Electron paramagnetic resonance and thermally stimulated luminescence studies of uranyl doped calcium sulphate

Electron paramagnetic resonance (EPR) and thermally stimulated luminescence (TSL) studies were conducted onγ-irradiated CaSO₄:UO ₂ ²⁺ to elucidate the role of the electron/hole traps in thermally stimulated reactions and to obtain the trap parameters (trap depth and frequency factor). Intense TSL glow peaks around 140, 375, 400 and 438±2K are observed and their spectral characteristics have shown that UO ₂ ²⁺ and UO ₆ ⁶⁻ act as luminescent centres. EPR studies have shown the peaks at 140 and 400/438K to be associated with the thermal destruction of O⁻ and SO ₄ ⁻ radical ion in two stages respectively. The maximum rate of thermal destruction of SO ₄ ⁻ ions (as seen by EPR) in various alkaline earth sulphate matrices investigated in our laboratory is also summarized. The activation energy which characterizes the electron transfer reaction between SO ₄ ⁻ and the dopant ion lies in the range of (0.95±0.15 eV). This value is independent of the dopant and therefore seems to be characteristic of the binding energy of hole in the SO ₄ ⁻ radical ion.     

Determination of refractory elements in U(3)O(8) by carrier distillation emission spectrography

An emission spectrographic method using carrier distillation for the determination of the refractory impurities Ta, Hf, Nb, Th, and W in uranium is described. Different carriers, such as Ga₂O₃, AgCl, AgCl + LiF, and AgCl + NaF in various proportions, were investigated: a 1% NaF + 9% AgCl mixture as carrier at 10% of total charge arced was found to be the most suitable. Spectra were excited in a d.c. arc at 12 A and were photographed with 35-sec exposures. Palladium was used as an internal standard. The lowest limits of determination lie in the range 1–10 ppm for a 100-mg charge. The precision of the method is about 16% or better.     

Spectrographic estimation of impurities in selenium

Summary An emission spectrographic method for the estimation of impurities of Al, As, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sb, Sn, Te, Ti, V, Zn and Zr in high purity selenium at concentrations less than 1 ppm has been developed. The impurities were separated from 1 g of selenium by volatilizing Se from its solution in nitric acid and sulphuric acid. The residue containing impurities was dissolved in small amounts of 6 M HCl and loaded along with the washing on 10 mg mixture containing graphite (90%) and sodium chloride carrier (10%), in the electrode crater. The spectra were excited in a d.c. arc carrying 13 A. The detection limits lie in the range 0.005–0.5 ppm for the different elements. The precision of the method ranges from 7–18% for these elements.

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Spektrographische Bestimmung von Verunreinigungen in Selen

Zusammenfassung Folgende Verunreinigungen werden in hochreinem Selen in Konzentrationen von <1 ppm bestimmt: Al, As, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sb, Sn, Te, Ti, V, Zn und Zr. Das Selen wird von den Verunreinigungen durch Verdampfen abgetrennt (Lösen einer 1 g-Probe in HNO₃/H₂SO₄). Der Rückstand wird in 6 M HCl gelöst und zusammen mit einem Graphit/NaCl-Gemisch (9010) in die Elektrodenbohrung gefüllt. Die Anregung erfolgt in einem Gleichstrombogen von 13 A. Die Nachweisgrenzen liegen im Bereich von 0,005–0,5 ppm, die Genauigkeit beträgt 7–18%.

     

Chemical separation and spectrographic estimation of rare earths and yttrium in PuO(2) and (U,Pu)O(2)

An emission spectrographic method for the estimation of rare-earth impurities in plutonium oxide and the mixed oxide (U,Pu)O(2) (30% PuO(2)-70% UO(2)) has been developed. Rare-earth impurities are separated from the matrix by solvent extraction with tri-n-octylamine in xylene and are estimated after concentration. Thulium is used as internal standard and LiF-AgCl as carrier. The spectra are excited in a d.c. arc. The detection limits lie in the range 0.004-0.1 mug and the coefficient of variation ranges from 5 to 23%.     

Spectrographic determination of trace impurities in sulphur

Summary An emission spectrographic method for the estimation of traces of some common impurites viz., Al, Ba, Bi, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, Ti and V in high-purity sulphur is described. The impurities separated from 1-g sample, after removing sulphur as SO₂ by heating it in air at about 300° C, were dissolved in a small amount of 6M hydrochloric acid and loaded on 10 mg of carrier mixture containing 90% graphite and 10% sodium chloride in the 1/4 electrode crater. The spectra were exited in a D. C. arc carrying 13 A current for 45 seconds. Cobalt was used as an internal standard and sodium chloride as a carrier. The lowest detection limits lie in the range 0.005 to 0.05 ppm for the different elements. The precision of the method ranges from 6–19% for the elements analysed.

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Zusammenfassung Eine emissionsspektrographische Methode zur Bestimmung üblicher Spuren-Verunreinigungen in hochgereinigtem Schwefel, wie Al, Ba, Bi, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, Ti und V, wurde beschrieben. Die aus 1 g Schwefel, nach dessen Entfernung als SO₂ durch Erhitzen an der Luft bei etwa 300° C, abgetrennten Verunreinigungen werden in wenig 6-m Salzsäure gelöst und mit 10 mg Trägergemisch, bestehend aus 90% Graphitpulver mit 10% Natriumchlorid, in die Vertiefung einer 1/4-Elektrode eingebracht. Das Spektrum wird im Wechselstrombogen von 13 A für 45 sec angeregt. Kobalt dient als interner Standard mit Kochsalz als Träger. Die unterste Nachweisgrenze liegt bei 0,005–0,05 ppm für die verschiedenen angegebenen Elemente. Die Genauigkeit beträgt 6–19%.

     

Diffusion in microstructured block copolymer melts

Forced Rayleigh scattering has been employed to measure tracer and self-diffusion in block copolymer melts, for both entangled and unentangled systems, and in both the ordered and disordered states. It is shown that entanglements are particularly effective in retarding the motion of copolymers parallel to the interface between microdomains. The mechanisms of “activated reptation” and “block retraction” are proposed for parallel diffusion. The importance of large amplitude composition fluctuations in the disordered state near the ordering transition is also demonstrated, for both copolymer and homopolymer tracers; the results suggest that copolymer tracers are more affected than homopolymers of comparable molecular weight.     

Molecular addition compounds. 18. Borane adducts with hydroxydialkyl sulfide borates for hydroboration. New, essentially odorless, water-soluble sulfide borane acceptors for hydroboration.

Hydroxydialkyl sulfides of general formula RS(CH2CH2)nH (R = Et, t-Bu, i-Am; n = 1-3) and thiodiethanol monomethyl ether (9) have been synthesized and used as borane carriers. The compounds 3 and 6 (R = Et, n = 2, 3), 7 (R = t-Bu, n = 3), and 9 are completely miscible with water and exhibit only very mild odor. The sulfides were transformed into the corresponding borates by treatment either with boric acid or with diborane. The borates complex 3 mol of borane per 1 mol of borate to give highly reactive, stable, liquid adducts, hydroborating 1-octene in 15 min at room temperature. The adducts derived from water soluble sulfides 3 and 9, selected for the hydroboration of more hindered olefins, reacted readily with (-)-beta-pinene, 1-methylcyclohexene, and 2,3-dimethyl-2-butene. The carrier borates liberated from the adducts during hydroboration are readily hydrolyzed to give 3 and 9, which can be washed off with water from trialkylboranes or oxidation products. Consequently, hydroxydialkyl sulfides 3 and 9 are the first completely water-soluble sulfide borane carriers that can be washed off in the workup of hydroboration products. The adducts derived from 3 and 9 are new, highly promising reagents suitable for large scale hydroborations and reductions.     

Validation of a method for measurement of 14C in air and its application for estimation of 14C levels around Tarapur nuclear site

Journal of Radioanalytical and Nuclear Chemistry - A method for the determination of 14C in air was validated with 4&nbsp;N NaOH solution as absorbent medium. The chemical yield of the whole...