• 대한화학회지
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• 제20권1호
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• pp.48-55
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• 1976

N-(2,4-dinitrophenyl)-benzimidoyl chloride의 여러가지 유도체의 가수분해 속도상수를 측정하여 넓은 pH 범위에서 잘 맞는 반응속도식을 구하였다. 이 식에 의하면 아직 잘 알려져 있지 않은 산성과 염기성 용액속에서 가수분해 반응메카니즘을 정량적으로 잘 설명할 수 있었다. 즉 pH 7.0 이하에서는 carbonium ion 중간체를 거쳐 반응이 진행되는 $S_n1$ 반응과정이며, pH 8.5 이상에서는 hydroxide ion과 imidoyl chloride 농도에 비례하는 $S_n2$ 반응메카니즘에 의해 가수분해가 진행되며, pH 7.0∼8.5 사이에서는 이 두 반응이 경쟁적으로 일어남을 알았다.

• 대한용접접합학회:학술대회논문집
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• 대한용접접합학회 2002년도 Proceedings of the International Welding/Joining Conference-Korea
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• pp.276-281
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• 2002

A metallurgical model for bainite transformation kinetics in the coarse-grained heat affected zone(CGHAZ) on the basis of an Avrami-type equation was studied. Isothermal transformation tests were carried out to obtain the empirical equations for incubation time and Avrami kinetic constants for C-Mn-Mo-Ni steel. The effect of prior austenite grain size(PAGS) on the reaction rate of bainite was also investigated. Compared with experimental transformation behavior of bainite, the predicted behavior was in good agreement. It was also found that a smaller grain size retard the bainite reaction rate, contrary to the classical grain size effect and this is considered to be caused by constraint of grain size to bainite growth.

• International Journal of Korean Welding Society
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• 제2권1호
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• pp.11-14
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• 2002

A metallurgical model for bainite transformation kinetics in the coarse-grained heat affected zone(CGHAZ) on the basis of an Avrami-type equation was studied. Isothermal transformation tests were carried out to obtain the empirical equations for incubation time and Avrami kinetic constants for C-Mn-Mo-Ni steel. The effect of prior austenite grain size(PAGS) on the reaction rate of bainite was also investigated. Compared with experimental transformation behavior of bainite, the predicted behavior was in good agreement. It was also found that a smaller grain size retard the bainite reaction rate, contrary to the classical grain size effect and this is considered to be caused by constraint of grain size to bainite growth.

• 대한화학회지
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• 제38권6호
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• pp.442-448
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• 1994

${\alpha}$-(n-Butyl)-N-Phenylnitrone 유도체의 첨가 반응속도상수를 25^{\circ}C$의 수용액에서 자외선 분광광도법으로 측정하여 넓은 pH범위에서 잘 맞는 반응속도식을 유도하였다. 첨가반응생성물은 ${\alpha}$-phenylthiobutylidene-aniline이었으며, 첨가반응속도상수 측정과 반응속도식의 유도, 일반기염 효과, 치환기 효과 및 최종생성물의 결과로부터 반응 메카니즘을 제안하였다. 즉, pH 3.0 이하에서는 티오페놀의 첨가로 반응이 시작되며, pH 3.0∼10.0에서는 티오페놀과 티오페녹시드 음이온이 경쟁적으로 첨가되어 진행되며, pH10.0이상에서는 티오페녹시드 음이온의 첨가에 의해서 반응이 진행된다.

• Elastomers and Composites
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• 제50권2호
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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.

• 한국연소학회:학술대회논문집
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• 한국연소학회 1999년도 제19회 KOSCO SYMPOSIUM 논문집
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• pp.155-163
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• 1999

A numerical study for simulating a swirling pulverized coal combustion in axisymmetric geometry is done here by applying the weighted sum of gray gases model (WSGGM) approach with the discrete ordinate method (DOM) to model the radiative heat transfer equation. In the radiative transfer equation, the same polynomial equation and coefficients for weighting factors as those for gas are adopted for the coal/char particles as a function of partial pressure and particle temperature. The Eulerian balance equations for mass, momentum, energy, and species mass fractions are adopted with the standard ${\kappa}-{\varepsilon}$ turbulence model, whereas the Lagrangian approach is used for the particulate phase for soot. The eddydissipation model is employed for the reaction rate for gaseous mixture, and the single-step first-order reaction model for the devolatilization process for coal. By comparing the numerical results with experimental ones, the models used here are confirmed and found to be one of good alternatives for simulating the combustion as well as radiative characteristics.

• Nuclear Engineering and Technology
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• 제29권2호
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• pp.99-109
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• 1997

A dynamic model for hydrogen generation by Fuel-Coolant Interactions(FCI) is developed with separate models for each FCI stage, coarse mixing and stratification. The model includes the physical concept of FCI, semi-empirical heat and mass transfer correlation and the concentration diffusion equation with the general non-zero boundary condition. The calculated amount of hydrogen, which is mainly generated in stratification, is compared with the FITS experiments. The model developed in this study shows a good agreement within a range of 10 % fuel oxidation rate and predicts the controlled mechanism of the chemical reaction very well. And this model predicts more accurately than the previous works. It is shown from the sensitivity study that the higher initial temperature of fuel particle is, the larger the reaction rate is. Up to 2700 K of temperature of the particle, the reaction rate increases rapid, which can lead to metal ignition.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.51-56
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• 2014

The solvolysis rate constants of 2,4-dimethoxybenzenesulfonyl chloride (1) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $0.93{\pm}0.14$ and $0.65{\pm}0.06$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.4 to $14.6kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -15.5 to -$32.3kcal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effects (SKIE) were 1.74 to 1.86, which is also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The values of product selectivity (S) for solvolyses of 1 in alcohol/water mixtures was 0.57 to 6.5, which is also consistent with the proposed bimolecular reaction mechanism. Third-order rate constants, $k_{ww}$ and $k_{aa}$, were calculated from the rate constants ($k_{obs}$), together with $k_{aw}$ and $k_{wa}$ calculated from the intercept and slope of the plot of 1/S vs. [water]/[alcohol]. The calculated rate constants, $k_{calc}$ ($k_{ww}$, $k_{aw}$, $k_{wa}$ and $k_{aa}$), are in satisfactory agreement with the experimental values, supporting the stoichiometric solvation effect analysis.

• Bulletin of the Korean Chemical Society
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• 제33권12호
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• pp.4117-4121
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• 2012

The solvolysis rate constants of allyl chloroformate ($CH_2=CHCH_2OCOCl$, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with the sensitivity values of $0.93{\pm}0.05$ and $0.41{\pm}0.02$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.5 to 13.4 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -34.4 to -37.3 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.16 was also in accord with the $S_N2$ mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.

• 한국연소학회지
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• 제20권2호
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• pp.46-53
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• 2015

The relationship between mass transfer and reaction within the washcoat is investigated in a monolith type micro-scale Pt-catalytic combustor. Nondimensionalized balance equation of butane is applied in a simplified washcoat geometry having the shape of slab. Both Thiele modulus and effectiveness factor are considered to compare reaction rate and diffusion rate according to the operation temperature and the diameter of alumina nano-pores. The effect of reaction becomes stronger as the temperature increases, while the effect of diffusion becomes relatively dominant as the diameter of nano-pores increases. From the analysis of butane distribution within the washcoat, design criterion for the thickness of washcoat is discussed.