the lower side for 10 MeV and in the higher side for 12.5 MeV.
Abstract
The reaction cross-sections for 64Ni(n, γ) 65Ni at E n = 0.025 eV and 58Ni (n, p) 58Co at E n = 3.7 MeV have been experimentally determined using activation and off-line γ-ray spectrometric technique. The thermal neutron flux used is from the thermal Column of the reactor APSARA at BARC, Mumbai, whereas the neutron energy of 3.7 MeV is from the 7Li(p, n) reaction at Pelletron facility, TIFR, Mumbai. The 64Ni(n, γ) 65Ni and 58Ni(n, p) 58Co reactions cross-sections from present work are compared with the available literature data and found to be in good agreement. The 58Ni(n, p) 58Co reaction as a function of neutron energy is also calculated theoretically using TALYS computer code version 1.2 and found to be higher than the experimental data.
