An alpha-aminomethyl carbanion equivalent via a novel Barbier reaction: (1H-naphtho[1,8-de]-1,2,3-triazin-2-yl)methyl anion

A novel sonication-promoted Barbier reaction putatively generated the titled species from the corresponding naphthotriazinylmethyl chloride and magnesium in THF: its formal addition to a variety of carbonyl compounds in situ occurred in excellent yields. Subsequent catalytic hydrogenolysis of the triazine moiety demasked the amine, thus defining a route to various phenylethylamines (including the alkaloid 'mescaline'), or ethanolamines (in two cases), in excellent overall yields. (C) 2000 Elsevier Science Ltd. All rights reserved.

Polarization Characteristics of Porous Electrode Systems with Adsorbed Intermediates Participating in the Electrode Reaction

Current-potential relationships are derived for porous electrode systems following a homogeneous model and whenadsorbed intermediates participate in the electrode reaction. Limiting Tafel slopes were deduced and compared with thecorresponding behavior on planar electrode systems. The theoretical results showed doubling of Tafel slopes when theslow-step is a charge-transfer reaction and a nonlogarithmic current-voltage behavior when the slow-step is a chemical reaction.Comparison of the experimental results with theory for the case of oxygen reduction on carbon surfaces in alkalinemedia indicates that a slow chemical reaction following the initial charge-transfer reaction to be the likely rate-controllingstep. Theoretical relationships are utilized to determine the exchange current density and the surface coverage by the adsorbedintermediates during the course of oxygen reduction from alkaline solutions on "carbon." Tafel slope measurementson planar and porous electrodes for the same reaction are suggested as one of the diagnostic criteria for elucidatingthe mechanistic pathways of electrochemical reactions.

Chronopotentiometry with power-law perturbation functions at an expanding plane electrode with and without a preceding blank period for systems with a coupled first-order homogeneous chemical reaction

The systems formalism is used to obtain the interfacial concentration transients for power-law current input at an expanding plane electrode. The explicit results for the concentration transients obtained here pertain to arbitrary homogeneous reaction schemes coupled to the oxidant and reductant of a single charge-transfer step and the power-law form without and with a preceding blank period (for two types of power-law current profile, say, (i) I(t) = I0(t−t0)q for t greater-or-equal, slanted t0, I(t) = 0 for t < t0; and (ii) I(t) = I0tq for t greater-or-equal, slanted t0, I(t) = 0 for t < t0). Finally the potential transients are obtained using Padé approximants. The results of Galvez et al. (for E, CE, EC, aC) (J. Electroanal. Chem., 132 (1982) 15; 146 (1983) 221, 233, 243), Molina et al. (for E) (J. Electroanal. Chem., 227 (1987) 1 and Kies (for E) (J. Electroanal. Chem., 45 (1973) 71) are obtained as special cases.

Effect of Nanostructuring and Ex situ Amorphous Carbon Coverage on the Lithium Storage and Insertion Kinetics in Anatase Titania

Implications of nanostructuring and conductive carbon interface on lithium insertion/removal capacity and insertion kinetics innanoparticles of anatase polymorph of titania is discussed here.Sol-gel synthesized nanoparticles of titania (particle size similar to 6 nm) were hydrothermally coated ex situ with a thin layer of amorphous carbon (layer thickness: 2-5 nm) and calcined at a temperature much higher than the sol-gel synthesis temperature. The carbon-titania composite particles (resulting size similar to 10 nm) displayed immensely superior cyclability and rate capability (higher current rates similar to 4 g(-1)) compared to unmodified calcined anatase titania. The conductive carbon interface around titania nanocrystal enhances the electronic conductivity and inhibits crystallite growth during electrochemical insertion/removal thus preventing detrimental kinetic effects observed in case of unmodified anatase titania. The carbon coating of the nanoparticles also stabilized the titania crystallographic structure via reduction in the accessibility of lithium ions to the trapping sites. This resulted in a decrease in the irreversible capacity observed in the case of nanoparticles without any carbon coating.

Reaction of beta-haloenones with tetrathiomolybdate: Synthesis of vinyl disulfides

beta -Haloenones react readily with benzyltriethylammonium tetrathiomolybdate to form the corresponding vinyl disulfides in good yields.

A novel fiber-coated strong base-type anion exchanger with superfast kinetics. Removal and recovery of silver thiosulfate from aqueous solutions

A commercial acrylic fiber with 92% (w/w) acrylonitrile content was partially hydrolyzed converting a fraction of the nitrile (-CN) groups to carboxylic acid (-COOH) groups, to coat the fiber with polyethylenimine (PEI) resin, which was then crosslinked with glutaraldehyde and further quaternized with ethyl chloroacetate to produce a novel strong-base anionic exchanger in the form of fiber. Designated as PAN(QPEI.XG)(Cl-), the fibrous sorbent was compared with a commercial bead-form resin Amberlite IRA-458(Cl-) in respect of sorption capacity, selectivity, and kinetics for removal of silver thiosulfate complexes from aqueous solutions. Though the saturation level of [Ag(S2O3)(2)](3-) on PAN(QPEI.XG)(Cl-) is considerably less than that on IRA-458(Cl-), the gel-coated fibrous sorbent exhibits, as compared to the bead-form sorbent, a significantly higher sorption selectivity for the silver thiosulfate complex in the presence of excess of other anions Such as S2O32-, SO42-, and Cl-, and a remarkably faster rate of both sorption and stripping. The initial uptake of the sorbate by the fibrous sorbent is nearly instantaneous, reaching up to similar to 80% of the saturation capacity within 10 s, as compared to only similar to 12% on the bead-form sorbent. The high initial rate of uptake fits a shell-core kinetic model for sorption on fiber of cylindrical geometry. With 4M HCl, the stripping of the sorbed silver complex from the fibrous sorbent is clean and nearly instantaneous, while, in contrast, a much slower rate of stripping on the bead-form sorbent leads to its fouling due to a slow decomposition of the silver thiosulfate complex in the acidic medium.

Design and fabrication of an automated temperature programmed reaction system to evaluate 3-way catalysts Ce1-x-y(La/Y)(x)PtyO2-delta

A completely automated temperature-programmed reaction (TPR) system for carrying out gas-solid catalytic reactions under atmospheric flow conditions is fabricated to study CO and hydrocarbon oxidation, and NO reduction. The system consists of an all-stainless steel UHV system, quadrupole mass spectrometer SX200 (VG Scientific), a tubular furnace and micro-reactor, a temperature controller, a versatile gas handling system, and a data acquisition and analysis system. The performance of the system has been tested under standard experimental conditions for CO oxidation over well-characterized Ce1-x-y(La/Y)(y)O2-delta catalysts. Testing of 3-way catalysis with CO, NO and C2H2 to convert to CO2, N-2 and H2O is done with this catalyst which shows complete removal of pollutants below 325 degrees C. Fixed oxide-ion defects in Pt substituted Ce1-y(La/Y)(y)O2-y/2 show higher catalytic activity than Pt ion-substituted CeO2

REACTION OF THIOPHOSPHORYL FLUORIDE AND THIOPHOSPHORYL CHLORIDE WITH DIMETHYL SULPHOXIDE

Solid complexes of thiophosphoryl fluoride and thiophosphoryl chloride with dimethyl sulphoxide (DMSO) have been prepared and characterized.

On Application Of The Method Of Kinetic Invariants To The Description Of Dissolution Accompanied By A Chemical Reaction

The dissolution, accompanied by chemical reaction, of monodisperse solid particles has been analysed. The resulting model, which accounts for the variation of mass transfer coefficient with the size of the dissolving particles, yields an approximate analytical form of a kinetic function. Rigorous numerical and approximate analytical solutions have been obtained for the governing system of nonlinear ordinary differential equations. The transient nature of the dissolution process as well as the accuracy of the analytical solution is brought out by the rigorous numerical solution. The analytical solution is fairly accurate for the major part of the range of operational times encountered in practice.

Vapor phase oxidation of p-xylene

The kinetics of the vapor phase oxidation of p-xylene over ferric molybdate catalyst were studied in an isothermal, differential, tubular flow reactor in the temperature range of 360 to 420° C. The major product obtained was p-tolualdehyde with small amounts of maleic anhydride and p-toluic acid. No terephthalic acid or CO2 were observed. The reaction rate data collected fit the redox model given by Equation 1. The values of activation energies Ex, Eo and frequency factors Ax, Ao obtained are 72, 63 kJ/mol and 0.64, 2.89 m3/kg catalyst s respectively. The reaction mechanism was established by studying the oxidation of p-tolualdehyde, toluic and terephthalic acids. It is concluded that the reaction follows a parallel-consecutive scheme. On a étudié la cinétique de l'oxydation, en phase gazeuse, du para-xylène sur un catalyseur consistant en molybdate ferrique; cette oxydation s'est faite dans un réacteur à écoulement tubulaire, isothermique et différentiel, dans une échelle de températures comprises entre 360°C et 420°C. Le produit principal obtenu a été le para-tolualdéhyde; on a aussi trouvé de faibles quantités d'anhydride maléique et d'acide para-toluique, mais on n'a pas noté la présence d'acide téréphtalique ni d'anhydride carbonique (CO2). Les résultats obtenus en ce qui a trait à la vitesse de réaction concordent bien avec les données du modèle redox indiquées par l'équation 1. Les valeurs des énergies d'activation Ex et Eo ainsi que des facteurs de fréquence Ax et Ao obtenus sont respectivement 72 et 63 kilojoules/mol. et 0.64 × 103 et 2.89 m3/kg de catalyseur. On a établi le mécanisme de la réaction en étudiant l'oxydation du para-tolualdéhyde et des acides toluique et téréphtalique. On conclut que la réaction se fait d'une manière parallèle et consécutive.

Reaction of Thiophosphoryl Fluoride and Thiophosphoryl Chloride with Dimethyl Sulphoxide

Solid complexes of thiophosphoryl fluoride and thiophosphoryl chloride with dimethyl sulphoxide (DMSO) have been prepared and characterized.

Design and fabrication of an automated temperature programmed reaction system to evaluate 3-way catalysts Ce1-x-y(La/Y)(x)PtyO2-delta

A completely automated temperature-programmed reaction (TPR) system for carrying out gas-solid catalytic reactions under atmospheric flow conditions is fabricated to study CO and hydrocarbon oxidation, and NO reduction. The system consists of an all-stainless steel UHV system, quadrupole mass spectrometer SX200 (VG Scientific), a tubular furnace and micro-reactor, a temperature controller, a versatile gas handling system, and a data acquisition and analysis system. The performance of the system has been tested under standard experimental conditions for CO oxidation over well-characterized Ce1-x-y(La/Y)(y)O2-delta catalysts. Testing of 3-way catalysis with CO, NO and C2H2 to convert to CO2, N-2 and H2O is done with this catalyst which shows complete removal of pollutants below 325 degrees C. Fixed oxide-ion defects in Pt substituted Ce1-y(La/Y)(y)O2-y/2 show higher catalytic activity than Pt ion-substituted CeO2.