Measurement of photo-fission yields and photo-neutron cross-sections in 209Bi with 50 and 65 MeV bremsstrahlung

The photo-fission yields and photo-neutron cross-sections of ( $ \gamma$ , 3n) and ( $ \gamma$ , 4n) on ²⁰⁹Bi induced by 50 and 65MeV bremsstrahlung have been measured by using a recoil catcher and an off-line $ \gamma$ -ray spectrometric technique. The mass-yield distribution of fission products in ²⁰⁹Bi induced by bremsstrahlung photons from the present work and literature data in the energy range 28-85MeV is symmetric around 103 mass units. However, the full width at half maximum of the yields distribution increases from 19 mass units at 28-40MeV to 23 mass units at 85MeV. The ( $ \gamma$ , 3n) reaction cross-section in the 50MeV and the ( $ \gamma$ , 4n) reaction cross-section in the 50 and 65MeV bremsstrahlung-induced reaction of ²⁰⁹Bi were determined for the first time.     

Volumetric determination of uranium in a mixture of uranium and plutonium employing Fe(III) as titrant

Summary A method for the determination of U in the presence of Pu based on the reduction of U to U(IV) and Pu to Pu(III) by zinc amalgam followed by oxidimetry of U(IV) has been developed. Fe(III) perchlorate was chosen as the most suitable titrant for the selective oxidation of U(IV) as conventional oxidising titrants fail in the presence of Pu(III). The potentiometric titration of U(IV) with Fe(III) is known to be slow. This problem, however, has been overcome by selecting a suitable buffer medium and complexing agent to alter the potentials of the Fe(III)/Fe(II) and U(VI)/U(IV) systems in the favourable direction. Results of the titration of U(IV) with Fe(III) at pH 2 in the presence of ferrozine as complexing agent for Fe(II) are summarized. R.S.D. obtained for twenty determinations of 3–5 mg of U was 0.3 % in the presence of 1–4 mg of Pu.

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Volumetrische Bestimmung von Uran in einem U/Pu-Gemisch mit Hilfe von Fe(III)

Zusammenfassung Das Verfahren beruht auf der Reduktion von U zu U(IV) und Pu zu Pu(III) mit Hilfe von Zinkamalgam und anschließender Titration mit Fe(III)-perchlorat. Dieses Reagens hat sich für die selektive Oxidation des U(IV) am besten bewährt, da andere Oxidationsmittel in Gegenwart von Pu(III) versagen. Die Endpunktsindikation erfolgt potentiometrisch, wobei die an sich langsame Einstellung des Endpunktes dadurch beschleunigt wird, daß durch Zusatz eines geeigneten Puffers und eines Komplexierungsmittels (Ferrozin) für Fe(II) die Redoxpotentiale von Fe(III)/Fe(II) und U(VI)/U(IV) entsprechend verschoben werden. Die relative Standardabweichung für die Bestimmung von 3–5 mg U in Gegenwart von 1–4 mg Pu liegt bei 0,3%.

     

Track etching characteristics of polyester track detector and its application to uranium estimation in seawater samples

Garware Polyester Film, an indigenously available material has been evaluated systematically as a nuclear track detector for the detection of fission fragments. The relative fission track detection efficiency of this film was found to be (86.0±4.0)%. The bulk etch rate, determined by the gravimetric method, was found to be 0.75±0.05 μm/h. The track etch rate was determined as 15.0±1.5 μm/h. This detector was employed for the estimation of uranium in seawater samples and the results obtained were compared with the results obtained by using the commonly used Lexan detector. Uranium fractions after chemical separation from seawater samples were also analyzed by alpha-spectrometry and neutron activation analysis techniques and the results were compared with that obtained by the fission track method. Fission track method has the advantage, as it does not require any chemical separation. The indigenously available polyester film (polyethylene terphthalate) appears to be a good substitute of Lexan as nuclear track detector.     

Determination of metallic impurities in U3O8 using energy dispersive X-ray fluorescence spectrometry

In order to examine the capability of energy dispersive X-ray fluorescence spectrometry for the determination of some common metallic impurities in nuclear grade U₃O₈ matrix, a series of synthetic U₃O₈ standards, containing impurities such as Ca, Co, Cr, Cu, Fe, Mn, Mo, Ni ,V, W and Zn in the concentration range, 100–1000 μg/g, were prepared. Using these standards, calibration curves were set up for different elements after optimizing the spectrometer parameters. Two synthetic samples and five reference standards obtained through an inter-laboratory comparison exercise within analytical laboratories of Department of Atomic Energy, India were analyzed to evaluate the performance of the newly developed analytical methods. The estimates for most of the analytes were in good agreement with the added amounts. The method is fast, since it requires no chemical treatment. The method has good precision for the analytes determined.     

Evaluation of calix-crown ionophores for selective separation of radio-cesium from acidic nuclear waste solution

Extraction of Cs-137 from nitric acid was carried out using nitrobenzene solutions of calix-crowns such as calix[4]arene-bis(crown-6) (CC-A), calix[4]arene-bis(benzo crown-6) (CC-B) and calix[4]arene-bis(napthocrown-6) (CC-C). CC-C was found to be superior extractant for Cs(I) as compared to the other two calix-crown ligands used in the present study. The effect of diluent on the extraction of Cs(I) indicated the trend: nitrobenzene>dichloroethane>chloroform>decanol>carbon tetrachloride approximately n-hexane approximately toluene. Subsequently, the studies were carried out with nitrobenzene solutions of the calix-crown ligands (mainly CC-C) on the effects of (a) aqueous phase acidity, (b) ligand concentration, and (c) cesium concentration on Cs extraction from nitric acid media. Conditions for quantitative extraction and stripping were optimized and the extracted species conformed to {[CsL]+.[NO3]-.nH2O}. Selectivity studies were carried out using an irradiated natural U target involving tracer amount of fission products activities. Extraction of Cs(I) from a synthetic high level waste solution was also carried out. The promising results obtained in the present studies indicate possible use of the calix-crown ligand for Cs(I) recovery from the acidic high level waste.     

Potentiometric determination of uranium in the presence of plutonium in H2SO4 medium

The potentiometric determination of uranium is widely carried out in phosphoric acid medium to suppress the interferences of plutonium by complexation. Owing to the complexity of the recycling plutonium from the phosphate based waste involving manifold stages of separation, a method has been proposed in the present paper which does not use phosphoric acid. Uranium and plutonium are reduced to U/IV/ and Pu/III/ in 1M H₂SO₄ by Ti/III/, and NaNO₂ is chosen to selectively oxidize Pu/III/ and the excess of Ti/III/. The unreacted NaNO₂ is destroyed by sulphamic acid and excess Fe/III/ is added following dilution. The equivalent amount of Fe/II/ thus liberated is titrated against standard K₂Cr₂O₇. R.S.D. obtained for the determination of uranium /1–2 mg/ is 0.3% with plutonium being present upto 4.0 mg.     

Titrimetric determination of uranium in the presence of plutonium in sulphuric acid medium

Present work summairzes a method for the estimation of uranium in the presence of plutonium involving the reduction of uranium to U/IV/ and plutonium to Pu/III/ by Zn/Hg/ followed by the selective oxidation of Pu/III/to Pu/IV/with HNO₃ catalyzed by molybdate in the presence of large sulphate concenration [5M H₂SO₄+1.5M /NH₄/₂SO₄]. The oxidation of U/IV/ by K₂Cr₂O₇ is then carried out in the presence of excess of Fe/III/ and Al/NO₃/₃ to a sharp potentiometric end point. R.S.D. obtained for 20 determinations of uranium /3–6 mg/ was 0.3% in the presence of 0.35 mg of plutonium. Larger quantity for plutonium was found to interfere.     

Kinetics of Complexation of Uranium with 2-(5-Bromo-2-Pyridylazo)-5-(Diethylamino) Phenol (Br-PADAP) in a 1:1 Water-Ethanol Medium

2-(5-Bromo-2-pyridylazo)-5-(diethylamino) phenol (Br-PADAP) forms a 1:1 complex with the uranyl ion in the presence of sulphosalicylic acid, which acts as stabilizer for this complex in the triethanol amine/perchloric acid buffer system. A change in the stoichiometry of the complex was seen at pH<5. Kinetic measurements were carried out using stopped-flow spectrophotometer in the presence of an excess concentration of U(VI) in the pH range 6.5 to 8. The dependence of the pseudo-first-order rate constant, k(obs), on the concentrations of U(VI), ligand and hydrogen ion showed that Br-PADAP reacts with UO₂(OH)⁺ to form an intermediate species (equilibrium constant = 1.28×10⁴mol.dm⁻³) that then rearranges (rate constant = 5.6×10⁻²s⁻¹) to form the product species. UO₂(OH)⁺ is present in equilibrium with the unreactive species UO₂(OH)₂, as well as with the unreactive sulfosalicylic acid complex.     

Extraction studies of Am(III) and Eu(III) with a tris-bipyridyl macrobicyclic ligand

Complexation of Am(III) with a tris-bipyridine cryptand (L) has been carried out in a nonaqueous medium (CH₃CN–CHCl₃). Subsequently the complexation behaviour was investigated using the reverse extraction tracer technique with dinonyl naphthalenesulphonic acid (HD) in toluene as the organic phase and varying concentration of HCl (upto 2M) as the aqueous phase. Equilibrium is attained in the two-phase system at a rate dependent on the hydrogen ion concentration in the aqueous phase. Whereas it takes only a few minutes to attain the equilibrium state at pH 6.0, a phase contact period of 50 days was insufficient if the acidity is greater than 0.4M, presumably due to the slow dissociation of the cryptate formed. The large enhancement in the distribution ratio value in the synergistic system with 1M HCl as the aqueous phase under non-equilibrium conditions is employed for the analytical separation of Am(III) from Eu(III).