• Bulletin of the Korean Chemical Society
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• v.21 no.10
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• pp.957-958
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• 2000

The addition effect of $CH^3Br$ on the ignition of methane was investigated in the temperature range of 1537-1920 K behind reflected shock waves. The ignition delay times were measured by the sudden increase of pres-sure and OH emission in the $CH_4-O_2-Ar$ system containing small amount of $CH_3Br.$ The delay times of mix-tures with $CH_3Br$ were shorter than those without $CH_3Br.$ The promotion of ignition by $CH_3Br$ was caused by the relative fast decomposition rate in additive. To clarify the addition effect of $CH_3Br$ from the viewpoint of the reaction mechanism, computational analyses were performed in $CH_4-CH_3Br-O_2-Ar$ mixtures.

• Clean Technology
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• v.16 no.3
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• pp.198-205
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• 2010

Two sets of thermal reaction experiment for chlorinated hydrocarbons were performed using an isothermal tubular-flow reactor in order to investigate thermal decomposition, including product distribution of chlorinated hydrocarbons. The effects of $H_2$ or Ar as the reaction atmosphere on the thermal decomposition and product distribution for dichloromethane($CH_2Cl_2$) was examined. The experimental results showed that higher conversion of $CH_2Cl_2$ was obtained under $H_2$ atmosphere than under Ar atmosphere. This phenomenon indicates that reactive-gas $H_2$ reaction atmosphere was found to accelerate $CH_2Cl_2$ decomposition. The $H_2$ plays a key role in acceleration of $CH_2Cl_2$ decomposition and formation of dechlorinated light hydrocarbons, while reducing PAH and soot formation through hydrodechlorination process. It was also observed that $CH_3Cl,\;CH_4,\;C_2H_6,\;C_2H_4$ and HCl in $CH_2Cl_2/H_2$ reaction system were the major products with some minor products including chloroethylenes. The $CH_2Cl_2$/Ar reaction system gives poor carbon material balance above reaction temperature of $750^{\circ}C$. Chloroethylenes and soot were found to be the major products and small amounts of $CH_3Cl$ and $C_2H_2$ were formed above $750^{\circ}C$ in $CH_2Cl_2$/Ar. The thermal decomposition reactions of chloroform($CHCl_3$) with argon reaction atmosphere in the absence or the presence of $CH_4$ were carried out using the same tubular flow reactor. The slower $CH_3Cl$ decay occurred when $CH_4$ was added to $CH_3Cl$/Ar reaction system. This is because :$CCl_2$ diradicals that had been produced from $CHCl_3$ unimolecular dissociation reacted with $CH_4$. It appears that the added $CH_4$ worked as the :$CCl_2$ scavenger in the $CHCl_3$ decomposition process. The product distributions for $CHCl_3$ pyrolysis under argon bath gas were distinctly different for the two cases: one with $CH_4$ and the other without $CH_4$. The important pyrolytic reaction pathways to describe the important features of reagent decay and intermediate product distributions, based upon thermochemistry and kinetic principles, were proposed in this study.

• Bulletin of the Korean Chemical Society
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• v.7 no.6
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• pp.466-468
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• 1986

Reaction of $Ir(ClO_4)(CO)(PPh_3)_2$ with trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ produces a new cationic iridium(I) complex, [Ir (trans-$C_6H_5CH$ = $CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ where trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ seems to be coordinated through the carbonyl oxygen rather than through the $\pi$-system of the olefinic group according to the spectral data. It has been found that Ir$(ClO_4)(CO)(PPh_3)_2$ catalyzes the hydrogenation of $CH_2$ = $CHCO_2C_2H_5$, trans-$CH_3CH$ = $CHCO_2C_2H_5$ and trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ to $CH_3CH_2CO_2C_2H_5$, $CH_3CH_2CH_2CO_2C_2H_5$ and $C_6H_5CH_2CH_2CO_2C_2H_5$, respectively at room temperature under the atmospheric pressure of hydrogen. The relative rates of the hydrogenation of the unsaturated esters are mostly understood in terms of steric reasons.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.8-14
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• 1980

Solvolysis rate constants for methylchloroformate, $CH_3O$(CO)Cl, methylthiono-chloroformate, $CH_3O$(CS)Cl, and methylthiolchloroformate, $CH_3S$(CO)Cl, have been determined conductometrically in acetone-water and acetonitrile-water mixtures, and activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, have been derived. Results show that in water-rich regions the order of rate increases as $$CH_3O(CO)Cl while in dipolar aprotic solvent-rich region this order reverses. The plots of log k vs. solvent parameters, Y, $\frac{D-1}{2D+1}$ and log($H_2$) show that the order of rate increase in water-rich region is the results of increase in $S_N1$ character. It is concluded that $CH_3S$(CO)Cl solvolyzes via $S_N1$ mechanism whereas $CH_3O$(CO)Cl reacts via $S_N2$ and $CH_3O$(CS)Cl via intermediate mechanism in water-rich region.

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.811-817
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• 2002

Gibbs ensemble Monte Carlo simulations were performed to calculate the vapor-liquid coexistence properties for the binary mixtures $CO_2/CH_3OH$, $CO_2/C_2H_5OH$, and $CO_2/CH_3CH_2CH_2OH.$ The configurational bias Monte Carlo method was used in the simulation of alcohol. Density of the mixture, composition of the mixture, the pressure-composition diagram, and the radial distribution function were calculated at vapor-liquid equilibrium. The composition and the density of both vapor and liquid from simulation agree considerably well with the experimental values over a wide range of pressures. The radial distribution functions in the liquid mixtures show that $CO_2$ molecules interact more stogly with methyl group than methylene group of $C_2H_5OH$ and $CH_3CH_2CH_2OH$ due to the steric effects of the alcohol molecules.

• Korean Journal of Materials Research
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• v.21 no.4
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• pp.207-211
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• 2011

Ni 8 wt.%-doped tin oxide ($SnO_2$) thick films were fabricated into gas sensors by the method of screen printing onto alumina substrates. The particle size of $SnO_2$ was controlled by changing the ball-mill time between 0~120 h. The structural and morphological properties of these thick films were investigated using X-ray diffraction and scanning electron microscopy. The structural properties of $SnO_2$ powders showed a tetragonal phase with (110) dominant orientation. The particle size of the $SnO_2$:Ni powders after ball-mill of 120 h was about 0.05 ${\mu}m$. The gas sensitivity (S = Rg/Ra) to 5 ppm $CH_4$ gas and $CH_3CH_2CH_3$ gas was measured at room temperature by comparing the resistance in air (Ra) with that of the target gases (Rg). The sensitivity of the $SnO_2$ gas sensors was enhanced by increasing the ball-mill time. There was an association between the sensitivity of both the $CH_4$ gas and the $CH_3CH_2CH_3$ gas and the particle size of the $SnO_2$. $SnO_2$ gas sensors prepared by 72 h ball-mill showed a sensitivity of about 13 to 5 ppm $CH_4$ gas and $CH_3CH_2CH_3$ gas. The response time of the $SnO_2$:Ni gas sensors to the $CH_4$ gas was about 20 seconds.

• Korean Journal of Materials Research
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• v.21 no.10
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• pp.546-549
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• 2011

Nano-sized $SnO_2$ thick films were prepared by a screen-printing method onto $Al_2O_3$ substrates. The sensing characteristics were investigated by measuring the electrical resistance of each sensor in a test box as a function of the detection gas. The nano-sized $SnO_2$ thick film sensors were treated in a $N_2$ atmosphere. The structural properties of the nano $SnO_2$with a rutile structure according to XRD showed a (110) dominant $SnO_2$ peak. The particle size of $SnO_2$:Ni nano powders at Ni 8 wt% was about 45 nm, and the $SnO_2$ particles were found to contain many pores according to the SEM analysis. The sensitivity of the nano $SnO_2$-based sensors was measured for 5 ppm $CH_4$ gas and $CH_3CH_2CH_3$ gas at room temperature by comparing the resistance in air with that in the target gases. The results showed that the best sensitivity of $SnO_2$:Ni and $SnO_2$:Co sensors for $CH_4$ gas and $CH_3CH_2CH_3$ gas at room temperature was observed in $SnO_2$:Ni sensors doped with 8 wt% Ni. The response time of the $SnO_2$:Ni gas sensors was 10 seconds and recovery time was 15 seconds for the $CH_4$ and $CH_3CH_2CH_3$ gases.

• Journal of the Korean Chemical Society
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• v.24 no.4
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• pp.288-294
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• 1980

Methanolysis rate constants were determined for $CH_3O(CO)Cl,\;CH_3S(CO)Cl\;and\;CH_3S(CS)Cl\;in\;CH_3OH-CH_3CN$ mixtures. Results show that the rates are not predominantly influenced by the bulk solvent properties but are partly influenced by specific electrophilic solvation.Polarity of the solvent is not a dominant factor but it nevertheless plays a role in charge stabilization of the $S_N1$ like transition state. The methanolysis proceeds through $S_N1$ mechanism for $CH_3S(CS)Cl$ for which both specific solvation of leaving group by methanol and charge stabilization by a high dielectric medium are important, while for $CH_3O(CO)Cl\;methanolysis occurs\;via\;S_N2$ mechanism in which both of the solvent effects are unimportant.

• Korean Journal of Materials Research
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• v.23 no.4
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• pp.211-214
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• 2013

The effects of a Ni coating on the sensing properties of nano ZnO:Ni based gas sensors were studied for $CH_4$ and $CH_3CH_2CH_3$ gases. Nano ZnO sensing materials were prepared by the hydrothermal reaction method. The Ni coatings on the nano ZnO surface were deposited by the hydrolysis of zinc chloride with $NH_4OH$. The weight % of Ni coating on the ZnO surface ranged from 0 to 10 %. The nano ZnO:Ni gas sensors were fabricated by a screen printing method on alumina substrates. The structural and morphological properties of the nano ZnO : Ni sensing materials were investigated by XRD, EDS, and SEM. The XRD patterns showed that nano ZnO : Ni powders with a wurtzite structure were grown with (1 0 0), (0 0 2), and (1 0 1) dominant peaks. The particle size of nano ZnO powders was about 250 nm. The sensitivity of nano ZnO:Ni based sensors for 5 ppm $CH_4$ gas and $CH_3CH_2CH_3$ gas was measured at room temperature by comparing the resistance in air with that in target gases. The highest sensitivity of the ZnO:Ni sensor to $CH_4$ gas and $CH_3CH_2CH_3$ gas was observed at Ni 4 wt%. The response and recovery times of 4 wt% Ni coated ZnO:Ni gas sensors were 14 s and 15 s, respectively.

• Korean Journal of Materials Research
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• v.25 no.6
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• pp.300-304
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• 2015

Nanorod ZnO and spherical nano ZnO for gas sensors were prepared by hydrothermal reaction method and hydrazine method, respectively. The nano-ZnO gas sensors were fabricated by a screen printing method on alumina substrates. The gas sensing properties were investigated for hydrocarbon gas. The effects of Co concentration on the structural and morphological properties of the nano ZnO:Co were investigated by X-ray diffraction and scanning electron microscope (SEM), respectively. XRD patterns revealed that nanorod and spherical ZnO:Co with a wurtzite structure were grown with (100), (002), (101) peaks. The sensitivity of nanorod and spherical ZnO:Co sensors was measured for 5 ppm $CH_4$ and $CH_3CH_2CH_3$ gas at room temperature by comparing the resistance in air with that in target gases. The highest sensitivity to the $CH_4$ and $CH_3CH_2CH_3$ gas of spherical nano ZnO:Co sensors was observed at Co 6 wt%. The spherical nano ZnO:Co sensor exhibited a higher sensitivity to hydrocarbon gas than nanorod ZnO.