• Title/Summary/Keyword: Stoichiometric effect

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Stoichiometric Effects. Correlation of the Rates of Solvolysis of Isopropenyl Chloroformate

  • Ryu, Zoon-Ha;Lee, Young-Ho;Oh, Yung-Hee
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1761-1766
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    • 2005
  • Solvolysis rates of isopropenyl chloroformate (3) in water, $D_2O$, $CH_3OD$ and in aqueous methanol, ethanol, 2,2,2-trifluoroethanol (TFE), acetone, 1,4-dioxane as well as TFE-ethanol at 10 ${^{\circ}C}$ are reported. Additional kinetic data for pure water, pure ethanol and 80%(w/w) 2,2,2-trifuoroethanol (T)-water (W) at various temperatures are also reported. These rates show the phenomena of maximum rates in specific solvents (30% (v/v) methanol-water and 20% (v/v) ethanol-water) and, variations in relative rates are small in aqueous alcohols. The kinetic data are analyzed in terms of GW correlations, steric effect, kinetic solvent isotope effects (KSIE), and a third order model based on general base catalysis (GBC). Solvolyses based on predominately stoichiometric solvation effect relative to medium solvation are proceeding in 3 and the results are remarkably similar to those for p-nitrobenzoyl chloride (4) in mechanism and reactivity.

The Effect of Spray Characteristics on Flue Gas Desulfurization Yield in Spray Drying Sorber (반건식 세정기의 슬러리 분무 특성에 따른 산성가스 제거효율)

  • Yang, Hyun-Mo;Kim, Sang-Soo
    • Proceedings of the KSME Conference
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    • 2001.06d
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    • pp.79-84
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    • 2001
  • The effect of spray characteristics on desulfurization yield was evaluated by performing experiments with pilot spray drying sorber (SDS). Among the variables of operating conditions, the slurry-spraying conditions were chosen as major parameters; Stoichiometric ratio and Sauter mean diameter of slurry droplet were varied for the different gas temperatures and $SO_{2}$ concentrations in the inlet gas flow. From the experimental results, we proposed semi-empirical models of desulfurization yield for both Stoichiometric ratio and Sauter mean diameter of droplets. The optimal condition of spray can be determined based on these results, which might be applied to the design or scale-up of SDS systems.

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Characteristics of Laminar Lifted Flame in High Temperature Coflow (고온 동축류에서 층류 화염의 부상특성)

  • Kim, Kil-Nam;Won, Sang-Hee;Cha, Min-Suk;Chung, Suk-Ho
    • Journal of the Korean Society of Combustion
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    • v.7 no.2
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    • pp.1-6
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    • 2002
  • Characteristics of laminar lifted flames of propane highly-diluted with nitrogen have been investigated at various temperatures of coflow air. At various fuel mole fractions, the base of laminar lifted flames has the structure of tribrachial (or triple) flame. The liftoff heights are correlated well with the stoichiometric laminar burning velocity considering initial temperature at a given coflow velocity. It shows that lifted flames are stabilized on the basis of the balance mechanism between local flow velocity and the propagation speed of tribrachial flame, regardless of the temperature of coflow and fuel mole fraction. Lifted flames exist for a jet velocity even smaller than the stoichiometric laminar burning velocity, and liftoff velocity increases more rapidly than stoichiometric laminar burning velocity as coflow temperature increases. These can be attributed to the buoyancy effect due to the density difference.

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STATIC CHARACTERISTICS OF A UREA-SCR SYSTEM FOR NOx REDUCTION IN DIESEL ENGINES

  • Nam, J.G.
    • International Journal of Automotive Technology
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    • v.8 no.3
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    • pp.283-288
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    • 2007
  • This paper presents the static characteristics of a urea-SCR system. The static characterization of the urea-SCR system was generated by sweeping urea flow rates at common engine torque/speed operating points. Several experiments were performed using engine operating points at different raw NOx emission levels, space velocities, and SCR catalyst temperatures. The recorded NOx emissions from the engine exhaust outlet and engine tailpipe are then compared. The urea-SCR static system results indicated that a $50{\sim}60%$ NOx conversion is achievable at most engine operating points using the stoichiometric $NH_3/NOx$ ratio, and a high 98% NOx conversion is possible by exceeding the stoichiometric $NH_3/NOx$ ratio. The effect of the pre-oxidation catalyst volume was also investigated and found to have a profound impact on experimental results, particularly the static NOx conversion.

Stoichiometric Solvation Effects. Solvolysis of Methanesulfonyl Chloride

  • Gu, In Seon;Yang, Gi Yeol;An, Seon Gyeong;Lee, Jong Gwang;Lee, Ik Chun
    • Bulletin of the Korean Chemical Society
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    • v.21 no.10
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    • pp.955-956
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    • 2000
  • Solvolyses of methanesulfonyl chloride in water, $D^2O$, $CH^3OD$, and in aqueous binary mixtures of acetone, eth-anol and methanol are investigated at 25, 35 and $45^{\circ}C.$ The Grunwald-Winstein plot of first-order rate con-stants for the solvolytic react ion of methanesulfonyl chloride with YCl (based on 2-adamantyl chloride) shows marked dispersions into three separate lines for three aqueous mixtures with a small m value (m < 0.30), and shows a rate maximum for aqueous alcoholic solvents. Stoichiometric third-order rate constants, kww and kaa were calculated from the observed first-order rate constants and (kaw + kwa) was calculated from the kww and kaa values. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed and/or SAN/SN2 reaction mechanism for methanesulfonyl chloride solvolyses based on mass law and stoichiometric solvation effect studies.

Stoichiometric Solvation Effects. Solvolysis of Isopropylsulfonyl Chloride

  • Koo, In-Sun;Yang, Ki-Yull;Shin, Hyeon-Bae;An, Sun-Kyoung;Lee, Jong-Pal;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.25 no.5
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    • pp.699-703
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    • 2004
  • Solvolyses of isopropylsulfonyl chloride (IPSC) in water, D_2O,\;CH_3OD$, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25, 35 and 45$^{\circ}C$. The Grunwald-Winstein plot of first-order rate constants for the solvolytic reaction of IPSC with $Y_{Cl}$ (based on 2-adamantyl chloride) shows marked dispersions into three separate lines for three aqueous mixtures with a small slope (m < 0.30). The extended Grunwald-Winstein plots for the solvolysis of IPSC show better correlation. The kinetic solvent isotope effects determined in water and methanol are in consistent with the proposed mechanism of the general base catalyzed and/or $S_AN/S_N2$ reaction mechanism for IPSC solvolyses based on mass law and stoichiometric solvation effect studies.

Stoichiometric Solvation Effects. Product-Rate Correlation for Solvolyses of Phenyl Chloroformate in Alcohol-Water Mixtures

  • 구인선;양기율;강금덕;오혁근;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.17 no.6
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    • pp.520-524
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    • 1996
  • Solvolyses of phenyl chloroformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0 ℃. Product selectivities are reported at 25 ℃ for a wide range of ethanol-water and methanol-water solvent compositions. The Grunwald-Winstein plots of first-order rate constants for phenyl chloroformate with YCl (based on 2-adamantyl chloride) show marked dispersions into three separate lines for the three aqueous mixtures with a small m value (m< 0.2) and a rate maximum for aqueous alcohol solvents. Third-order rate constants, kww, kaw, kwa and kaa were calculated from the observed kww and kaa values together with kaw and kwa calculated from the intercept and slope of the plot of 1/S vs. [alcohol]/[water]. The calculated rate constants, kcalc and mol % of ester agree satisfactorily with those of the observed rate constants, kobs and mol % of ester, supporting the stoichiometric solvation effect analysis. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed and/or carbonyl addition for phenyl chloroformate solvolyses based on mass law and stoichiometric solvation effect studies.

Effect of Glycine on L-Ornithine Production by a Citrulline Auxotroph of Brevibacterium ketoglutamicum and Stoichiometric Analysis

  • Nam, Soo-Wan;Choi, Dae-Keon;Ryu, Wuk-Sang;Jang, Hyung-Wook;Chung, Bong-Hyun;Park, Young-Hoon
    • Journal of Microbiology and Biotechnology
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    • v.4 no.2
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    • pp.95-101
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    • 1994
  • The effects of glycine on cell growth and L-omithine production were investigated in shake-flask and jar fermentor cultures of a citrulline auxotrophic mutant, Brevibacterium ketoglutamicum BK 1046. In the shake-flask culture, the optimal concentration of glycine for L-ornithine production was found to be 20 g/l. In the jar fermentor culture with the glycine at an initial concentration of 20 g/l, L-ornithine production increased by 28%, compared to that of the culture with no glycine added. 37 g/l of L-ornithine was produced when additional feeding of glycine (5 g/l) was made. This was a significant improvement in L-ornithine production compared to that (ca. 24 g/l) of the corresponding batch culture conducted without glycine. According to the stoichiometric analysis with the batch fermentation results, the experimental and theoretical L-ornithine yields based on the glucose consumption were 0.24 and 0.59, respectively. This indicates that the performance of L-ornithine fermentation can further be improved by the supplementation of glycine and the development of a mutant strain possessing a higher growth yield.

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Stoichiometric Solvation Effects. Solvolysis of Trifluoromethanesulfonyl Chloride

  • Koo, In-Sun;Yang, Ki-Yull;Park, Jong-Kuen;Woo, Mi-Young;Cho, Jun-Mi;Lee, Jong-Pal;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.8
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    • pp.1241-1245
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    • 2005
  • Solvolyses of trifluoromethanesulfonyl chloride (TFMSC) in water and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25, 35 and 45 ${^{\circ}C}$. The Grunwald-Winstein plot of first-order rate constants for the solvolytic reaction of TFMSC with YCl (based on 2-adamantyl chloride) shows marked dispersions into three separate curves for three aqueous mixtures. The extended Grunwald-Winstein plots for the solvolysis of TFMSC show better correlation. The large negative ${\Delta}S^{\neq}$ and relatively small positive ${\Delta}H^{\neq}$ reveals that the solvolytic reaction proceeds via a typical bimolecular reaction mechanism. The l and m values determined in various solvents are consistent with the proposed mechanism of the general base catalysis $S_AN/S_N2$reaction mechanism for TFMSC solvolyses based on mass law and stoichiometric solvation effect studies.

Optimal Operation Condition of Spray Drying Sorber for Simultaneous Removal of Acidic and Organic Gaseous Pollutants (산성 및 유기성 가스의 동시제거를 위한 준건식 세정시스템의 적정 운전 조건)

  • 백경렬;구자공
    • Journal of Environmental Science International
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    • v.10 no.1
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    • pp.59-64
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    • 2001
  • The effect of major operating parameters in spray drying sorber(=SDS) for automatic control for the simultaneous removal of acidic and organic gaseous pollutants from solid waste incinerator was performed. The field experiment was carried out in pilot scale test for the quantification of major operating parameters of hydrophilic and the hydrophobic pollutants. The removal efficiencies of $SO_2$and HCI in the 5wt% slurry condition were being increased with the increase of the stoichiometric ration which is the molecular ratio of lime to the pollutant concentration, and with the decrease of inflow flue gas temperature in the pilot SDS reactor. The removal efficiency along the height of spray drying sorber was closely related to the temperature profile, and more than 90% of total removal efficiency was achieved in an absorption region. For the removal of acidic gas the optimum operating condition considering the economics and a stable operation is the 5wt% of slurry concentration, 1.2 of stoichiometric ratio and 25$0^{\circ}C$ of inflow flue gas temperature. For the organic gases of benzene and toluene the removal efficiencies were 20-60% which is much lower than that of acidic gas. The best removal efficiency was obtained at 1.5 of stoichiometric ratio and 25$0^{\circ}C$ of inflow flue gas temperature. The organic\`s removal efficiency along the height of spray drying sorber was quite different from that of acidic gas, that is, more than 60% of the total removal efficiency for benzene and 90% of the total removal for toluene were achieved in the dried adsorption region, which was formed at the lower or exit part of the reactor.

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