• 공학논문집
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• 제6권1호
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• pp.97-109
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• 2004

CaO의 첨가량에 따라 $CO_2$가스를 불어넣고 반응시간 변화에 따라 용매로 $C_2 H_5 OH$을 사용하여 에틸렌글리콜을 첨가한 CaO-$C_2 H_5 OH$-$CO_2$계의 기.액반응으로부터 비정질 $CaCO_3$의 합성과 결정구조를 전기전도도, X-선회절 및 주사전자현미경으로 조사하였다. 이 반응에서 900ml의 $C_2 H_5 OH$에 에틸렌글리콜 100ml를 첨가하고 CaO의 양을 10~40g으로 하여 $CO_2$가스를 1$\ell$/min의 유속으로 흡입시켜 얻은 합성분말의 겔형 물질을 신속히 여과, 감압하의 $60^{\circ}C$에서 건조하여 1${\mu}m$이하의 구형 vaterite상과 무정형인 비정질 $CaCO_3$을 얻었다. 그리고 비정질 $CaCO_3$의 일부는 중간생성물로서 연쇄형 calcite로 변화하는 것을 알 수 있었고 침강성 $CaCO_3$의 생성보다 먼저 초기 반응생성물은 비정질 $CaCO_3$이었고 이 경우 생성역역은 pH 7-9의 범위로 상당한 영향을 준다. 또한 비정질 $CaCO_3$은 용액 속에서 불안정하여 용해반응으로 인해서 결국 calcite로 결정화한다. 특히 비정질 $CaCO_3$은 CaO-$C_2 H_5 OH$-$CO_2$계의 반응에 의해서 침강되어 생성되거나 또는 gel상으로 된다.

• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.993-999
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• 1998

Acid catalyzed hydrolysis of 1-phenoxyethyl propionate, Ⅰ, has been studied using the PM3 method in the gas phase. The first step of the reaction is the protonation of basic sites, three different oxygens in Ⅰ, producing three protonated species Ⅱ, Ⅲ and Ⅳ. All possible reaction pathways have been studied from each protonated structure. Changes in the reaction mechanisms have also been discussed from the results obtained by varying a nucleophile from a water monomer to a water dimer to a complex between one water molecule and an intermediate product (propionic acid or phenol) produced in the preceding unimolecular dissociation processes. Minimum energy reaction pathway is 2-W among the possible pathways, in which water dimer acts as an active catalyst and therefore facilitates the formation of a six-membered cyclic transition state. Lower barrier of 2-W is ascribed to an efficient bifunctional catalytic effect of water molecules. PM3-SM3.1 single point calculations have been done at the gas-phase optimized structure (SM3.1/PM3//PM3) to compare theoretical results to those of experimental work.

• Bulletin of the Korean Chemical Society
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• 제12권6호
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• pp.658-661
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• 1991

The gas-phase nucleophilic substitution reaction of pentafluoroanisole with $OH^-$ and ${NH_2}^-$ nucleophiles have been studied theoretically using the AM1 method. Three reaction channels, $S_N2$, IPSO and $S_NAr$ (scheme 1), are all very exothermic so that all are accessible despite the varying central energy barriers which are much lower than the reactants level. In the IPSO and $S_NAr$ channels, the reactants form directly a stable ,${\sigma}$-anion complex which proceeds to form a proton transfer complex via a transition barrier corresponding to a loose ${\pi}$-type complex with the F-(or ${OCH_3}^-$) leaving group. Due to a greater number of probable reaction sites available for $S_NAr$ compared to the other two processes, the $S_NAr$ channel is favored as experimentally observed.

• Bulletin of the Korean Chemical Society
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• 제24권5호
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• pp.583-592
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• 2003

The gas phase identity nucleophilic substitution reactions of halide anions (X = F, Cl, Br) with cyclopentadienyl halides (1) are investigated at the B3LYP/6-311+G**, MP2/6-311+G** and G2(+)MP2 levels involving five reaction pathways: σ-attack $S_N2$, β-$S_N$2'-syn, β-$S_N$2'-anti, γ-$S_N$2'-syn and γ-$S_N$2'-anti paths. In addition, the halide exchange reactions at the saturated analogue, cyclopentyl halides (2), and the monohapto circumambulatory halide rearrangements in 1 are also studied at the same three levels of theory. In the σ-attack $S_N2$ transition state for 1 weak positive charge develops in the ring with X = F while negative charge develops with X = Cl and Br leading to a higher energy barrier with X = F but to lower energy barriers with X = Cl and Br than for the corresponding reactions of 2. The π-attack β-$S_N$2' transition states are stabilized by the strong $n_C-{\pi}^{*}_{C=C}$ charge transfer interactions, whereas the π-attack γ-$S_N$2' transition states are stabilized by the strong $n_C-{\sigma}^{*}_{C-X}$ interactions. For all types of reaction paths, the energy barriers are lower with X = F than Cl and Br due to the greater bond energy gain in the partial C-X bond formation with X = F. The β-$S_N$2' paths are favored over the γ-$S_N$2' paths only with X = F and the reverse holds with X = Cl and Br. The σ-attack $S_N2$ reaction provides the lowest energy barrier with X = Cl and Br, but that with X = F is the highest energy barrier path. Activation energies for the circumambulatory rearrangement processes are much higher (by more than 18 kcal $mol^{-1}$) than those for the corresponding $S_N2$ reaction path. Overall the gas-phase halide exchanges are predicted to proceed by the σ-attack $S_N2$ path with X = Cl and Br but by the β-$S_N$2'-anti path with X = F. The barriers to the gas-phase halide exchanges increase in the order X = F < Br < Cl, which is the same as that found for the gas-phase identity methyl transfer reactions.

• 한국재료학회지
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• 제14권6호
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• pp.407-412
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• 2004

Photo decomposition of gas phase benzene by $TiO_2$ thin films chemically deposited on alumina balls were investigated under UV irradiation. Photo decomposition rates were measured in real time during the reaction using a photo ionization detector, which ionizes C-H bonding of benzene molecules and then converts into volatile organic compounds (VOCs) concentrations. From the measuring results, the VOCs concentration increased instantly when IN irradiated because C-H bonds of benzene molecules strongly absorbed on the surface of $TiO_2$ films before the IN irradiation was destroyed by photo decomposition. After that, the VOCs concentration decreased with increasing surface area of $TiO_2$ and reaction time under the IN irradiation. At the optimal conditions for the photo decomposition of gas phase benzene, the reaction rate of the photo decomposition for high concentrations (over 60 ppm) was slow but that of relatively low concentration (under 60 ppm) was fast, due to limited surface area of $TiO_2$ thin films for the reaction. Thus, it is concluded that the photo decomposition rate was mainly affected by the surface area of $TiO_2$ or absorption reaction.

• 한국수소및신에너지학회논문집
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• 제27권1호
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• pp.13-21
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• 2016

The Sulfur-Iodine thermochemical hydrogen production process (SI process) consists of the Bunsen reaction section, the $H_2SO_4$ decomposition section, and the HI decomposition section. The $HI_x$ solution ($I_2-HI-H_2O$) could be recycled to Bunsen reaction section from the HI decomposition section in the operation of the integrated SI process. The phase separation characteristic of the Bunsen reaction using the $HI_x$ solution was similar to that of $I_2-H_2O-SO_2$ system. On the other hands, the amount of produced $H_2SO_4$ phase was small. To investigate the effects of $SO_2$ solubility on Bunsen reaction, the continuous Bunsen reaction was performed at variation of the amounts of $SO_2$ gas. Also, it was carried out to make sure of the effects of partial pressure of $SO_2$ in the condition of 3bar of $SO_2-O_2$ atmosphere. As the results, the characteristic of Bunsen reaction was improved with increasing the amounts and solubility of $SO_2$ gas. The concentration of Bunsen products was changed by reverse Bunsen reaction and evaporation of HI after 12 h.

• 공업화학
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• 제8권6호
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• pp.901-906
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• 1997

유기금속화합물인 Tetraethylorthosilicate(TEOS)를 출발원료로 기상열분해법을 이용하여 초미립 실리카분말을 제조하였다. 반응온도, 가스유량, 반응물질의 농도, 및 반응물질의 예비가열온도가 초미립 실리카분말의 입자크기 특성에 미치는 영향을 조사하였다. 반응온도가 증가할수록 또한 체류시간이 감소할수록 생성분말의 입자크기가 작아지는 것을 알 수 있었다. 반응물농도가 증가할수록 입자크기가 증가하였고, 또한 반응물질의 예비가열온도가 증가하여도 입자크기는 큰 변화가 없음을 알 수 있었다. 본 연구조건에서 제조된 초미립 실리카분말의 평균 입자크기는 30~58 nm이었다.

• 한국수소및신에너지학회논문집
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• 제27권5호
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• pp.494-502
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• 2016

A 1-dimensional heterogeneous reactor model with the gas-solid interfacial phase gradients was developed for the simulation of the packed bed reactor where the exothermic reversible water gas shift reaction for the natural gas steam reformed gas was proceeding in adiabatic mode. Experimental results obtained over the WGS catalyst, C18-HA, were best simulated when the frequency factor of the reaction rate constant was adjusted to a half the value reported over another WGS catalyst, EX-2248, having the same kinds of active components as the C18-HA. For the reactor of the inside diameter 158.4 mm and the bed length 650 mm, the optimum feeding temperature of the reformed gas was simulated to be $194^{\circ}C$, giving the lowest CO content in the product gas by 1.68 mol% on the basis of dried gas. For reactors more extended in the bed length, the possible lowest CO content in the product gas with the optimum feeding temperature of the reformed gas were suggested.

• Asian Journal of Atmospheric Environment
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• 제9권2호
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• pp.158-164
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• 2015

The estimation of the concentration of hydroxyl radical (OH) in the atmosphere is essential to build atmospheric models and to understand the mechanisms of the reactions involved in OH. Although water vapor is one of the most abundant species in the troposphere, only a few studies have been performed for the reaction of OH and water vapor. Here I demonstrate an ab initio study on the complex forming reation of OH with $H_2O$ in the gas phase performed based on density functional theory to calculate the reaction rate and the energy states of the reactant and the OH-$H_2O$ complex. The structure of the complex, which belongs to the Cs point group, was optimized at global minima. The transition state was not found at the B3LYP and MP2 levels of theory. Rate constants of the forward and the reverse reactions were calculated as $1.1{\times}10^{-16}cm^3\;molecule^{-1}\;s^{-1}$ and $5.3{\times}10^9\;s^{-1}$, respectively. The extremely slow rates of complex forming reaction and the resulting hydrogen atom exchange reaction of OH and $H_2O$, which are consistent with experimentally determined values, imply a negligible possibility of a change in OH reactivity through the title reaction.

• Archives of Pharmacal Research
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• 제27권1호
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• pp.25-30
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• 2004

Combinatorial homoserine lactone mixtures and individual products were obtained from the methionine-functionalized resin in solid-phase synthesis. The four-step process consisting of a coupling step of an N-Fmoc-L-methionine, deprotection of N-Fmoc group, N-coupling with a carboxylic acid, and cleavage reaction through a polymer supported strategy is described. Gas chromatography-mass selective detector (GC-MSD) techniques provide the most powerful methods for identifying both the combinatorial mixtures and individual products.