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Yoshito Oshima – One of the best experts on this subject based on the ideXlab platform.

  • 110th Anniversary: Effects of Alcohol Concentration on the Reactions of Ethyl Acetate and Diethyl Malonate in Hot Compressed Water–Alcohol Mixed Solvents
    Industrial & Engineering Chemistry Research, 2019
    Co-Authors: Makoto Akizuki, Kohki Ito, Yoshito Oshima
    Abstract:

    The effects of the alcohol concentration of a hot compressed water–alcohol (mEthanol or Ethanol) mixture on acid-catalyzed ester reactions were investigated. In the water and water–mEthanol mixture, ethyl acetate reactions were promoted by the autocatalytic effect of the produced acetic acid, while diethyl malonate reactions were promoted by the catalytic effect of the solvent molecules. The kinetic analyses indicated that the catalytic effect of H+ derived from the dissociation of acetic acid decreased as mEthanol concentration increased. The catalytic effect of water molecules was highest in a mixed solvent of 10 mol % mEthanol, and that of mEthanol molecules increased as mEthanol concentration increased. In the water–Ethanol mixture, the hydroxyl-decarboxylation of diethyl malonate to ethyl acetate and hydrolysis of ethyl acetate to acetic acid proceeded consecutively. The secondary ethyl acetate hydrolysis was suppressed in the water–Ethanol mixture because of the differences in the effects of alcohol…

  • 110th anniversary effects of alcohol concentration on the reactions of ethyl acetate and diethyl malonate in hot compressed water alcohol mixed solvents
    Industrial & Engineering Chemistry Research, 2019
    Co-Authors: Makoto Akizuki, Kohki Ito, Yoshito Oshima
    Abstract:

    The effects of the alcohol concentration of a hot compressed water–alcohol (mEthanol or Ethanol) mixture on acid-catalyzed ester reactions were investigated. In the water and water–mEthanol mixture, ethyl acetate reactions were promoted by the autocatalytic effect of the produced acetic acid, while diethyl malonate reactions were promoted by the catalytic effect of the solvent molecules. The kinetic analyses indicated that the catalytic effect of H+ derived from the dissociation of acetic acid decreased as mEthanol concentration increased. The catalytic effect of water molecules was highest in a mixed solvent of 10 mol % mEthanol, and that of mEthanol molecules increased as mEthanol concentration increased. In the water–Ethanol mixture, the hydroxyl-decarboxylation of diethyl malonate to ethyl acetate and hydrolysis of ethyl acetate to acetic acid proceeded consecutively. The secondary ethyl acetate hydrolysis was suppressed in the water–Ethanol mixture because of the differences in the effects of alcohol…

  • kinetic analysis on alcohol concentration and mixture effect in supercritical water oxidation of mEthanol and Ethanol by elementary reaction model
    Journal of Supercritical Fluids, 2007
    Co-Authors: Rumiko Hayashi, Masato Onishi, Masakazu Sugiyama, Seiichiro Koda, Yoshito Oshima
    Abstract:

    Abstract Reaction kinetics of mEthanol and Ethanol oxidation in supercritical water at 520–530 °C and 24.7 MPa were investigated both experimentally and by computational simulation. Furthermore, studies were performed on the oxidation of the two alcohols in binary mixtures. For the mEthanol system, experimental data showed that the mEthanol conversion decreased with increasing initial mEthanol concentration in the low concentration range (from 6.48 × 10−6 to 3.94 × 10−5 mol/l), whereas the conversion increased for initial concentrations in the high concentration range (from 2.23 × 10−4 to 1.55 × 10−3 mol/l). Kinetic analyses based on the elementary reaction model showed that production of OH from the reaction of H2O with HO2 seemed to play an important role at the low mEthanol concentrations and that the characteristic dependence of mEthanol conversion on initial mEthanol concentration was due to the very high concentration of H2O in supercritical water oxidation of mEthanol. For the binary system, it was found that mEthanol conversion was accelerated by Ethanol addition whereas Ethanol oxidation was slightly retarded by the presence of mEthanol. Calculation with an elementary reaction model could reproduce the phenomenological mutual effects of alcohols with respect to reaction rates, and it was found that the acceleration/retardation effect of conversions could be well characterized by the time profile of OH radical, rather than HO2 radical.

Robert F Savinell – One of the best experts on this subject based on the ideXlab platform.

  • evaluation of Ethanol 1 propanol and 2 propanol in a direct oxidation polymer electrolyte fuel cell a real time mass spectrometry study
    Journal of The Electrochemical Society, 1995
    Co-Authors: Jiangtao Wang, S Wasmus, Robert F Savinell
    Abstract:

    Ethanol, 1-propanol, and 2-propanol have been evaluated as alternative fuels for direct mEthanol/oxygen fuel cells. The relative product distributions for the electro-oxidation of these alcohols under fuel-cell conditions were determined using on-line mass spectrometry. For water/Ethanol mole ratios between 5 and 2, Ethanol is the main product, while CO{sub 2} is a minor product. However, an increase of the water/Ethanol mole ratio increased the relative product distribution of CO{sub 2} slightly. Propanol was the main product of the electro-oxidation of 1-propanol with a similar percentage of CO{sub 2} being formed as for Ethanol. In contrast, the electro-oxidation of 2-propanol yielded practically only acetone. Between 150 and 190 C, the product distributions for the electro-oxidation of Ethanol, 1-propanol, and 2-propanol do not depend significantly on the temperature. No differences in the product selectivities of Pt-Ru and Pt-black were found. Ethanol is a promising alternative fuel for direct mEthanol fuel cells (DMFCs) with an electrochemical activity comparable to that of mEthanol. Conversely, 1-propanol and 2-propanol are not suitable as fuels for DMFCs due to their low electrochemical activity.

  • Evaluation of Ethanol, 1‐Propanol, and 2‐Propanol in a Direct Oxidation Polymer‐Electrolyte Fuel Cell A Real‐Time Mass Spectrometry Study
    Journal of The Electrochemical Society, 1995
    Co-Authors: Jiangtao Wang, S Wasmus, Robert F Savinell
    Abstract:

    Ethanol, 1-propanol, and 2-propanol have been evaluated as alternative fuels for direct mEthanol/oxygen fuel cells. The relative product distributions for the electro-oxidation of these alcohols under fuel-cell conditions were determined using on-line mass spectrometry. For water/Ethanol mole ratios between 5 and 2, Ethanol is the main product, while CO{sub 2} is a minor product. However, an increase of the water/Ethanol mole ratio increased the relative product distribution of CO{sub 2} slightly. Propanol was the main product of the electro-oxidation of 1-propanol with a similar percentage of CO{sub 2} being formed as for Ethanol. In contrast, the electro-oxidation of 2-propanol yielded practically only acetone. Between 150 and 190 C, the product distributions for the electro-oxidation of Ethanol, 1-propanol, and 2-propanol do not depend significantly on the temperature. No differences in the product selectivities of Pt-Ru and Pt-black were found. Ethanol is a promising alternative fuel for direct mEthanol fuel cells (DMFCs) with an electrochemical activity comparable to that of mEthanol. Conversely, 1-propanol and 2-propanol are not suitable as fuels for DMFCs due to their low electrochemical activity.

Zihao Wang – One of the best experts on this subject based on the ideXlab platform.

  • vapour pressure measurement for binary and ternary systems containing water mEthanol Ethanol and an ionic liquid 1 ethyl 3 ethylimidazolium diethylphosphate
    The Journal of Chemical Thermodynamics, 2007
    Co-Authors: Xiaochuan Jiang, Junfeng Wang, Chunxi Li, Lamei Wang, Zihao Wang
    Abstract:

    Abstract Vapour pressure data were measured for three binary systems containing water, mEthanol or Ethanol with an ionic liquid (IL) 1-ethyl-3-ethylimidazolium diethylphosphate([EEIM][DEP]) and for three ternary systems, i.e. (water + Ethanol + [EEIM][DEP]), (water  + mEthanol + [EEIM][DEP]), and (Ethanol + mEthanol + [EEIM][DEP]), at varying temperature and IL-content ranging from mass fraction of 0.10 to 0.85 by a quasi-static method. The vapour pressure data of the binary systems were correlated by NRTL equation with average absolute relative deviation (ARD) within 0.0091. The binary NRTL parameters were used to predict the vapour pressure of the ternary systems (Ethanol + water + [EEIM][DEP]), (water + mEthanol + [EEIM][DEP]), and (Ethanol +  mEthanol + [EEIM][DEP]) with an overall ARD of 0.037 and the maximum deviation of −0.1295. The results indicate that ionic liquid [EEIM][DEP] can give rise to a negative deviation from the Raoult’s law for the solvents of water, mEthanol and Ethanol, but to a varying degree leading to the variation of relative volatility of a solvent and even removal of azeotrope for (water + Ethanol).

  • Vapor Pressure Measurement and Prediction for Ethanol + MEthanol and Ethanol + Water Systems Containing Ionic Liquids
    Journal of Chemical & Engineering Data, 2006
    Co-Authors: Jin Zhao, Zihao Wang
    Abstract:

    Vapor pressure data for ternary systems Ethanol + mEthanol + [MMIM][DMP] (1-methyl-3-methylimidazolium dimethyl phosphate), Ethanol + mEthanol + [EMIM][DEP] (1-ethyl-3-methylimidazolium diethyl phosphate), Ethanol + mEthanol + [BMIM][DBP] (1-butyl-3-methyl imidazolium dibutyl phosphate), and Ethanol + water + [MMIM][DMP] were measured at ionic liquid (IL) mass fraction of 50 % by a quasi-static method. The vapor pressure data were correlated with the NRTL model for nonelectrolyte solution, and the average absolute relative deviations of vapor pressure for the above systems were 0.55 %, 0.42 %, 0.67 %, and 1.68 %, respectively. On the basis of the predicted isothermal vapor−liquid equilibrium data for the Ethanol + mEthanol and Ethanol + water systems at 320 K and ionic liquid mass fraction of 50 %, it is found that all ILs show salting-out effect for Ethanol. The salting-out effect follows the order [EMIM][DEP] > [MMIM][DMP] > [BMIM][DBP] for the Ethanol + mEthanol system. Moreover, the azeotropic phenome…