Vaporization thermodynamics of thorium tetrafluoride

The thermal decomposition kinetics of Pr₂(SO₄)₃ to Pr₂O₂SO₄ have been studied by isothermal weight change determination. The reaction was found to obey a linear law up to α = 0.5; beyond α = 0.5 it could be described as a phase-boundary controlled process. A dependence of the activation energy upon the sample weight was observed. The changes in surface area and density which occur during the decomposition are also given.     

Microwave assisted low temperature synthesis of sodium zirconium phosphate (NaZr<Subscript>2</Subscript>P<Subscript>3</Subscript>O<Subscript>12</Subscript>)

Sodium zirconium phosphate [NaZr₂P₃O₁₂], a potential ceramic matrix for fixation of high level nuclear waste, was synthesized by heating the mixture of sodium carbonate [Na₂CO₃], zirconyl nitrate hydrate [ZrO(NO₃)₂·5H₂O] and ammonium dihydrogen phosphate [NH₄H₂PO₄] in air, in a resistance heated furnace and a microwave heating system respectively in the temperature range 450 to 650°C. The mixture heated for 1 h in a resistance furnace at 450°C yielded a poorly crystalline NaZr₂P₃O₁₂ [NZP]. Increasing the temperature to 650°C produced a highly crystalline product. The same mixture heated in a microwave oven at 450°C for 1 h however, yielded the most crystalline NZP.In an alternate method, the mixture of sodium dihydrogen phosphate (NaH₂PO₄), zirconium dioxide (ZrO₂) and diammonium hydrogen phosphate [(NH₄)₂HPO₄] heated in resistance furnace at 650°C for the same period did not react in air. It also did not yield the pure product at 450°C when heated in microwave assembly for 1 h.The authors thank the Board of Research in Nuclear Sciences (BRNS) of the Department of Atomic Energy (DAE) for the financial support for this work under the project No. 2000/37/19/BRNS/1959 dtd09-02-02.     

Alkynenitriles: chelation-controlled conjugate additions

[reaction: see text] Chelation between gamma-hydroxybutynenitrile and Grignard reagents triggers a particularly facile anionic conjugate addition reaction. Structurally diverse Grignard reagents add with equal efficiency, providing an intermediate anion that stereoselectively alkylates benzaldehyde in an overall addition-alkylation reaction.     

Recovery of americium from nitric acid solutions containing calcium by different co-precipitation methods

Recovery of americium from nitric acid solutions was studied by co-precipitation as hydroxide with various ions like calcium, ferric, nickel using sodium hydroxide and ammonium hydroxide. Studies were also carried out to recover americium using lanthanum fluoride and bismuth phosphate co-precipitation. All the methods are able to co-precipitate Am quantitatively. However, co-precipitation of Am with optimum concentration iron using ammonia is found to be better from nitric acid solutions containing large concentrations of calcium ions. Approximately 2 g of Am was recovered from 150 litres of solution batch wise using iron.     

Alkynenitriles: stereoselective chelation controlled conjugate addition-alkylations

Chelation-controlled conjugate addition of Grignard reagents to γ-hydroxyalkynenitriles stereoselectively generates tri- and tetra-substituted alkenenitriles. t-BuMgCl-initiated deprotonation of hydroxyalkynenitriles followed by addition of a second Grignard reagents triggers a facile conjugate addition leading to a cyclic magnesium chelate. Protonation of the chelate stereoselectively generates trisubstituted nitriles whereas the addition of t-BuLi causes conversion to an ‘ate’ complex that allows alkylation with aldehyde electrophiles. The chelation-controlled conjugate addition-alkylation generates tri- and tetra-substituted alkenenitriles that are otherwise difficult to synthesize.     

Extraction of Am(III) from different acid media by di-2-ethyl hexyl phosphoric acid containing phosphorous pentoxide

The extraction of Am(III) from nitric, hydrochloric, oxalic, phosphoric and hydrofluoric acids was studied using 0.4F di-2-ethyl hexyl phosphoric acid (HDEHP) containing 0.1M phosphorous pentoxide (P₂O₅) in dodecane/xylene. The extraction with pure 0.4F HDEHP was found to be negligible from all the media studied. However, the presence of a small amount of P₂O₅ in it increased the extraction substantially. The distribution ratios of Am(III) obtained for HDEHP - P₂O₅ mixture 3M nitric acid containing different concentrations of oxalic acid/phosphoric acid/hydrofluoric acid are in the order of 200-250. The same for 3M hydrochloric acid is very high (800). These distribution ratios are sufficiently high for the quantitative extraction of Am(III) from all the acid media studied. Different reagents such as ammonium oxalate, sodium oxalate, oxalic acid, hydrofluoric acid, sodium carbonate and potassium sulphate were explored for the back extraction of Am(III) from 0.4F HDEHP + 0.1M P₂O₅ in dodecane/xylene. Of these, 0.35M ammonium oxalate and 1M sodium carbonate were found to be most suitable. The back extraction of Am(III) was also attempted with water and 1M H₂SO₄, HNO₃, HClO₄ and HCl solutions after allowing the extracted organics to degrade on its own. It was found that more than 90% of Am could be back extracted with these acids. Using this method more than 90% of Am(III) was recovered from nitric acid solutions containing calcium and fluoride ions.     

Catalytic activity of CeO2 and Pr2O3 for the liquid-phase benzylation of o-xylene to 3,4 – dimethyldiphenylmethane

The liquid phase benzylation of o-xylene with benzyl chloride over rare earth oxide catalysts like CeO₂ and Pr₂O₃ was studied in a batch reactor at atmospheric pressure and 363 K. Surface area, pore volume, DTA, acid strength distribution on the catalyst surface and optimum temperature of the catalyst are reported.     

Physicochemical studies of molecular hyperpolarizability of imidazole derivatives

A series of substituted imidazoles have been synthesized in very good yield under solvent free condition by grinding 1,2-diketone, arylaldehyde, arylamine and ammonium acetate in the presence of molecular iodine as the catalyst. The short reaction time, good yield and easy workup make this protocol practically and economically attractive and the imidazoles are characterized by NMR spectra, X-ray, mass and CHN analysis. The push-pull character of series of imidazoles have been analyzed by the quotient of the occupations of the bonding (π) and anti-bonding (π*) orbitals of the central linking -N=C-C=C- unit. Excellent correlation of the push-pull parameter with the corresponding bond lengths d(CN) and d(CC) strongly recommend both the occupation quotients (π*/π) and the corresponding bond lengths are reasonable sensors for quantifying the push-pull character and for the molecular hyperpolarizability ?(0) of these compounds. To support the experimental results, theoretical calculations (heat of formation, NLO, NBO and vibrational analysis) were also made. Within this context, reasonable conclusions concerning the steric hindrance in the chromospheres, push-pull character, hyperpolarizability of the imidazoles and their application as NLO materials will be drawn.     

Liquid chromatography–tandem mass spectrometry method for simultaneous quantification of urapidil and aripiprazole in human plasma and its application to human pharmacokinetic study

A sensitive and selective liquid chromatography–tandem mass spectrometry (LC–MS/MS) method was developed and validated for simultaneous determination of urapidil and aripiprazole in human plasma. A simple liquid–liquid extraction with ethyl acetate was used for the sample preparation. Chromatographic separation was achieved on a Phenomenex C₁₈ (4.6 × 50 mm, 5 µm) column with 0.1% formic acid–acetonitrile (10:90, v/v) as the mobile phase with flow rate of 0.6 mL/min. The quantitation of the target compounds was determined in a positive ion multiple reaction monitoring mode. Calibration plots were linear over the range of 2.0–2503.95 ng/mL for urapidil and 1.0–500.19 ng/mL for aripiprazole. The lower limit of quantitation for urapidil and aripiprazole was 2.0 and 1.0 ng/mL, respectively. Mean recovery was in the range of 69.94–75.62% for both analytes and internal standards. Intra‐day and inter‐day precisions of the assay at three concentrations were 2.56–5.89% with accuracy of 92.31–97.83% for urapidil, and 3.14–6.84% with accuracy of 91.38–94.42% for aripiprazole. The method was successfully applied to human pharmacokinetic study of urapidil and aripiprazole in healthy human male volunteers. Copyright © 2013 John Wiley & Sons, Ltd.