• Bulletin of the Korean Chemical Society
• /
• v.31 no.6
• /
• pp.1726-1728
• /
• 2010

• Bulletin of the Korean Chemical Society
• /
• v.20 no.5
• /
• pp.577-580
• /
• 1999

Solvolyses of phenyl chlorothionoformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of firstorder rate constants for phenyl chlorothionoformate with Ycl (based on 2-adamantyl chloride) show a dispersion phenomenon, and also the extended Grunwald-Winstein plots show a poor correlation for the solvolyses of phenyl chlorothionoformate. The ring parameter (I) has been shown to give considerable improvement when it is added as an hI term to the original and extended Grunwald-Winstein correlations. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by the conjugation between the reaction center and the aromatic ring in the vicinity of the reaction center. This study has shown that the magnitude of l and m values associated with a change of solvent composition leads to predict the SN2 transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed SN2 mechanism.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.2
• /
• pp.519-523
• /
• 2012

A kinetic study is reported on nucleophilic displacement reactions of benzyl 2-pyridyl carbonate 6 with alkalimetal ethoxides, EtOM (M = Li, Na, and K), in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of pseudo-firstorder rate constant $k_{obsd}$ vs. [EtOM] curve upward, a typical phenomenon reported previously for alkaline ethanolysis of esters in which alkali-metal ions behave as a Lewis-acid catalyst. The kobsd value for the reaction of 6 with a fixed EtOK concentration decreases rapidly upon addition of 18-crown-6-ether (18C6), a complexing agent for $K^+$ ion up to [18C6]/[EtOK] = 1.0 and then remains constant thereafter, indicating that the catalytic effect exerted by K+ ion disappears in the presence of excess 18C6. The reactivity of EtOM towards 6 increases in the order $EtO^-$ < EtOLi < EtONa < EtOK, which is contrasting to the reactivity order reported for the corresponding reactions of 2-pyridyl benzoate 4, i.e., $EtO^-$ < EtOK < EtONa < EtOLi. Besides, 6 is 1.7 and 3.5 times more reactive than 4 towards dissociated $EtO^-$ and ion-paired EtOK, respectively. The reactivity difference and the contrasting metal-ion selectivity are discussed in terms of electronic effects and transition-state structures.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.6
• /
• pp.1217-1223
• /
• 2008

A series of Zr,S co-doped $TiO_2$ were synthesized by a modified sol-gel method and characterized by various spectroscopic and analytical techniques. The presence of sulfur caused a red-shift in the absorption band of $TiO_2$. Co-doping of sulfur and zirconium (Zr-$TiO_2$-S) improves the surface properties such as surface area, pore volume, and pore diameter and also enhances the thermal stability of the anatase phase. The Zr-$TiO_2$-S systems are very effective visible-light active catalysts for the degradation of toluene. All reactions follow pseudo firstorder kinetics with the decomposition rate reaching as high as 77% within 4 h. The catalytic activity decreases in the following order: Zr-$TiO_2$-S >$TiO_2$-S >Zr-$TiO_2$>$TiO_2$$\approx$ P-25, demonstrating the synergic effect of codoping with zirconium and sulfur. When the comparison is made within the series of Zr-$TiO_2$-S, the catalytic performance is found to be a function of Zr-contents as follows: 3 wt % Zr-TiO2-S >0.5 wt % Zr-$TiO_2$-S> 5 wt % Zr-$TiO_2$-S >1 wt % Zr-$TiO_2$-S. Higher calcination temperature decreases the reactivity of Zr-$TiO_2$-S.

• Journal of Korean Society of Environmental Engineers
• /
• v.31 no.3
• /
• pp.186-192
• /
• 2009

In this study, The effects of three different activated carbon materials (each coal, coconut and wood based activated carbons), empty bed contact time (EBCT) and water temperature on the removal of pharmaceutical 4 species (oxytetracycline, tetracycline, trimethoprime and caffeine) in BAC filters were investigated. Experiments were conducted at three water temperature (5, 15 and $25^{\circ}C$) and four EBCTs (5, 10, 15 and 20 min). The results indicated that coal based BAC retained more attached bacterial biomass on the surface of the activated carbon than the other BAC, increasing EBCT or increasing water temperature increased the pharmaceutical 4 species removal in BAC columns. In the coal-based BAC columns, removal efficiencies of oxytetracycline and tetracycline were 87~100% and removal efficiencies of trimethoprime and caffeine were 72~99% for EBCT 5~20 min at $25^{\circ}C$. The kinetic analysis suggested a firstorder reaction model for pharmaceutical 4 species removal at various water temperatures (5~$25^{\circ}C$). The pseudo-first-order reaction rate constants and half-lives were also calculated for pharmaceutical 4 species removal at 5~$25^{\circ}C$. The reaction rate and half-lives of pharmaceutical 4 species ranging from 0.0360~0.3954 $min^{-1}$ and 1.75 to 19.25 min various water temperatures and EBCTs, could be used to assist water utilities in designing and operating BAC filters.