• Bulletin of the Korean Chemical Society
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• v.28 no.2
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• pp.181-182
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• 2007

• Journal of the Korean Society for Industrial and Applied Mathematics
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• v.11 no.3
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• pp.7-20
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• 2007

We examined the steady state solution for a strongly exothermic mixtures in some class A geometries subjected to different boundary conditions under Arrhenius, Bimolecular and Sensitised reactions. The solution of the governing nonlinear reaction diffusion equation was obtained using the variational method formulation executed in Mathematica package. The paper elucidates the influence of geometry, boundary conditions and types of reaction on the thermal ignition of the reactive mixture. Apart from validating known results in literature, the solution gave further insight into the influence of material properties and conditions on the occurrence of thermal ignition.

• Journal of the Institute of Electronics Engineers of Korea SD
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• v.43 no.2 s.344
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• pp.13-17
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• 2006

Pentacene channel for organic thin film transistor was deposited on the SiOC film by thermal evaporation. The growth of pentacene is related with the Diels-Alder reaction and the nucleophilic reaction by the thermal induction. The surface is an important factor to control the recursive Diels-Alder reaction for growing of pentacene on SiOC far The terminal C=C double bond of pentacene molecule was broken easily as a result of attack of the nucleophilic reagents on the surface of SiOC film. The nucleophilic reaction can be accelerated by increasing temperature on surface, and it maks pentacene to grow hardly on the SiOC film with a flow rate ratio of $O_2/(BTMSM+O_2)=0.5$ due to its inorganic property. The nucleophlic reaction mechanism is $SN_2(bimolecular nucleophilic substitution)$ type.

• Journal of the Korean Chemical Society
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• v.9 no.1
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• pp.23-28
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• 1965

Halogen exchanges between benzyl chloride and chloride ion have been studied in 90% ethanol-water mixture, and activation parameters in the exchange reaction have been determined; ${\Delta}H^{\neq}$ = 18. 50 Kcal and ${\Delta}S^{\neq}$ = -22. 09 e. u. Results indicated that the reaction proceeded via a typical bimolecular mechanism. The importance of nucleophilic ability of attacking anion in $S_N2$ process has been stressed giving some experimental evidence. The order of reactivity of halides in the exchange reaction is better explained with the Swain's nucleophilic parameter than with the bond dissociation energies.

• Bulletin of the Korean Chemical Society
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• v.24 no.5
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• pp.671-673
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• 2003

• Bulletin of the Korean Chemical Society
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• v.13 no.4
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• pp.398-404
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• 1992

We have investigated the kinetics of diffusion-influenced bimolecular reactions in which one reactant has an internal mode, called the gating mode, that activates or deactivates its reactivity intermittently. The rate law and an expression for the time-dependent rate coefficient have been obtained from the general formalism based on the hierarchy of kinetic equations involving reactant distribution functions. The analytic expression obtained for the steady-state reaction rate constant coincides with the one obtained by Szabo et al., who derived the expression by employing the conventional concentration-gradient approach. For the time-dependent reaction rate coefficient, we obtained for the first time an exact analytic expression in the Laplace domain which was then inverted numerically to give the time-domain results.

• Journal of the Korean Society for Industrial and Applied Mathematics
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• v.21 no.4
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• pp.215-224
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• 2017

The moment closure method is an approximation method to compute the moments for stochastic models of chemical reaction systems. In this paper, we develop an analytic estimation of errors generated from the approximation of an infinite system of differential equations into a finite system truncated by the moment closure method. As an example, we apply the result to an essential bimolecular reaction system, the dimerization model.

• Journal of the Korean Chemical Society
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• v.61 no.1
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• pp.25-28
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• 2017

Solvolyses with the reaction center being the sulfur of 4-(chlorosulfonyl)biphenyl ($C_6H_5C_6H_4SO_2Cl$, 1) was studied under solvolytic conditions and the extended Grunwald-Winstein equation was applied. The thirty five kinds of solvents gave a reasonable extended Grunwald-Winstein plot with a correlation coefficient (R) of 0.940. The sensitivity values (l = 0.60 and m = 0.47) of 1 were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, 2; l = 1.10 and m = 0.61) proposed to undergo dissociative $S_N2$ mechanism. These l and m values for the solvolyses of 1 can be considered to support a $S_N2$ pathway with some ionization reaction. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction. The kinetic solvent isotope effect (KSIE) of 1.26 is also in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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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.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1897-1901
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• 2011

This report shows the rates of solvolyses for phenyl methanesulfonyl chloride ($C_6H_5CH_2SO_2Cl$, I) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Three representative solvents, studies were made at several temperatures and activation parameters were determined. The thirty kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, coefficient (R) of 0.954. The sensitivity values (l = 0.61 and m = 0.34, l/m = 1.8) of phenyl methanesulfonyl chloride (I) were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, II; l = 1.01 and m = 0.61) and 2-propanesulfonyl chloride ($(CH_3)_2CHSO_2Cl$, III; l = 1.28 and m = 0.64). As with the two previously studied solvolyses, an $S_N2$ pathway with somewhat ionization reaction is proposed for the solvolyses of I. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.34 in $CH_3OH/CH_3OD$ is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.