• 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.

• Journal of the Korean Chemical Society
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• v.42 no.2
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• pp.150-155
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• 1998

Kinetic studies on the reaction of isoquinoline with para-substituted benzylbromides were conducted under various pressures (1 ~1000 bar) in acetonitrile. From the rate constants obtained, the activation parameters such as$\DeltaV^{\neq}, \Delta\beta^{\neq}, \DeltaH^{\neq}, \DeltaS^{\neq}, \DeltaG^{\neq}$ and Ea were evaluated. Reaction rate increasing the pressure and temperature. The activation compressibility coefficient and the activation entropy showed negative values. From the substituent effect and the results, it was found that the reaction proceeds through $S_N2$ mechanism, but the structure of transition state was slightly changed with substituents and pressure.

• Korean Chemical Engineering Research
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• v.47 no.3
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• pp.373-379
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• 2009

Cesium carbonate was used as an adsorbent to capture carbon dioxide from gaseous stream of carbon dioxide, nitrogen, and moisture in a fixed-bed to obtain the breakthrough data of $CO_2$. The deactivation model in the non-catalytic heterogeneous reaction systems is used to analyze the sorption kinetics among carbon dioxide, carbonate, and moisture using the experimental breakthrough data. The experimental breakthrough data are fitted very well to the deactivation model than the adsorption isotherm models in the literature.

• Journal of the Korean Chemical Society
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• v.54 no.1
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• pp.88-92
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• 2010

Isopropyl mercaptan is an important pharmaceutical intermediate and chemical material. And thiourea and triglycol are the main materials for the synthesis of isopropyl mercaptan. Therefore the dissolution of thiourea in triglycol solution is very important for the production of isopropyl mercaptan. The aims of this study are to examine the dissolution kinetics of thiourea in triglycol solution, and to present an alternative process for producing isopropyl mercaptan. In order to investigate the dissolution kinetics of thiourea in triglycol solution, the concentrations of solution and reaction temperature were selected as experimental parameters. It was determined that the dissolution rate of thiourea increased with the increase in solution concentration and temperature. An empirical equation was used in fitting the data. Statistical analysis indicated small errors and the results should be reliable.

• 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.

• Journal of the Korean Chemical Society
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• v.37 no.8
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• pp.695-701
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• 1993

Rate constants of solvolysis of 2-thiophenesulfonyl chloride were determined in aqueous binary mixtures with methanol, ethanol, acetone in water and in methanol. These data are interpreted using the equation of Grunwald-Winstein and Kivinen relationship. Also, kinetic solvent isotope effects in water and in methanol and product selectivities in alcohol-water mixtures were determined. Kinetic solvent isotope effect for hydrolysis of 2-thiopenesulfonyl chloride was 2.24 and 1.47 for methanol and water, respectively. Selectivity values for formation of ester relative to acid in ethanol-water mixtures show maximum S value. From kinetic solvent isotope effect in methanol and water, selectivity data in aqueous alcoholic solvents and solvent effects, it is proposed that the reaction channel favoured in low polarity solvents is general-base catalysis and/or is possibly addition elimination (S$_A$N) reaction pathway and in high polarity solvents iS S$_N$2 reaction mechanism.

• 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 Chemical Society
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• v.28 no.4
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• pp.265-268
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• 1984

Rates of reactions of nine m-or p-substituted phenacyl bromides with quinoline in methanol were measured by an electric conductivity method. These reactions were found to proceed through an $S_N2$ path and were accelerated by both electron-donating and electron-withdrawing substituents. A plausible reaction mechanism for this observation was proposed. Some activation parameters for these reactions were also calculated.

• Journal of the Korean Chemical Society
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• v.28 no.2
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• pp.143-146
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• 1984

• Journal of the Korean Chemical Society
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• v.41 no.9
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• pp.443-448
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• 1997

Kinetics for the solvolyses of acyl chlorides and alkyl chlorides in hydroxylic solvent mixtures have been measured by conductometric method at various temperatures and pressures. The activation parameters (${\Delta}V^{\neq},\; {\Delta}H^{\neq},\; {\Delta}S^{\neq}$) were estimated from the rate constants. The reactivities of these reactions were also estimated from the correlation of the activation volumes with the activation entropies.