• Journal of the Korean Ceramic Society
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• v.33 no.4
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• pp.379-384
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• 1996

The H2S sensing mechanism of CuO-SnO2 was confirmed by analyzing the electrical-resistance variation with temperature under an H2S atmosphere. While the resistance of CuO-SnO2 thick film at N2+H2S atmosphere was almost invariant with change in temperature it increased with increasing temperature for air +H2S atmos-phere. This behavior was analyzed using an equation derived from a basic assumption based on the H2S sensing mechanism proposed before. the experimental results are sufficiently explained with the equation derived which showed that the H2S sensing mechanism was reasonable. The equation also gave a detailed analysis and physical meaning to the behavior of the resistance variation with change in H2S concentration.

• Transactions of Materials Processing
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• v.15 no.2 s.83
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• pp.112-117
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• 2006

Sliding wear mechanism of a high nitrogen austenitic 18Cr-18Mn-2Mo-0.9N steel has been investigated. Dry sliding wear tests of the steel were carried out at various loads of IN-10N under a constant sliding speed condition of 0.15m/s against AISI 52100 bearing steel balls. Solution ($1050^{\circ}C$) and isothermal aging ($900^{\circ}C$) heat treatments were performed on the steel and the effect of the heat treatments on the wear was investigated. Wear rates of the solution-treated steel specimen remained low until 5N load, and then increased abruptly at loads above 5N. The rates of isothermally aged specimens were low and increased gradually with the applied load. Worn surfaces, their cross sections, and wear debris of the steel specimens were examined with a scanning electron microscopy. Phases of the heat-treated specimen and the wear debris were identified using XRD. The transformed phase underneath a sliding track was investigated and analyzed using a TEM. Effects of the phase transformation during the wear and $Cr_{2}N$ precipitates formed during the isothermal aging on the wear of the austenitic steel were discussed.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4117-4121
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• 2012

The solvolysis rate constants of allyl chloroformate ($CH_2=CHCH_2OCOCl$, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with the sensitivity values of $0.93{\pm}0.05$ and $0.41{\pm}0.02$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.5 to 13.4 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -34.4 to -37.3 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.16 was also in accord with the $S_N2$ mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.

• Proceedings of the Korean Society for Technology of Plasticity Conference
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• 2005.10a
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• pp.105-108
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• 2005

Sliding wear mechanism of a high nitrogen austenitic 18Cr-18Mn-2Mo-0.9N steel has been investigated. Dry sliding wear tests of the steel were carried out at various loads of 1N-10N under a constant sliding speed condition of 0.15m/s against AISI 52100 bearing steel balls. Solution $(1050^{\circ}C)$ and isothermal aging $(900^{\circ}C)$ heat treatments were performed on the steel and the effect of the heat treatments on the wear were investigated. Wear rates of the solution-treated steel specimen remained low until 5N, and then increased abruptly at loads above 5N. The rates of isothermally aged specimens were low and increased gradually with the applied load. Worn surfaces, their cross sections, and wear debris of the steel specimens were examined with a scanning electron microscopy. Phases of the heat-treated specimen and the wear debris were identified using XRD. Phases transformed underneath the sliding track during the wear were investigated and analyzed using TEM. Effects of the phase transformation during the wear and $Cr_2N$ precipitates formed during the isothermal aging on the wear of the austenitic steel were discussed.

• 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.

• Journal of the Korean Chemical Society
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• v.49 no.6
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• pp.554-559
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• 2005

• Journal of the Korean Chemical Society
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• v.41 no.6
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• pp.313-319
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• 1997

Diazidophenylmethane derivatives(X: p-H, $p-OCH_3,\;p-F,\;p-CH_3$) were synthesized and the rate constants of hydrolysis of diazidophenylmethane derivatives were determined by UV spectrophotometry in 50:50(v/v) aqueous methanol at 25$^{\circ}C$. On the basis of rate equation, substituent effect, activation parameters, solvent effect, salt effect, and product analysis, it may be concluded that the hydrolysis of diazidophenylmethane derivatives proceed through $S_N2_CA$ mechanism below pH 2.0, while above pH 12.0 through $S_N2$ mechanism, and in the range of pH from 2 to 12 through $S_N1$ mechanism respectively.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2413-2418
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• 2009

Rates of solvolyses of 4-nitrophenyl phenyl thiophosphorochloridate (4-N$O_2$PhOP(S)(Cl)OPh, $\underline{1}$) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, and 2,2,2-trifluroethanol (TFE) are reported. Thermodynamic parameters were determined at several temperatures in three representative solvents. The extended Grunwald-Winstein equation was applied to 29 solvents and the correlation coefficient (R) showed 0.959. The sensitivities (l = 1.37 and m = 0.62) are similar to those obtained for diphenyl thiophosphorochloridate (($PhO)_2$PSCl, $\underline{2}$), diphenyl phosphorochloridate (($PhO)_2$POCl, $\underline{3}$), diphenyl phosphinic chloride ($Ph_2$POCl, $\underline{4}$), and diphenyl thiophosphinic chloride ($Ph_2$PSCl, $\underline{5}$). The solvolytic reaction mechanism of 4-nitrophenyl phenyl thiophosphorochloridate ($\underline{1}$) is suggested to be proceeded a $S_N$2 process as previously reported result. The activation enthalpies are shown as slightly low as ${\Delta}H^{\neq}\;=\;9.62\;to\;11.9\;kcal{\cdot}mol^{-1}$ and the activation entropies are shown as slightly high negative value as ${\Delta}S^{\neq}\;=\;-34.1\;to\;-44.9\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$ compared to the expected $S_N$2 reaction mechanism. Kinetic solvent isotope effects are accord with a typical $S_N$2 mechanism as shown in the range of 2.41 in MeOH/ MeOD and 2.57 in $H_2O/D_2O$ solvent mixtures.

• 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.

• Journal of the Korean Chemical Society
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• v.23 no.6
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• pp.368-373
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• 1979

Kinetic studies have been carried out on solvolyses and halide exchanges $(Cl^-,\;Br^-,\;I^-)$ of N,N-dimethyl-, N,N-diethylcarbamoyl chlorides, and solvolyses of N,N-diphenylcarbamoyl chloride. Kinetic results together with simple MO analysis indicated that: (a) N,N-dialkylcarbamoyl chlorides reacted via the $S_N2$ mechanism, while N,N-diphenylcarbamoylchloride reacted via the $S_N1$ mechanism; (b) in chloride exchanges, the bond-breaking appeared to be important, whereas in bromide and iodide exchanges, the bond-formation was shown to be important.