• Bulletin of the Korean Chemical Society
• /
• 제32권4호
• /
• pp.1187-1194
• /
• 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
• /
• 제3권1호
• /
• pp.25-32
• /
• 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.

• 한국연소학회지
• /
• 제19권1호
• /
• pp.39-44
• /
• 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
• /
• 제50권2호
• /
• pp.92-97
• /
• 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.

• 대한화학회지
• /
• 제38권10호
• /
• pp.705-709
• /
• 1994

1M 황산용액에서 세륨(Ⅳ) 이온에 의한 말론산의 산화반응에 관한 반응속도를 분광광도법으로 연구하였다. 말론산이 과량으로 존재하는 조건하에서 측정된 유사일차 속도상수, $k_{obs}$는 말론산의 농도, [MA]에 따라 크게 의존함을 보였으며 $k_{obs}$ = (0.592[MA])/(1+14.5[MA]$^2$)의 관계를 만족하였다. 이에 근거하여 반응메카니즘을 제안하였다. 말론산의 산해리에 의해 생성된 enolate형 음이온과 Ce(Ⅳ)간의 전자이동반응이 반응속도 결정단계이며, MA의 고농도하에서 Ce(Ⅳ)과 enolate형 음이온간의 1:2 chelate생성반응에 의하여 Ce(Ⅳ)의 농도가 감소하여 산화반응이 억제됨을 알 수 있었다. 본 연구에서 제안된 메카니즘에 근거하여 Sengupta 등에 의해 연구된 pH 의존성을 설명할 수 있었다.

• 한국안전학회지
• /
• 제27권5호
• /
• pp.77-87
• /
• 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
• /
• 제14권5호
• /
• pp.539-542
• /
• 1999

의 대량생산과 분리.정제 기술의 개발을 위해 Arthrobacter ureafaciens KCTC 3387 균주를 이용한 발효 및 분리정제된 효소반응을 통한 DFAIII의 생산과 회수에 대하여 조사하였다. 첫 번째 방법으로는 Arthrobacter ureafaciens 균주를 발효배양하여 DFAIII 양이 최고가 되는 시점에서 발효정지 시킨후 silica gel를 통해 gel filtration을 분리하였고, 두 번째 방법으로는 정제된 효소로 반응시킨 다음 silica gel을 통해 gel filtration을 하여 분리하였으며, 세 번째 방법으로는 발효배양상등액에 에탄올을 첨가하여 생산물을 침전시켜 DFAIII를 분리하였다. 25 g/L의 초기 inulin 농도로부터 각각 1.57, 4.40, 0.34 g/L 의 정제분말이 얻어져 각각 6.3, 17.6, 1.4%의 수율로 회수되었고, 81, 97, 87%의 순도를 각각 나타내었다. 효소반응을 통한 DFAIII 생산 및 회수가 가장 높은 수율과 순도로 회수되었으며, 발효배양을 통한 DFAIII의 생산은 초기기질농도 25 g/L의 50%에 해당하는 DFAIII가 생산되었으나 효소반응에 의한 생산보다는 낮은 수율로 회수되었고 순도는 세 가지 방법 중 가장 낮았으며, 에탄올 침전반응은 가장 낮은 수율을 나타내었다.

• Korean Chemical Engineering Research
• /
• 제56권3호
• /
• pp.416-420
• /
• 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.

• 한국세라믹학회지
• /
• 제31권11호
• /
• pp.1249-1258
• /
• 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).

• 대한화학회지
• /
• 제50권5호
• /
• pp.404-414
• /
• 2006

연구에서는 고등학교 과학 교과서에 제시된 화학반응속도 측정을 위한 실험을 수행할 때 관찰되는 현상을 이해함으로써 교과서 실험의 문제점과 그 원인을 분석하여 개선 방안을 제시하였다. 이를 위하여 화학반응속도 측정과 관련된 단원의 교과서 내용을 분석하였으며, 실험을 수행할 때 발견되는 문제점을 실험 분석을 통해 제시하였다. 교과서에 제시된 수상치환법으로 실험을 하였을 때 부피 변화가 지연되어 관찰되는 현상과 반응속도가 초기에 증가하는 현상이 관찰되었다. 이러한 문제를 해결하기 위한 개선된 실험 방법을 제안하였다. 개선된 실험에서 반응속도는 시간에 대해 일정하게 측정되었고, 그 결과를 수소이온 농도와 마그네슘 리본의 표면적의 관점에서 해석하였다.