• Journal of the Korean Chemical Society
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• v.34 no.1
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• pp.19-28
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• 1990

The rate of chlorine-exchange reaction of antimony trichloride with benzyl, $\alpha$-phenyl ethyl and diphenyl methyl chlorides in nitrobenzene have been determined. The results indicate that the chlorine-exchange reaction follows second-order kinetics with respect to antimony trichloride and first-order kinetics with respect to organic chlorides. Rate = $k_3[SbCl_3]^2$ [Org-Cl] The rate constants of chlorine-exchange of antimony trichloride with organic chloride increase in the following order of the organic chlorides. Benzyl chloride < $\alpha$-phenyl ethyl chloride < diphenyl methyl chloride The mechanism of the chlorine-exchange reactions has been proposed.

• Polymer(Korea)
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• v.24 no.1
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• pp.16-22
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• 2000

Poly(butylene terephthalate- co-oxybenzoate)(PBOT) containing mesogenic oxybenzoate units in the main chain was synthesized through ester exchange reaction by melt mixing of poly(butylene terephthalate)(PBT) and p-acetoxybenzoic acid (ABA). From the kinetics of the copolymerization reaction, the activation energies and the rate constants of homopolymerization and copolymerization, k$_{h}$ and k$_{c}$, could be determined. From the reaction conditions of different compositions, 4/6, 5/5, and 6/4 of PBT/ABA, at 250, 260, and 27$0^{\circ}C$, it was revealed that copolymerization between PBT and ABA proceeds on a pseudo-second order reaction if the ABA content and its conversion are low. In this case, the ratio of rate constants of homopolymerization to copolymerization was in the range from 1.08 to 3.17, indicating that the copolymer with more notable block character was obtained at the higher mole fraction of ABA and at higher temperature.e.e.

• Transactions of the Korean hydrogen and new energy society
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• v.10 no.1
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• pp.9-17
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• 1999

The hydriding and dehydriding kinetics were studied for a Mg-25wt.%Ni mixture which has the most excellent hydrogen-storage characteristics among many mechanically-alloyed mixtures. The hydriding and dehydriding rates were measured and the rate-controlling steps were determined by comparing the hydriding and dehydriding rates with the theoretical rate equations. The rate-controlling step in the hydriding reaction is the Knudsen flow and the ordinary gaseous diffusion of hydrogen molecules through interparticle channels, cracks, etc. in the various ranges of weight percentage of absorbed hydrogen $H_a$ below $H_a$=4.0. In the $H_a$ range 4.0 < $H_a{\leq}4.25$, the diffusion of hydrogen atoms through the growing hydride layer is considered the rate-controlling step. The rate-controlling step in the dehydriding reaction is the Knudsen flow and the ordinary gaseous diffusion of hydrogen molecules for all the ranges of weight percentage of desorbed hydrogen $H_d$.

• Applied Chemistry for Engineering
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• v.3 no.4
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• pp.649-656
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• 1992

The synthesis of epichlorohydrin was carried out by the epoxidation of allyl chloride with tert-butyl hydroperoxide(TBHP) over silica supported molybdenum catalyst. Kinetic study was performed at $60-80^{\circ}C$ and 10 atm with the molar ratio of TBHP/Allyl chloride between 0.01 and 0.1 in a batch reactor. The epoxidation of allyl chloride was inhibited by tert-butyl alcohol and kinetic data could be represented by Michaelis-Meten type rate equation. The reaction mechanism could be explained by the combination of reversible adsorption of TBHP and tert-butyl alcohol accompanied by reaction of allyl chloride with TBHP adsorbed on $Mo/SiO_2$ catalyst.

• Resources Recycling
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• v.11 no.6
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• pp.38-46
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• 2002

Fundamental investigations were conducted far the recovery process of waste organic solvent by fractional distillation in the aspects of equilibrium and kinetics. Mixture of toluene and xylene, which were both being used in the largest amount as industrial organic solvent, was taken as the artificial waste organic solvent and their distillation behaviors were studied. The purity of recovered solvent was investigated by Cir Chromatography and shown to be in the range of 94～98%. Based upon equilibrium calculations, the changes in the Gibbs free energy, standard enthalpy, and standard entropy for distillation reaction have been estimated. The standard enthalpy changes for toluene and xylene were shown to be 44.833 and 47.044 kJ $mol^{-1}$ respectively, which were similar to their molar heats of evaporation. The activation energies of distillation fur toluene and xylene obtained from kinetic studies were 3.281 and 2.699 kJ $mol^{-1}$ and they were about one tenths of the standard enthalpy changes of distillation reaction. The highness of the purity of recovered organic solvents suggested the possibility that the recovered waste organic sol-vent could partly replace the original solvent.

• Journal of the Korean Chemical Society
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• v.22 no.3
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• pp.150-157
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• 1978

The rate constants for the hydrolysis of the derivatives of N-(p-nitrophenyl)-benzohydrazonyl azide (p-$CH_3,\;p-CH_3O,\;p-NO_2$, p-Cl, p-Br) have been determined by UV spectrophotometry in 50% dioxane-water at $25^{\cicr}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 5, the rate of hydrolysis of hydrazonyl azides is accelerated by electron-donating group ($\rho$ = -0.47), whereas at the pH values greater than 7, the $\rho$-value is 0.68. The effect of salt, solvent, substituent and azide ion on the rate of hydrolysis are rationalized in terms of $S_N1$ and $S_N2$ mechanism; below pH 5, the hydrolysis proceed through $S_N1$, however, above pH 7, the hydrolysis is started by the attack of hydroxide ion and in the range of pH 5∼7, these two reactions occur competitively.

• Journal of the Korean Chemical Society
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• v.38 no.5
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• pp.366-371
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• 1994

The kinetics of the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives was investigated by ultraviolet spectrophotometry in $H_2O$ at 25$^{\circ}C$. A rate equation which can be applied over a wide pH range was obtained. The substituent effects on the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives were studied and the rate of hydrolysis was shown to be accelerated by electron donating groups. Final product of the hydrolysis was 2-(N-acetylaminoethylthio)-acetoacetanilide enol from Judging from the results of the rate equation, general base effect, activation parameters and final products, the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives seemed to be initiated by the neutral $H_2O$ molecule which does not dissociate at pH below 10.0, but proceeded by the hydroxide ion at pH above 11.0, and those two reactions occurred competively at pH 10.0∼11.0 range. On the basis of these findings a plausible mechanism for the hydrolysis of 5,6-dihydro-1,4-thiazine derivative was proposed.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.346-353
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• 2011

Base hydrolysis of 7-hydroxy-2H-chromen-2-one (HC) and 7-hydroxy-2H-chromen-2-one-4-acetic acid (HCA) in aqueous-methanol and aqueous-acetone mixtures were studied kinetically at temperature range from 283 to 313 K. The activation parameters of the reactions were evaluated and discussed. Moreover, the change in the activation energy barrier of the investigated compounds from water to water-methanol and water-acetone mixtures was estimated from the kinetic data. It is observed that the change in activation barriers is more or less the same for the hydrolysis of HC and HCA. Base hydrolysis of HC and HCA follows a rate law with $k_{obs}=k_2[OH^-]$. The decrease in the rate constants of HC and HCA as the proportion of methanol or acetone increases is due to the destabilization of $OH^-$ ion. The high negative values of entropy of activation support the proposal mechanism, i.e. the investigated reaction takes place via the formation of an intermediate complex. Moreover, these values refer to the rigidity and stability of the intermediate complex. Thus, the ring opening of the intermediate complex would be the rate controlling step.

• Journal of the Korean Chemical Society
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• v.26 no.6
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• pp.407-413
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• 1982

The rate constants of the nucleophilic addition of cysteine to 3,4-methylenedioxyphenylmethylene malononitrile were determined by UV Spectrophotometry and a rate equation which can be applied over wide pH range was obtained. On the basis of rate equation, it may be concluded that the rate constants were dependent upon only the concentration of hydroxide ion above pH 9.0, however, below pH 6.0, the reaction were initiated by the addition of neutral cysteine molecule to carbon-carbon double bond and at pH 7.0~9.0, the addition of a neutral cysteine molecule and it's anion occurred competitively.

• Korean Journal of Materials Research
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• v.5 no.6
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• pp.667-672
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• 1995

Cure kinetics of DGEBA(diglycidyl ether of bisphenol A)/MDA(4, 4'-methylene dianiline)/SN(succinonitrile) system and DGEBA/MDA/SN/HQ(hydroquinone) system was studied by Kissinger equation and Fractional life method through DSC in the temperature range of 85∼150$^{\circ}C$. As cure temperature was increased, reaction rate increased and reaction order was almost constant. The reaction rate of the system with HQ as a catalyst was more higher and activation energy of that was lower about 20% than those of the system without HQ. Starting temperature of cure reaction for DGEBA/MDA/SN/HQ system decreased about 30$^{\circ}C$ than that of DGEBA/MDA/SN system.