• Journal of the Korean Chemical Society
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• v.7 no.4
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• pp.288-292
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• 1963

The rates of reaction of various Korean anthracites with carbon dioxide were measured at temperatures ranging from $850^{\circ}C$ to $1100^{\circ}C$ with coal -6, +8 sieve size and the residence time of reactant gas in the fixed coal bed 14.0 to 15.0 seconds. The primary variables studied were the coal sources and temperature. The reactivity was considerably varies with the coal sources and the general trends show that the reactivity sharply increases with increasing reaction temperature except the Yongwol coal where the increase is not so sharp, which is considered to be due to high reactivity and high-pore structure of the coal. It was also found that a straight line was produced when a logarithm of the rate constant is plotted against the reciprocal of the absolute temperature up to 1000^${\circ}C$, but above that temperature it deviates from linearity. The information obtained will be of value in the design of the coal gasifier using Korean anthracites.

• Journal of the Korean Ceramic Society
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• v.37 no.5
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• pp.505-510
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• 2000

In this investigation, we fabricated RBSN (Reaction Bonded Silicon Nitride) using the static nitriding system which could be advantageous for commercialization. Firstly, Si compacts of different sizes were made, and then nitridation rates were investigated as a function of added static gas pressure. The reaction schedule was obtained by pre-experiments. In case of small samples, the variation of ${\alpha}$, ${\beta}$ phases between the inside and the outside region of the specimens was examined after the samples were nitrided under 1 bar and 1.5 bar reaction pressure. On the other hand, large samples of Si compact with the size of 36 mm for diameter and 23 mm for thickness were nitrided for 26 hours of the total nitridation time, which showed a complete and homogeneous nitriding reaction from the outside to the inside of the samples, although the time was considerably shorter than that needed for convertional nitridation. Nitridation rates obtained at the early stage of reaction were proportional to the reaction gas pressures. The sequences of the nitridation reaction with the thickness were as follows 1) the outside, 2) the inside and 3) the intermediate area of the specimen. These results wer eobtained from the coloration of cross sectioned specimens that had various nitridation rates. Total nitriding reaction kinetics was controlled by chemical reaction, not by diffusion of the nitrogen gas.

• Elastomers and Composites
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• v.50 no.2
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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.

• Bulletin of the Korean Chemical Society
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• v.27 no.8
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• pp.1181-1185
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• 2006

By using two different computer simulation methods, of which one produces exact results while the other is based on the Wilemski-Fixman closure approximation, we evaluate the utility of closure approximation in calculating the rates of diffusion-controlled reactions involving a reactant with multiple reaction sites. We find that errors in the estimates of steady-state rate constants due to closure approximation are not so large. We thus propose an approximate analytic expression for the rate constant based on the closure approximation.

• Journal of the Korean Chemical Society
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• v.40 no.5
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• pp.302-307
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• 1996

Diethanolamine dithiocarbamate is known to react with dichlorobis(ethylenediamine)cohalt(Ⅲ) chloride to form [Co(dtc)3](dtc=diethanolamine dithiocarbamate) in which two sulfur atoms of the dithiocarbamate are bound to cobalt. The complex is moderately soluble in acetone, but sparingly soluble in carbon disulfide. Kinetics and mechanisms of the reaction of dichlorobis(ethylenediamine)cobalt(Ⅲ) chloride with diethanolamine dithiocarbamate have been studied in aqueous solution. Activation parameters have been calculated from the kinetic data for the reaction and from these results a possible mechanism for the reaction has been proposed.

• Bulletin of the Korean Chemical Society
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• v.13 no.1
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• pp.37-41
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• 1992

The reactions of nitrous acid with hydrogen peroxide in acidic aqueous solution in the presence of several added anions have been studied at $0^{\circ}C$ and pH 2-4 to investigate the nucleophilic catalysis of these anions. From the dependence of reaction rates on the anion concentrations, significant catalytic effects were found for $Cl^-,\;Br^-,\;SCN^-$, in order of effect $SCN^-\;{\approx}\;Br^->Cl^-$, while no observable effect was found for ${ClO_4}^-$ and ${NO_3}^-$. These results support O-nitrosation reaction is the rate-determining step and NOX formed in the presence of an anion ($X^-$) also acts as a nitrosating agent and accelerates the overall reaction rate. The order of reactivity was found to be NOCl>NOBr>NOSCN, which is consistent with the results of N-nitrosation and S-nitrosation reactions.

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.444-449
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• 1993

Anaerobic oxidation of D-penicillamine by Fe(III) in acidic solution has been studied kinetically by the use of stopped-flow system. The reaction is biphasic with a rapid complexation of 1: 1 complex, $Fepen^+$ (pen= D-penicillamine dianion) which is then internally reduced to Fe(II) and disulfide. Rates of both the complexation and the redox process are pH dependent and also are affected by the presence of chloride ion. Different from the reaction of Cu(II) with D-penicillamine, partially oxidized mixed-valence complex is not formed even transiently in this reaction.

• Bulletin of the Korean Chemical Society
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• v.20 no.9
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• pp.1031-1034
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• 1999

Tin oxide films have been grown employing the chemical vapor deposition technique under reduced pressure conditions using tetramethyltin as the precursor and oxygen as the oxidant. An activation energy derived for the deposition reaction under representative deposition conditions has a value of 89±3 kJ mol-1, suggesting a typical kinetic control. Deposition rates of tin oxide films exhibit a near first order dependence on tetramethyltin partial pressure and a zeroth order dependence on oxygen partial pressure. This study provides the first quantitative information about the growth kinetics of tin oxide films from tetramethyltin by the cold-wall low-pressure chemical vapor deposition.

• Bulletin of the Korean Chemical Society
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• v.23 no.11
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• pp.1513-1518
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• 2002

Kinetic studies on the water-gas shift reaction catalyzed by magnetite/chromium oxide and copper/zinc oxide were carried out by using an in situ photoacoustic spectroscopic technique. The reactions were performed in a closed-circulation reactor system using a differential photoacoustic cell at total pressure of 40 Torr in the temperature range of 100 to $350^{\circ}C.$ The CO2 photoacoustic signal varying with the concentration of CO2 during the catalytic reaction was recorded as a function of time. The time-resolved photoacoustic spectra obtained for the initial reaction stage provided precise data of CO2 formation rate. The apparent activation energies determined from the initial rates were 74.7 kJ/mol for the magnetite/chromium oxide catalyst and 50.9 kJ/mol for the copper/zinc oxide catalyst. To determine the reaction orders, partial pressures of CO(g) and H2O(g) in the reaction mixture were varied at a constant total pressure of 40 Torr with N2 buffer gas. For the magnetite/chromium oxide catalyst, the reaction orders with respect to CO and H2O were determined to be 0.93 and 0.18, respectively. For the copper/zinc oxide catalyst, the reaction orders with respect to CO and H2O were determined to be 0.79 and 0, respectively.

• Journal of the Korean Chemical Society
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• v.30 no.4
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• pp.383-388
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• 1986

Kinetics of the reaction of 2-phenylethylarenesulfonates with pyridine in acetonitrile were investigated by an electric conductivity method under 1 to 2,000 bars and at 40∼60${\circ}C$. The rates of these reactions were increased with raising temperatures and pressures, but less than those of the reactions of benzyl benzenesulfonate with pyridine in acetoneitrile were investigated by an electric conductivity method under 1 to 2,000 bars and at 40~60${\circ}C$ .The rates of these reactions were increased with raising temperatures and pressures, but less than those of the reaction of benzyl benzenesulfonate with pyridine in acetone. The activation volumes and activation entropies of 2-phenylethyl m-nosylate were more negatively large than those of benzyl benzenesulfonate. From these phenomena it can be deduced that 2-phenylethyl system has more firmly $S_N2$ character in tranistion state. The Hammett reaction constants are also estimated from the second-order reaction constants. With increasing pressures the reaction parameters $({\rho})$ were decreased, but the $S_N2$ characters were increased. From these results, the reaction mechanism can be adequately described as typical $S_N2$ process under high pressure.