• Journal of the Korean Chemical Society
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• v.22 no.3
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• pp.150-157
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• 1978

The rate constants for the hydrolysis of the derivatives of N-(p-nitrophenyl)-benzohydrazonyl azide (p-$CH_3,\;p-CH_3O,\;p-NO_2$, p-Cl, p-Br) have been determined by UV spectrophotometry in 50% dioxane-water at $25^{\cicr}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 5, the rate of hydrolysis of hydrazonyl azides is accelerated by electron-donating group ($\rho$ = -0.47), whereas at the pH values greater than 7, the $\rho$-value is 0.68. The effect of salt, solvent, substituent and azide ion on the rate of hydrolysis are rationalized in terms of $S_N1$ and $S_N2$ mechanism; below pH 5, the hydrolysis proceed through $S_N1$, however, above pH 7, the hydrolysis is started by the attack of hydroxide ion and in the range of pH 5∼7, these two reactions occur competitively.

• Journal of the Korean Chemical Society
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• v.38 no.5
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• pp.366-371
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• 1994

The kinetics of the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives was investigated by ultraviolet spectrophotometry in $H_2O$ at 25$^{\circ}C$. A rate equation which can be applied over a wide pH range was obtained. The substituent effects on the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives were studied and the rate of hydrolysis was shown to be accelerated by electron donating groups. Final product of the hydrolysis was 2-(N-acetylaminoethylthio)-acetoacetanilide enol from Judging from the results of the rate equation, general base effect, activation parameters and final products, the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives seemed to be initiated by the neutral $H_2O$ molecule which does not dissociate at pH below 10.0, but proceeded by the hydroxide ion at pH above 11.0, and those two reactions occurred competively at pH 10.0∼11.0 range. On the basis of these findings a plausible mechanism for the hydrolysis of 5,6-dihydro-1,4-thiazine derivative was proposed.

• Journal of the Korean Chemical Society
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• v.34 no.1
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• pp.19-28
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• 1990

The rate of chlorine-exchange reaction of antimony trichloride with benzyl, $\alpha$-phenyl ethyl and diphenyl methyl chlorides in nitrobenzene have been determined. The results indicate that the chlorine-exchange reaction follows second-order kinetics with respect to antimony trichloride and first-order kinetics with respect to organic chlorides. Rate = $k_3[SbCl_3]^2$ [Org-Cl] The rate constants of chlorine-exchange of antimony trichloride with organic chloride increase in the following order of the organic chlorides. Benzyl chloride < $\alpha$-phenyl ethyl chloride < diphenyl methyl chloride The mechanism of the chlorine-exchange reactions has been proposed.

• Resources Recycling
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• v.26 no.3
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• pp.17-25
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• 2017

Electric arc furnace steelmaking dust has various physicochemical properties as volatile components generated in the melting process of steel scraps in an electric arc furnace, which is captured in oxide form as fine powder by reacting with oxygen in the air. In order to efficiently recycle these electric arc furnace dust, a kinetic basic experiment and a pilot production test were carried out in parallel. As a result, it was found that the electric arc furnace dust contain a large amount of Cl and alkali components, thus it was expected that the compounds have a great adverse effect on the actual operation for the recycling. It was confirmed that the volatilization behavior was progressing actively at $1100^{\circ}C$ and the electric arc furnace dust was melted at $1250^{\circ}C$. These results are the same as a result of pilot test for the formation behavior of zinc oxide and reduced iron. These results should be useful as basic data for designing the recycling plant of the electric arc furnace dust and establishing the operating conditions.

• Journal of the Korean Chemical Society
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• v.19 no.3
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• pp.156-162
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• 1975

Rates of reactions of methanesulfonyl chloride with various substituted anilines have been measured in methanol. Substituent effects in aniline are found to be linearly correlated with pKa(Bronsted relation with ${\beta}$ = 0.84) and ${\rho}$(Hammett equation with ${\rho}$ = -2.46) respectively. The results are interpreted in terms of degree of bond-formation at the transition state, which was found to have progressed relatively further. The rates for o-methylaniline deviated from the Bronsted plot established by meta and para substituted anilines because of a steric effect of ortho position in aniline. Activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ have also been determined. The enthalpy of activation showed a regular variation in that electron donating substituents in the p-substituted aniline decrease ${\Delta}H^{\neq}$ and increase the negative value of ${\Delta}S^{\neq}$.

• Journal of the Korean Chemical Society
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• v.29 no.1
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• pp.15-22
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• 1985

Kinetic studies of nucleophilic substitution reaction of substituted benzoyl cyanides and benzoyl chlorides with pyridines were conducted at 25$^{\circ}C$ in pure acetone solvent. Results showed that (ⅰ) magnitudes of $_{\rho}_S$, $_{\rho}_N$ and ${\beta}$ associated with a change of substituent in the nucleophile indicate relatively advanced bond-formation in the transition state, (ⅱ) the potential energy surface model is able to predict the reaction mechanism, but it is unable to predict the transition state variation to a more product-like transition state, where bond-formation is much more progressed than bond breaking, upon changing the leaving group to that with better leaving ability (ⅲ) the quantum mechanical model predicted the product-like transition state and slightly better leaving ability of CN- as compared with Cl-.

• Journal of the Korean Society of Propulsion Engineers
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• v.19 no.5
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• pp.15-21
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• 2015

The thermal decomposition characteristics of the ZPP(Zirconium/Potassium perchlorate), widely used as a primary charge of initiators, were investigated by differential scanning calorimetry(DSC). The DSC results with different heating rates were elaborated with AKTS-Thermokinetics software for the determination of the kinetic parameters of the thermal decomposition of ZPP. There was good agreement between the experimental and the simulation curves, based on the determined kinetic parameters, which indicates the validity of the kinetic description of the thermal decomposition process of ZPP.

• Journal of the Korean Chemical Society
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• v.14 no.1
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• pp.45-48
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• 1970

The WLF equation is derived from the theory of rate processes in conjunction with the theory of liquids of significant structures. The empirical parameters in the WLF equation are discussed and compared with the corresponding quantities in the derived equation.

• Applied Biological Chemistry
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• v.38 no.5
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• pp.455-462
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• 1995

The new six herbicidal N-[(pyrimidin-2-yl)aminocarbonyl]-2-substituted-6-(1-hydroxy-2-fluoroethyl)benzenesulfonamide derivatives(S) were synthesized and rate constants for the hydrolysis of thier in the range of pH $1.0{\sim}10.0$ have been studied in 15%(v/v) aqueous acetonitrile solution at $45^{\circ}C$. From the basis of the results, pH-effect, solvent effect, ortho-substituent effect, thermodynamic parameters(${\Delta}H^{\neq}$ & ${\Delta}S^{\neq}$), pKa constant(4.80), rate equation, analysis of hydrolysis products(2-(1-hydroxy-2-fluoroethyl)benzenesulfonamide & 4,6-dimethoxyaminopyrimidine), it may be concluded that the general acid catalyzed hydrolysis through $A-S_E2$ mechanism and specific acid catalyzed hydrolysis through A-2 type(or $A_{AC}2$) mechanism proceeds via conjugate acid($SH^+$) and tetrahedral intermediate(I) below pH 8.0, whereas, above pH 9.0, the general base catalyzed hydrolysis by water molecules(B) through $(E_1)_{anion}$ mechanism proceeds via conjugate base(CB). In the range between $pH\;7.0{\sim}pH\;9.0$, these two reactions occur competitively.

• Journal of the Korean Chemical Society
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• v.24 no.6
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• pp.413-420
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• 1980

Die Geschwindigkeitskonstanten der Solvolyse-Reaktionen von 9-Chlormethylanthracen wurden bei verschiedenen Temperaturen in unterschiedlichen binadren Losungsmittelgemischen (Wasser/Aceton, Wasser/Acetonitril, Wasser/Methanol, Wasser/Athanol) mit Hilfe der Leitfahigkeitsmeßungen bestimmt. Die Aktivierungsparameter $E_a$, ${\Delta}H^{\neq}$ und ${\Delta}S^{\neq}$ wurden berechnet. Die Meßergebnisse deuten darauf hin, daß die Solvolyse von 9-Chlormethylanthracen in protonischen Losungsmitteln schneller ablauft als in aprotonischen Losungsmitteln; in den Meßreihen mit protonsichen bzw. mit aprotonischen Losungsmitteln steigt die Reaktionsgeschwindigkeit mit der Zunahme der Dielektrizitatskonstanten des Losungsmittels an, und die Aktivierungsparameter nehmen mit steigendem Wassergehalt zu. Es wurde festgestellt, daß die Reaktion nach einem $S_N1$-Mechanismus ablauft. Die experimentellen Daten deuten darauf hin, daß Wasser einerseits als Nucleophil und andererseits als allgemeine Base am Reaktionsmechanismus beteiligt ist.