• Journal of the Korean Chemical Society
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• v.17 no.2
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• pp.130-135
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• 1973

The rate-constants of hydrolysis of 3, 4-methylenedioxyphenylmethylenemalononitrile are determined by ultraviolet spectrophotometry at various pH and a rate equation which can be applied over wide pH range is obtained. The rate equation reveals that below pH 5.0 and above pH 9.0, the hydrolysis is initiated by the addition of water and hydroxide ion respectively. However, at pH 6.0-8.0 the competitive addition of water and hydroxide ion occurs. The catalytic contribution of hydroxide ion and water can be fully explained by the rate equation obtained.

• 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.36 no.2
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• pp.180-184
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• 1992

Kinetic studies for the reaction of pyridine with substituted benzoyl chlorides were conducted under various pressures (1-1000 bar) in acetonitrile. From rate constants, the activation parameters (${\Delta}V^{\neq}$, ${\Delta}{\beta}^{\neq}$,${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and ${\Delta}G^{\neq}$) were evaluated. Rates of these reaction increased with an increase in the pressure. The activation volume, the activation compressibility coefficient and the activation entropy were negative. From substituents effect and these results, it was found that these reactions proceed through $S_N2$ mechanism, but the structure of transition state was slightly changed with substituents and pressure.

• Journal of the Korean Chemical Society
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• v.34 no.1
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• pp.10-18
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• 1990

Solvolyses of p-substituted benzyl bromides have been studied in dimethylsulfoxide-water and N,N-dimethylformamide-water mixtures by kinetic method. To determine the ionizing power, Y and the nucleophilicity, $N_{BS}$, the solvolyses of 1-adamantyl halides, t-butyl halides, and methyl tosylate in the same solvent mixtures have been investigated. The solvatochromic parameters for each dimethylsulfoxide-water mixtures have been determined by substituting into the Taft's linear solvatochromic energy relationships with measured $ν_{max}$. The solvolyses of p-substituted benzyl bromides have been found to proceed by borderline mechanism in which bond formation is more advanced than bond cleavage in the transition state based on the m, l values and ${\beta},{\rho}_s$, values.

• Journal of the Korean Chemical Society
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• v.40 no.1
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• pp.11-19
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• 1996

The cationic polymerization of energetic substituted oxetanes which have pendant energetic group such as azido and nitrato are investigated theoretically, using semiempirical HF/3-21G, MINDO/3, MNDO and AM1 method. The stereo- and electronic structure of binary molecular complex composed of energetic substituted oxetane and boron trifluoride can be explain by molecular orbital theory. The reactivity of propagation in the copolymerization of oxetanes can be presented by the positive charge on carbon(C2) atom of oxetane and energy level of the lowest unoccupied molecular orbital(LUMO) of propagating species of oxetanes. The reactivity ratios for copolymerization of oxetanes are a random copolymer-zation which is agree with MO calculated and experimental results. The relative equlibrium concentration of cyclic oxonium and open carbenium ions is found to be a major determinant of mechanism, owing to the rapid equilibrium of these cation forms and the expectation based on calculation that in the prepolymer propagation step, SN1 mechanism will be at least as fast as that for SN2 mechanism.

• Journal of the Korean Chemical Society
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• v.30 no.5
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• pp.409-414
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• 1986

The reduction of $VO_2^+$ ion by ethanol in sulfuric acid leads to the formation of vanadyl sulfate. Spectrophotometric measurements on the solution containing products, vanadyl sulfate, are also reported. Kinetic studies on reduction of $VO_2^+$ by ethanol have been carried out at 35${\circ}C$ and 50${\circ}C$. The reaction mechanism for reduction of $VO_2^+$ is discussed.

• Journal of Korean Tunnelling and Underground Space Association
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• v.9 no.3
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• pp.299-307
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• 2007

In this study, a new concept for simulating a physical damage of tunnel shotcrete lining due to a long-term chemical deterioration has been proposed. It is known that the damage takes place mainly by internal cracks, reduction of stiffness and strength, which results mainly from volume expansion of the lining and corrosion of cement materials, respectively. This damage mechanism of shotcrete lining appears similar in most kinds of chemical reactions in tunnels. Therefore, the mechanical deterioration mechanism induced by a series of chemical reactions was generalized in this study and mathematically formulated in the framework of thermodynamics. The numerical model was implemented to a 3D finite element code, which can be used to simulate behaviour of tunnel structures undergoing external loads as well as chemical deterioration in time. A number of illustrative examples were given to show a feasibility of the model in tunnel designs.

• Journal of the Korean Chemical Society
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• v.40 no.2
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• pp.139-143
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• 1996

• Journal of the Korean Chemical Society
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• v.41 no.7
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• pp.351-356
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• 1997

Extended Huckel Molecular Orbital (EHMO) calculations of haloallene (1-halo-3-phenyl-1,2-propadiene) derivatives have been performed. From the MO calculation data and kinetic experimental results, the mechanism for the hydrolysis of haloallenes is proposed.; Below pH 8.0, the hydrolysis proceeds through a solvent assisted $S_N1$ mechanism involving the formation of carbonium ion Ⅱ as intermediate. However above pH 9.5, the hydrolysis proceeds through an $S_N2'$ mechanism via transition state Ⅲ.

• Proceedings of the Materials Research Society of Korea Conference
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• 1996.11a
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• pp.162-163
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• 1996