• Bulletin of the Korean Chemical Society
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• v.22 no.8
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• pp.842-846
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• 2001

Solvolyses of N-methyl-N-phenylcarbamoyl chlorides in aqueous binary mixtures of acetone, ethanol, methanol and in water, D2O, and 50% D2O-CH3OD are investigated at 25.0 $^{\circ}C.$ The Grunwald-Winstein plots of first-ord er rate constants for N-methyl-N-phenylcarbamoyl chlorides with YCl (based on 2-adamantyl chloride) show a dispersion phenomenon. The ring parameter (I) has been shown to give considerable improvement when it is added as an hI term to the original Grunwald-Winstein and extended Grunwald-Winstein correlations for the solvolyses of N-methyl-N-phenylcarbamoyl chlorides. This study has shown that the magnitude of l, m and h values associated with a change of solvent composition is able to predict the dissociative SN2 transition state. The kinetic solvent isotope effects determined in deuterated water are consistent with the proposed mechanism of the general base catalyzed and/or a dissociative SN2 mechanism channel for N-methyl-N-phenylcarbamoyl chlorides solvolyses.

• 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 Ceramic Society
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• v.39 no.3
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• pp.217-221
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• 2002

Si and ${\alpha}-Si_3N_4$ powder mixtures added with 3 wt% $Y_2O_3$ were reacted under 5 MPa nitrogen pressure. The reaction products contained ${\alpha}-Si_3N_4$ particles with elongated shapes. Length and width of the elongated grains were the maximum when the starting powder mixture of 50 wt% Si - 47 wt% ${\alpha}-Si_3N_4$ and 3 wt% $Y_2O_3$ was used. Aspect ratio of the elongated grains were between 4.4 and 5. When the starting powder mixture contained 70 wt% Si, large particles with irregular shapes appeared. Meanwhile, the reaction did not proceed when the starting powder mixture contained 30 wt% Si and less. The SHS product was easy to crush and the elongated particles obtained from the starting powder mixtures of 40 wt% Si - 57 wt% ${\alpha}-Si_3N_4$ - 3 wt% $Y_2O_3$ and 50 wt% Si - 47 wt% ${\alpha}-Si_3N_4$ - 3 wt% $Y_2O_3$ were good candidates for the seeds.

• Journal of the Korean Society of Combustion
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• v.10 no.4
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• pp.33-40
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• 2005

The propagation rates of advancing and retreating non-premixed edge flames in a slot-jet counterflow were measured as a function of strain rate for varying jet spacing, mixture strength, stoichiometric mixture fractions $(Z_{st})$ and Lewis numbers (Le). Methane and propane fuels were tested and nitrogen and carbon dioxide were used as inerts. As results, we could identify igniting fronts, retreating fronts, two total extinction limits, and short-length edge flames. A burner separation affected to a low extinction limit only. Regimes for advancing and retreating edges together with total extinction were mapped in terms of normalized flame thickness and heat loss factor for $CH_4/O_2/N_2$ mixtures. Edge flames for $Z_{st}$ > 0.5 behaved like a stronger mixture while for $Z_{st}$ < 0.5 showed deteriorated feature, because of relative locations of a non-premixed flame and intermediate species such as CO and $H_2$. Furthermore, due to the relative importance of heat loss, propagating speeds of edge flames were significantly enhanced in $CH_4/O_2/CO_2$ mixtures (Le < 1) demonstrating increasing stability limits. However $C_3H_8/O_2/N_2$ mixtures (Le > 1) showed opposite result.

• Bulletin of the Korean Chemical Society
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• v.20 no.12
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• pp.1451-1456
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• 1999

Solvolyses of α-methoxy-α-(trifluoromethyl)phenylacetyl chloride in H₂O, D₂O, CH₃OD, 50% D₂O-CH₃OD, and in aqueous binary mixtures of acetone, dioxane, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of first-order rate constants for α-methoxy- α-(trifluoromethyl)phenylacetyl chloride with $Y_{Cl}$ show a dispersion phenomenon. Solvent nucleophilicity N has been shown to give considerable im-provement when it is added as an 1N term to the original Grunwald-Winstein for the solvolyses of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by solvent nucleophilicity. The magnitude of l and m values associated with a change of solvent composition predicts the associative $S_N2$ transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed associative $S_N2$ or $S_AN$ mechanism for the of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride.

• Journal of the Korean Chemical Society
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• v.63 no.3
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• pp.160-165
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• 2019

A series of reactions between an amino alcoholic ligand, cis-2-((2-((2-hydroxyethyl)amino)ethyl)amino)cyclohexan-1-ol (HEAC), with the mixtures of group 12 metals including, $HgCl_2/CdCl_2$, $HgCl_2/CdI_2$, $ZnCl_2/CdCl_2$ and $ZnCl_2/CdCl_2/HgCl_2$ was experimentally and theoretically studied to determine the most stable product of these reactions. Furthermore, the Cambridge Structural Database (CSD) studies were done to evaluate the theoretical results. The products were characterized by elemental analysis, FT-IR, Raman, $^1H$ NMR spectroscopy and single-crystal X-ray diffraction. Based on these investigations a binuclear structure of cadmium, [$Cd_2(HEAC)_2({\mu}-Cl)_2Cl_2$] (1), is the most stable product that was formed in all studied reactions between HEAC and metals mixtures. In this structure, the cadmium atom has a $CdN_2O({\mu}-Cl)_2Cl$ environment and distorted octahedral geometry.

• JSTS:Journal of Semiconductor Technology and Science
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• v.1 no.4
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• pp.197-201
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• 2001

The influence of argon, oxygen, and nitrogen admixtures on the dissociation of $Cl_2$ molecules in a glow discharge low-temperature plasma under the constant pressure conditions was investigated. For $Cl_2/Ar$ and $Cl_2/O_2$mixtures, the concentration of chlorine atoms was observed to be a practically constant at argon or oxygen concentrations up to 50%. This invariability is a most pro bably explained by relative increase in rate of $Cl_2$ direct electron impact dissociation due to the changes in electrophysical parameters of plasma such as EEDF, electron drift rate and mean energy. For all the considered mixtures, the contribution of stepwise dissociation involving active species from gas additives (metastable atoms and molecules, vibrationally excited molecules) was found to be negligible.

• 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 Ceramic Society
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• v.29 no.11
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• pp.837-842
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• 1992

SiC and Si mixtures dispersed by 0.5~10.0 wt% of Al2O3 and reinforced by SiC whisker were sintered to Si3N4 bonded SiC bodies at 140$0^{\circ}C$ in a N2 gas atmosphere, and the nitridation and mechanical properties of sintered bodies were investigated. From these observation, it is concluded that relative density and bending strength increased with the rising of nitridation and the highest nitridation ratio was obtained for a specimen having 1.5 wt% Al2O3. On the other hand, the amount of $\beta$-Si3N4 in the specimens containing Al2O3 more than 5.0 wt% was increased abruptly and the best in fracture toughness was sintered for a composits having 30 wt% SiC whiskers.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.26 no.4
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• pp.555-560
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• 2002

Numerical simulations of freely propagating flames burning stoichiometric CH$_4$/O$_2$/$N_2$mixtures are performed at atmospheric pressure in order to understand the effect of the $O_2$enrichment level on CH$_4$/Air flame. A chemical kinetic mechanism is employed, the adopted scheme involving 54 gas-phase species and 632 forward reactions. The calculated flame speeds are compared with the experiments for the flames established at several $O_2$enrichment level, the results of which is in excellent agreement. As a result of the increased $O_2$enrichment level from 0.21 to 1, the mole fraction of CO in the burred gas is increased. The flame speed and the temperature in the burned gas are also increased, but the thickness of the flame is severely shrunken in the preheat region. The maximum of the calculated EINO is obtained around 0.6 and 0.7 of the $O_2$enrichment level in cases of flames for fuel-lean mixtures.