• Korean Journal of Materials Research
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• v.3 no.3
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• pp.215-222
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• 1993

Malononitrile(MN) as a reactive additive was added to Diglycidyl ether of bisphenol A (DGEBA)/Methylene dianiline (MDA) system in order to modify a thermosetting epoxy resin. Cure ki. netics and cure mechanism of this modified system were investigated by using DSC(differential scanning calorimetry) and FT-IR(fourier transform infrared spectrometry). Cure kinetics gave an information that the DGEBA/MDA system modified with MN should cure at over $110^{\circ}C$ after curing at about $80^{\circ}C$ for the complete curing. The activation energy of the first cure was nearly constant and that of the second cure was increased as the MN content was increased. Cure mechanism for the system was investigated with the samples cured every $30^{\circ}C$, from $80^{\circ}C$ to $170^{\circ}C$, for Ihr. It was known that the cure reactions of the epoxy-diamine system were composed of PA -E, SA - E and E-OH reactions. Beside these three reactions, in the DGEBA/MDA/MN system PA-CN and CN-OH reaction was found.

• Journal of the Korean Chemical Society
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• v.28 no.1
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• pp.20-25
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• 1984

Sodamide-containing complex base induced dehydrohalogenations from trans-1,2-dihalocyclohexanes were investigated. Isomerization, deuterium isotope effect along with element effect and others provided strong evidence in favor of E2 reaction mechanism.

• Journal of the Korean Chemical Society
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• v.22 no.4
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• pp.268-274
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• 1978

The kinetics of the bulk polymerization of propylene sulfide initiated by o-sulfobenzoic anhydride were investigated, which proceeded by a zwitterionic mechanism.The instantaneous concentrations of monomer and initiator were determined by means of ir-and nmr-spectroscopy. The rate constant of propagation was found to be about three order of magnitude higher than that of initiation and this should be caused by a zwitterion mechanism.

• Journal of the Korean Chemical Society
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• v.31 no.4
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• pp.352-358
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• 1987

Rate constants for the hydrolysis of para-substituted phenyl N-(p-chlorobenzoyl)chloroformimidate (I) derivatives in 1 : 4 dioxane-water at $25^{\circ}C$ have been determined. Rate data, substituent effect $(\rho\>{\rho}^+)$, product analysis and MO calculation indicate that the uncatalyzed reaction proceeds through an $S_N1$ mechanism involving the formation of azocarbonium ion (II) below pH 3.0, and the base-catalyzed reaction proceeds through an $S_N2$ mechanism via transition state (III) above pH 4.0. The relative stability of four peri planar conformational isomers were (E-ap) > (Z-ap) > (E-sp) > (Z-ap), respectively, and the most stable stereo structures shows that the Y-substituted phenyl group $(C_6H_4-Y)$ occupy vertical $(90^{\circ})$ position on the plane of the benzimidochloroformyl group in (E-ap) conformer. The nucleophilic substitution of water molecule occurs by sigma attack to the activatived azomethine carbon atom of (I) derivatives.

• Journal of the Korean Chemical Society
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• v.20 no.1
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• pp.48-55
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• 1976

The rate constants of the derivatives of N-(2,4-dinitrophenyl)-benzimidoyl chloride were determined at various pH and a rate equation which can be applied over wide pH range was obtained. The reaction mechanism of hydrolysis of N-(2,4-dinitrophenyl)-benzimidoyl chloride which has not been studied carefully earlier in acidic and basic solution can be fullly explained by the rate equation obtained. The rate equation reveals that, beow pH 7.00, the hydrolysis of benzimidoyl chloride proceeds through $S_N2$ reaction to form a carbonium ion intermediate.Above pH 8.5, however, the hydrolysis proceeds through the $S_N2$ type reaction which depends on hydroxide ion and imidoyl chloride concentration. At pH 7.0∼8.5, two reactions occur competitively.

• Journal of the Korean Chemical Society
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• v.21 no.6
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• pp.404-412
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• 1977

Electrochemical reduction of nitrobenzene (${\phi}NO_2$) and its derivatives on Pb electrode was studied by means of galvanostatic measurements and coulometric electrolysis in ethanol-water solvent. In acidic solutions phenylhydroxyl amine and aniline ethanol-water solvent. In acidic solutions phenylhydroxyl amine and aniline were produced while nitrosobenzene and coupled products such as azo-and hydrazobenzene were produced in basic solutions. Nitrosobenzene (${\phi}NO$) was not found to be an intermediate in the reduction reactions of ${\phi}NO_2$ in acidic solutions. No direct coupling between ${\phi}NO\;and\;{\phi}NHOH$ was observed to occur in the electrolyte solutions used. Mechanisms of the production of phenylhydroxylamine and nitrosobenzene are deduced from Tafel slope, pH dependence and reaction order with respect to nitrobenzene. Mechanism for the reduction of substituted nitrobenzenes seems to be identical to that of nitrobenzene.

• Journal of the Korean Chemical Society
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• v.41 no.2
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• pp.69-76
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• 1997

Kinetic studies for the nucleophilic substitution reactions of the benzoic anhydrides with anilines in methanol-acetonitrile mixtures at$35.0{\circ}C$have been carried out in order to elucidate the reaction mechanism. Individual rate constants$k_{XY}$and$k_{XZ}$were decided from the ratios of the reaction products for the competitive substitution reaction at either one of the two carbonyl carbons in benzoic anhydride. Transition state structure and reaction mechanism were elucidated by the Hammett$p_x,\;p_y$and$p_z$values and cross interaction constant$p_x\;p_y$and$p_zvalues. The reaction of the benzoic anhydride has been proposed to proceed by a frontside attack$S_N2 $mechanism with four-membered ring transition state from unusually large magnitude of the$ρ_X,\;ρ_{XY},\;ρ_{XZ}$and positive$p_Y$values.

• Journal of the Korean Chemical Society
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• v.32 no.5
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• pp.476-482
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• 1988

Kinetic studies and theoretical investigations were made to illustrate the mechanism of the aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3$, NO$_2^-$, NCS$^-$, $H_2O$) in $Hg^{2+}$ aqueous solution UV/vis-spectrophotometrically. The aquation of cis-[Co(en)$_2$YCl]$^{r+}$ have been found to be the second order for overall reaction as first order for each of substrate and Hg$^{2+}$+ catalyst. The reaction rate was increased in the order of Y=NH$_3$ < NCS$^-$- < $H_2O$ < $NO_2^-$, which are neighboring group of Cl. The step of bond formation was found to be the rate determining one, because the net charge of central metal ion run parallel with the observed rate constant. On the basis of rate determining step, kinetic data and the observed activation parameters, we have proposed the Id mechanism for the reaction system. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation.

• Journal of the Korean Chemical Society
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• v.37 no.2
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• pp.199-205
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• 1993

The decomposition of hydrogen peroxide by copper-amines complexes was studied in the pH range of 7.3∼11.3 by measuring the rate of the decreasing concentration of $H_2O_2$. Decomposition rate of hydrogen peroxide increased with increasing pH, and then decreased with increasing pH successively. The mechanism for this type of reaction involves the formation of peroxo complexes in the rate-determining step preceding deprotonation of hydrogen peroxide and copper-amines complexes.

• Journal of Environmental Science International
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• v.5 no.5
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• pp.579-583
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• 1996

This study is involved to develop new catalysts to decompose plastics, detergents and surfactants containing synthetic peptide bonds. As the first year research, the catalytic-hydrolysis of amide bond in copper complex was accomplished. The hydrolysis reaction in aqueous solution was monitored by UV/VIS spectroscopy. As the pH of the solution Is increased and the temperature is raised, the reaction rate increases. The reaction rate is observed as the first order kinetic behavior for the copper complex. The metal catalyzed hydrolysis mechanism is proposed cia metal-hydroxide in the pH region of 5.5 to 6.3. The results of characterization of the catalytic reaction mechanism can be applied to develop new catalysts for peptide bond degradation in further research.