Dissolution kinetics of ulexite in acetic acid solutions

Ulexite is an important boron mineral used for the production of boron compounds. The aims of this study are to examine the dissolution kinetics of ulexite in acetic acid solutions, and to present an alternative process to produce boric acid. In order to investigate the dissolution kinetics of ulexite in acetic acid solutions, the concentration of solution, reaction temperature, solid-to-liquid ratio, and particle size were selected as experimental parameters. It was determined that the dissolution rate of ulexite increased with increasing solution concentration and temperature and decreasing particle size and solid-to-liquid ratio. The activation energy of the process was found to be 55.8 kJ/mol.     

Effect of carbon surface oxidation on platinum supported carbon particles on the performance of gas diffusion electrodes for the oxygen reduction reaction

The effect of carbon surface oxidation on platinum supported carbon particles (Pt/C) with nitric acid was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, polarization experiments and chronoamperometry. Cyclic voltammograms, polarization curves and electrochemical impedance spectra showed that the treated catalyst had much larger active surface area and higher ionic conductivity than the untreated catalyst, and provided enhanced performance for oxygen reduction. The formation of acidic groups was examined by IR spectra. The Pt/C surface oxidation had a large effect on the performance of a gas diffusion electrode for oxygen reduction reaction.     

Oxidation of some aliphatic polyols on anodically deposited MnO2

Galvanostatic steady state current potential measurements were carried out for oxidation of a series of aliphatic alcohols having varying number of hydroxyl groups. The anodically deposited layer of MnO₂ on platinum was used as the electrode material. The deposit was characterised by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrode potential measurements. The catalytic role of MnO₂ in the electro-oxidation of alcohols was indicated by the chronopotentiograms and the cyclic voltammograms. An analysis of the electrochemical data indicated a catalytic EC mechanism in which Mn (V) is generated electrochemically and consumed chemically in succession. Based on this and the hydrogen bonding interaction between alcoholic hydroxyl groups and MnO₂ layer, a mechanism was proposed which accounts for the variation in the observed electrochemical reaction orders. Tafel behaviour was found to be followed only approximately. Current efficiency of the electrochemical oxidation of polyols was studied. Replacement of platinum by carbon as current collector was found to leave the electrocatalytic activity of the MnO₂ deposit practically unaltered.     

Synthesis and structural characterization of methacrylic acid/octadecyl acrylate‐graft‐poly(methylhydrosiloxane) by hydrosilylation

Methylmethacrylate (MMA) and octadecyl acrylate (OA) were grafted to poly(methylhydrosiloxane) (PMHS) by hydrosilylation, respectively, with hexachloroplatinic acid as catalyst, and the former was further hydrolyzed to prepare methacrylic acid (MAA)‐graft‐PMHS under the alkaline condition. Through orthogonal experiment, main factors affecting the graft reaction between OA and PMHS were discussed and arranged in a decreasing order according to their abilities of the effect on the hydrosilylation of OA with PMHS: catalyst dosage, reaction temperature, reaction time, material ratio, and solvent dosage. It was found that the hydrosilylation of OA with PMHS was easier to that of MMA with PMHS. Under optimal conditions, the grafting ratios of MMA with PMHS and OA with PMHS reached about 90 and 95%, respectively. FTIR and ¹H NMR spectra indicated that the hydrosilylation reactions followed the Markovnikov's rule and played a strong preference toward β‐1,2‐addition. The test of contact angle indicated that surface energy of a system was mainly dependent on the polar groups. The surface energy of OA‐graft‐PMHS (35.07 mN/m) was similar to those of PMHS (35.62 mN/m) and polyoctadecyl acrylate (36.57 mN/m), and lower than that of MAA‐graft‐PMHS (43.50 mN/m). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Continuous hydrogen evolution from cyclohexanes over platinum catalysts supported on activated carbon fibers

The continuous production of hydrogen from cyclohexanes is achieved effectively using Pt/ACF (ACF = activated carbon fiber) catalysts in a fixed-bed flow reactor. The Pt catalysts are more effective than a Pd/ACF catalyst for the reaction. Besides cyclohexane, methylcyclohexane, 1,4-dimethylcyclohexane, and p-menthane can also be employed as hydrogen source in the reaction system.     

粉状阳离子聚丙烯酰胺的研制

用聚丙烯酰胺胶体,在≥20％浓度的硫酸盐溶液中,进行Mannich反应,经真空干燥后,制取水溶性阳离子型高分子。初步探讨了盐浓度、温度、时间、配比对产物的阳离子度、溶解性的影响。     

SYNTHESIS OF CHEMICAL REACTION PATHS: ECONOMIC AND SPECIFICATION CONSTRAINTS

The synthesis of alternative reaction paths leading to a desired chemical has received increasing attention in the recent past. A procedure to develop new reaction schemes in a systematic manner was reviewed by the authors ( [ 1 -3] ). The algorithm presented in these earlier papers implied the generation of an infinite number of reaction paths. The thermodynamic feasibility is a preliminary screening which reduces the number of chemical production schemes. Further screening is necessary, taking into account considerations which are related to economics, processing, safety and so on. Some constraints related with role specification, gross added value and demand/supply requirements are analysed in this paper. Examples illustrate the application of the screening procedure, showing that the addition of a few constraints results in a dramatic decrease of alternative reaction paths.     

Kinetics of oxygen absorption in aqueous sodium dithionite solutions

The absorption and reaction of oxygen in aqueous alkaline solutions of sodium dithionite has been experimentally investigated in a novel gas-liquid contactor. The novel gas-lift bubble column contactor was used to study the kinetics over wide ranges of reactant concentrations, temperature, and pH. The oxygen-sodium dithionite reaction was found to be first-order with respect to dithionite in the range of dithionite concentration < 0.1 M, and second-order in the range of dithionite concentration > 0.1 M. The reaction with respect to oxygen was found to be zero-order for all dithionite concentrations. These results and experimental investigations of the effect of solution alkalinity and temperature on the reaction rate are consistent with previous findings obtained in different gas-liquid contactors. The results thus confirm the feasibility of using the gas-lift bubble column for the kinetics of gas-liquid reactions.     

Drying with Chemical Reaction in Cocoa Beans

Desirable flavor qualities of cocoa are dependent on how the cocoa beans are fermented, dried, and roasted. During fermentation and drying, polyphenols such as leucocyanidin and apecatechin are oxidized by polyphenols oxidase to form o-quinone, which later react nonenzymatically with a hydroquinone in a condensation reaction to form browning products and moisture. The objective of this article is to model the cocoa beans drying together with the browning reaction. A Luikov drying model for the moisture and a simple Fick's law diffusion model combined with first-order reactions for both the enzymatic oxidation and nonenzymatic condensation reactions were constructed. Both models were used to identify moisture diffusivity coefficient and total polyphenols diffusivity in cocoa beans from experimental drying and polyphenols degradation data and published kinetic data of the reactions. The theoretical drying model fitted the experimental cocoa bean drying curves with low mean square of residuals. The polyphenols diffusion and reaction model also fitted the experimental polyphenols degradation curves with minimum mean residual squares. The rate of polyphenols degradation in the cocoa beans increases at higher temperature and higher relative humidity. This is because the increasing reaction rate of polyphenols oxidation reaction as well as higher moisture diffusion at higher relative humidity and temperature. The effective moisture diffusivity in cocoa beans is estimated to be between 8.194 × 10^-9 and 8.542 × 10^-9 m²·s^-1, which is of the same order of magnitude as published data. The effective total polyphenols diffusivity is estimated to be between 8.333 × 10^-12 to 1.000 × 10^-11 m²·s^-1 with minimum mean residual squares. It is three orders of magnitude less than the estimated moisture diffusivity because of the larger polyphenols molecules. The estimated polyphenols diffusivity is very close to those published in the literature for sorption and ultrafiltration processes.     

A novel methanol-tolerant Ir-Se chalcogenide electrocatalyst for oyxgen reduction

A novel methanol-tolerant oxygen-reduction catalyst, Iridium-selenium (Ir-Se) chalcogenide, was synthesized by chemical precipitation in an organic solvent. Auger electron spectroscopy (AES) analysis confirmed that the synthesized Ir-Se chalcogenide had a chemical formula of Ir₄Se. This chalcogenide showed strong catalytic activity towards the oxygen reduction reaction (ORR) and a high methanol tolerance. It was found that most of the oxygen could be directly reduced to water through a four-electron pathway with less than 10% hydrogen peroxide (H₂O₂) being produced during the ORR. The improvement in catalytic activity of the Ir-Se chalcogenide in comparison with that of pure Ir might be attributed to the effect of a bimetallic interaction.