• Bulletin of the Korean Chemical Society
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• v.16 no.7
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• pp.595-600
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• 1995

The kinetics of the reaction between O(3P) and C2H4 was investigated by measuring time-dependent concentrations of OH resulting from the reaction by using the LIF detection. Oxygen atoms were generated by titrating microwave discharged N2/He with NO to the chemiluminescent end point. The operating pressures in the flow reactor ranged from 5 to 15 torr and the mixtures consisted of He/O(3/P)/C2H4 in the approximate ratios from 100/1/0.1 to 100/1/1. The controlled residence time prior to the detection were estimated to be 0.8-17 ms at the reactor pressure of 7 torr. Experimentally determined profiles both in shape and magnitude were compared with the computed OH density for a specified set of experimental parameters, allowing us to arrive at a complete mechanism for the reaction of O(3P) with ethylene.

• Bulletin of the Korean Chemical Society
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• v.6 no.6
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• pp.362-366
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• 1985

The hydrogen atom transfer reaction between substituted methane, $CH_3X,$ and its radical, $CH_2X(X=H,F,CH_3,CN,OH\;and\;NH_2$ was studied by MINDO/3 method. The transition state(TS) structure and energy barriers were determined and variation of the transition state and of the reactivity due to the change of X were analyzed based on the potential energy surface characteristics. It was found that the greater the radical stabilization energy. the looser the TS becomes; the TS occurs at about 15% stretch of the C-H bond, which becomes longer as the radical stabilization energy of $CH_2X$ increasers. The intrinsic barrier, ${\Delta}E*_{x.x},$ of the reaction with X was found to increase in the order $H The degree of bond stretch of the C-H bond stretch of the C-H bond at the TS also had the same order indicating that the homolytic bond cleavage of the C-H bond is rate-determining. Orbital interactions at the TS between LUMO of the fragment $C{\ldots}H{\ldots}C$ and the symmetry adapted pair of nonbonding, $n{\pm}(=n_1{\pm}n_2),$ or pi orbitals of the two X atoms were shown to be the dominant contribution in determining tightness or looseness of the TS. The Marcus equation was shown to apply to the MINDO/3 barriers and energy changes of the reaction.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2135-2138
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• 2014

A kinetic study is reported for the SNAr reaction of 1-Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1h) with OH- in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The second-order rate constant ($k_{OH^-}$) increases as the substituent Y in the leaving group changes from an electron-donating group (EDG) to an electronwithdrawing group (EWG). The Br${\o}$nsted-type plot for the reactions of 1a-1h is linear with ${\beta}_{lg}$ = -0.16, indicating that the reactivity of substrates 1a-1h is little affected by the leaving-group basicity. A linear Br${\o}$nsted-type plot with ${\beta}_{lg}=-0.3{\pm}0.1$ is typical for reactions reported previously to proceed through a stepwise mechanism in which formation of a Meisenheimer complex is the rate-determining step (RDS). The Hammett plot correlated with ${\sigma}_Y{^{\circ}}$ constants results in a much better correlation than that correlated with ${\sigma}_Y{^-}$constants, implyng that no negative charge is developing on the O atom of the leaving group (or expulsion of the leaving group is not advanced at all in the TS). This excludes a possibility that the $S_NAr$ reaction of 1a-1h with $OH^-$ proceeds through a concerted mechanism or via a stepwise pathway with expulsion of the leaving group being the RDS. Thus, the current reactions have been concluded to proceed through a stepwise mechanism in which expulsion of the leaving group occurs rapidly after the RDS.

• Bulletin of the Korean Chemical Society
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• v.25 no.10
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• pp.1538-1544
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• 2004

Fragmentations and proton transfer reactions of mono-, di-, and triethanolamines were studied using FTMS. It was found that the most abundant fragment ion was $[M-CH_2OH]^+$. The $[M-CH_2OH-H_2O]^+$ was observed in the mass spectra of diethanolamine and triethanolamine. By increasing the ion trapping time in the ICR cell, the $[M+H]^+$ and $[M+H-H_2O]^+$ ions were notably increased for all the samples while the $[M+H-2H_2O]^+$ was observed in the mass spectra of diethanolamine and triethanolamine. The proton transfer reactions between the fragment ions and neutral molecules occurred predominantly by increasing the ion trapping time. The rate constants for the proton transfer reactions were calculated from experimental results. The proton transfer reaction of $CHO^+$ was the fastest one, which is consistent with the heats of reaction. The rate constants for proton transfer reactions of triethanolamine were much slower than those of ethanolamine and diethanolamine because of the steric hindered structure of triethanolamine. The plausible structures of observed ions and heats of reaction for proton transfer were calculated with AM1 semiempirical method.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.429-434
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• 2009

The OH($X^2{\Pi},\;{\nu}$"=0, 1) internal state distributions from the reaction of electronically ground state oxygen atoms with HSi$Cl_3$ were measured using laser-induced fluorescence. The ground-state O$(^3P_J)$ atoms with kinetic energies above the reaction barrier were produced by photolysis of N$O_2$ at 355 nm. The OH product revealed strong vibrational population inversion, P(${\nu}$"=1)/P(${\nu}$"=0) = 4.0 ${\pm}$ 0.6, and rotational distributions in both vibrational states exhibit substantial rotational excitations to the limit of total available energy. However, no preferential populations in either of the two $\Lambda$ doublet states were observed from the micropopulations, which supports a mechanism involving a direct abstraction of hydrogen by the atomic oxygen. It was also found that the collision energy between O and HSi$Cl_3$ is effectively coupled into the excitation of the internal degrees of freedom of the OH product ($$ = 0.62, and $<\;f_{rot}>$ = 0.20). The dynamics appear consistent with expectations for the kinematically constrained reaction which supports the reaction type, heavy + light-heavy $\rightarrow$ heavy-light + heavy (H + LH′ $\rightarrow$ HL + H′). The dynamics of oxygen atom collision with HSi$Cl_3$ are discussed in comparison to those with Si$H_4$.

• Journal of the Korean Ceramic Society
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• v.24 no.5
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• pp.500-506
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• 1987

In order to synthesize monodispersed spherical silica fine particles, we investigated the reaction of hydrolysis of 0.05∼4.0 mole Si(OC2H5)4-0.01∼7.60mole NH3 -0.24∼38.40 mole H2O-2.62∼16.88mole C2H5OH systems. The range of the composition of solution which spherical silica particles were formed was enlarged according to an increase in concentration of Si(OC2H5)4. Larger particles were obtained at higher molar ratios of Si(OC2H5)4/C2H5OH, NH3/H2O and H2O/Si(OC2H5)4 and at a lower reaction temperature.

• Journal of the Korean Society of Combustion
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• v.4 no.1
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• pp.27-38
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• 1999

We constructed a wire-cylinder type pulsed corona discharge system for $NO_x$ removal, which was operated in room temperature. A emission spectrometer was built with a boxcar averager and monochrometer equipped with photo-multiplier tube detector. The sensitivity of the emission spectrometer was greatly improved by synchronizing the emission spectrometer with pulsed corona discharge system using a triggered spark-gap switch. $N_2$ spectrum($c^3{\Pi}_u{\rightarrow}X^1{\Sigma}_g{^+}$) was measured in the range of 300 - 450 nm and oxidizing OH radical emission($A^2{\Sigma}^+{\rightarrow}X^2{\Pi}$) was measured in case $N_2$ was supplied with water bubbling. As wet gas composition of inlet $N_2$ supplied in the discharge system increased, the intensity of OH emission was increased and saturated at wet gas composition 50%. We also investigated additive effect of $C_2H_4,\;H_2O,\;H_2O_2$ on the intensity of OR emission and $NO/NO_2/NO_x$ reduction and analysed the related reaction mechanism in corona discharge process. $H_2O_2$ additive increased the intensity of OH emission and $NO/NO_x$ reduction.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.2
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• pp.184-190
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• 2005

A new VFAs production process from sewage sludge using Fenton's oxidation was investigated. Optimum concentrations of $H_2O_\;and\;Fe^{2+}$ as well as optimum reaction temperature for VFAs production were studied. In the presence of $Fe^{2+}$ as catalyst, the VFAs formation rate increased about 4 times compared to $H_2O_2$ oxidation process without $Fe^{2+}$. Optimum concentrations of $H_2O_2$ and $Fe^{2+}$ were 0.62 M and 0.007 M, respectively. VFAs formation reaction proceeded rapidly within 1 min and VFAs formed degraded partly to acetic acid and $CO_2$, which exhibited series reaction characteristics. Based on the economic aspect, reaction temperature of $25^{\circ}C$ and 10 min of reaction time were thought to be proper reaction conditions. The effect of initial pH in the range of $3{\sim}6.3$ on the VFAs formation was not observed.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.33 no.1
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• pp.15-21
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• 2023

To prepare zinc oxide powder, three types of sodium-based alkali precipitants such as NaOH, Na₂CO₃, NaOH/NaHCO₃ were compared to the differences in the manufacturing process of zinc oxide powder from zinc precipitate products like intermediates with the consideration of thermodynamic reaction. The prepared zinc precipitate products by the reaction with the sodium-based alkali precipitant were confirmed to respectively hydroxy zinc chloride (Zn₅(OH)₈Cl₂·H₂O) and zinc carbonate hydroxide (Zn₅(OH)₆(CO₃)₂·H₂O) from XRD analysis. Zinc oxide particles were compared in heat treatment at 800℃ according to sodium-based alkali precipitants. The mixed NaOH and NaHCO₃ of alkali precipitant reaction was contributed to synthesize the more uniform zinc oxide particles.

• Korean Journal of Crystallography
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• v.11 no.4
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• pp.224-230
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• 2000

We have been investigated the flaking mechanism of the soda-line glass. The pH of aqueous solution approached to 10 and increased with reaction time by ion exchange reaction between Na/sup +/ ion of glass and H/sup +/ ion of aqueous solution under the conditions of below pH 9 of start solution. The relationship between the pH of solution and reaction time shows logarithm. Total dissolution reaction of glass components by OH/sup -/ ion in aqueous seems to be dominant after the pH solution reached to 10 and the dissolution rate linearly increased with reaction time. The above tow reactions are simultaneously occurred. The dissolved Ca/sup 2+/ ions are reprecipitated on the glass surface to Ca-compound. The flakes are formed by the separation of leached layer of glass due to the different thermal expansion coefficient.