• Journal of the Korean Chemical Society
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• v.22 no.3
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• pp.111-116
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• 1978

The kinetics of phenylmethanesulfonyl chloride in methanol-water, ethanol-water, acetone-water and acetonitrile-water has been investigated. The rate was faster in protic solvents than in aprotic solvents while susceptibility of rate to the ionizing power, i. e., m of the Winstein plot and solvation number of the transition state were much smaller in protic solvents. This was considered in the light of initial state stabilization by hydrogen-bonding solvation of the protic solvents. It was concluded that the reaction proceeds by an $S_N2$ mechanism in which bond-formation precedes bond-breaking at the transition state in all solvent systems.

• Transactions of the Korean Society of Mechanical Engineers
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• v.10 no.6
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• pp.830-836
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• 1986

In this study, the effect of hydrogen absorbed in welding process on the fatigue behaviour of the weld bond was quantitatively made clear. The influence of cyclic loading rate on the fatigue characteristics of the manual arc weld bond was inspected under the condition of constant amount of hydrogen. Moreover, the fatigue cracking mechanism concerning the diffusible hydrogen in the welded part was discussed in connection with fractographs of the fracture surfaces.

• Macromolecular Research
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• v.14 no.3
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• pp.354-358
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• 2006

Polybutadiene (BR) was pyrolyzed at $540-860^{\circ}C$ and the effect of pyrolysis temperature on variations in the relative abundance of the major pyrolysis products (C4-, C5-, C6-, C7-, and C8-species) was investigated. Formation of the C4-, C5-, C6-, and C7-species competed with that of the C8-species. Relative intensity of the C8-species decreased with increasing pyrolysis temperature, while that of the C5-, C6-, and C7-species increased. Pyrolysis paths were became more complicated with increasing pyrolysis temperature. We suggested the operation of double bond migration and succeeding rearrangements for the formation of the C5- and C7-species and various rearrangements, including a double bond, for the formation of the C6-species at high temperature. The activation energies for the pyrolysis product ratios of(C5+C6+C7)/C4 and C8/C4 were used to explain the competition reactions to form the pyrolysis products.

• Bulletin of the Korean Chemical Society
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• v.20 no.6
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• pp.712-714
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• 1999

The rate constants for the nucleophilic addition of potassium cyanide to α,N-diphenylnitrone and its derivatives (p-OCH3, p-CH3, p-Cl, and p-NO2) were determined by ultraviolet spectrophotometer at 25℃, and the rate equations which can be applied over a wide pH range were obtained. On the basis of pH-rate profile, adduct analysis, general base catalysis and substituent effect, a plausible mechanism of this addition reaction was proposed: At high pH, the cyanide ion to carbon-nitrogen double bond was rate controlling, however, in acidic media, the reaction proceeded by the addition of hydrogen cyanide molecule to carbon-nitrogen double bond after protonation at oxygen of a,N-diphenylnitrone. In the range of neutral pH, these two reactions occured competitively.

• Bulletin of the Korean Chemical Society
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• v.18 no.9
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• pp.1010-1013
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• 1997

Nucleophilic substitution reactions of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines were investigated in acetonitrile at 60 ℃ under respective pressures. The magnitudes of the Hammett reaction constants, ρX, ρY and ρZ indicate that a stronger nucleophile leads to a greater degree of bond formation of C-N and a better leaving group is accompanied by a less degree of bond breaking. The magnitude of correlation interaction term, ρij can be used to determine the structure of the transition state (TS) for the SN reaction. As the pressure is increased, the Hammett reaction constants, ρX and |ρY|, are decreased, but correlation interaction coefficient, ρXZ and |ρYZ|, are increased. The results indicate that the reaction of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines probably moves from a dissociative SN2 to early-type concerted SN2 mechanism by increasing pressure. This result shows that the correlation interaction term ρij can be useful tool to determine the structure of TS, and also the sign of the product ρXZ·ρYZ can be predict the movement of the TS.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1172-1176
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• 1999

Nucleophilic substitution reaction of Y-benzyl bromide with X-pyridines are investigated in DMSO at 45.0℃. Biphasic rate dependence is observed on varying the substituents in the substrate (Y) as well as in the nucleophile (X). The two well-defined straight lines in the Hammett (ρy) and Bronsted ( βx) plots are interpreted to indicate the changes in transition-state structure, a decrease in bond cleavage as the substituent on the substrate is changed from electron-donors ( ρy < 0) to electron-acceptors ( ρy > 0), and an increase in the extent of bond formation with the corresponding changes of the substituent on the pyridine. A Jencks' type analysis of separate polar (ρ) and resonance (ρr) effects can also be accounted for by the change of the transition-state structure, not by the variable combination of polar and resonance effects.

• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.193-196
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• 1987

The gas phase pyrolyses of eight esters have been studied by MNDO-MO method. In the ethylformate pyrolysis, ${\alpha}$-methylation had a steric releasing effect whereas ${\beta}$-methylation had a steric crowding in the transition state; the latter, however, is over-compensated by a greater electronic repulsion resulting in a net steric releasing effect. Considerations of formal charges and geometrical changes involved in the activation led us to propose a pyrolysis mechanism in which a preequilibrium of acidic proton transfer is followed by the rate-limiting bond polarization of $C_{\alpha}$-O bond in a cyclic transition state.

• Bulletin of the Korean Chemical Society
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• v.12 no.3
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• pp.301-303
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• 1991

The rate constants for the nucleophilic addition of thiophenol to $\alpha$, N-diphenylnitrone and it's derivatives (p-$OCH_3$, p-Cl, p-$NO_2$) were determined from pH 3.0 to 13.0 by UV spectrophotometry and rate equations which can be applied over a wide pH range were obtained. On the basis of rate equation, general base and substituent effect a plausible addition mechanism of thiophenol to ${\alpha}$, N-diphenylnitrone was proposed: At high pH, the addition of sulfide ion to carbon-nitrogen double bond was rate controlling, however, in acidic solution, reaction was proceeded by the addition of thiophenol molecule to carbon-nitrogen double bond after protonation at oxygen of ${\alpha}$, N-diphenylnitrone.

• Bulletin of the Korean Chemical Society
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• v.3 no.4
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• pp.153-157
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• 1982

$C_4$-Photocycloaddition of 8-methoxypsoralen (8-MOP) and 5,7-dimethoxycoumarin (DMC) to maleimide was studied in order to elucidate the mechanism of the photobiological activities of these molecules. The photoreaction was carried out in chloroform solution and frozen aqueous solution state. The major product was isolated and characterized by spectroscopic methods. The photoadduct between 8-MOP and maleimide was shown to be an 1:1 $C_4$-cycloadduct through the photocycloaddition of 4',5'-furyl double bond of 8-MOP to maleimide. The stereochemistry of cyclobutane ring of this photoadduct is consistent with the anti configuration. The photoadduct between DMC and maleimide was shown to be an 1:1 $C_4$-cycloadduct through the photocycloaddition of 3,4-pyrone double bond of DMC to maleimide.

• Journal of the Korean GEO-environmental Society
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• v.23 no.1
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• pp.15-23
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• 2022

This paper presents the results of full-scale load tests performed frictional anchors to various lengths at several sites in Korea. Various rock types were tested, ranging from highly weathered shale to sound gneiss. In many tests, rock failure was reached and the ultimate loads were recorded along with observations of the shape and extent of the failure surface. Laboratory tests were also conducted to investigate the influence of the corrosion protection sheath on the bond strength. Based on test results, the main parameters governing the uplift capacity of the rock anchor system were determined. By evaluation of the ultimate uplift capacity of anchor foundations in a wide range of in situ rock masses, rock classification suitable for structural foundation was developed. Finally, a very simple and economical design procedure is proposed for rock anchor foundations subjected to uplift tensile loads.