• Title/Summary/Keyword: Stoichiometric model

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Transition-State Variation in the Solvolyses of para-Substiuted Phenyl Chloroformates in Alcohol-Water Mixtures

  • 구인선;양기율;강금덕;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.968-973
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    • 1998
  • Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.

A Modeling Approach: Effects of Wetland Plants on the Fate of Metal Species in the Sediments (퇴적물에서 금속 이온 거동에 미치는 습지 식물의 영향에 관한 모델 연구)

  • Choi, Jung Hyun
    • Journal of Korean Society on Water Environment
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    • v.24 no.5
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    • pp.603-610
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    • 2008
  • A mathematical model was developed to understand how the presence of plants affects vertical profiles of electron acceptors, their reduced species, and trace metals in the wetland sediments. The model accounted for biodegradation of organic matter utilizing sequential electron acceptors and subsequent chemical reactions using stoichiometric relationship. These biogeochemical reactions were affected by the combined effects of oxygen release and evapotranspiration driven by wetland plants. The measured data showed that $SO_4{^{2-}}$ concentrations increased at the beginning of the growing season and then gradually decreased. Based on the measured data, it was hypothesized that the limitation of the solid phase sulfide in direct contact with the roots may result in the gradual decrease of $SO_4{^{2-}}$ concentrations. With the dynamic formulation for the limitation of the solid phase sulfide, model simulated time variable sulfate profiles using published model parameters. Oxygen release from roots produced divalent metal species (i.e. $Cd^{2+}$) as well as oxidized sulfur species (i.e. $SO_4{^{2-}}$) in the sediment pore water. Evapotranspiration-induced advection increased flux of divalent metal species from the overlying water column into the rhizosphere. The increased divalent metal species were converted to the metal sulfide with sufficient FeS around the rhizosphere, which contributed to the decrease of bioavailability and toxicity of divalent metal activity in the pore water. Since the divalent metal activity is a good predictor of the metal bioavailability, this model with a proper simulation of solid phase sulfide plays an essential role to predict the dynamics of trace metals in the wetland sediments.

Ramjet Mode Combustion Test for a Dual-Mode Ramjet Engine Model with a Large Backward-Facing Step (큰 후향 계단이 있는 이중 모드 램젯 엔진 모델의 램젯 모드 연소 시험)

  • Yang, Inyoung;Lee, Kyung-jae;Lee, Yang-ji;Kim, Chun-taek
    • Journal of the Korean Society of Propulsion Engineers
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    • v.20 no.6
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    • pp.83-90
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    • 2016
  • Ramjet mode combustion test was performed for a dual-mode ramjet engine model. The engine model consists of an air intake, a combustor and a nozzle. The combustor in the model has a large backward-facing step, designed to be used as a part of a rocket-based combined cycle engine. The test was performed at the flight speed of Mach 5 and the altitude of 24 km. Strong combustion was established only when the fuel was injected from both of the bottom-side and cowl-side wall. When the total fuel stoichiometric ratio was 1.0, distributed as 0.5 on the cowl side and 0.5 on the bottom side, the flow became subsonic at some portion in the combustor by thermal choking, i.e., ramjet mode was established for this condition.

A Study on the Microstructures and Tensile Properties of Heat-Treated Cast Ti-(44-54)at.%Al Alloys (Ti-(44-54)at.%Al 열처리 주조합금의 미세조직과 인장특성에 관한 연구)

  • Jung, Jae-Young
    • Journal of Korea Foundry Society
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    • v.37 no.6
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    • pp.199-206
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    • 2017
  • In this study, the variations of microstructures and tensile properties of Ti-(44-54)at.%Al binary alloys were investigated. The heat-treated microstructure depended greatly on their solidification structure and annealing temperature. We measured the variations of volume fractions of primary and secondary lamellar structure as a function of the heat treatment temperature in a Ti-47at.%Al alloy. The variation of ductility as a function of Al content was in good agreement with the change of fracture mode in the tensile fracture surface. It can be inferred that the variations of yield stress and hardness of ${\gamma}$ phase in a single ${\gamma}$-phase field region are enhanced by anti-site defects created by deviations from the stoichiometric composition. In a Ti-47at.%Al alloy within the (${\alpha}_2+{\gamma}$) two-phase field, the yield stress tended to be the maximum at a near equal volume fraction of lamellar and ${\gamma}$ grains. The ductility depended sensitively on the overall grain size and Al content. The calculation of fracture strain using Chan's model indicated that the change of ductility as a function of annealing temperature was primarily determined by the variations in the overall grain size and lamellar volume fraction.

Mapping of Carbon Flow Distribution in the Central Metabolic Pathways of Clostridium cellulolyticum: Direct Comparison of Bacterial Metabolism with a Soluble versus an Insoluble Carbon Source

  • DESVAUX, MICKAEL,
    • Journal of Microbiology and Biotechnology
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    • v.14 no.6
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    • pp.1200-1210
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    • 2004
  • Metabolic flux analysis was established by adapting previous stoichiometric model developed during growth with cellulose to cell grown with cellobiose for further direct comparison of the bacterial metabolism. In carbon limitation with cellobiose, a shift from acetate-ethanol fermentation to ethanol-lactate fermentation is observed and the pyruvate overflow is much higher than with cellulose. In nitrogen limitation with cellobiose, the cellodextrin and exopolysaccharide overflows are much higher than on cellulose. In carbon and nitrogen saturation with cellobiose, the cellodextrin, exopolysaccharide, and free amino acids overflows reach the highest levels observed but all remain limited on cellulose. By completely shunting the cellulosome, the use of cellobiose allows to reach much higher carbon consumption rates which, in return, highlights the metabolic limitation of C. cellulolyticum. Therefore, the physical nature of the carbon source has a profound impact on the metabolism of C. cellulolyticum and most probably of other cellulolytic bacteria. For cellulolytic bacteria, the use of soluble carbon substrate must carefully be taken into consideration for the interpretation of results. Direct comparison of metabolic flux analysis from cellobiose and cellulose revealed the importance of cellulosome, phosphoglucomutase and pyruvate-ferredoxin oxidoreductase in the distribution of carbon flow in the central metabolism. In the light of these findings, future directions for improvement of cellulose catabolism by this bacterium are discussed.

Morphological Analysis of Engineered PCC by Gas-Liquid Mixing Conditions (기체-액체 혼합조건에 따른 Engineered PCC의 형태학적 분석)

  • Lee, Tai-Ju;Seo, Jin-Ho;Kim, Hyoung-Jin
    • Journal of Korea Technical Association of The Pulp and Paper Industry
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    • v.43 no.3
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    • pp.113-120
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    • 2011
  • Precipitated calcium carbonate(PCC), particularly calcite crystal, is extensively used as a pigment, filler or extender in various industries such as paper, paint, textile, detergents, adhesives, rubber and plastics, food, cosmetics, and biomaterials. PCC is conventionally produced through the gas-liquid carbonation process, which consists on bubbling gaseous $CO_2$ through a concentrated calcium hydroxide slurry. This study is aimed to find some factors for controlling the morphology of engineered PCC in lab-scaled mixing batch. The experimental designs were based on temperature variables, $Ca(OH)_2$ concentration, $CO_2$ flow rate, and electrical conductivity. The model of engineered PCC morphology was finally controlled by adjustment of electrical conductivity(6.0~7.0 mS/cm) and $Ca(OH)_2$ concentration(10 g/L). Orthorhombic calcite crystals were mostly created at high concentration and electrical conductivity conditions because the increased ratio of $Ca^{2+}$ and $CO{_3}^{2-}$ ions affects the growth rate of orthorhombic faces. Excess calcium spices were contributed to the growth of faces in calcium carbonate crystal, and the non-stoichiometric reaction was occurred between $Ca^{2+}$ and $CO{_3}^{2-}$ ions during carbonation process.

Simulation of flame propagation in suspension of coal particles (석탄입자가 존재하는 공기중에서의 화염전파에 관한 모사)

  • 윤길원;백승욱
    • Transactions of the Korean Society of Mechanical Engineers
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    • v.12 no.1
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    • pp.36-43
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    • 1988
  • A two phase model for the simulation of flame propagation has been developed and applied to a mixture of coal air. The effects associated with changes in the initial coal partial equivalence ratio and the initial diameter of particles on the structure of laminar flame propagation have been studied qualitatively and quantitatively. Especially the flame structure, the burning velocity, and the thermal behavior were evaluated. It was found that the radiative heat transfer absolutely dominates over the conduction mode. The increase in particle size was seen to contribute to an obvious increase in burning velocity for fuel lean and stoichiometric mixture. But for fuel rich mixture, the burning velocity was found to exhibit a weaker dependence on particle size.

An Analysis of Concept Description and Model and Student Understanding About Ionic Compound in Textbooks Developed Under the 2009 Revised National Curriculum (2009 개정 교육과정에 따른 교과서에서 이온 화합물의 설명 개념과 모형 및 학생 이해도 분석)

  • Shin, He Young;Woo, Ae Ja
    • Journal of the Korean Chemical Society
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    • v.60 no.5
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    • pp.362-373
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    • 2016
  • In this study, ionic compound in the science textbooks developed under the 2009 revised national curriculum were analyzed in terms of the scientific concept and model description and the student understanding through the questionnaires. Analysis of textbooks was performed for science2 of middle school and chemistry I & II of high school. Questionnaire was carried out with 194 students including middle school 2nd grade and high school 1st-3rd grade. The results are as follows: First, as a result of analysis of textbooks, scientific concepts and models used to explain the ionic compound showed differences depending on the types of textbooks. In addition, scientific models were provided with or without explanation for the scientific concepts. Second, analysis of the questionnaire showed that students didn’t properly understood scientific concepts and models in the ion formation, stoichiometric ratio between ions.

Inhibition of Citrate Synthase Thermal Aggregation In Vitro by Recombinant Small Heat Shock Proteins

  • Gong, Weina;Yue, Ming;Xie, Bingyan;Wan, Fanghao;Guo, Jianying
    • Journal of Microbiology and Biotechnology
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    • v.19 no.12
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    • pp.1628-1634
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    • 2009
  • Small heat shock proteins (sHSPs) function as molecular chaperones that protect cells against environmental stresses. In the present study, the genes of hsp17.6 and hsp17.7, cytosolic class I sHSPs, were cloned from a tropical plant, Ageratina adenophorum. Their C-terminal domains were highly conserved with those of sHSPs from other plants, indicating the importance of the C-terminal domains for the structure and activity of sHSPs. The recombinant HSP17.6 and HSP17.7 were applied to determine their chaperone function. In vitro, HSP17.6 and HSP17.7 actively participated in the refolding of the model substrate citrate synthase (CS) and effectively prevented the thermal aggregation of CS at $45^{\circ}C$ and the irreversible inactivation of CS at $38^{\circ}C$ at stoichiometric levels. The prior presence of HSP17.7 was assumed to suppress the thermal aggregation of the model substrate CS. Therefore, this report confirms the chaperone activity of HSP17.6 and HSP17.7 and their potential as a protectant for active proteins.

Abnormal Behavior of Ordinary Heterotrophic Organism Active Biomass at Different Substrate/Microorganisms Ratios in Batch Test (회분식 실험 Substrate/Microorganisms 비에 따른 종속영양미생물의 특이거동 연구)

  • Lee, Byung-Joon;Wentzel, M.C.;Ekama, G.A.;Min, Kyung-Sok
    • Journal of Korean Society on Water Environment
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    • v.20 no.3
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    • pp.197-205
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    • 2004
  • Batch test methods have developed for a long time to measure kinetic and stoichiometric parameters which are required to perform steady state design and mathematical modelling of activated sludge processes. However, at various So/Xo ratios, abnormal behaviors of ordinary heterotrophic organism in batch tests have been reported in many researches. Thus, in this research, abnormal behaviors of heterotrophs in batch tests were investigated at various So/Xo conditions by measuring and interpreting oxygen utilization rate. As So/Xo ratio increased, the calculated values of maximum specific growth rates, ${\mu}_{H,max}$ and $K_{MP,max}$, increased. However, at a certain point of So/Xo (around 10mgCOD/mgMLAVSS), ${\mu}_{H,max}$ and $K_{MP,max}$ values started to decrease. According to this observation, three prominent behaviours of heterotrophs were identified at various So/Xo conditions. (1) At low So/Xo region (below 5 mgCOD/mgMLAVSS), the oxygen utilization rate of heterotrophs in batch tests were almost stable and consequently yielded lower maximum specific growth rate. (2) At high So/Xo region (up to 5~10 mgCOD/mgMLAVSS), oxygen utilization rate incresed sharply with time and indicated more upward curvature than the predicted OUR with conventional activated sludge model, which consists of single hetetrotrophs group. Thus, in this region, competition model of two organisms, fast-grower and slow-grower, seemed to be appropriate. (3) At extremely high So/Xo region (over 10mgCOD/mgMLAVSS), significant oxygen utilization rate was still observed even after depletion of readily biodegradable COD. This might be caused by retarded utilization of intermediates which were generated by self inhibition mechanism in the process of RBCOD uptake.