• Journal of the Korean Chemical Society
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• v.39 no.8
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• pp.650-656
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• 1995

Rate Constants of hydrolysis of N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl chlorides were determined by UV spectrophotometry in 50% (v/v) aqueous methanol at 25$^{\circ}C.$ On the basis of rate equation, substituent effect, solvent effect, salt effect, thermodynamic parameters and hydrolysis product analysis, it may be concluded that the hydrolysis of N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl chlorides proceed through $S_N1$ mechanism via azocarbonium ion intermediate below pH 9.0, while aebove pH 10.0 the hydrolysis proceeds through nucleophilic addition-elimination ($Ad_{N-E}$) mechanism.

• Journal of the Korean Chemical Society
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• v.41 no.6
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• pp.299-303
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• 1997

The rate constants($k_{OH}$) for the alkaline hydrolysis of the 4-substituted phenyl ethyl benzylphosphonates were determined in various buffer solutions by UV(Vis spectrophotometer. The activation entropies of the title reactions show negative values and this result is not consistent with a dissociative mechanism (EA) for which a positive or slightly negative value of the entropy of activation should be expected. An associative mechanism(AE) is favorable because the negligible negative charge is generated on the leaving group in the rate determining step from a good Hammett relationship(ρ=1.89). By the results of a kinetic study, we conclude that a dissociative mechanism is not proceeded in the title reactions.

• Journal of the Korean Chemical Society
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• v.34 no.4
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• pp.319-324
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• 1990

Kinetic of substitution of dibenzoylmethanate (dbm) for one acetylacetonate (acac) in VO (acac)$_2$ have been studied in various solvents by spectrophotometry. Under the condition [VO (acac)$_2$] 》[Hdbm], the rate law for the substitution reaction is expressed as, rate = k$_2$K[VO(acac)$_2$] [Hdbm] / (1 ＋ K[VO(acac)$_2$]) where K = [VO (acac)$_2$dbmH] / [VO(acac)$_2$][Hdbm] and the rate constant k$_2$ corresponds to that of proton transfer from coordinated Hdbm to leaving acac- in VO(acac)$_2$dbmH.

• Journal of the Korean Society of Clothing and Textiles
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• v.16 no.2
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• pp.181-187
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• 1992

일반적으로 면섬유는 햇빛에 의해서 변색되거나 약해지며 또 그 외에도 여러가지 물리적, 화학적인 변화를 일으키게 된다. 구체적인 화학반응의 메카니즘은 사용되는 광선의 스펙트럼, 대기조건(실내인 경우는 실내 환경조건) , 산소의 유무 그리고 염료 등 첨가물의 종류와 같은 여러 요소에 의해 크게 영향을 받게 된다. 환경조건 중에서 산소의 존재는 매우 중요하지만 open system에서 산소의 농도가 일정하다고 가정할 때 면섬유가 접하고 있는 환경조건 중에서 온도와 습도는 photodegradation의 속도를 결정짓는 중요한 요인으로 작용하게 된다. 박물관,:기념관, 도서관 등의 소장품이 자연광선이나 인공조명으로부터 손상되는 것을 막기 위해서는 먼저 이들의 photodegradation 현상에 대한 연구를 필요로 한다. 본 연구에서는 면시칩포를 자연광선과 가장 흡사한 스펙트럼을 가진 xenon arc lamp를 사용한 내후도 시험기내에서 온도와 습도를 조절하여 이에 따른 반응속도의 차이를 인열강도의 감소와 중합도 저하로 측정하였다. 1차 반응식은 실험결과를 설명하는데 유용하였으며 온 · 습도의 증가는 반응속도를 증가시키는 것으로 나타나 기존의 상반된 연구결과의 차이를 입증하였다. 또 온도와 습도는 상호관련이 있는 것으로 나타났으며 고온인 경우습도의 영향을 더 크게 받는 것으로 분석되었다. 반응의 활성에너지는 $30\~75\%$ RH에서는 12 kcal/mole 정도이며 수분의 함량이 낮을수록 활성화에너지는 커지는 것으로 나타나 수분은 섬유소 분자구조내에서 가소제 (plasticizer)의 역할을 하는 것으로 판명되었다.

• Journal of the Korean Chemical Society
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• v.34 no.1
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• pp.10-18
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• 1990

Solvolyses of p-substituted benzyl bromides have been studied in dimethylsulfoxide-water and N,N-dimethylformamide-water mixtures by kinetic method. To determine the ionizing power, Y and the nucleophilicity, $N_{BS}$, the solvolyses of 1-adamantyl halides, t-butyl halides, and methyl tosylate in the same solvent mixtures have been investigated. The solvatochromic parameters for each dimethylsulfoxide-water mixtures have been determined by substituting into the Taft's linear solvatochromic energy relationships with measured $ν_{max}$. The solvolyses of p-substituted benzyl bromides have been found to proceed by borderline mechanism in which bond formation is more advanced than bond cleavage in the transition state based on the m, l values and ${\beta},{\rho}_s$, values.

• Journal of the Korean Chemical Society
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• v.20 no.1
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• pp.73-86
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• 1976

Four unreported derivatives of N-arylsulfonylbenzamide and six derivatives of N-arylsulfonylbenzimidothiophenyl ester were prepared. These were; p-methyl-N-(arylsulfonyl)benzamide, m-methyl-N-(arylsulfonyl)benzamide, m-nitro-N-(arylsulfonyl)benzamide, p-methoxy-N-(arylsulfonyl)benzamide, p-methyl-N-(arylsulfonyl)benzimidothiophenyl esters, p-chloro-N-(arylsulfonyl)benzimidothiophenyl ester, m-methyl-N-(arylsulfonyl)benzimidothiophenyl ester, p-nitro-N-(arylsulfonyl)benzimidothiophenyl ester, m-nitro-(arylsulfonyl)benzimidothiophenyl ester and p-methoxy-N-(arylsulfonyl)benzimidothiophenyl ester. The rate constants of the hydrolysis of N-arylsulfonylbenzimidothiophenyl esters were determined by ultraviolet spectrophotometry at various pH and rate equations which can be applied over a wide pH range were obtained. From the rate equation and substituent effects, one can conclude that above pH 11, the hydrolysis of N-arylsulfonylbenzimidothiophenyl esters are initiated by the attack of hydroxide ion, however, below pH 9, started by the addition of a water molecule on the azomethine group. At pH 9∼11, the competitive reaction between a water molecule and hydroxide ion is anticipated to occur.

• Journal of the Korean Chemical Society
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• v.22 no.1
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• pp.30-36
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• 1978

The kinetics of hydrolysis of ${\alpha}$-nitrobenzaldehydephenylhydrazone derivatives (p-$NO_2$, m-$NO_2$, p-Cl, p-$CH_3$) have been investigated by UV spectrometry in 25% dioxane-water at $25^{\circ}C$ and a rate equation which can be applied over wide pH range was obtained. From the rate equation and the effect of solvent, substituent and pKa on the rate equation, the following reaction mechanisms were proposed. Below pH 3.0 the hydrolysis of ${\alpha}$-nitrobenzaldehydephenylhydrazone proceeds by $S_N1$ mechanism, while above pH 4.0 the hydrolysis proceeds through 1,3-dipole ion mechanism. In the range of pH from 3.0 to 4.0 these two reactions occur competitively.

• Journal of the Korean Chemical Society
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• v.43 no.5
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• pp.527-534
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• 1999

Solvolyses of para-substituted cinnamoyl chlorides in aqueous binary mixtures of acetone, ethanol, methanol were investigated at 25.0$^{\circ}C$. These data were interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for para-substituted cinnamoyl chlorides with $Y_{CI}$ showed marked dispersions into three separate curves for the three aqueous mixtures with a large m vaIue for aqueous alcohol solvents. This study has shown that the potential energy surface and quanturm mechanical model predict transition state variation correctly for $S_N1$ like $S_N2$ reaction mechanism of para-substituted cinnamoyl chlorides.

• Journal of the Korean Chemical Society
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• v.17 no.4
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• pp.269-274
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• 1973

The rate constants of the hydrolysis of ${\alpha}$-Cyano-${\beta}$-piperonylacrylic acid were determined by Ultraviolet spectrophotometry at various pH and a rate equation which can be applied over wide pH range was obtained. The reaction mechanism of hydrolysis of ${\alpha}$-Cyano-${\beta}$-piperonylic acid and especially the catalytic contribution of hydroxide ion which not studied carefully before in acidic media, can be fully explained by the rate equation obtained. The rate equation reveals that; below pH 4.0, the reaction is initiated by the addition of water molecule to ${\alpha}$-Cyano-${\beta}$-piperonyl acrylic acid. At pH $5.0{\sim}7.5$, ${\alpha}$-Cyano-${\beta}$-piperonylacrylic acid compete with ${\alpha}$-Cyano-${\beta}$-piperonyl acrylate ion in adding of water. At pH 8.0, water is the only nucleophile for ${\alpha}$-Cyano-${\beta}$-piperonylacrylate ion, however, above pH 12.0, hydroxide ion is an addendum and the accepter is ${\alpha}$-Cyano-${\beta}$-piperonylacrylate ion.

• Korean Chemical Engineering Research
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• v.61 no.4
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• pp.561-569
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• 2023

Furfural is a platform chemical that is produced from xylose, one of the hemicellulose components of lignocellulosic biomass. Furfural can be used as an important feedstock for phenolic compounds or biofuels. In this study, we compared and optimized the conditions for producing furfural from xylose in a batch system using two types of catalysts: sulfuric acid, which is commonly used in the furfural production process, and formic acid, which is an environmentally friendly catalyst. We investigated the effects of xylose initial concentration (10 g/L~100 g/L), reaction temperature (140~200 ℃), sulfuric acid catalyst (1~3 wt%), formic acid catalyst (5~10 wt%), and reaction time on the furfural yield. The optimal conditions according to the type of catalyst were as follows. For sulfuric acid catalyst, 3 wt% of catalyst concentration, 50 g/L of xylose initial concentration, 180 ℃ of temperature, and 10min of reaction time resulted in a maximum furfural yield of 59.0%. For formic acid catalyst, 5 wt% of catalyst concentration, 50 g/L of xylose initial concentration, 180 ℃ of temperature, and 150 min of reaction time resulted in a furfural yield of 65.3%.