• Journal of the Korean Chemical Society
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• v.52 no.3
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• pp.217-222
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• 2008

We investigate the kinetics of diffusion-influenced catalytic reactions occurring in small reaction volume. From a simple exact model study, we find that the reaction rate coefficient decreases with the size of reaction volume. The explicit expression for the average reaction rate constant is presented, which can be regarded as a generalization of well-known Collins-Kimball rate constant into the reactions occurring in a small reaction volume. It turns out that the traditional diffusion influenced reaction dynamics is followed by a single exponential relaxation phase with a rate constant dependent on the reaction volume for the catalytic reactions occurring in small reaction volumes.

• Applied Chemistry for Engineering
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• v.5 no.6
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• pp.1062-1067
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• 1994

The chemistry of 5-methyl-4-imidazolecarboxylic acid ester synthesis involves three distinct reaction steps. Of these the rate of formation of diketone was found to be a function of oxime and HCl concentration and temperature by the batch experiment. The decomposition of diketone was found to be a slow process whereas temperature was the only variable to affect it significantly. An empirical rate expression for the net formation of diketone fits the experminetal data satisfactorily. The principal objectives of this study are to study the kinetics of the diketone formation reaction and to develop the empirical rate expression.

• 한국신재생에너지학회:학술대회논문집
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• 2007.11a
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• pp.623-626
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• 2007

킬른형 열분해 반응기를 이용하여 혼합폐플라스틱의 열분해로부터 얻어진 고분자성분의 열적분해 특성에 관한 연구를 TGA와 GC-MS를 이용하여 수행하였다. 열적분해의 속도론적 연구는 $10{\sim}50^{\circ}C/min$ 사이의 여러 가열속도에서 비등온 질량감소 기술을 이용하여 수행하였으며 활성화 에너지 및 반응 차수와 같은 속도 상수들에 대한 정보를 얻기 위하여 문헌에 제시된 여러 가지의 속도론 해석방법을 이용하여 질량감소곡선 및 그 미분 값을 해석하였다. 또한 회분식 열분해 반응기를 이용하여 반응온도에 따른 액상 생성물의 수율변화를 고찰하였으며 GC-MS를 이용하여 액상 생성물의 반응온도 증가에 따른 특성연구를 수행하였다.

• Journal of the Korean Chemical Society
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• v.53 no.6
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• pp.709-716
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• 2009

A Kinetics pathway of oxidation of Cefpodoxime Proxetil by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically. The reaction showed first order kinetics in permanganate ion concentration and an order less than unity in cefpodoxime acid and alkali concentrations. Increasing ionic strength of the medium increase the rate. The oxidation reaction proceeds via an alkali-permanganate species which forms a complex with cefpodoxime acid. The latter decomposes slowly, followed by a fast reaction between a free radical of cefpodoxime acid and another molecule of permanganate to give the products. Investigations of the reaction at different temperatures allowed the determination of activation parameters with respect to the slow step of proposed mechanism and fallows first order kinetics. The proposed mechanism and the derived rate laws are consistent with the observed kinetics.

• Applied Chemistry for Engineering
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• v.17 no.3
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• pp.296-302
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• 2006

The kinetics of the thermal-oxidative decomposition of waste polyurethane (PU) according to oxygen concentration has been studied using a non-isothermal thermogravimetric technique at several heating rates from 10 to $50^{\circ}C/min$. A kinetic model accounting for the effects of the oxygen concentration by the differential and integral method based on Arrhenius equation was proposed to describe the thermal-oxidative decomposition of waste PU. To obtain the information on the kinetic parameters such as activation energy, reaction order, and pre-exponential factor, the thermogravimetric analysis curves and its derivatives have been analyzed using the kinetic analysis method proposed in this work. From this work, it was found that reaction orders for oxygen concentration had a negative sign, and activation energy decreased as the oxygen concentration increased. It was also found that the kinetic parameters obtained from the integral method using the single heating rate experiments varied with heating rates. Therefore, it is thought that the differential method using the multiple heating rate experiments more effectively represents the thermal-oxidative decomposition of waste polyurethane.

• Korean Chemical Engineering Research
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• v.46 no.2
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• pp.301-309
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• 2008

In this study, the effect of formaldehyde to phenol (F/P) molar ratios, catalyst wt%, and reaction temperature on the chemical structure was studied utilizing a two-level full factorial experimental design. The effect of three variables on the chemical structure was analyzed by using three-way ANOVA of SPSS. Concentration of methyrol-substituted phenols after 300 min addition reaction increased with higher the F/P mole ratio, lower the reaction temperature and lower the catalyst wt%. Resol catalysed by barium hydroxide showed higher addition of formaldehyde onto ortho positions of phenolic rings. A simplified elementary reaction model for resole type phenolic resin formation which do not consider the dissociation of phenolic compounds and the fraction of formaldehyde in the form of methylene glycol was proposed and compared with Zavitsas' type models. Elementary reaction model showed error of 2.79% compared to the error of 3.27% in Zavitsas' type models. It was thought that the elementary reaction model could be used to predict the behavior of addition reaction in resol formation.

• 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.

• Applied Chemistry for Engineering
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• v.5 no.4
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• pp.731-736
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• 1994

Cure kinetics of DGEBA/MDA/MN system with and without HQ were studied by Fractional life method and Kissinger equation. And the effect of HQ as a catalyst was studied. As cure temperature increased, the reaction rate increased and reaction order was almost constant. The activation energy of the system with HQ was lower about 13% and the reaction rate was higher than that of the system without HQ. It was because hydroxyl group of HQ formed a transition state with epoxide group and amine group and opened the epoxide ring easily and rapidly.

• Journal of the Korean Chemical Society
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• v.54 no.1
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• pp.88-92
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• 2010

Isopropyl mercaptan is an important pharmaceutical intermediate and chemical material. And thiourea and triglycol are the main materials for the synthesis of isopropyl mercaptan. Therefore the dissolution of thiourea in triglycol solution is very important for the production of isopropyl mercaptan. The aims of this study are to examine the dissolution kinetics of thiourea in triglycol solution, and to present an alternative process for producing isopropyl mercaptan. In order to investigate the dissolution kinetics of thiourea in triglycol solution, the concentrations of solution and reaction temperature were selected as experimental parameters. It was determined that the dissolution rate of thiourea increased with the increase in solution concentration and temperature. An empirical equation was used in fitting the data. Statistical analysis indicated small errors and the results should be reliable.

• Proceedings of the Korean Environmental Sciences Society Conference
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• 2001.11a
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• pp.134-137
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• 2001