• Bulletin of the Korean Chemical Society
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• v.32 no.4
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• pp.1187-1194
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• 2011

The hydrogen abstraction reaction of $CF_3CH_2CHO$ + OH has been studied theoretically by dual-level direct dynamics method. Two stable conformers, trans- and cis-$CF_3CH_2CHO$, have been located, and there are four distinct OH hydrogen-abstraction channels from t-$CF_3CH_2CHO$ and two channels from c-$CF_3CH_2CHO$. The required potential energy surface information for the kinetic calculation was obtained at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. The rate constants, which were calculated using improved canonical transitionstate theory with small-curvature tunneling correction (ICVT/SCT) were fitted by a four-parameter Arrhenius equation. It is shown that the reaction proceeds predominantly via the H-abstraction from the -CHO group over the temperature range 200-2000 K. The calculated rate constants were in good agreement with the experimental data between 263 and 358 K.

• Carbon letters
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• v.3 no.1
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• pp.25-32
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• 2002

Aligned multi-wall carbon nanotubes (MWNTs) were synthesized through the catalytic decomposition of hydrocarbons in a quartz tube reactor. In this study, we investigated the influence of reaction parameters such as gas flow rate, ferrocene-xylene ratio and partial pressure, and reaction time on the yield and structure of vertically aligned carbon nanotubes produced by the floating catalyst method. The MWNTs produced had diameters in the range of 20~l00 nm, length around $100{\mu}m$ and bulk density about $0.51g/cm^3$ at a pressure of l0000 psi. It was possible to produce MWNTs with much faster growth rate of $12{\mu}m/min$ than that reported previously by the increase of ferrocene-xylene partial pressure.

• Journal of the Korean Society of Combustion
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• v.19 no.1
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• pp.39-44
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• 2014

A short reaction mechanism for premixed $CH_4/CHF_3/Air$ flames was developed with a reduction method of the combined application of simulation error minimization (SEM) which included connectivity method and principal component analysis. It consisted of 43 species and 403 elementary reactions at the condition of less than 5% of maximum error. The calculation time operated with a short mechanism was over 5 times faster than one with a detailed reaction mechanism. Good agreement was found between the flame speeds calculated by the short reaction mechanism and those by the detailed reaction mechanism for the entire range of $CHF_3/CH_4$ mole ratios and equivalence ratios. In addition excellent agreements were determined for the profiles of temperature, species concentration, and the production rates of the various species. So the short reaction mechanism was able to accurately predict the flame structure for premixed $CH_4/CHF_3/Air$ flames.

• 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.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.705-709
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• 1994

The kinetics of the oxidation reaction of malonic acid by ceric ion in 1 M sulfuric acid solution at $20^{\circ}C$ have been investigated by spectrophotometric method. The reaction rate at a large excess of malonic acid was found to be pseudo-first order. The observed pseudo-first order rate constants, $k_{obs}$, are dependent on the concentration of malonic acid, [MA], of which relationship has been found to be $k_{obs}$ = (0.592[MA])/(1+14.5[MA]$^2$). A mechanism for the reaction has been suggested on the basis of the above rate equation. The rate determining step may be the electron transfer reaction between enolate type malonate anion, which is formed by the acid dissociation reaction of malonic acid, and Ce(IV). The rate depression in the range of high concentration of MA has been explained by the formation of 1 : 2 chelate between Ce(IV) and malonate. According to the mechanism, the pH dependence of the rate, which was studied by Sengupta et al., has also been explained.

• Journal of the Korean Society of Safety
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• v.27 no.5
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• pp.77-87
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• 2012

Compared to a batch reactor, where all reactants are initially charged to the reactor, the semi-batch reactor presents serious advantages. The feed of at least one of the reactants provides an additional way of controlling the reaction course, which represents a safety factor and increases the constancy of the product quality. The aim of this study was to investigate the characteristics of thermal hazard such as a feed time, catalysis concentration and solvent concentration in methylthioisocyanate(MTI) synthesis reaction process. The experiments were carried out by the Multimax reactor system and Accelerating rate calorimeter(ARC). The MTI synthesis reaction process has many reaction factors and complicated reaction mechanism of multiphase reaction. Through this study, we can use as a tool for assessment of thermal hazard of other reaction processes by applying experiment method provided.

• KSBB Journal
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• v.14 no.5
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• pp.539-542
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• 1999

For the mass production of DFAIII and for the development of techniques of separation and purification of it, the methods of production of DFAIII and its recovery was investigated by fermentation with the strain of Arthrobacter ureafaciens KCTC 3387 and by enzyme reaction. In the first method, DFAIII was produced by fermentation with the strain of Arthrobacter ureafaciens KCTC 3387 and recovered from culture supernatant with silica gel gy filtration, in the second method, it was produced by enzyme reaction and recoverd with the same method of the first, and in third method it was produced by fermentation and recovered by addition of ethanol to the culture supernatnat.Against 25g/L of initial concentration of inulin, 1.57, 4.40, 0.34 g/L of powder of DFAIII was recovered respectively and the rate of recovery was 6.3, 17.6 1.4% and the purity was estimated at 81, 97, 87% respectively. For the production of DFAIII and its recovery, enzyme reaction method was the highest in the rate of recovery and its purity. By fermentation method, DFAIII was produced with 50% fo initial concentration of substrate but th rate of recovery was lower than enzyme reaction method and purity was lowest among the three methods. Ethanol pricipitation method showed the lowest rate of recovery.

• Korean Chemical Engineering Research
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• v.56 no.3
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• pp.416-420
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• 2018

A comprehensive kinetic study has been conducted on dimethyl carbonate synthesis by transesterification reaction of ethylene carbonate with methanol. An alkali base metal (KOH) was used as catalyst in the synthesis of DMC, and its catalytic ability was investigated in terms of kinetics. The experiment was performed in a batch reactor at atmospheric pressure. The reaction orders, the activation energy and the rate constants were determined for both forward and backward reactions. The reaction order for forward and backward reactions was 0.87 and 2.15, and the activation energy was 12.73 and 29.28 kJ/mol, respectively. Using the general factor analysis in the design of experiments, we analyzed the main effects and interactions according to the MeOH/EC, reaction temperature and KOH concentration. DMC yield with various reaction conditions was presented for all ranges using surface and contour plot. Furthermore, the optimal conditions for DMC yield were determined using response surface method.

• Journal of the Korean Ceramic Society
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• v.31 no.11
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• pp.1249-1258
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• 1994

Titanium carbide was synthesized by reacting the prepared titanium powder and carbon black using SHS method sustains the reaction spontaneously, utilizing heat generated by the exothermic reaction itself. In this process, the effect of the particle size of titanium powder on combustion temperature and combustion wave velocity was investigated. By controlling combustion temperature and combustion wave velocity via mixing Ti and C powder with TiC, the reaction kinetics of TiC formation by SHS method was considered. Without reference to the change of combustion temperature and combustion wave velocity, TiC was easily synthesized by combustion reaction. As the particle size of titanium powder was bigger, or, as the amount of added diluent(TiC) increased, combustion temperature and combustion wave velocity were found to be decreased. The formation of TiC by combustion reaction in the Ti-C system seems to occur via two different mechanisms. At the beginning of the reaction, when the combustion temperatures were higher than 2551 K, the reaction was considered to be controlled by the rate of dissolution of carbon into a titanium melt with an apparent activation energy of 148 kJ/mol. For combustion temperatures less than 2551 K, it was considered to be controlled by the atomic diffusion rate of carbon through a TiC layer with an apparent activation energy of 355 kJ/mol. The average particle size of the synthesized titanium carbide was smaller than that of the starting material(Ti).

• Journal of the Korean Chemical Society
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• v.50 no.5
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• pp.404-414
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• 2006

this study we analyzed and improved an experiment measuring chemical reaction rates introduced in the high school science textbooks through an understanding of the phenomena observed in carrying out the experiment. For this purpose, the contents of textbooks related to the experiment were analyzed, and the problems observed in carrying out the experiment were addressed through experimental analysis. When the experiment was carried out by the method of aquatic transposition presented in textbooks, the observed volume change of H2 gas was delayed and chemical reaction rate was increased in the early stage of reaction period. To resolve these problems, an improved method for measuring the reaction rates was suggested. In the improved experiment the reaction rate was measured to be constant on time, which was interpreted in terms of the concentration of H+ and the surface area of magnesium.