• 대한화학회지
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• 제42권2호
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• pp.150-155
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• 1998

Acetonitrile 용매내에서 isoquinoline과 치한된 benzylbromide의 반응을 압력변화(1~1000bar)에 따라 반응속도론적으로 연구하였다. 속도상수로부터 활성화파라미터들을 TEX>$\(DeltaV^{\neq}, \Delta\beta^{\neq}, \DeltaH^{\neq}, \DeltaS^{\neq}, \DeltaG^{\neq},Ea)$구하였다. 온도가 증가함에 따라 속도상수는 증가 하고, TEX>$\DeltaV^{\neq}, \Delta\beta^{\neq},및 \DeltaS^{\neq}$는 모두 음의 값으로 나타내었다. 치환기효과와 실험 결과로 부터 반응메카니즘을 고찰한 결과 전체적인 반응은 $S_{N}2$반응 메카니즘으로 진행되나, 치환체와 압력변화에 따라 전이상태 구조에 약간의 변화가 있었다.

• 대한화학회지
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• 제41권1호
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• pp.22-46
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• 1997

25℃와 35℃에서 메탄올-아세토니트릴 혼합용매계에 대한 할로겐화 펜아실과 피리딘 치환체와의 친핵성치환반응을 속도론적으로 연구하였다. 전이상태 파라미터인 ΔH≠와 ΔS≠ 및 Brosted β값으로 보아 $S_N2$반응 메카니즘을 예상할 수 있었고, 이탈기 변화에 따른 QM모형의 적용으로 이들 반응의 전이상태 역시 생성물 닮은 구조임을 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제10권1호
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• pp.50-57
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• 1989

A pressure effect of the dehydrogenation of ethylalcohol catalyzed by alcoholdehydrogenase was observed in Tris-HCl buffer, pH 8.8 from $25^{\circ}C$ to $35^{\circ}C$ under high pressure system by using our new theory. The theory makes it possible for us to obtain all rate and equilibrium constants for each step of all enzymatic reaction with a single intermediate. We had enthalpy and volume profiles of the dehydrogenation to suggest a detail and reasonable mechanism of the reaction. In these profiles, both enthalpy and entropy of the reaction are positive and their values decrease with enhancing pressure. It means that the first step is endothermic reaction, and its strength decrease with elevating pressure. At the same time, all activation entropies have large negative values, which prove that not only a ternary complex has a more ordered structure at transition state, but also water molecules make a iceberg close by the activated complex. In addition to this fact, the first and second step equilibrium states are controlled by enthalpy. The first step kinetic state is controlled by enthalpy but the second step kinetic state is controlled by entropy.

• Bulletin of the Korean Chemical Society
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• 제8권5호
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• pp.408-414
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• 1987

The rate of bromine-exchange reaction between antimony tribromide and ${\alpha}-phenyl-n-butyl$ bromide in nitrobenzene has been determined, using antimony tribromide labelled with Br-82. The results indicate that the exchange reaction follows the first-order kinetics with respect to the organic bromide, and either the second- or first-order kinetics with respect to antimony tribromide depending on its concentration. The third-order rate constant obtained was 7.50 ${\times}10^{-2}l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. Similar study on the bromine-exchange reaction between antimony tribromide and ${\alpha}$-phenyl-i-butyl bromide has also been carried out. The results of the study show the same kinetic orders as the ones observed with $\alpha$-phenyl-n-butyl bromide. The third-order rate constant observed was 2.40 ${\times} 10^{-2} l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. The activation energy, the enthalpy of activation and the entropy of activation for the two exchange reactions mentioned above have been determined. The reaction mechanisms for the exchange reactions are discussed.

• 한국운동역학회지
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• 제20권1호
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• pp.49-55
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• 2010

The purpose of the study was to analyze kinetic factors required to the three-point jump shot of the basketball games through 3-D analysis and ground reaction force(GRF) analysis. Six university male players participated in this study. The results of the study were showed that (1) resultant velocity in the center of mass(COM) was $0.84{\pm}0.27\;m/s$ since a player didn't shot a ball in the highest peak and shot ball at the moment of going up forward and vertical movement. Therefore, it is necessary to find a proper timing to shot a ball; (2) the angular velocity was largely increased in upper arm and fore arm out of the upper-limb segments and the hands had the largest angular velocity since the body is in a fixed situation and angular speed is rapidly increased by the wrist' snap with the rapid movement of upper arm and forearm at the time of release a ball; (3) it is judged that a player can shot a ball at the accurate and high release point when the player collects power vertically to the maximum by keeping GRF to the right and the rear in a proper way and by keeping the body's balance so that a large power may not be dispersed.

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1939-1944
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• 2011

The nucleophilic substitution reactions of bis(Y-aryl) chlorophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 35.0 $^{\circ}C$. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorophosphates (2). The substrate 1 has one more identical substituent Y compared to substrate 2. The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of cross-interaction constant (CIC) from negative ${\rho}_{XY}$ = -1.31 (2) to positive ${\rho}_{XY}$ = +1.91 (1), indicating the change of reaction mechanism from a concerted $S_N2$ (2) to a stepwise mechanism with a rate-limiting leaving group departure from the intermediate (1). The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines ($XC_6H_4ND_2$) show secondary inverse, $k_H/k_D$ = 0.61-0.87. The DKIEs invariably increase as substituent X changes from electron-donating to electron-withdrawing, while invariably decrease as substituent Y changes from electron-donating to electron-withdrawing. A stepwise mechanism with a rate-limiting bond breaking involving a predominant backside attack is proposed on the basis of positive sign of ${\rho}_{XY}$ and secondary inverse DKIEs.

• 한국수소및신에너지학회논문집
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• 제13권3호
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• pp.214-223
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• 2002

Kinetic and effectiveness factors for methanol steam reforming using commercial copper-containing catalysts in a plug flow reactor were investigated over the temperature ranges of $180-250^{\circ}C$ at atmospheric pressure. The selectivity of $CO_2$/$H_2$ was almost 100%, and CO products were not observed under reaction conditions employed in this work. It was indicated that $CO_2$ was directly produced and CO was formed via the reverse water gas shift reaction after methanol steam reforming. The intrinsic kinetics for such reactions were well described by the Langmuir-Hinshelwood model based on the dual-site mechanism. The six parameters in this model, including the activation energy of 103kJ/mol, were estimated from diffusion-free data. The significant effect of internal diffusion was observed for temperature higher than $230^{\circ}C$ or particle sizes larger than 0.36mm. In the diflusion-limited case, this model combined with internal effectiveness factors was also found to be good agreement with experimental data.

• Bulletin of the Korean Chemical Society
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• 제23권10호
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• pp.1459-1462
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• 2002

The kinetics of the addition of X-substituted benzylamines (BA) to Y-substituted Benzylideneacetylacetones (BAA) have been investigated in acetonitrile at $25.0^{\circ}C$. The reaction is studied under pseudo-first-order conditions by keeping a large excess of BA over BAA. The addition of BA to BAA occurs in a single step in which the addition of BA to $C_\alpha$ of BAA and proton transfer from BA to $C_\beta$ of BAA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($p_X$) and Bronsted ($\beta_x$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the cross-interaction constant, $p_{XY}$ (= -0.49), is comparatible to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($K_H/K_D$ > 1.0) and relatively low $\Delta$H^{${\neq}$}$ and large negative $\Delta$S^{${\neq}$}$ values are also consistent with the mechanism proposed.

• Preventive Nutrition and Food Science
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• 제1권1호
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• pp.41-45
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• 1996

This study was conducted to develop the fermentation kinetic model for the prediction of acidity and pH changes in Kimchi as a function of fermentation temperatures. The fitness of the model was evaluated using traditional two-step method and an alternative non-linear regression method. The changes in acidity and pH during fermentation followed the pattern of the first order reaction of a two-step method. As the fermentation temperature increased from 4$^{\circ}C$ to 28, the reaction rates of acidity and pH were increased 8.4 and 7.6 times, respectively. The activation energies of acidity and pH were 16.125 and 16.003kcal/mole. The average activation energies of acidity and pH using a non-linear method were 16.006 by the first order and 15.813 kcal/mole by the zero order, respectively. The non-linear procedure had better fitting 개 experimental data of the acidity and pH than two-step method. The shelf-lives based on the time to reach the 1.0% of acidity were 33.1day at 4$^{\circ}C$ and 2.8 day 28$^{\circ}C$.

• Korean Chemical Engineering Research
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• 제59권3호
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• pp.467-479
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• 2021

Abstract: A kinetic model was developed for the dehydration of ethanol to ethylene based on two parallel reaction pathways. Kinetic parameters were estimated by fitting experimental data of powder catalysts in a lab-scale test, and the effectiveness factor was determined using data from pellet-type catalysts in bench-scale experiments. The developed model was used to design a multitubular fixed-bed reactor (MTR) and an adiabatic reactor (AR) at a 10 ton per day scale. The two different reactor types resulted in different process configurations: the MTR consumed the ethanol completely and did not produce the reaction intermediate, diethyl ether (DEE), resulting in simple separation trains at the expense of high equipment cost for the reactor, whereas the AR required azeotropic distillation and cryogenic distillation to recycle the unreacted ethanol and to separate the undesired DEE, respectively. Quantitative analysis based on the equipment and annual energy costs showed that, despite high equipment cost of the reactor, the MTR process had the advantages of high productivity and simple separation trains, whereas the use of additional separation trains in the AR process increased both the total equipment cost and the annual energy cost per unit production rate.