• Journal of the Korean Chemical Society
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• v.18 no.4
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• pp.251-258
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• 1974

The rate constants for the nucleophilic substitution reactions of substituted benzoyl chlorides with p-nitroaniline in such solvents as acetone, acetonitrile, methanol, ethanol, etc. were conductometrically determined, and the activation thermodynamic parameters were also evaluated. In result, the reaction rates were faster in protic solvents than in aprotic solvent; in the solvents of similar property, the reaction rate in the solvent of the large dielectric constant was faster than that in the solvent of the small dielectric constant. Hammett plots in individual solvents showed the straight lines with positive slope; and we concluded that the reaction occurred via the addition-elimination mechanism.

• Journal of the Korean Chemical Society
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• v.48 no.3
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• pp.254-260
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• 2004

The reaction rates of para-substituted benzoyl chlorides ($p-CH_3$, p-H, $p-NO_2$) with pyridine have been measured employing the conductometry method in acetonitrile. The pseudo first-order and second-order rate constants were determined at various pressures and temperatures. The activation parameters (${\Delta}V{\ddagger},\;{\Delta}{\beta}{\ddagger},\;{\Delta}H{\ddagger},\;{\Delta}S{\ddagger},\;{\Delta}G{\ddagger}$) and the Hammett ${\rho}$-values are determined from the values of rate constant. The values of ${\Delta}V{\ddagger},\;{\Delta}{\beta}{\ddagger}\;and\;{\Delta}S{\ddagger}$ are all negative. The Hammett ${\rho}$-values are positive for the substrate (${\rho}_Y$) over the given pressure range. The results of kinetic studies, for the pressure and substituent changes, show that these reactions are proceeded by a typical $SN_2$reaction mechanism and its bond formation is favored with elevating pressure.

• Polymer(Korea)
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• v.29 no.1
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• pp.59-63
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• 2005

Kinetic study of a reaction between poly(caprolactone diol) and aliphatic isocyanate was investigated by FTIR spectroscopy. The reaction rate was obtained from analyzing the absorbance change of NCO peak (2265 $cm^{-1}$) in series IR spectra. In the results, the overall reaction between PCL and isocyanate conformed to the simple second-order law, and the rate constant increases with increasing reaction temperature. The activation energies obtained from the evaluation of kinetic data were 25.4∼30.9 kJ/mol for hexamethylene diisocyanate and 16.8∼22.1 kJ/mol for cyclohexylmethane diisocyanate, respectively.

• Journal of the Korean Chemical Society
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• v.22 no.1
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• pp.30-36
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• 1978

The kinetics of hydrolysis of ${\alpha}$-nitrobenzaldehydephenylhydrazone derivatives (p-$NO_2$, m-$NO_2$, p-Cl, p-$CH_3$) have been investigated by UV spectrometry in 25% dioxane-water at $25^{\circ}C$ and a rate equation which can be applied over wide pH range was obtained. From the rate equation and the effect of solvent, substituent and pKa on the rate equation, the following reaction mechanisms were proposed. Below pH 3.0 the hydrolysis of ${\alpha}$-nitrobenzaldehydephenylhydrazone proceeds by $S_N1$ mechanism, while above pH 4.0 the hydrolysis proceeds through 1,3-dipole ion mechanism. In the range of pH from 3.0 to 4.0 these two reactions occur competitively.

• Microbiology and Biotechnology Letters
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• v.26 no.5
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• pp.465-469
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• 1998

The quantitative and rapid method for measuring the biodegradation of polymer materials in soil was developed. In this study, cellophane film was used as a model biodegradable polymer and the biodegradation was assayed by measuring the amount of glucose which was produced by a hydrolysis reaction using HCl after collecting the film from soil. Cellophane film was degraded 41.2% in 4 months during winter while it was degraded 76.5% in 2 months during summer. It means that biodegradation in soil is affected by environmental conditions. The biodegradation was also measured in an incubator (30$^{\circ}C$, humidity 50-55%) to exclude the environmental variations. Cellophane film was degraded 94% in that condition in 40 days. The biodegradation showed the first order kinetics and the rate constant was 0.067 (1/day). Acceleration of the biodegradation in soil was also studied. We added cultured soil microorganisms or nutrients such as N, P, and S into the soil. While the addition of microorganisms showed the temporary increase of rate constant, the addition of nutrients not only showed the increase of rate constant from 0.096 (1/day) to 0.21 (1/day) but also maintained the effect continuously.

• Journal of the Korean Chemical Society
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• v.27 no.3
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• pp.201-207
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• 1983

The rate constants for solvated electrons with benzene in the binary mixture (tetrahydrofuran-water) were measured at a various temperatures$(-18{\circ}C{\sim}+51{\circ}C)$ by photolysis. From Arrhenius plots of rate constants it was observed that the activation energies were decreased with increasing tetrahydrofuran(THF) content. Decreasing the viscosity of solvent mixtures by adding water, the rate constants were also decreased. It indicates that the reaction of solvated electrons are not controlled by diffusion. The change of activation enthalpy in kcal $M^{-1}$ and the rate constants in$ M^{-1}sec^{-1}$ were 4.90 and $8.80{\times}10^8$ for 30M% of THF, 2.80 and $5.14{\times}10^8$ for 49M% of THF, and -0.30 and %1.43{\times}10^8$ for 75M% of THF, respectively. The slope of the linear plot of activation enthalpies against activation entropies was $244{\circ}K$, which supports the reaction parameter is the change of activation entropy in the range of the experimental temperature. From the solvent effect on the activation energy, it was found that the step of the reaction, ${e_s}^-+B{\rightleftharpoons}B^-$ shifted to the exothermic reaction with increasing THF content.

• 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.

• Elastomers and Composites
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• v.33 no.4
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• pp.274-280
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• 1998

Order of reaction, rate constant, activation energy for vulcanization reaction, crosslinking density, and elastic constant of the network produced by sulfur curing were investigated on the SBR/BR blends containing silica and carbon black under same cure system. The reaction order was shown to be first order regardless of filler types. The carbon black filled rubber compounds showed higher rate constant compared to silica filled compounds. But activation energy appeared to be same regardless of filler type and rubber blend ratio. The crosslinking density and elastic constant is higher in the carbon black filled compound compared to silica filled compounds because of strong interaction between rubber and carbon black. On the other hand, crosslinking density and elastic constant were decreased with increasing the butadine rubber content in rubber blends. From the comparison of combined sulfur content in the vulcanized rubber, sulfur content in the silica filled compound become constant 20min later after reaction initiates but sulfur content in the carbon black filled compound become constant 10min later after reaction starts. The silica compound has a longer induction time ($t_2$) and optimum cure time($t_{90}$) compared to those of the carbon black filled compound.

• Applied Chemistry for Engineering
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• v.17 no.3
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• pp.296-302
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• 2006

The kinetics of the thermal-oxidative decomposition of waste polyurethane (PU) according to oxygen concentration has been studied using a non-isothermal thermogravimetric technique at several heating rates from 10 to $50^{\circ}C/min$. A kinetic model accounting for the effects of the oxygen concentration by the differential and integral method based on Arrhenius equation was proposed to describe the thermal-oxidative decomposition of waste PU. To obtain the information on the kinetic parameters such as activation energy, reaction order, and pre-exponential factor, the thermogravimetric analysis curves and its derivatives have been analyzed using the kinetic analysis method proposed in this work. From this work, it was found that reaction orders for oxygen concentration had a negative sign, and activation energy decreased as the oxygen concentration increased. It was also found that the kinetic parameters obtained from the integral method using the single heating rate experiments varied with heating rates. Therefore, it is thought that the differential method using the multiple heating rate experiments more effectively represents the thermal-oxidative decomposition of waste polyurethane.

• Journal of the Korean Chemical Society
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• v.38 no.6
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• pp.442-448
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• 1994

The rate constants of the nucleophilic reaction of ${\alpha}$-(n-butyl)-N-phenylnitrone and its derivatives have been determined by ultraviolet spectrophotometry at $25^{\circ}C$ and a rate equation which can be applied over a wide pH range was obtained. Final product of the addition reaction was $\alpha$-phenylthiobutylidene-aniline. Base on the rate equation, genernal base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Below pH 3.0 the reaction was inititated by the addition of thiophenol, and in the range of pH 3.0∼10.0, proceeded by the competitive addition of thiophenol and thiophenoxide anion. Above the pH 10.0, the reaction proceeded through the addition of a thiophenoxide anion.