• Journal of the Korean Chemical Society
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• 제37권2호
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• pp.228-236
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• 1993

The effect of ferric ion on the reaction of CH_3$MgI with benzylbromide was investigated by determining the product ratio between cross-coupling product, ethylbenzene (A) and homocoupling product, bibenzyl (B) in the presence of ferric ion. When CH_3$MgI prepared with pure magnesium was used, the ratio of A to B was 22 to 78 and with reagent grade magnesium, the ratio became 33 to 67 indicating that metallic impurities in magnesium affect the reaction mechanism to lead less homocoupling product, B. The ratio changes became significant when ferric chloride was added in the reaction mixture in catalytic amounts and the ratio of A to B reached to 80 to 20 at maximum. The reaction in the presence of ferric ion seems to follow mainly an ionic mechanism which involves iron-benzyl bromide ${\pi}$-complex formation. The complex formation is expected to be able to enhance ionic attack of CH_3$MgI on benzyl carbon to give more A.

• Membrane Journal
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• 제17권2호
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• pp.146-160
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• 2007

A parametric study on pervaporation-facilitated esterification was performed by using a practical model based on non-perfect separation through membrane which is not perfectly permselective to water. Thus, membrane selectivity as well as membrane capability to remove water should be taken into account in establishing the simulation model to explain how the membrane separation influence the esterification reaction process. It was shown by simulation that in the reaction systems with non-perfect separation, the permeation of reactants which are acid or/and alcohol retards the reaction by inducing the backward reaction so that reaction conversion curve is located between a reaction system coupled with pervaporation process having a perfect permselectivity to water and a reaction system without pervaporation process. The volume change of reaction system occurs as a result of the permeation through the membrane. The reaction volume change which can be characterized by the reaction ratio of $r_{\Psi}\;to\;r_{{\Psi}=1}$ affects reaction kinetics by concentrating reactants and products, respectively, with different extent with time; reactant-concentrating effect is dominant during the initial stage of reaction, resulting in facilitating the reaction, and then product-concentrating effect is exerted more on reaction, causing to slow down the reaction. When pervaporative dehydration is applied to the reaction system plays an important role in the reaction as well. The effect of timing to impose pervaporation on reaction system affected the reaction kinetics in terms of reaction rate and reaction conversion. A relationship was derived to explain membrane unit capacity and reaction parameters that will be used as a design tool to determine membrane unit capacity at a given reaction conditions or reaction parameters at a membrane unit capacity.

• Journal of the Korean Vacuum Society
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• 제4권4호
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• pp.350-357
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• 1995

SiH4와 Si2H6를 1-3 Torr 정도의 저압에서 열분해시켰을 때, 반응물의 농도 변화를 살펴보고 이로부터 열분해의 반응 기구를 예측하였다. 분석기로는 질량 분석기를 이용하였으며, 분해 온도 범위는 SiH4의 경우는 $350~475^{\circ}C$, Si2H6의 경우는 275-375$^{\circ}C$이었다. SiH4의 분해 양상은 1차 비가역 반응에 잘 들어 맞았으며, 그 속도 상수는 문헌에 보고되어 있는 상압에서의 속도보다 작았다. Si2H6는 낮은 온도 범위에서도 잘 분해되었으며, 중간 생성물로 많은 양의 SiH4를 만들었다. 그리고, SiH4는 고분자화되는 반응을 거치지 않고 고체실리콘을 생성하지만, Si2H6는 중간 생성물로 만들어진 SiH4와 SiH2에 의하여, 고분자화 반응을 거쳐서 고체실리콘을 만들 수 있음을 알았다.

• Applied Chemistry for Engineering
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• 제17권6호
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• pp.638-643
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• 2006

Pyrolytic reaction study of dichloromethane ($CH_{2}Cl_{2}$) in excess hydrogen was performed to investigate pyrolytic reaction pathways at a pressure of 1 atm with residence times of 0.3~2.0 sec in the temperature range of $525{\sim}900^{\circ}C$. A constant feed molar ratio $CH_{2}Cl_{2}$:$H_{2}$ of 4:96 was maintained through the experiment. Reagent loss and product formation were monitored by using an on-line gas chromatograph, where batch samples were analyzed by GC/MS. Complete destruction(99%) of the parent reagent was observed at temperature near $780^{\circ}C$ with residence time over 1 sec. Major products observed were $CH_{3}Cl$, $CH_{4}$, $C_{2}H_{4}$, $C_{2}H_{6}$, and HCl. Minor products included $CHClCCl_{2}$, CHClCHCl, $CH_{2}CHCl$, and $C_{2}H_{2}$. The pyrolytic reaction pathways to describe the important features of intermediate product distributions and reagent loss, based upon thermodynamic and kinetic principles, were suggested. The results of this work provided a better understanding of pyrolytic decomposition processes which occur during the pyrolysis of $CH_{2}Cl_{2}$ and similar chlorinated methanes.

• Resources Recycling
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• 제5권1호
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• pp.42-49
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• 1996

The synthesis or amorphous calc~um carbonale in the reacllons oi cslcn~m hydroxide suspension - CO1 systcni !\.;is studied by uslng rneasulemel~ts of eleclrical conductivity, x-ray diftractorneter and t~ansmission eleclron microscope. The m~tial product of reactious was noncrystalline shape oI amorphous calcium carbo~iale confirmed by x-ray diffraction analyses. The amorphous calcium carbonate covered lhc surlace of calcium hydroxldc grains. Tlic electrical conductivity of suspension dec~eascd dramatically when the amorphous calcium carhonate was synlliesizcd. A portion or the amorplious calcmm carbonale clia~iged ilito [he chain calcite as an intermcdrate product. Thc continuo~~cso nrluctivity measurements of suspension were ahle to delennine the starting point of the synthesis and the mechallism of carbonation process

• Journal of the Korea Academia-Industrial cooperation Society
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• 제8권3호
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• pp.632-638
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• 2007

Pyrolysis experiments of HDPE and LDPE were carried out in the stainless steel reactor of internal volume of 40 $cm^3$. Pyrolysis reactions were performed at temperature $410{\sim}460^{\circ}C$ and the pyrolysis products were collected separately as liquid and gas products. The molecular weight distributions(MWDs) and composition of each product were determined by HPLC-GPC and GC analysis. It was represented that the yield and the molecular weight of liquid product were decreased with the increase of reaction temperature and time. The chain-end scission rate parameters, respectively, were determined to be 63.0kcal/mole of HDPE, 45.7kcal/mole of LDPE by the Arrhenius plot.

• Journal of Korean Society of Environmental Engineers
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• 제27권2호
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• pp.215-223
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• 2005

Non-thermal plasma decomposition of gas-phase styrene was investigated in this study using three different types of plasma reactors; dielectric-barrier discharge (DBD) reactor, surface discharge (SD) reactor and plasma-driven catalyst (PDC) reactor packed with 2.0 wt% $Ag/TiO_2$ catalysts. The main parameters used for the comparative assessment of the plasma reactors include the decomposition efficiency, carbon balance, byproduct distribution, COx ($CO+CO_2$) selectivity and COx yield. The SD and the DBD reactors showed better conversion efficiency of styrene than that of the PDC reactor due to their larger capability in ozone formation. On the other hand, the PDC reactor showed better carbon balance, the yield and the selectivity of COx. The required specific input energies to achieve 100% carbon balance from the decomposition of 100 ppmv styrene using the plasma alone reactors and the PDC reactor were 420 J/L and 110 J/L, respectively. The major decomposition products in gas-phase were CO, $CO_2$ and HCOOH regardless of the types of plasma reactors. In the case of SD and DBD reactors, the $CO_2$ selectivity ranged in $39.5{\sim}60%$. The $CO_2$ selectivity in the PDC reactor was in range of $68.5{\sim}75.5%$.

• Transactions of the Korean hydrogen and new energy society
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• 제12권4호
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• pp.293-305
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• 2001

최근 디젤 대체 연료 및 발전용 연료로서 그 가능성을 인정받고 있는 DME(dimethyl ether, $CH_{3}OCH_{3}$)를 이용하여 수소를 생산하는 방법으로 DME 수증기 개질반응의 기초 실험을 수행하였다. DME 개질 반응의 생성물의 평형 조성 분포를 온도, 압력, 원료의 공급비$(H_{2}O/DME)$를 변수로 하여 열역학적으로 해석하였고, DME, 에탄올, 또는 메탄올 수증기 개질 반응의 생성물의 분포를 비교하여 수소 생산을 위한 공급원료로의 가능성을 검토하였다. 여러 종류의 개질 촉매를 사용하여 DME 개질 반응을 수행해 본 결과, 반응온도 $300^{\circ}C$, 반응압력 1atm, 원료 공급비$(H_{2}O/DME)=3$인 반응조건에서 1.0wt% $Pd/{\gamma}$-alumina가 가장 좋은 활성 및 60% 이상의 수소 선택도를 보여주었으, 또한 원료의 공급비가 증가함에 따라 DME의 전환율 및 주 생성물인 수소의 수율이 현저하게 증가함을 보여주었다.

• Clean Technology
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• 제17권1호
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• pp.56-61
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• 2011

In this study, hydrocarcking of vacuum residue was carried out in an autoclave reactor at $450^{\circ}C$ and $500^{\circ}C$ with a commercial catalyst (HDM) and the quantitative product distributions were analyzed by GC-SIMDIS method or simple distillation. During catalytic hydrocracking, thermal cracking also occurred together with catalytic cracking and the higher conversion and selectivity of gasoline and naphtha were obtained at high reaction temperature. GC-SIMDIS and simple distillation revealed different results for the analysis of products produced at different hydrocracking temperatures; almost same results were obtained for the product produced at $500^{\circ}C$ but different ones for the product produced at $450^{\circ}C$. In the analysis of product produced at $450^{\circ}C$, the GC-SIMDIS showed that a main product was VGO while a main product in the simple distillation was diesel, which implies that the simple distillation for the $450^{\circ}C$ reaction was not accurate due to thermal cracking of the product by the simple distillation.

• Journal of the Korean Chemical Society
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• 제22권3호
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• pp.164-172
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• 1978

Carboxypeptidase A-catalyzed hydrolysis of ester substrates was carried out at room temperature in the presence of a number of external reagents. If the acyl-enzyme intermediate, an anhydride, is attacked by the external reagents, products formed by trapping at the acyl portion or at the enzyme portion of the anhydride group can be obtained. Examination of the uv/vis spectral properties of the reaction products and of changes in enzyme activity indicated that such trapping reactions did not occur. Also performed was evaluation of enzymatic rate parameters for the the hydrolysis of O-(o-hydroxyphenylacetyl)-L-${\beta}$-phenyllactate. Detection of 2-coumaranone possibly formed by attack of the o-hydroxy group as an intramolecular trapping group at the acyl-enzyme intermediate was tried, but no evidences for the intramolecular trapping reaction were obtained. Failure to trap the intermediate was discussed in terms of steric hindrance imposed on the approach of the trapping reagents to the anhydride group of the acyl-enzyme intermediate and of the fast enzymatic breakdown of the intermediate.