• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2219-2225
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• 2007

The reaction mechanisms for the cyclizations of N-methyl-2-(2-chloropyridin-3-yloxy)acetamide to 1-methylpyrido[ 3,2-b][1,4]oxazin-2-one and 1-methyl-pyrido[2,3-b][1,4]oxazin-2-one were investigated using ab initio Hartree-Fock, second-order Moller-Plesset perturbation, single point coupled cluster with both single and double substitution, and density functional theory methods. The 5-membered spiro intermediate (2) is optimized from the cyclization of the acyclic reactants through the proton-transfer reaction, and this intermediate proceeds continuously to the 6-membered intermediate through either a stepwise or a concerted reaction. In the stepwise reaction, an N-bridge-type intermediate as a stable structure is optimized, whereas, in the concerted reaction, the O-bridge-type intermediate is not optimized.

• Journal of the Korean Ceramic Society
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• v.28 no.11
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• pp.885-891
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• 1991

Calcium hydroxyapatite have been synthesized by a direct precipitation reaction between 0.05 M calcium hydroxide suspension and 0.3 M orthophosphoric acid solution. 0.01 M calcium hydroxide solution was added during the reaction in order to increase the total Ca/P mol ration and reaction pH of the solution. The stoichiometric hydroxyapatite was synthesized over 1.75 as total Ca/P mol ratio, but the calcium-deficient hydroxyapatite was prepared under 1.725 as total Ca/P mol ratio. The nonstoichiometry of the precipitates were interpreted in terms of the pH change during the reaction.

• Journal of the Korean Ceramic Society
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• v.15 no.1
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• pp.21-27
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• 1978

Hadong Kaolin (Halloysite) was granulated cylindrically and treated with 1N aqueous sodium hydroxide solution for 6-48 hrs at 60-10$0^{\circ}C$. The crystalling structure of surface of the products was studied by X-ray powder diffraction method. The reaction rate of halloysite to sodium A zeolite showed a gradual decrease from surface to inner layer. At the surface layer, the reaction mechanism was observed as first order consecutive reaction as follows: halloysitelongrightarrowamorphous aluminosilicatelongrightarrowsodium A zeolitelongrightarrowhydroxysodalite By applying the above reaction mechanism, the rate constants and activation energies was measured.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2438-2442
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• 2014

A kinetic study is reported for $S_NAr$ reaction of 1-fluoro-2,4-dinitrobenzene (5a) and 1-chloro-2,4-dinitrobenzene (5b) with alkali-metal ethoxides (EtOM, M = Li, Na, K and 18-crown-6-ether complexed K) in anhydrous ethanol. The second-order rate constant increases in the order $k_{EtOLi}$ < $k_{EtO^-}$ < $k_{EtONa}$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for the reaction of 5a and $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for that of 5b. This indicates that $M^+$ ion behaves as a catalyst or an inhibitor depending on the size of $M^+$ ion and the nature of the leaving group ($F^-$ vs. $Cl^-$). Substrate 5a is more reactive than 5b, although the $F^-$ in 5a is ca. $10pK_a$ units more basic than the $Cl^-$ in 5b, indicating that the reaction proceeds through a Meisenheimer complex in which expulsion of the leaving group occurs after the rate-determining step (RDS). $M^+$ ion would catalyze the reaction by increasing either the nucleofugality of the leaving group through a four-membered cyclic transition state or the electrophilicity of the reaction center through a ${\pi}$-complex. However, the enhanced nucleofugality would be ineffective for the current reaction, since expulsion of the leaving group occurs after the RDS. Thus, it has been concluded that $M^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through a ${\pi}$-complex between $M^+$ ion and the ${\pi}$-electrons in the benzene ring.

• 한국연소학회:학술대회논문집
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• 2003.05a
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• pp.247-253
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• 2003

Burning velocities of conventional methane flame and oxygen-enriched methane flame were determined by experimentally and numerically at atmospheric pressure in order to examine the validity of various detailed reaction mechanisms in oxygen-enriched flame. The schlieren system was adopted to obtain the burning velocity of flame stabilized on a circular nozzle. Premix code was employed to compute the burning velocity. Three reaction mechnisms were tested at several oxygen enrichment level, whose names are GRI 3.0, MB(Miller and Bowman) and LKY(Lee Ki Yong) reaction mechanism. Sensitivity analysis was also performed to discriminate dominantly affecting reaction on burning velociy. The results showed that conventional reaction mechanisms originally based on methane-air flame were underpredict the burning velocity at high oxygen-enrichment level. The modified GRI 3.0 reaction mechanism based on our experimental results was suggested and shows a good agreement in estimating the burning velocity and the NO number density of oxygen-enriched flame.

• Journal of the Korean Ceramic Society
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• v.30 no.6
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• pp.478-484
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• 1993

The influence of reaction conditions on the MnZn ferrite coprecipitation process were investigated using mixed metla sulfate solution and ammonium oxalate. In order to minimize the metallic ion losses and to control the particle size, the optimum reaction conditions were as follows; reaction temperature $25^{\circ}C$, metal sulfate concentration 0.3M, molar ratio of ammonium oxalate/mixed metal sulfate 1.1:1. The production yield was as high as 97.6% of theoretical yield at optimum reaction condition.

• Applied Chemistry for Engineering
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• v.1 no.2
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• pp.207-214
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• 1990

The catalytic reaction between CO and NO on polycrystalline Pt surface, which is very important in the development of catalyst for automobile exhaust gas control, has been studied using thermal desorption spectrometry(TDS) and steady-state experiment under ultra-high vacuum(UHV) conditions. With the pressures of CO and NO of each $1{\times}10^{-7}Torr$, the $CO_2$ formation rate showed a maximum at 560K. At the reaction temperature of 560K and the NO pressure of $1{\times}10^{-7}Torr$, the production of $CO_2$ was first order in $CO_2$ was first order in CO pressure below $1.35{\times}10^{-7}Torr$ of CO pressure whereas at higher CO pressures the rate became minus 0.3 order in CO. But the efforts of reactant pressure on the reaction was understood in consideration of the surface concentrations of adsorbates. With the results, we proposed a new reaction mechanism for this reaction.

• Journal of KSNVE
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• v.11 no.1
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• pp.68-75
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• 2001

A method for actively controlling dynamic reaction forces in flexible structures subject to persistent excitations is presented. Since reaction forces are not directly measured in flexible structures, reaction forces are estimated by using the Kalman filter. The estimated reaction force is used as an error signal in the adaptive feedforward disturbance cancellation controller. In order to compensate the static effect of the truncated modes in the reaction forces, the residual flexibility matrix is used with the Kalman filter. The paper presents the formulation of the reaction forces in conjunction with the Kalman filter estimator and the adaptive feedforward controller. The results show that the dynamic reaction forces at its supports in a flexible beam test rir are well suppressed.

• Journal of the Korean Society of Combustion
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• v.5 no.1
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• pp.7-18
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• 2000

Numerical simulations of counterflow non-premixed $CH_4/C_2HCl_3/Air$ flames added 8%(by volume) C2HCl3 on the fuel side are conducted at atmospheric pressure using a detailed chemical reaction mechanism in order to understand the effect of strain rates. A detailed sensitivity analysis is also performed in order to assess the relative influence of each reaction on the flame established at a strain rate of 200s-1. The structure of flames (i.e., temperature, velocity, and concentration of species) established at both a strain rate of 150s-1 and 300s-1 are investigated. As the strain rate increases, the "flame zone" is restricted to a narrower range and the position of maximum temperature is shifted to the fuel side. The concentrations of major species, H2O, CO, H2, HCl, Cl2, and Cl are decreased with increased strain rate. The reaction involving chlorine, CH4 + Cl $\rightarrow$ CH3 + HCl, instead of the reaction, CH4 + H $\rightarrow$ CH3 + H2 influences the consumption of methane. C2HCl3 + OH $\rightarrow$ CHCl2 + CHOCl and HCl + OH $\rightarrow$ H2O + Cl, are major reactions, through which OH radicals are consumed.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.993-999
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• 2011

The photoreactive prepolymers with multifunctional cinnamate and bisphenol Atype cinnamate groups that could perform photodimerization without photoinitiators were synthesized by the reaction of t-cinnamic acids (CAs) and epoxy resins. Their photocure reaction rates and the extent of reaction conversion were measured with Fourier transform infrared spectroscopy, and these increased with the intensity of UVirradiation. The experimental data of these reaction rates showed the characteristics of nth-order kinetics reaction, and all kinetic constants of each photoreactive polymer with this equation were summarized. Although the GTR-1800-HCA and KWG1-EP-HCA with hydroxyl group substituted cinnamate showed lower reaction conversion rates and rate constant than GTR-1800-CA and KWG1-EP-CAwith an unsubstituted cinnamate group, GTR-1800-MCAand KWG1-EP-MCAwith methoxy group substituted cinnamate showed similar and higher reaction conversion rates than the former, respectively. These results were explained in terms of segmental mobility for photopolymerization by molecular interactions.