• Title/Summary/Keyword: Bond mechanism

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Korea Emissions Inventory Processing Using the US EPA's SMOKE System

  • Kim, Soon-Tae;Moon, Nan-Kyoung;Byun, Dae-Won W.
    • Asian Journal of Atmospheric Environment
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    • v.2 no.1
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    • pp.34-46
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    • 2008
  • Emissions inputs for use in air quality modeling of Korea were generated with the emissions inventory data from the National Institute of Environmental Research (NIER), maintained under the Clean Air Policy Support System (CAPSS) database. Source Classification Codes (SCC) in the Korea emissions inventory were adapted to use with the U.S. EPA's Sparse Matrix Operator Kernel Emissions (SMOKE) by finding the best-matching SMOKE default SCCs for the chemical speciation and temporal allocation. A set of 19 surrogate spatial allocation factors for South Korea were developed utilizing the Multi-scale Integrated Modeling System (MIMS) Spatial Allocator and Korean GIS databases. The mobile and area source emissions data, after temporal allocation, show typical sinusoidal diurnal variations with high peaks during daytime, while point source emissions show weak diurnal variations. The model-ready emissions are speciated for the carbon bond version 4 (CB-4) chemical mechanism. Volatile organic carbon (VOC) emissions from painting related industries in area source category significantly contribute to TOL (Toluene) and XYL (Xylene) emissions. ETH (Ethylene) emissions are largely contributed from point industrial incineration facilities and various mobile sources. On the other hand, a large portion of OLE (Olefin) emissions are speciated from mobile sources in addition to those contributed by the polypropylene industry in point source. It was found that FORM (Formaldehyde) is mostly emitted from petroleum industry and heavy duty diesel vehicles. Chemical speciation of PM2.5 emissions shows that PEC (primary fine elemental carbon) and POA (primary fine organic aerosol) are the most abundant species from diesel and gasoline vehicles. To reduce uncertainties in processing the Korea emission inventory due to the mapping of Korean SCCs to those of U.S., it would be practical to develop and use domestic source profiles for the top 10 SCCs for area and point sources and top 5 SCCs for on-road mobile sources when VOC emissions from the sources are more than 90% of the total.

The Study on Dielectric Property and Thermal Stability of $Ta_2O_{5}$ Thin-films ($Ta_2O_{5}$ 커패시터 박막의 유전 특성과 열 안정성에 관한 연구)

  • Kim, In-Seong;Lee, Dong-Yun;Song, Jae-Seong;Yun, Mu-Su;Park, Jeong-Hu
    • The Transactions of the Korean Institute of Electrical Engineers C
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    • v.51 no.5
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    • pp.185-190
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    • 2002
  • Capacitor material utilized in the downsizing passive devices and dynamic random access memory(DRAM) requires the physical and electrical properties at given area such as capacitor thickness reduction, relative dielectric constant increase, low leakage current and thermal stability. Common capacitor materials, $SiO_2$, $Si_3N_4$, $SiO_2$/$Si_3N_4$,TaN and et al., used until recently have reached their physical limits in their application to several hundred angstrom scale capacitor. $Ta_2O_{5}$ is known to be a good alternative to the existing materials for the capacitor application because of its high dielectric constant (25 ~35), low leakage current and high breakdown strength. Despite the numerous investigations of $Ta_2O_{5}$ material, there have little been established the clear understanding of the annealing effect on capacitance characteristic and conduction mechanism, design and fabrication for $Ta_2O_{5}$ film capacitor. This study presents the structure-property relationship of reactive-sputtered $Ta_2O_{5}$ MIM capacitor structure processed by annealing in a vacuum. X-ray diffraction patterns skewed the existence of amorphous phase in as-deposited condition and the formation of preferentially oriented-$Ta_2O_{5}$ in 670, $700^{\circ}C$ annealing. On 670, $700^{\circ}C$ annealing under the vacuum, the leakage current decrease and the enhanced temperature-capacitance characteristic stability. and the leakage current behavior is stable irrespective of applied electric field. The results states that keeping $Ta_2O_{5}$ annealed at vacuum gives rise to improvement of electrical characteristics in the capacitor by reducing oxygen-vacancy and the broken bond between Ta and O.

Kinetic Studies for the Reactions of Pyridine with Benzoylchlorides under High Pressure and High Vacuum (고압 및 고진공에서의 피리딘과 벤조일클로라이드류의 반응에 관한 속도론적 연구)

  • Kim, Se-Kyong
    • Journal of the Korean Chemical Society
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    • v.48 no.3
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    • pp.254-260
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    • 2004
  • The reaction rates of para-substituted benzoyl chlorides ($p-CH_3$, p-H, $p-NO_2$) with pyridine have been measured employing the conductometry method in acetonitrile. The pseudo first-order and second-order rate constants were determined at various pressures and temperatures. The activation parameters (${\Delta}V{\ddagger},\;{\Delta}{\beta}{\ddagger},\;{\Delta}H{\ddagger},\;{\Delta}S{\ddagger},\;{\Delta}G{\ddagger}$) and the Hammett ${\rho}$-values are determined from the values of rate constant. The values of ${\Delta}V{\ddagger},\;{\Delta}{\beta}{\ddagger}\;and\;{\Delta}S{\ddagger}$ are all negative. The Hammett ${\rho}$-values are positive for the substrate (${\rho}_Y$) over the given pressure range. The results of kinetic studies, for the pressure and substituent changes, show that these reactions are proceeded by a typical $SN_2$reaction mechanism and its bond formation is favored with elevating pressure.

Test and simulation of circular steel tube confined concrete (STCC) columns made of plain UHPC

  • Le, Phong T.;Le, An H.;Binglin, Lai
    • Structural Engineering and Mechanics
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    • v.75 no.6
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    • pp.643-657
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    • 2020
  • This study presents experimental and numerical investigations on circular steel tube confined ultra high performance concrete (UHPC) columns under axial compression. The plain UHPC without fibers was designed to achieve a compressive strength ranged between 150 MPa and 200 MPa. Test results revealed that loading on only the UHPC core can generate a significant confinement effect for the UHPC core, thus leading to an increase in both strength and ductility of columns, and restricting the inherent brittleness of unconfined UHPC. All tested columns failed by shear plane failure of the UHPC core, this causes a softening stage in the axial load versus axial strain curves. In addition, an increase in the steel tube thickness or the confinement index was found to increase the strength and ductility enhancement and to reduce the magnitude of the loss of load capacity. Besides, steel tube with higher yield strength can improve the post-peak behavior. Based on the test results, the load contribution of the steel tube and the concrete core to the total load was examined. It was found that no significant confinement effect can be developed before the peak load, while the ductility of post-peak stage is mainly affected by the degree of the confinement effect. A finite element model (FEM) was also constructed in ABAQUS software to validate the test results. The effect of bond strength between the steel tube and the UHPC core was also investigated through the change of friction coefficient in FEM. Furthermore, the mechanism of circular steel tube confined UHPC columns was examined using the established FEM. Based on the results of FEM, the confining pressures along the height of each modeled column were shown. Furthermore, the interaction between the steel tube and the UHPC core was displayed through the slip length and shear stresses between two surfaces of two materials.

Determination of Potimal Conditions for Cytosolic Progesterone Receptor Assay in Rat Uterus (흰쥐 자궁에서의 Cytosolic Progesterone 수용체 측정에 관한 연구)

  • Park, T.K.;Park, K.H.;Seo, K.;Rhee, K.S.;Yun, M.C.;Ryu, K.J.
    • Clinical and Experimental Reproductive Medicine
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    • v.13 no.2
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    • pp.187-193
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    • 1986
  • The purpose of this study was to establish optimal conditions for progesterone receptor assay using rat uterus, therby applying this system to understand action mechanism of progesterone in female reproductive organ and to evaluate physiological and pathological conditions in female reproduction. The results obtained were as follows 1. $^3H-R5020$ seemed to be more stable than 3H-progesterone as a ligand. 2. Optimal incubation time for ligand and receptor binding was 4-5 hrs at $4^{\circ}C$. 3. For the separation of bond and free ligand, optimal charcoal incubation time was 20 mins. 4. 2-3 mg cytosolic protein/ml was optimal for the binding of ligand. 5. Endogenous progesterone did not influence binding of ligand and receptor unless endogenous progesterone levels were extremely high as in case of pregnancy. 6. Dissociation rate for progesterone receptor was 1.22 nM. 7. $^3H-R5020$ did not bind to corticoid binding globulin (CBG), suggesting that addition of cortisol is saturate CBG was, not necessary as far as $^3H-R5020$ was used as a radioligand. It is, therefore, considered that this assay system established with these conditions might be used for the research as well as clinical routine purposes.

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Kinetics for the Reaction of Benzyl Benzenesulfonate with Pyridine in Acetone Under High Pressure (Benzyl Benzenesulfonate와 피리딘과의 고압반응에 대한 반응속도론적 연구)

  • Jung-Ui Hwang;Soo-Dong Yoh;Jong-Gi Jee
    • Journal of the Korean Chemical Society
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    • v.24 no.2
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    • pp.150-154
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    • 1980
  • Kinetic studies of the reaction of benzyl benzenesulfonate with pyridine in acetone were carried out by the electric conductivity method under 1 to 2000 bars and at 20 to $40^{\circ}C$. The rate increases with increasing pressure and temperature. The activation enthalpy $({\Delta}H^{\neq}),\;entropy\;({\Delta}S^{\neq})$ and activation volume $({\Delta}V^{\neq})$ of the reaction are obtained by the above experiment. The isokinetic relationship between $({\Delta}H^{\neq})\;and\;({\Delta}S^{\neq})$ for pressure change in the reaction was shown, and its isokinetic temperature was $342^{\circ}K$. From all of the above results it was found that this reaction precedes on the $S_N2$ reaction mechanism in which the rate of the reaction was determined by $C{\cdots}N$ bond formation at transition state.

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On the Electrochemical Reduction of O, O-Dimethyl-O-(3-Methyl-4-Nitrophenyl)-Phosphorthioate (Fenitrothion) Pesticide in Acetonitrile Solution (Acetonitrile 용액중에서 살충제 O, O-Dimethyl-O-(3-Methyl-4-Nitrophenyl)-Phosphorothioate (Fenitrothion)의 전기화학적 환원)

  • Il-Kwang Kim;Youn-Geun Kim;Hyun-Ja Chun
    • Journal of the Korean Chemical Society
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    • v.32 no.3
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    • pp.186-194
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    • 1988
  • The electrochemical reduction of O,O-dimethyl-O-(3-methyl-4-nitrophenyl)-phosphorothioate (Fenitrothion) has been studied in acetonitrile solution containing surfactant micelle by direct current (DC)-differential pulse (DP) polarography, cyclic voltammetry (CV) and controlled potential coulometry (CPC). The partially reversible electron transfer-chemical reaction(EC, EC mechanism) of fenitrothion reduction proceeded by four electron transfer to form O,O-dimethyl-O-(3-methyl-4-hydroxyaminophenyl)-phosphorothioate which undergoes single bond of the phosphorus atom and phenoxy group cleaves to give p-amino-m-cresol and dimethyl thiophosphinic acid as major product by two electron transfer-protonation at higher negative potential. The polarograpic reduction waves shown to suppressed due to inhibitory effect of sodium lauryl sulfate micelle solution and split up on selectivity of anionic micelle effect in two step at the first reduction peak.

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Kinetic Studies on the Nucleophilic Addition of 3-Mercaptopropionic Acid to ${\beta},\;{\beta}$-Diethoxycarbonylstyrene Derivatives (${\beta},\;{\beta}$-Diethoxycarbonylstyrene 유도체에 대한 3-Mercaptopropionic Acid의 친핵성첨가반응에 관한 반응속도론적 연구)

  • Tae-Rin Kim;Yun-Chung Choi;Myung-Sook Chung
    • Journal of the Korean Chemical Society
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    • v.33 no.1
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    • pp.127-134
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    • 1989
  • The rate constants of the nucleophilic addition reaction of 3-mercaptopropionic acid to the ${\beta},\;{\beta}$-diethoxycarbonylstryene derivatives (H, p-OCH$_3$, 3,4,5-(OCH$_3)_3$, 3,4-methylenedioxy) were determined by ultraviolet spectrophotometry, and rate equation which could be applied over a wide pH range was obtained. On the basis of pH-rate profile and the presence of general base catalysis, a plausible mechanism of this addition reaction was propound:Below pH 6.0 the reaction was initiated by the addition of neutral 3-mercaptopropionic acid molecule, and in the range of pH 6.0∼8.0, a neutral 3-mercaptopropionic acid molecule and a sulfide anion competitively attacked to the double bond. Above pH 8.0, the reaction proceeded through the addition of a sulfide anion.

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The Nucleophilic Substitution Reactions of the Nitrate Group. The Kinetics of Substituted Benzyl Nitrates with Anilines in Acetonitrile (질산기의 친핵성 치환반응. 아세토니트릴용매에서 질산치환벤질류와 아닐린류와의 반응속도론)

  • Wang Ki Kim;Chang Kook Sohn
    • Journal of the Korean Chemical Society
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    • v.33 no.1
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    • pp.31-36
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    • 1989
  • The second-order rate constants for the nucleophilic substitution reactions of para-substituted benzyl nitrates with para-substituted anilines in acetonitrile were conductometrically determined. Hammett ${\rho}$x and ${\rho}$y values and Bronsted ${\beta}$ values were obtained from these kinetic data. The reactions of Benzyl nitrates with the series of anilines showed linear Hammett plots with negative slopes. For the change of substituents in the benzyl nitrates, nonlinear Hammett plots with a concave upwards curve were obtained. We applied the potential energy surface and the quantum mechanical models in order to examine the transition state variations caused by changes in substituents on the nucleophile and the substrate. The results showed that the reaction was proceeded via the $S_{N}2$-type reaction mechanism in which the extent of bond-formation was greatly changed depending on the property of the substituents in substrate.

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Kinetic Studies for the Nucleopilic Substitution Reactions under High Pressure (친핵성 치환반응에 관한 고압에서의 속도론적 연구)

  • Kim Young Cheul;Kim Se Kyong
    • Journal of the Korean Chemical Society
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    • v.37 no.6
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    • pp.577-584
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    • 1993
  • The reaction rates of para-substituted benzoyl chlorides with substituted pyridines have been measured employing the conductometry method in acetonitrile, and pseudo-first order and second order rate constants are determined at various pressures and temperatures. The activation parameters (${\Delta}V^\neq, {\Delta}{\beta}^{\neq}, {\Delta}H^{\neq}, {\Delta}S^{\neq} {\Delta}G^{\neq}$) and the Hammett ρ-values are determined from the values of rate constants. The values of △${\Delta}V^\neq, {\Delta}{\beta}^{\neq}and {\Delta}S^{\neq}$ are all negative. The Hammett ρ-values are negative for the nucleophile (ρ$_X$), and positive for the substrate (ρ$_Y$) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S$_N$2 reaction mechanism and in bond formation favored with elevating pressure.

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