• Journal of the Korean Chemical Society
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• v.46 no.4
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• pp.323-330
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• 2002

The protonation equilibrium of 5-substituted 2-furaldehydes is investigated spectrophotometrically in aqueous sulfuric acid at $25^{\circ}C$ and the basicity constants(p$K_{BH+}$) of the substrates is calculated by means of the excess acidity method. The basicity constant of 5-metyl-2-furaldehyde having electron donating group is larger than that of 5- nitro-2-furaldehyde having electron withdrawing group. Difference between the basicity constants(p$K_{BH+}$) of these two compounds was about 3.25 pK unit. The m value which is the degree of solvation of the protonated substrate is similar to that of acetophenone having same protonation site. The dependence of p$K_{BH+}$ on m value shows good linear cor-relation.

• Carbon letters
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• v.2 no.1
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• pp.15-21
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• 2001

In this work, activated carbon fibers (ACFs) were plated with copper metal using electroless plating method and the effects of surface properties and pore structures on chromium adsorption properties were investigated. Surface properties of ACFs have been characterized using pH and acid/base values. BET data with $N_2$ adsorption were used to obtain the structural parameters of ACFs. The electroless copper plating did significantly lead to a decrease in the surface acidity or to an increase in the surface basicity of ACFs. However, all of the samples possessed a well-developed micropore. The adsorption capacity of Cr(III) for the electroless Cu-plated ACFs was higher than that of the as-received, whereas the adsorption capacity of Cr(VI) for the former was lower than that of the latter. The adsorption rate constants ($K_1$, $K_2$, and $K_3$) were also evaluated from chromium adsorption isotherms. It was found that $K_1$ constant for Cr(III) adsorption depended largely on surface basicity. The increase of Cr(III) adsorption and the decrease of Cr(VI) adsorption were attributed to the formation of metal oxides on ACFs, resulting in increasing the surface basicity.

• Journal of the Korean Applied Science and Technology
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• v.9 no.2
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• pp.141-148
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• 1992

Transesterification reactions (methyl methacrylate with diethanolamine, ethylene glycol with dimethylphthalate) were kinetically investigated in the presence of zinc compound catalysts at $120{\sim}170^{\circ}C$ The amount of reactants was measured by gas chromatography. and the reaction rates also measured from the amount of reaction products and reactants upon each catalyst. The transesterification reactions were carried out under the first order conditions respect to the concentration of reactants, respectively, The overall reaction order was 2nd. The apparent rate constant (k') was found to obey first kinetics with respect to the concentration of catalyst. It shows that according to an increase in basicity of anionic species the rate constant increase, and that a linear relationship exists between ln k and pKa in transesterification reaction of methyl methacrylate with diethanolamine.

• Bulletin of the Korean Chemical Society
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• v.31 no.8
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• pp.2357-2360
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• 2010

Kinetic studies on the pyridinolysis of aryl dithiocyclopentanecarboxyaltes 2 were carried out at $60.0^{\circ}C$ in acetonitrile. In the aminolysis of 2, the $\beta_X$ values were 0.5 - 0.8 with anilines, and there was no breakpoint. However, in the pyridinolysis of 2, biphasic Bronsted plots were obtained, with a change in slope from a large value ($\beta_X{\cong}0.7$) to a small value ($\beta_X{\cong}0.4$) at $pK_{a}^0$ = 5.2. This was attributed to a change in the rate-limiting step from breakdown to the formation of a zwitterionic tetrahedral intermediate, $T^{\pm}$, in the reaction path, with an increase in the basicity of the pyridine nucleophile. An obvious change in the cross-interaction constant ${\rho}_{XZ}$ from a large positive ($\rho_{XZ}$ = +1.02) value to a small negative value (${\rho}_{XZ}$ = -0.17) supports the proposed mechanistic change.

• Bulletin of the Korean Chemical Society
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• v.27 no.12
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• pp.2011-2018
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• 2006

We have investigated the solvent effects on $\Delta log\;K_s $(the difference of stability constant of binding) and the different free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, i.e., the selectivity of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 using a Monte Carlo simulation of statistical perturbation theory (SPT) in diverse solvents. The stability constant ($\Delta log\;K_s $) of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, in $CH_3OH$ was calculated in this study as -1.06 agrees well with the different experimental results of -0.44~-0.6, respectively. We have reported here the quantitative solvent-polarity relationships (QSPR) studied on the solvent effects the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6. From the calculated coefficients of QSPR, we have noted that solvent polarity (ET) and Kamlet -Tafts solvatochromic parameters (b ) dominate the differences in relative solvation Gibbs free energies of $Nd^{3+}$ and $Eu^{3+}$ ions but basicity (Bj) dominates the negative values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 and acidity (Aj) dominates the positive values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6.

• Bulletin of the Korean Chemical Society
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• v.25 no.7
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• pp.1041-1045
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• 2004

Kinetic studies of the pyridinolysis $(XC_5H_4N)$ of aryl dithiomethylacetates $(CH_3CH_2C(=S)SC_6H_4Z,\;1)$ are carried out in acetonitrile at $60.0^{\circ}C$. A biphasic Bronsted plot is obtained with a change in slope from a large $({\beta}X\;{\cong}\;0.8)$ to a small $({\beta}X\;{\cong}\;0.2)$ value at $pK_a^{\circ}$ = 5.2, which is attributed to a change in the rate limiting step from breakdown to formation of a zwitterionic tetrahedral intermediate, $T^{\pm}$, in reaction path as the basicity of the pyridine nucleophile increases. This mechanism is supported by the change of the cross-interaction constant ${\rho}xz$ from a large positive ( ${\rho}xz$ = +1.36) for the weakly basic pyridines to a small negative ( ${\rho}_xz$ = -0.22) value for the strongly basic pyridines. The magnitudes of ${\rho}z$ and activation parameters are also consistent with the proposed mechanism.

• Journal of the Korean Chemical Society
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• v.16 no.3
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• pp.149-156
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• 1972

The responsive characteristics of hydrogen-responsive glass electrode in various buffer solutions of methanol, N,N-dimethylformamide and acetonitrile were examined. The potentials were attained more rapidly with an electrode stored in the same solvent medium than that stored in water before use. However, the time to be required for a stable potential increased with the basicity of buffer solution, and it was not provide a constant potential in the strong basic solution of these solvent. Even in acidic solution, the potential was varied according to the past usage of the electrode.

• Journal of the Korean Chemical Society
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• v.10 no.1
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• pp.15-17
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• 1966

Intermolecular hydrogen-bonding between phenol and N,N'-dimethylanilines (DMA) has been studied by infrared spectrophotometry. Results show that DMA acts as n-and ${\pi}$-donor although n-complex predominates. O-H stretching frequency shifts (${\Delta}{\nu}$) were proportional to basicitys of DMA and excellent linearity was observed between ${\Delta}{\nu}$ and the Hammett substituent constant, ${\sigma}$.

• Bulletin of the Korean Chemical Society
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• v.25 no.2
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• pp.203-206
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• 2004

The kinetics of reactions between Z-aryl thiophene-2-carbodithioates and X-pyridines in acetonitrile at 60.0 $^{\circ}C$ have been investigated. The Bronsted plots obtained for the pyridinolysis of aryl thiophene-2-carbodithioates are curved, with the center of curvature at $pK_a$ ~ 5.2 ($pK_a^{\circ}$). The Bronsted plots for these nucleophilic reactions show a change in slope from a large ( ${\beta}_X{\cong}$0.78-0.87) to a small ( ${\beta}_X{\cong}$0.33-0.35) value, which can be attributed to a change in the rate-determining step from breakdown to formation of a zwitterionic tetrahedral intermediate in the reaction path as the basicity of the pyridine nucleophile increases. A clear-cut change in the crossinteraction constants, ${\rho}_{XZ}$, from +0.92 to -0.23 supports the proposed mechanistic change. The breakpoint at $pK_a$ = 5.2 for R = thiophene ring in the present work is in agreement with those for the pyridinolysis of R = Me and 2-furyl, and attests to the insignificant effects of acyl group, R, on the breakpoint.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2405-2408
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• 2007

Oxidation of alkylaromatics including toluene and p-methoxytoluene has been carried out over alkali metal (AM)-containing catalysts such as AM-V/TiO2 and AM-VSb/Al2O3 in vapor-phase using oxygen as an oxidant. The selectivity for partial oxidations increases with incorporation of an alkali metal or with increasing the basicity of alkali metals (from Na to Cs), irrespective of the supports or reactants. However, the conversion is nearly constant or slightly decreasing with the addition of alkali metals in the catalyst. The increased selectivity may be related with the decreased acidity even though more detailed work is necessary to understand the effect of alkali metals in the oxidation. The AM-VSb/Al2O3 may be suggested as a potential selective catalyst for vapor-phase oxidations.