• Macromolecular Research
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• 제13권1호
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• pp.68-72
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• 2005

A low-molecular-weight poly(lactic acid) was synthesized through the condensation reaction of L-lactic acid. The effects that the catalyst and temperature have on the reaction rate were studied to determine the optimum reaction conditions. The reaction kinetics increased with temperature up to $210^{\circ}C$, but no further increase was observed above this temperature. Among a few selective catalysts, sulfuric acid was the most effective because it maximized the polymerization reaction rate. Reduction of the pressure was another important factor that enhanced this reactions kinetics.

• Bulletin of the Korean Chemical Society
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• 제32권5호
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• pp.1679-1684
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• 2011

Interfacial reactions kinetics often differ from kinetics of bulk reactions. Here, we describe how the density change of an immobilized reactant influences the kinetics of interfacial reactions. Self-assembled monolayers (SAMs) of alkanethiolates on gold were used as a model interface and the Diels-Alder reaction between immobilized quinones and soluble cyclopentadiene was used as a model reaction. The kinetic behavior was studied using varying concentrations of quinones. An unusual threshold density of quinones (${\Gamma}_c$ = 5.2-7.2%), at which the pseudo-first order rate constant started to vary as the reaction progressed, was observed. This unexpected kinetic behavior was attributed to the phase-separation phenomena of multi-component SAMs. Additional experiments using more phase-separated two-component SAMs supported this explanation by revealing a significant decrease in ${\Gamma}_c$ values. When the background hydroxyl group was replaced with carboxylic or phosphoric acid groups, ${\Gamma}_c$ was observed at below 1%. Also, more phase-separated thermodynamically controlled SAMs produced a lower critical density (3% < ${\Gamma}_c$ < 4.9%) than that of the less phaseseparated kinetically controlled SAMs (6.5% < ${\Gamma}_c$ < 8.9%).

• Journal of Electrochemical Science and Technology
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• 제8권4호
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• pp.344-355
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• 2017

In this study, a numerical approach is adopted to investigate the effectiveness factors for distributed electrochemical reactions in thin active reaction layers of solid oxide fuel cells (SOFCs), taking into account the Butler-Volmer reaction kinetics. The mathematical equations for the electrochemical reaction and charge conduction process were formulated by assuming that the active reaction layer has a small thickness, homogeneous microstructure, and high effective electronic conductivity. The effectiveness factor is defined as the ratio of the actual reaction rate (or equivalently, current generation rate) in the active reaction layer to the nominal reaction rate. From extensive numerical calculations, the effectiveness factors were obtained for various charge transfer coefficients of 0.3-0.8. These effectiveness data were then fitted to simple correlation equations, and the resulting correlation coefficients are presented along with estimated magnitude of error.

• Bulletin of the Korean Chemical Society
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• 제33권3호
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• pp.963-970
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• 2012

We review novel chemical kinetics proposed for quantitative description of fluctuations in reaction times and in the number of product molecules in a heterogeneous biological system, and discuss quantitative interpretation of randomness parameter data in enzymatic turnover times of ${\beta}$-galactosidase. We discuss generalization of renewal theory for description of chemical fluctuation in product level in a multistep biopolymer reaction occurring in a dynamically heterogeneous environment. New stochastic simulation results are presented for the chemical fluctuation of a dynamically heterogeneous reaction system, which clearly show the effects of the initial state distribution on the chemical fluctuation. Our stochastic simulation results are found to be in good agreement with predictions of the analytic results obtained from the generalized master equation.

• 한국염색가공학회지
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• 제13권5호
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• pp.24-24
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• 2001

Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Blue 79(B-79) which is 4-N, N-diacetoxyethyl-2-acylamino-5-ethoxy -2′-bromo-4′,6′-dinitroazobenzene were investigated. The color strength of B-79 in acetone/water solutions of various NaOH concentrations decreased continuously. The hydrolysis rate of B-79 increased with increasing alkali concentration and appeared following first order reaction. The observed rate constants for various concentrations of B-79 showed similar values, and B-79 was hydrolyzed by first order reaction for dye concentration. Therefore, it was confirmed that the overall reaction follow second order kinetics and proceed via S/sub n/2 reaction. From the study on kinetics and spectrometric analysis, it was proposed that the rate determining step of the hydrolysis reaction of B-79 is the nucleophilic substitution reaction - that is the reaction of the rapid attack of $OH^{-}$ on the carbon atom, which is in acceptor ring, adjacent to azo group to break the C-N bond. And it was also found that the final hydrolysis products of B-79 include both the acceptor ring in the form of sodium salt and the donor ring possessing 4-N,N-dihydroxyethyl group converted from 4-N,N-diacetoxyethyl group.

• 한국염색가공학회지
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• 제13권5호
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• pp.312-319
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• 2001

Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Blue 79(B-79) which is 4-N, N- diacetoxyethyl -2- acylamino-5-ethos y -2'-bromo-4',6'-dinitroazobenzene were investigated. The color strength of B-79 in acetone/water solutions of various NaOH concentrations decreased continuously. The hydrolysis rate of B-79 increased with increasing alkali concentration and appeared following first order reaction. The observed rate constants for various concentrations of B-79 showed similar values, and B-79 was hydrolyzed by first order reaction for dye concentration. Therefore, it was confirmed that the overall reaction follow second order kinetics and proceed via $S_N2$ reaction. From the study on kinetics and spectrometric analysis, it was proposed that the rate determining step of the hydrolysis reaction of B-79 is the nucleophilic substitution reaction - that is the reaction of the rapid attack of OH- on the carbon atom, which is in acceptor ring, adjacent to auto group to break the C-N bond. And it was also found that the final hydrolysis products of B-79 include both the acceptor ring in the form of sodium salt and the donor ring possessing 4-N,N-dihydroxyethyl group converted from 4-N, N-diacetoxyethyl group.

• 자원리싸이클링
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• 제24권6호
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• pp.3-8
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• 2015

일정 온도에서 중량 변화를 통하여 가스화 반응 특성을 살펴볼 수 있는 열중량 분석기(thermobalance)를 이용하여 하수슬러지의 수증기 가스화 특성 및 발생 가스의 농도 분석을 실시하였다. 반응 온도 및 수증기의 분압이 증가할수록 가스화 반응이 촉진되어 반응 속도가 증가하는 것으로 나타났다. 반응 kinetics 해석은 기체-고체 화학반응의 세 가지 모델이 이용되었다. 이 중 하수슬러지 촤의 수증기 가스화는 modified volumetric reaction model이 반응 kinetics를 가장 잘 나타내었으며, 이 때 activation energy와 빈도 인자는 각각 155.5 kJ/mol, $14,087s^{-1}atm^{-1}$로 분석되었다. 또한, 수증기의 분압에 따른 반응 차수는 0.68이었다. 합성가스의 발생 특성을 살펴보고자 $900^{\circ}C$에서 생성 합성가스를 분석한 결과 수소의 농도가 가장 높았으며 수증기 분압이 증가할수록 생성기체의 농도 특히 수소 농도가 급격히 증가하였다. 가스화와 동시에 수성가스화 변환반응이 진행되어 생성기체의 수소 생성 농도가 일산화탄소에 비하여 2-4배 높은 값을 나타내었다.

• Elastomers and Composites
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• 제50권2호
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• pp.92-97
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• 2015

A study on reaction kinetics for a PTMG/TDI prepolymer with 2,2'-dichloro-4,4'-methylenedianiline (MOCA), of which formulations may be generally used for fabricating high performance polyurethane elastomers, was peformed using non-isothermal differential scanning calorimetry (DSC). A number of thermograms were obtained at several constant heating rates, and analysed using Flynn-Wall-Ozawa (FWO) isoconversional method for activation energy, $E_a$ and extended-Avrami equation for reaction order, n. Urea formation reaction of the present system was observed to occur through the simple exothermic reaction process in the temperature range of $100{\sim}130^{\circ}C$ for the heating rate of $3{\sim}7^{\circ}C/min$. and could be well-fitted with generalized sigmoid function. Though activation energy was nearly constant as $53.0{\pm}0.5kJ/mol$, it tended to increase a little at initial stage, but it decreases at later stage by the transformation into diffusion-controlled reaction due to the increased viscosity. Reaction order was evaluated as about 2.8, which was somewhat higher than the generally well-known $2^{nd}$ order values for the various urea reactions. Both the reaction order and reaction rate explicitly increased with temperature, which was considered as the indication of occurring the side reactions such as allophanate or biuret formation.

• Korean Chemical Engineering Research
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• 제56권1호
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• pp.103-111
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• 2018

본 연구에서는 PET (Poly Ethylene Terephthalate)의 단량체인 BHET (bis (2-Hydroxyethyl) Terephthalate)와 1,4-BD(1,4-Butanediol)의에스테르교환반응을활용하여 PBT (Poly Butylene Terephthalate)의단량체인 BHBT (Bis (4-Hydroxybutyl Terephthate)를 생성하는 반응에 대하여 조사하였다. 이 반응의 촉매로 Zinc Acetate를 사용하였다. 회분식 반응기를 통하여 BHET, EG (Ethylene Glycol), THF (Tetrahydrofuran)의 양을 정량하여 반응 kinetics 모델을 구성하였다. 제시된 모델을 통하여 반응속도와 반응물의 조성 분포를 조사하였고, 이 모델의 예측 값과 실험 값들이 잘 일치함을 보였다.

• Korean Chemical Engineering Research
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• 제51권1호
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• pp.144-150
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• 2013

본 연구에서는 촉매로 zinc acetate를 사용하였고 dimethyl terephthalate(DMT)와 ethylene glycol(EG)의 에스테르 교환을 통하여 polyethylene terephthalate(PET)의 단량체인 bishydroxyethyl terephthalate(BHET)를 생성하는 반응에 대하여 알아보았다. 기존의 kinetics 연구는 에스테르 교환 반응에서 생성되는 메탄올이 반응계에서 제거되는 반회분식공정을 바탕으로 하여 이때 제거된 메탄올 양을 측정하여 역반응이 무시된 반응 kinetics 모델을 구성하였다. 본 연구에서는 회분식 반응기를 통하여 DMT와 메탄올의 양을 정량하여, 역반응을 고려한 보다 정확한 kinetics 모델을 제안하였고, 제안된 모델의 예측값들이 실험값들과 잘 일치하는 것을 보였다. 또한 모델과 실험값을 분석하여 여러 공정 변수들이 에스테르 교환 반응에 미치는 영향을 조사하였다.