• Journal of the Korean Chemical Society
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• v.23 no.1
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• pp.37-41
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• 1979

The kinetics of the reaction of benzyl m-nitrobenzenesulfonate with m-and p-substituted N,N-dimethylanilines in acetone have been investigated by an electric conductivity method. The effects of substituents on the reactivity of N,N-dimethylaniline and the existence of linear free energy relationship were discussed. The rate constants k were in the range 2.55∼487 $10^{-4}l{\cdot}mol^{-l}{\cdot}sec^{-1} (35^{\circ}C)$ and increased with the electron donating ability of substituents. In the present reaction, the Hammett plot was correlated with ${\sigma}$ substituent constant, especially using the new ${\sigma}$ value of 0.35 in p-MeO and it's ${\rho}$ value was found to be -1.37. r value for the reaction was very large than the value obtained in the reaction of benzyl bromide. $Br{\"{o}}nsted$ linear relationship was shown between rate constant and basicites except for p-MeO resulted from solvent effect. From the Bronsted plot, this reaction was suggested that the cleavage of the C${\cdot}{\cdot}{\cdot}$O bond in the $S_N2$ transition state proceed the bond formation.

• Journal of the Korean Chemical Society
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• v.58 no.1
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• pp.17-24
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• 2014

The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile -80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [$H^+$] and ionic strength. The reaction is acid catalysed, the order with respect to [$H^+$] is unity and the active oxidizing species is found to be $HCrO_3^+$. The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of $HCrO_3^+$ forming a sulfonium ion intermediate. The intermediate then undergoes ${\alpha}$,${\beta}$-cleavage leading to the liberation of $CO_2$. The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log $k_2$ and Hammett ${\sigma}$ constants with a negative value of reaction constant. The ${\rho}$ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.

• Journal of Environmental Health Sciences
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• v.35 no.6
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• pp.532-537
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• 2009

The tropospheric ozone production mechanism for the gas phase additive oxidation reaction of hydroxyl radical (OH) with isoprene (2-methyl-1,3-butadiene) has been studied using cavity ring-down spectroscopy (CRDS) at total pressure of 50 Torr and 298 K. The applicability of CRDS was confirmed by monitoring the shorter (~4%) ringdown time in the presence of hydroxyl radical than the ring-down time without the photolysis of hydrogen peroxide. The reaction rate constant, $(9.8{\pm}0.1){\times}10^{-11}molecule^{-1}cm^3s^{-1}$, for the addition of OH to isoprene is in good agreement with previous studies. In the presence of $O_2$ and NO, hydroxyl radical cycling has been monitored and the simulation using the recommended elementary reaction rate constants as the basis to OH cycling curve gives reasonable fit to the data.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.343-347
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• 1990

A thermal decomposition of the tert-butoxy radical has been studied in the gas phase over the pressure range of 1-200 torr at $413_{\circ}K$ using di-tert-butyl peroxide + trimethylsilane mixtures. The relative rate constants were obtained by studying the competitive reactions between tert-butoxy radical decomposition 4(t-BuO·→ CH_3COCH_3 + CH_3·)$ and hydrogen abstraction reaction from trimethylsilane $(t-BuO·+ HSi(CH_3)_3 → t-BuOH + Si(CH_3)_3)·).$ The conventional RRKM calculations were carried out to compare the observed fall-off behavior of the decomposition rate constant $({\kappa}_d)$ with the theoretical predictions using reasonable values of input parameters. In all cases the calculated half-rate pressure $(P_{1/2})$ were significantly higher than those observed. The failure of RRKM to reproduce the fall-off behavior led us to suggest that not all of vibrational modes contribute to excitation (leading to decomposition) on the same time scale.

• Journal of Environmental Health Sciences
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• v.30 no.5 s.81
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• pp.358-365
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• 2004

The photocatalytic oxidation of Rhodamine B(RhB) was studied using photocatalytic reactor filled with module of quartz tube. Module of quartz tube consisted of small quartz tube (inner diameter, 1.5 mm; outer diameter, 3 mm) bundle coated with powder $TiO_2$ and uncoated large quartz tube (inner diameter, 20 mm; outer diameter, 22 mm). Two 30 W germicidal lamp was used as the light source and the reactor volume was 0.5 l. The effects of parameters such as the coating materials and numbers, initial concentration, $H_{2}O_2$ dose and metal deposition (Ag, Pt and Fe) and simultaneous application of $H_{2}O_2$ and metal deposition. The results showed that the initial reaction constant of quartz module coated with powder $TiO_2$ was higher 1.4 time than that of the $TiO_2$ sol and optimum coating number is twice. In order to increase reaction rate, simultaneous application of photocatalytic and photo-fenton reaction using Fe coating and dose $H_{2}O_2$ dose increased reaction rate largely.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 1993.05a
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• pp.33-41
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• 1993

The objectives of this experiment performed were to determine the potential using of solar radiation to destroy organic contaminants in water by photolysis and to develop the process and improve its performance. We used lab, scale of recirculation photoreactor with 30, 50, 80ppm initial concentration of TCE and Ti $O_2$ anatase, respectively. Adsorption constant, reaction constant were obtained and compared using the Langmuir-Hinshelwood kinetics equation. Ti $O_2$ anatase demonstrated the highest conversion ratio co TCE among Ti $O_2$ anatase, ZnO and F $e_2$ $O_3$ in this experiment. It was shown that in case of two component system, TCE+ phenol, as the concentration of phenol increased in the feed solution, TCE decomposition rate decreased.

• Environmental Engineering Research
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• v.13 no.1
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• pp.28-32
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• 2008

The photocatalytic treatment of water contaminated with 2,4,6-trinitrotoluene (TNT) was explored in bench-scale experiments in batch mode using a Pyrex tube coated with a thin film of $TiO_2$ located inside a photoreactor. The reactor was aerated by purging it with compressed air before initiating the photocatalytic reaction. The rate of TNT degradation approximated first-order kinetics. The reaction rate constant decreased as the TNT concentration increased from 25 to 100 mg/L, while the first-order kinetics could be modeled using a Langmuir adsorption isotherm. The addition of the organic reductants methanol and EDTA significantly enhanced the rate of TNT degradation, with optimum results in the presence of 20% methanol by volume. EDTA increased the rate of TNT removal by enhancing the role of the reductants.

• Bulletin of the Korean Chemical Society
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• v.7 no.6
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• pp.462-465
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• 1986

Kinetics and Mechanism of $N_2H_4-KBrO_3$ reaction in the presence of allyl alcohol have been studied. The pseudo-first order rate constant for gas evolution was found to be $10^{-4}{\sim}10^{-2}\;sec^{-1}\;at\;25.0{\pm}0.1^{\circ}C$, increasing with concentration of hydrogen ion. When concentrations of sulfuric acid and allyl alcohol are both sufficiently high, the following overall reaction explains experimental results reasonably well: $N_2H_4\;+\;BrO_3^-\;+\;H^+\;{\to}\;N_2\;+\;HOBr\;+\;2H_2O,\;CH_2\;=\;CHCH_2OH\;+\;HOBr\;{\to}\;CH_2-OHCHBrCH_2OH$. More complicated reaction mechanisms at lower acidity conditions have been contemplated.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1267-1269
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• 2010

The pure crystalline $Li_{1.1}V_{0.9}O_2$ powder has been prepared by a simple solid state reaction of $Li_2CO_3$ and $V_2O_3$ precursors under nitrogen gas containing 10 mol % hydrogen gas flow. The structure of $Li_{1.1}V_{0.9}O_2$ powder was analyzed using Xray diffraction (XRD) and scanning electron microscope (SEM). The stoichiometric $Li_{1.1}V_{0.9}O_2$ powder was used as anode active material for lithium secondary batteries. Its electrochemical properties were investigated by cyclic voltammetry and constant current methods using lithium foil electrode. The observed specific discharge capacity and charge capacity were 360 mAh/g and 260 mAh/g during the first cycle, respectively. In addition, the cyclic efficiency of this cell was 72.2% in the first cycle. The specific capacity of $Li_{1.1}V_{0.9}O_2$ anode rapidly declines as the current rate increases and retains only 30 % of the capacity of 0.1C rate at 1C rate. The crystallinity of the $Li_{1.1}V_{0.9}O_2$ anode decrease as discharge reaction proceeds. However, the relative intensity of main peaks was almost recovered when the cell was charged up to 1.5 V.

• Journal of Korean Society of Environmental Engineers
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• v.32 no.2
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• pp.219-226
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• 2010

In order to evaluate a removal characteristic of chloramphenicol, salicylic acid and ketoprofen according to dose of oxidants, $Cl_2$, $O_3$ and $O_3/H_2O_2$ are used as oxidants in this study. In case of that $Cl_2$ is used for oxidizing harmaceuticals, chloramphenicol, salicylic acid and ketoprofen is not removed entirely at $Cl_2$ dose rang of 0.5~5.0 mg/L for 60 min. However, removal tendency of salicylic acid is so obviously at $Cl_2$ dose higher than 1.0 mg/L. In addition, as $Cl_2$ dose and contact time increase, the removal rate of salicylic acid is enhanced. When $O_3$ is used as oxidant, chloramphenicol and ketoprofen is not eliminated at $O_3$ dose range of 0.2~2.0 mg/L. On the contrary, 30~70% of salicylic acid is removed at $O_3$ dose of 1.0~5.0 mg/L. Only 30% removal of salicylic acid is achieved at contact time of 5 min, however, the removal rate is enhanced remarkably at contact time over 10 min. In experiments using $O_3/H_2O_2$ as an oxidant, we can find that $O_3/H_2O_2$ is much more effective than $O_3$ only for removal of 3 pharmaceuticals, and the efficiency is raised according to increase of $H_2O_2$ dose. On reaction rate constant and half-life of 3 pharmaceuticals depending on $Cl_2$, $O_3$ and $O_3/H_2O_2$ dose, experiments using $O_3/H_2O_2$ show that oxidation of pharmaceuticals is less effective as the $H_2O_2/O_3$ ratio increases to above pproximately 1.0 related to reaction rate constant. An oxidation of salicylic acid by $Cl_2$ and $O_3$ particularly has a comparatively high reaction rate constant comparing $O_3/H_2O_2$, and thus salicylic acid is easily eliminated in oxidation processes.