• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.517-522
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• 1992

The reaction of ${\beta}$-picoline with substituted benzoyl chlorides has been studied by means of conductometry under various pressures in acetonitrile. From the values of pseudo-first order and second order rate constants, the activation parameters (${\Delta}V{\neq}$, ${\Delta}{\beta}{\neq}$, ${\Delta}H{\neq}$, ${\Delta}S{\neq}$ and ${\Delta}G{\neq}$) and the pressure dependence of Hammett ${\rho}$ value were studied. The activation volume, the activation compressibility coefficient and the activation entropy were all negative. By increasing pressure the rate constant and Hammett ${\rho}$ value were increased, and the reaction mechanism was proceed in bond formation favored.

• Bulletin of the Korean Chemical Society
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• v.10 no.1
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• pp.47-50
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• 1989

The methanolysis reactions of phenylacetyl chlorides have been investigated in methanol-acetonitrile mixtures at temperatures ranging - $15.0-0.0^{\circ}C.$ Substituent and solvent effects on the rate supported an associative $S_N2$ mechanism for the solvolysis. Activation parameters indicated that the reaction is entropy controlled, while the a/s ratios of the Taft's solvactochromic correlation proved to be remarkably constant with a typical value of 0.50 that is consistent for the reactions proceeding by a typical $S_N2$ path.

• Textile Coloration and Finishing
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• v.2 no.4
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• pp.231-236
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• 1990

The diffusion coefficient of C.I. Disperse Red 4 in the dyeing of carrier-pretreated poly (ethylene terephthalate) film was Investigated by Sekido's film-rolled method. From the result it was shown that the diffusion coefficient increases exponentially with the content-ration of carrier in the film, and, for the films containing same concentration of carrier, the carrier effect was enhanced with the molar volume of the carriers. The greater carrier effect was accompanied by the decrease in diffusion activation energy and entropy, which shows that the carrier with larger molar volume plasticizes PET film to more extent.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.111-116
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• 2014

The kinetics and mechanism of oxidation of sulfanilic acid by N-chloro-p-toluene sulfonamide (chloramine-T) have been studied in acid medium. The species of chloramine-T were analysed on the basis of experimental observations and predominantly reactive species was taken into account for proposition of most plausible reaction mechanism. The derived rate law (1) conforms to such a mechanism. $$-\frac{d[CAT]}{dt}=\frac{kK_1[RNHCl][SA]}{K_1+[H^+]}$$ (1) All kinetic parameters were evaluated. Activation parameters such as energy and entropy of activation were calculated to be $(61.67{\pm}0.47)kJmol^{-1}$ and $(-62.71{\pm}2.48)kJmol^{-1}$ respectively employing Eyring equation.

• Bulletin of the Korean Chemical Society
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• v.4 no.5
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• pp.212-217
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• 1983

Depending on the range of shear rates, temperatures and concentrations, the potato starch suspension in water behaves as a typical dilatant system. The flow curves of the suspension at various concentrations and temperatures were obtained by using a Couette type rotational viscometer. The flow mechanism of the suspension is explained by a structure model of starch granules in the suspension. Based on the experimental results, a general flow equation for the dilatant system is proposed. By analyzing the temperature dependency of the relaxation time, the activation enthalpy and activation entropy for flow in the starch-water suspension were calculated, the former being about 10 kcal/mol.

• Textile Coloration and Finishing
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• v.2 no.3
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• pp.26-35
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• 1990

This study was carried out with the view of fundamental investigating to improve the tactile and the hygroscopicity of Poly(ethylene Terephthalate) (PET)fibers. Mono-sodium ethylene glycolate in ethylene glycol (MSEG-EG) solution was prepared and PET films were treated with it. The following conclusions were obtained. When PET films were decomposed in MSEG-EG solution, decomposition rate constant showed an exponential relationship with treating temperature; activition energy was 23.30 Kcal/mol, activation enthalpy was 22.52~22.60 Kcal/mol and activation entropy was -29.20~ -29.41 e.u. On the basis of the results obtained above and structure identification of decomposition products, it was found that the decomposition reaction proceeded through ester interchange reaction.

• Journal of the Korean Chemical Society
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• v.63 no.4
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• pp.233-236
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• 2019

In this study, the solvolysis of cyclohexanesulfonyl chloride (1) was studied by kinetics in ethanol-water, methanol-water, acetone-water, and 2,2,2-trifluoroethanol (TFE)-water binary solvent systems. The rate constants were applied to the extended Grunwald-Winstein equation, to obtain the values of m = 0.41 and l = 0.81. These values suggested $S_N2$ mechanism in which bond formation is more important than bond breaking in the transition state (TS). Relatively small activation enthalpy values (11.6 to $14.8kcal{\cdot}mol^{-1}$), the large negative activation entropy values (-29.7 to $-38.7cal{\cdot}mol^{-1}{\cdot}K^{-1}$) and the solvent kinetic isotope effects (SKIE, 2.29, 2.30), the solvolyses of the cyclohexanesulfonyl chloride (1) proceeds via the $S_N2$ mechanism.

• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1084-1090
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• 1998

The oxidation of triphenylphosphine by [(tpy)(phen)RuⅣ(O)]2+ and [(bpy)(p-tert-butylpy)RuⅣ(0)]2+ (tpy is 2,2': 6',2"-terpyridine, phen is 1,10-phenanthroline, bpy is 2,2'-bipyridine, and p-tert-butylpy is para-tertbutylpyridine) in CH3CN has been studied. Experiments using 18O-labeled complex show the oxyl group transfer from [RuⅣ=O]2+ to triphenylphosphine occured quantitatively within experimental error. Kinetic data were fit to a second-order for [RuⅣ=O]2+ and [PPh3]. The initial product, [RuⅡ-OPPh3]2+, was formed as an observable intermediate and then underwent slow solvolysis. The reaction proceeded as endothermic in activation enthalpy and a decrease in activation entropy. The oxidative reactivity of four representative ruthenium mono-oxo oxidants against triphenylphosphine was compared. These systems have been utilized as electrochemical oxidative catalysts.

• Textile Coloration and Finishing
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• v.12 no.1
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• pp.52-60
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• 2000

In the prior studies, we reported that the dye uptakes of C. I. Disperse Violet 1 on polyester fiber in hexane and cyclohexane were higher than those in the other solvents, as the number of carbon atoms of alkanes decreased, the dye uptake increased, and the logarithmic plot of the dye uptakes vs. the solubilities of the dye showed that the dye uptakes are inversely proportional to the solubilities. In this study, for Interpretation of dyeing behavior of C. I. Disperse Violet 1 on polyester in alkanes, the thremodynamic parameters of dyeing, such as standard affnity, heat of dyeing(enthalpy change), entropy change, diffusion coefficient, and activation energy of diffusion, were obtained from isotherms and dyeing rates at different temperature. As the number of carbon atoms of alkanes increased, the standard affinity decreased, but the heat of dyeing(enthalpy change) and the entropy change showed larger negative values. These results mean that as the number of carbon atoms of alkanes increases, the dye uptake decreases, but both the fraction of the dye molecules dyed at relatively highly aligned or compact region of polyester fiber and the regularity of dye aggregates in the fiber become increased. As the number of carbon atoms of alkanes increased, the diffusion coefficient decreased, but the activation energy of diffusion increased. In the alkane of larger number of carbon atoms, because the solubility of the dye is higher, the desorption rate of the dye is faster and the diffusion coefficient is smaller than those in the smaller alkanes. But the energy required to separate the dye molecules from the alkane molecules is much higher because the interaction between the alkane molecule and the dye molecule become strong with the number of carbon atoms.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.24 no.5
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• pp.340-344
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• 1991

On heating and fleering food-stuffs, it is very important to obtain informations about thermophysical properties of fishes for designing of freezing and heating equipment and analyzing of physico-chemical reaction during storage. It is particularly necessary to measure denaturation enthalpy, temperature, latent heat of freezing, activation energy, enthalpy, entropy and free energy on freezing and heating rate. In this study, DSC was used to study effects of freezing and heating rate on thermophysical properties and denaturation temperature on scanning rate $2.5-10.0^{\circ}C/min$. On increasing scanning rate, denaturation temperature of protein and lipid incresed and freezing point, activation energy, enthalpy, entropy were decreased. In freezing process free energy of fishes were found to be $14.2-18.9 kcal/mol$.