• Journal of the Korean Chemical Society
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• v.50 no.1
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• pp.46-52
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• 2006

studies of olefin oxidation using Al(III)-porphyrin complexes as catalyst are investigated in CH2Cl2, in which NaClO is used as terminal oxidant. Porphyrins are TPP(5,10,15,20-Tetraphenylporphyrin) and (p-X)TPP(X=CH3O, CH3, F, Cl). Olefins are styrene and (p-X)styrene (X=CH3O, CH3, Cl, Br). The values of Km and Vmax are calculated from the Michaelis-Menten equation. According to the substituents of substrate and catalyst, kinetic parameters will be measured. Investigating the correlation between the Michaelis-Menten rate parameters and the substituent constants, we were able to analyze the influence on the changes of catalytic activity or the rate determining step during the process of the formation and the dissociation of the M-oxo-olefin.

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.179-182
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• 2011

Second-order rate constants ($k_{OH^-}$) have been measured spectrophotometrically for reactions of Y-substituted phenyl phenyl thionocarbonates (4a-i) with $OH^-$ in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The $k_{OH^-}$ values for the reactions of 4a-i have been compared with those reported previously for the corresponding reactions of Y-substituted phenyl phenyl carbonates (3a-i) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and mechanism. Thionocarbonates 4a-i are less reactive than the corresponding carbonates 3a-i although 4a-i are expected to be more reactive than 3a-i. The Bronsted-type plot for reactions of 4a-i is linear with $\beta_{lg}$ = -0.33, a typical $\beta_{lg}$ value for reactions reported to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step (RDS). Furthermore, the Hammett plot correlated with $\sigma^o$ constants results in much better linearity than that correlated with $\sigma^-$ constants, indicating that expulsion of the leaving group is not advanced in the RDS. Thus, alkaline hydrolysis of 4a-i has been concluded to proceed through a stepwise mechanism with formation of an intermediate being RDS, which is in contrast to the forced concerted mechanism reported for the corresponding reactions of 3a-i. Enhanced stability of the intermediate upon modification of the electrophilic center from C=O to C=S has been concluded to be responsible for the contrasting mechanisms.

• Journal of the Korean Chemical Society
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• v.41 no.2
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• pp.77-81
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• 1997

The transport rates of transition metal cations were increased in order of Ni(II)$(NtnOenH_4)$and 1,12,15-triaza-3,4;9,10-dibenzo-5,8-dioxacyclo-heptadecane$(NdienOenH_4)$as carriers. The transport rates of transition metal cations was found to be of first order to the salt concentrations. It was also found that the dissociation process in the transport process is rate determining step. From the measurements of the transport rates at various temperatures, the partition free energies of hydration$({\Delta}G_p)$for the transition metal cations were calculated. The results showed that the order of transport rates of transition metal cations was found to be proportional to the magnitudes of negative value of the partition free energies of hydration$({\Delta}G_p)$.

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.2913-2917
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• 2009

Second-order rate constants (k$_{Nu–}$) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-i) with butane-2,3-dione monoximate ($Ox^-\;an\;\alpha$-nucleophile) and Z-substituted phenoxides in 80 mol% H$_2$O/20 mol% DMSO at 25.0${\pm}$0.1$^{\circ}C$. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for reactions of 1a-h with Ox$^–$ exhibit many scattered points. In contrast, the Yukawa-Tsuno plot results in a good linear correlation with ${\rho}_Y$ = 2.20 and r = 0.45, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS). A stepwise mechanism with expulsion of the leaving-group being the RDS has been excluded, since Y-substituted phenoxides are less basic and better nucleofuges than Ox$^–$. Thus, the reactions have been concluded to proceed through a concerted mechanism. Ox$^–$ is over 10$^2$ times more reactive than its reference nucleophile, 4-chlorophenoxide (4-ClPhO$^–$). One might suggest that stabilization of the transition-state (TS) through intramolecular general acid/base catalysis is responsible for the ${\alpha}$-effect since such general acid/base catalysis is not possible for the corresponding reactions with 4-ClPhO$^–$. However, destabilization of the ground-state (GS) of Ox$^–$ has been concluded to be mainly responsible for the ${\alpha}$-effect found in this study on the basis of the fact that the magnitude of the ${\alpha}$-effect is independent of the nature of the substituent Y.

• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.49-53
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• 2013

Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2455-2460
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• 2013

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the nucleophilic displacement reactions of 4-nitrophenyl X-substituted-cinnamates (4a-4e) and Y-substituted-phenyl cinnamates (5a-5e) with Z-substituted-phenoxide anions in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 4a-4e with 4-chlorophenoxide (4-$ClPhO^-$) consists of two intersecting straight lines, which might be taken as a change in the rate-determining step (RDS). However, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of substrates possessing an electron-withdrawing group in the cinnamoyl moiety through resonance interactions, since the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}X=0.89$ and r = 0.58. The Br${\o}$nsted-type plot for the reactions of 4-nitrophenyl cinnamate (4c) with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.76$. The Br${\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (5a-5d) with 4-chlorophenoxides (4-$ClPhO^-$) is also linear with ${\beta}_{lg}=-0.72$. The Hammett plot correlated with ${\sigma}^-$ constants for the reactions of 5a-5d results in a much better linear correlation than that correlated with ${\sigma}^o$ constants, indicating that a partial negative charge develops on the O atom of the leaving aryloxide. Thus, the reactions have been concluded to proceed through a concerted mechanism.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2325-2329
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• 2013

Second-order rate constants $k_N$ have been measured for reactions of benzyl 2-pyridyl thionocarbonate (4b) and t-butyl 2-pyridyl thionocarbonate (5b) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 4b and 5b have been compared with those reported previously for the corresponding reactions of benzyl 2-pyridyl carbonate (4a) and t-butyl 2-pyridyl carbonate (5a) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and reaction mechanism. The thiono compound 4b is more reactive than its oxygen analogue 4a. The Br${\o}$nsted-type plots for the reactions of 4a and 4b are linear with ${\beta}_{nuc}=0.57$ and 0.37, respectively. The reactions of 4a were previously reported to proceed through a concerted mechanism, while those of 4b in this study have been concluded to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step on the basis of the ${\beta}_{nuc}$ value of 0.37. Enhanced polarizability upon changing the C=O in 4a by C=S has been suggested to be responsible for the reactivity order and the contrasting reaction mechanisms. In contrast, the reactivity of 5a and 5b is similar, but they are much less reactive than 4a and 4b. Furthermore, the reactions of 5a and 5b have been concluded to proceed through the same mechanism (i.e., a concerted mechanism) on the basis of linear Bronsted-type plots with ${\beta}_{nuc}=0.45$ or 0.47. It has been concluded that the strong steric hindrance exerted by the t-Bu in 5a and 5b causes a decrease in their reactivity and forces the reactions to proceed through a concerted mechanism.

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.418-424
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• 1984

Rate constants for the hydrolysis of cinnamonitrile in the concentration range of 1 ∼ 5M of perchloric acid at 25$^{\circ}$C have been determined by UV spectrophotometry and from the Bunnett equations, hydration parameters (${\omega}$ = 9.8, ${\omega}^*$ = 0.42 & ${\phi}$=1.6) were obtained. CNDO/2 MO calculations were performed to determine relative stability, net charges, and overlap population of various conformational isomers. The results show that the (E)-planar is more stable than the (Z)-planar and protonation is favored on the nitrogen atom. On the basis of above findings, the acid hydrolysis is initiated by the protonation of the nitrogen atom of cinnamonitrile and then water molecule acting as nucleophile and as a proton transfer agent in the rate determining step. In the transition state of the acid hydrolysis, nucleophilic addition of water molecule occurs by sigma approach to the positively charged $C_7({\alpha}$) atom of the conjugate acid. As the results, we may conclude that the hydrolysis of cinnamonitrile in the strong acidic media proceeds through the A-2 type mechanism.

• Journal of the Korean Chemical Society
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• v.32 no.3
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• pp.179-185
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• 1988

The reaction of VO_2\;^+$ with benzyl alcohol in perchloric acid and aqueous dimethylformamide leads to the formation of $VO^{2+}$ and benzaldehyde. The products, $VO^{2+}$ and benzaldehyde, are identified by infrared spectroscopy and gas chromatography. Kinetic studies on the reaction of VO_2\;^+$ with benzyl alcohol have been carried out using visible spectroscopy. The empirical rate equation can be expressed as $-d[VO_2\;^+]/dt=2\{\\{k_O+k_H[HClO_4]\}\[VO_2\;^+][C_6H_5CH_2OH]$ The rate determining step for the reaction is the process for the formation of $VO^{2+}$ and $C_6H_5CHOH$. The activation parameters are ${\Delta}H^{\neq}=13.32{\pm}1.73\;kcalmol^{-1}$ and ${\Delta}S^{\neq}=-31.02{\pm}0.09\;calmol^{-1}K^{-1}$ for the oxidation of benzyl alcohol in aqueous dimethylformamide.

• Membrane and Water Treatment
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• v.10 no.6
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• pp.471-484
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• 2019

The complex combination of organic contaminants in the wastewater made water treatment challenging; hence, organic matter in water bodies is usually measured in terms of organic carbon. Since it is important to identify the types of compounds when deciding suitable treatment methods, this study implemented a quantitative and qualitative analysis of the organic matter content in an actual graywater sample from Ulsan, Republic of Korea using mass spectroscopy (MS). The graywater was treated using adsorption to remove the organic contaminants. Using orbitrap MS, the organic matter content between an untreated graywater and the treated effluent were compared which yielded a significant formula count difference for the samples. It was revealed that CHON formula has the highest removal count. Isotherm studies found that the Freundlich equation was the best fit with a coefficient of determination ($R^2$) of 0.9705 indicating a heterogenous GAC surface with a multilayer characteristic. Kinetics experiments fit the pseudo-second order equation with an $R^2$ of 0.9998 implying that chemisorption is the rate-determining step between the organic compounds and GAC at rate constant of $52.53g/mg{\cdot}h$. At low temperatures, the reaction between GAC and organic compounds were found to be spontaneous and exothermic. The conditions for optimization were set to achieve a maximum DOC and TN removal which yielded removal percentages of 94.59% and 80.75% for the DOC and TN, respectively. The optimum parameter values are the following: pH 6.3, 2.46 g of GAC for every 30 mL of graywater sample, 23.39 hrs contact time and $38.6^{\circ}C$.