• Journal of the Korean Chemical Society
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• v.48 no.5
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• pp.461-466
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• 2004

Kinetics for the nucleophiles have been studied under high vacuum and high pressures in various temperatures. Pseudo-first order rate constants, second order rate constants, thermodynamic parameters and Hammett ${\rho}$-values are determined. The values of ${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq}\;and\;{\Delta}S^{\neq}$are all negative. The Hammett r-values are negative for the nucleophile (${\rho}$x) over the pressure range studied. The results of kinetic studies for pressure and nucleophilet show that these reactions proceed in typical $S_N2$ reaction mechanism and change of mechanism.

• Journal of the Korean Chemical Society
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• v.20 no.6
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• pp.453-459
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• 1976

Rate constants for the reaction of methyl chloroformate with substituted anilines, and for the halogen exchanges in phenyl chloroformate have been determined in acetone. Although the rate data can be interpreted equally well with the addition-elimination mechanism($S_AN$) involving an intermediate, results of MO and isotope effect studies strongly favor the synchronous ($S_N2$) mechanism for the reactions studied. It was concluded that for the fast reacting nucleophiles the transition state is of "late" type while for the slow reacting nucleophiles it is of "early" type.

• Korean Journal of Materials Research
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• v.2 no.4
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• pp.257-262
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• 1992

The cure kinetics of a diglycidyl ether of bisphenol A (DGEBA) with 4, 4'-methylene dianiline (MDA) added succinonitrile was studied through the dynamic run method by applying the data to the Kissinger equation which analyses the effect of the heating rate on the temperature at maximum reaction rate using Differential Scanning Calorimetry (DSC) analyzer in the range of 3$0^{\circ}C$-35$0^{\circ}C$. In the DGEBA/MDA system with SN, the activation energy ($E_a$) and the pre-exponential factor (A) were calculated. From these results, the rate constants (k) were obtained according to the different SN contents.

• Journal of the Korean Chemical Society
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• v.41 no.6
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• pp.299-303
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• 1997

The rate constants($k_{OH}$) for the alkaline hydrolysis of the 4-substituted phenyl ethyl benzylphosphonates were determined in various buffer solutions by UV(Vis spectrophotometer. The activation entropies of the title reactions show negative values and this result is not consistent with a dissociative mechanism (EA) for which a positive or slightly negative value of the entropy of activation should be expected. An associative mechanism(AE) is favorable because the negligible negative charge is generated on the leaving group in the rate determining step from a good Hammett relationship(ρ=1.89). By the results of a kinetic study, we conclude that a dissociative mechanism is not proceeded in the title reactions.

• Applied Chemistry for Engineering
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• v.5 no.3
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• pp.517-523
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• 1994

The effects of cure kinetics and mechanism of DGEBA(diglycidyl ether of bisphenol A)/MDA(4,4'-methylene dianiline) with SN(succinonitrile) and HQ(hydroquinone) as an additive and accelerator were investigated. Cure kinetics was evaluated by Kissinger equation and fractional-life method through DSC analysis. The activation energy has hydroxyl group as an accelerator, the activation energy and the starting cure-temperature were lower than those of DGEBA/MDA/SN system. Cure mechanism of those systems was investigated through FT-IR according to the various SN contents. The ratio was SN : HQ = 4 : 1. It has been known that the cure reactions of an epoxy-diamine system are composed of primary amine-epoxy reaction, secondary amino-epoxy reaction and epoxy-hydroxyl group reaction. But in DGEBA/MDA/SN system, primary amino-CN group reaction and CN group-hydroxyl group reaction were added to the above mentioned reactions. These reactions attributed to the long main chain and the low crossliking density. And in DGEBA/MDA/SN/HQ system, hydroxyl group of HQ formed a transition state with epoxide group and amime group and also opened the ring of the epoxide group rapidly, then amino-epoxy reaction took place easily.

• Applied Chemistry for Engineering
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• v.17 no.6
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• pp.658-664
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• 2006

$\rho$, $\alpha$-dimethyl benzyl alcohol was resolved by the biphasic dynamic kinetic resolution (DKR). Acidic zeolite was used as a racemization catalyst while immobilized enzyme was employed for kinetic resolution. The effects of the process variables including nature of acyl donor, reaction temperature, substrate concentration, ratio of the two catalysts and stirring rate on the conversion and enantiomeric purity of the product were investigated. In DKR of $\rho$, $\alpha$-dimethyl benzyl alcohol, the product of 99% ee was obtained with a maximum yield of 88%. The high performance of the catalyst system was maintained in the condition of higher TON and under repeated use.

• Journal of the Korean Chemical Society
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• v.52 no.5
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• pp.476-481
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• 2008

• Journal of the Korean Institute of Gas
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• v.20 no.4
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• pp.65-77
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• 2016

Modeling for complex reacting flow in Fischer-Tropsch reactor is one of the challenges in the field of Computational Fluid Dynamics (CFD). It is hard to derive each and every reaction rate for all chemical species because Fisher-Tropsch reaction produces many kinds of hydrocarbons which include lots of isomers. To overcome this problem, after analyzing the existing methodologies for reaction rate modeling, non-Anderson-Schulz-Flory methodology is selected to model the detailed reaction rates. In addition, the inside flow has feature of multi-phase flow, and the methodologies for modeling multi-phase flow depend on the interference between the phases, distribution of the dispersed phase, flow pattern, etc. However, existing studies have used a variety of inside flow modeling methodologies with no basis or rationale for the feasibility. Modeling inside flow based on the experimental observation of the flow would be the best way, however, with limited resources we infer the probable regime of inside flow based on conventional fluid dynamics theory; select the appropriate methodology of Mixture model; and perform systematic CFD modeling. The model presented in this study is validated through comparisons between experimental data and simulation results for 10 experimental conditions.

• Journal of the Korean Chemical Society
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• v.37 no.6
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• pp.577-584
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• 1993

The reaction rates of para-substituted benzoyl chlorides with substituted pyridines have been measured employing the conductometry method in acetonitrile, and pseudo-first order and second order rate constants are determined at various pressures and temperatures. The activation parameters (${\Delta}V^\neq, {\Delta}{\beta}^{\neq}, {\Delta}H^{\neq}, {\Delta}S^{\neq} {\Delta}G^{\neq}$) and the Hammett ρ-values are determined from the values of rate constants. The values of △${\Delta}V^\neq, {\Delta}{\beta}^{\neq}and {\Delta}S^{\neq}$ are all negative. The Hammett ρ-values are negative for the nucleophile (ρ$_X$), and positive for the substrate (ρ$_Y$) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S$_N$2 reaction mechanism and in bond formation favored with elevating pressure.

• Proceedings of the Korean Environmental Sciences Society Conference
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• 2019.10a
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• pp.146-146
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• 2019