• Journal of the Korean Chemical Society
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• v.20 no.5
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• pp.358-363
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• 1976

Kinetic studies on solvolytic reactions of 1-and 2-naphthalene sulfonyl chlorides in ethanol-water mixtures have been carried out by means of conductometry at several temperatures. The rate constant for 2-naphthyl compound was larger than that for 1-naphthyl compound. This was contrary to the prediction of MO theory and could be rationalized as due to the peri-hydrogen effect in the transition state for 1-naphthyl compound. Based on m values of Winstein plots and n values of Kivinen pacolots it was concluded that the solvolytic displacement of the two naphthalene sulfonyl chlorides in ethanol-water mixtures proceed via $S_N2$ process.

• Proceedings of the Korean Society for Applied Microbiology Conference
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• 1986.12a
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• pp.508-508
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• 1986

이온성 계면활성제 존재하에서 유기용매에 물을 첨가하면 물이 계면활성제에 약해 둘러싸이면서 유기용매에 용해되어 의사 이상계가 형성된다. 이러한 계를 역미셀 또는 W/O microemulsion이라고 하며 계면활성제로 둘러 쌓인 물분자 집하체를 water pool이라고 한다. 그런데, 10여년 전 water pool에 bipolymer를 용해시킬 수 있다는 사실이 밟혀짐에 따라 이러한 체계를 생체막을 단순화시킨 모형막으로서 막을 통해 일어나는 여러 가지 현상의 규명에 이용하거나 물에 불용성인 기질의 효소 촉매반응의 반응계로 이용하는 연구가 꾸준히 이루어져 있다. 본 강연은 역미셀계에 리파제를 용해시켜 유지의 가수분해를 유도함으로써 지방산을 생산하는 방법에 관한 연구이다. 역미셀계에서 리파제의 특성은 에멀전계와 비교했을 때 큰 차이가 없었으며 물과 계면활성제의 몰 비율(R값)은 효소의 초기반응 속도에 커다란 영향을 끼치는 인자로 나타났다. 올리브유 농도가 5%(v/v), AOT농도가 0.1M, 초기 물 농도가 1.0M의 조건에서 유지의 회분식 가수분해 실험을 행한 결과 이 기질은 거의 완전히 가수분해되었으며, 이 반응계에서 R값과 초기 물 농도는 반응의 평형에 커다란 영향을 끼치는 것으로 나타났는데 초기 물 농도가 증가할수록 평형 가수분해율은 증가하였단 이러한 결과를 반응속도론 측면에서 분석한 결과 역미셀계에서 리파제 반응은 에멀전계에서와는 달리 2차 반응을 따르는 것으로 나타났다. 물 농도가 평형 가수 분해율과 속도 변수에 끼치는 영향을 수학적으로 표시하기 위하여 2차 가역적 반응 속도론에 근거하여 가수분해율, 평형상수, 속도상수 둥을 나타내는 식을 유도하였고 이를 바탕으로 여러 가지 실험 조건 하에서 리파제 반응의 반응 시간에 따른 가수분해율을 예측한 결과는 실제 실험 결과와 잘 일치하였다(편차는 5%). 또한 속도상수와 R값과의 관계식 및 유도한 방정식을 이용하여 추정한 초기속도와 평형 가수분해율을 최대화하는 R값은 각각 10.4 와 11.4 였다.

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.3-8
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• 1986

The investigation of the effect of solvent structure on the first-order solvolysis of cis-$[Co(en)_2ClNO_2]^+$ion has been extended to water + co-solvent mixtures where the co-solvents are glycerol, ethylene glycol, isopropyl alcohol and t-butyl alcohol. Rates of solvolysis have been evaluated by spectrophotometric method at temperature 25∼30$^{\circ}$C. The polarity of solvent has influence on the variation of rate constant. The non-linear plot of the rate constant in log scale versus $\frac{D-1}{2D+1}$ implies that change in solvent structure with composition plays an important role in determining the variation of rate constant. The linearity of the plot of the rate constant in log scale versus the Grundwald-Winstein Y factor confirms that the solvolysis is an Id-type process with considerable extension of the metal chloride bond in the transition state. In the Kivinen equation the slope of the plot of log k versus $log(H_2O)$ suggests that the solvolysis is also an Id-type process. The application of free energy cycle shows that the effect of solvent structure is greater in the transition state than in the initial state.

• Journal of the Korean Chemical Society
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• v.37 no.8
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• pp.695-701
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• 1993

Rate constants of solvolysis of 2-thiophenesulfonyl chloride were determined in aqueous binary mixtures with methanol, ethanol, acetone in water and in methanol. These data are interpreted using the equation of Grunwald-Winstein and Kivinen relationship. Also, kinetic solvent isotope effects in water and in methanol and product selectivities in alcohol-water mixtures were determined. Kinetic solvent isotope effect for hydrolysis of 2-thiopenesulfonyl chloride was 2.24 and 1.47 for methanol and water, respectively. Selectivity values for formation of ester relative to acid in ethanol-water mixtures show maximum S value. From kinetic solvent isotope effect in methanol and water, selectivity data in aqueous alcoholic solvents and solvent effects, it is proposed that the reaction channel favoured in low polarity solvents is general-base catalysis and/or is possibly addition elimination (S$_A$N) reaction pathway and in high polarity solvents iS S$_N$2 reaction mechanism.

• 한국생물공학회:학술대회논문집
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• 2000.11a
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• pp.761-762
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• 2000

Waste newspaper is many part of Municipal Solid Waste(MSW). Newspaper consist of cellulose, hemicellulose and lignin which biomass components. We could get various compound usable as fuel when pyrolysis of lignin. Therefore, we should get similar phenomena with pyrolysis of newspaper. Highest conversion rate when acetone was used as pyrolysis solvent was $350 {\sim}400^{\circ}C$, $40{\sim}50$minutes.

• Journal of the Korean Chemical Society
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• v.27 no.3
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• pp.167-177
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• 1983

The kinetics of 2-anthracenesulfonyl chloride in methanol-water, ethanol-water, acetone-water and acetonitrile-water has been studied by electroconductometric method. For media in which water has the same mole fraction, the rate was greater in protic solvent than in dipolar aprotic solvent and it was greater consistently in methanol-water than in ethanol-water over the whole range of solvent composition investigated, while the two rates in acetone-water and acetonitrile-water inverted at about 0.9 of mole fraction of water. Both m value, susceptibility of rate to the ionizing power and n value, solvent participation number in the transition state were much smaller in protic solvent. These values and the activation parameters show that solvolysis of 2-anthracenesulfonyl chloride proceeds by $ S_N2$ mechanism.

• Journal of the Korean Chemical Society
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• v.32 no.2
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• pp.85-93
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• 1988

Solvolyses of t-butylhalides (X = Cl, Br, I) in quasi isodielectric solvent system, MeOH-nitromethane, MeOH-nitrobenzene and MeOH-ethyleneglycol have been studied kinetically. Methanolyses for t-butylhalides in MeOH-NM and MeOH-NB show rate maxima at 40~100 % (v/v) MeOH. The rate maxima observed have been interpreted as a result of cooperative enhancement of polarity-polarizability and hydrogen bonddonor ability of solvents. The influences of polarity-polarizability and hydrogen bonddonor ability on reactivities of substrates have been discussed in terms of Y value changes. The solvolysis rates for t-butylhalides in E.G. are more than 20 fold faster than those in MeOH and this was attributed to the solvent structure of E.G.

• Journal of the Korean Ceramic Society
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• v.25 no.5
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• pp.50-50
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• 1988

The controlled Ti(CO2H5)4 hydrolysis reactions for the synthesis of Spherical Monodispersed Titania powders are described. Increasing the concentration of TEOT and the molar ratio of water to TEOT in alcohol solution decrease the reaction time and the particle size. The reaction time is delalyed by increasing the chain length and the number of carbon branches of alcohol as a solvent. The prepared powders with an average diameter of 0.8μ and the spherical monodispersed transfer to Rutile phase at 550℃.

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.624-628
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• 1998

The aromatic organic solvents(BTX) were decomposed in the fixed bed reactor packed with a 0.5% $Pt/{\gamma}-Al_2O_3$ catalyst, then, supercritical carbon dioxide(SC-$CO_2$) was used as the reaction media. And the conversion was dependent on the inlet concentration of BTX and the molar density of SC-$CO_2$. The conversion of BTX was decreased with increasing of inlet concentration, and was increased with temperature and pressure. The maximum conversion of benzene was 98.5% at $300^{\circ}C$ and 204.1 atm, and that of toluene and xylene were 82.0 and 76.5%, respectively, at $350^{\circ}C$ and 204.1 atm. The intermediate products of partial oxidation were identified as benzaldehyde, phenol, benzenemethanol, and so on. The BTX can be effectively converted into harmless $CO_2$ and $H_2O$ at appropriate operating condition. Thus, the nontoxic recovery process was suggested as the removal method of BTX.

• Journal of the Korean Electrochemical Society
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• v.1 no.1
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• pp.28-32
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• 1998

The electrochemical behavior of film and charge-discharge capacity of Li-ion cell in 1 M $LiPF_6/EC:DME$ (1 : 1, by volume ratio) electrolyte solution was studied using chronopotentiometry, cyclic voltammetry, chronoamperometry, and impedance spectroscopy. The first irreversible capacity was higher than the second irrversible capacity because of solvent decomposition. Especially, passivation film that is electron insulating and ionic conducting were formed on the MPCF by solvent decomposition during the first charge. The solvated Li is co-intercalated with solvent into MPCF electrode. Part of the MPCF is expoliated during co-intercalation of solvent-Li. The MPCF ends up nonuniformly covered by a relatively thick layer of exfoliated particles embedded in a matrix of product by solvent decomposition.