• Applied Chemistry for Engineering
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• v.5 no.2
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• pp.230-237
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• 1994

The reaction conversions of n-butyl acetate in the alkaline hydrolysis of n-butyl acetate by Aliquat 336 were measured in a flat agitator and a dispersion agitator. These measured data was used to analyze the complicated reaction mechanism of the liquid-liquid heterogeneous reaction by a phase transfer catalyst with a pseudo-first order reaction model, a interfacial reaction model and a bulk-body reaction model. The pseudo-firsts order reaction model and the interfacial reaction model could be explained by the experimental data from the dispersion agitator and the bulk-boby reaction model could be explained by those from the flat agitator and the reaction rate constants were $3.1{\times}10^{-4}$, $7.3{\times}10^{-4}$, $6.6m^3/kmol.s$ from these models at $25^{\circ}C$, respectively.

• Bulletin of the Korean Chemical Society
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• v.17 no.2
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• pp.138-142
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• 1996

The transition metal carbonylate, PPN+(${\eta}^5-MeCp)Mn(CO)_2Cl^-$ undergoes a novel ligand substitution reaction with PR3 (R=Me, Et, OEt, $C_6H_5$ in THF at elevated temperatures (40 $^{\circ}C$ up to 60 $^{\circ}C)$ under the pseudo-first-order reaction conditions (usually 20-fold excess of PR3 with respect to metal carbonylate concentrations) where chloride is displaced by PR3. The reaction follows overall first order dependence on [(${\eta}^5-MeCp)Mn(CO)_2Cl^-$]; however, the negative entropy changes of activation (${\Delta}S^{\neq}$=-19.3 e.u. for $P(OEt)_3$; ${\Delta}S^{\neq}$=-16.4 e.u. for $PPh_3$) suggest the existence of the intermediate, ((η3-MeCp)Mn(CO)2(THF)Cl-, which eventually transforms to the product (${\eta}^5-MeCp)Mn(CO)_2(PR_3)$.

• Journal of Energy Engineering
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• v.8 no.2
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• pp.279-284
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• 1999

Thermal analyses were conducted in a thermogravimetric analyzer by isothermal technique in order to characterize the Korean anthracites-nitrogen oxides reaction. The tested coal sample was Dogae anthracites and compared with SP-1 graphite. Carbon-NO and carbon-N$_2$O reactions were carried out with respect to isothermal reaction temperatures (550$^{\circ}C$-900$^{\circ}C$) and reactant gas partial pressures (5 kPa∼20 kPa). In NO reaction, measured reaction orders of NO concentration and activation energy were 0.45∼0.96 and 39∼l12 kJ/mol, respectively. In N$_2$O reaction, measured reaction orders of N$_2$O concentration and activation energy were 0.62∼0.87 and 190∼215.3 kJ/mol, respectively. Compared the Korean anthracites-nitrogen oxides reaction with the combustion reaction, the reaction rate in the oxidation below 700$^{\circ}C$ decreases in the order O$_2$>NO>N$_2$O. But above 700$^{\circ}C$, the reaction rate of N$_2$O is faster than that of NO.

• Journal of Korean Society for Atmospheric Environment
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• v.18 no.1
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• pp.51-58
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• 2002

Destruction process of toluene using a wire-cylindrical BBD (Dielectric Barrier Discharge) reactor packed with catalysts was investigated to characterize the synergetic effects of non-thermal plasma and catalyst process. The catalysts used in the present study were ${\gamma}$-Al$_2$BO$_3$ and Pt/${\gamma}$-Al$_2$O$_3$. Under the numerous test conditions, specific energy density (SED (J/L)) and the conversion of toluene, defined as (1 -[C$_{f}$]/[C$_{i}$]), were measured. The test results showed that toluene decomposition efficiency followed the pseudo-first order in the case of plasma only process. The pseudo-first order process, however, was modified to pseudo-zeroth order reaction in the case of catalyst-assisted plasma process. This modification of the reaction order was verified based on a simple kinetic model proposed in the present study. Owing to the modification of reaction order, which resulted from the catalytic process, the specific energy to achieve the high removal efficiencies, i.e. 80~90%, was reduced significantly.y.y.

• Journal of the Korean Chemical Society
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• v.36 no.3
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• pp.405-411
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• 1992

The substitution reaction and structrue of products obtained from the reaction of Equatorial-Skew-[Co(TRDTRA)($OH_2$)] (TRDTRA = trimethylenediaminetriacetate) with $CN^-, NO^{-}_{2}$ and $NCS^-$ ions have been investigated by means of electronic absorption spectroscopy and theoretical calculation based on the Yamatera's theory. According to kinetic data, the substitution reaction order for the complexes such as $CN^-, NO^{-}_{2}$ and $NCS^-$ was the first order, respectively, and overall reaction order was second order. It has been determined that the structure of products having $CN^{-} and NO^{-}_{2}$ ions was Polar-Chair type complexes which were accompanying with isomerization and having $NCS^-$ ion was Equatorial-Skew type complex which was not accompanying with isomerization.

• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2269-2273
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• 2012

Pseudo-first-order rate constants $k_{amine}$ have been measured spectrophotometrically for the reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{amine}$ vs. [amine] curve upward, indicating that the reactions proceed through a stepwise mechanism with two intermediates, a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$. This contrasts to the report that the corresponding reactions of benzyl 2-pyridyl carbonate 5 proceed through a forced concerted pathway. The $k_{amine}$ values for the reactions of 6 have been dissected into the second-order rate constant $Kk_2$ and the thirdorder rate constant $Kk_3$. The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}=0.94$ and 1.18 for $Kk_2$ and $Kk_3$, respectively. The $Kk_2$ for the reaction of 6 is smaller than the second-order rate constant $k_N$ for the corresponding reaction of 5, although 4-pyridyloxide in 6 is less basic and a better nucleofuge than 2-pyridyloxide in 5.

• Analytical Science and Technology
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• v.11 no.3
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• pp.156-160
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• 1998

SiC is synthesized by sol-gel and carbothermal reaction method from various carbon sources and Si source and characterized through the results of DSC and XRD. More SiC has been formed in carbothermal reaction than sol-gel method. From the XRD results, the degree of formation of SiC increases in the order of petroleum cokes, activated carbon, artificial graphite all in two introduced methods. Based on the DSC data, the enthalpy values for the exothermic reaction decrease in the order of activated carbon, petroleum cokes, artificial graphite in carbothermal reaction methods, while those for the endothermic reactions increase in the reverse order. But, the enthalpy values for the exothermic reactions decrease in the order of petroleum cokes, activated carbon, artificial graphite in sol-gel methods.

• Journal of the Korean Chemical Society
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• v.14 no.1
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• pp.85-89
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• 1970

The rate of the bromine-exchange reaction between gallium bromide and isopropyl bromide in nitrobenzene was measured at 19$^{\circ},\;25^{\circ}$ and 40$^{\circ}C$., using isopropyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to isopropyl bromide. The third-order rate constant determined at 19$^{\circ}C$. was 3.2 ${\times}10^{-2}l^2{\cdot}mole^{-2}sec^{-1}$. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined.

• Journal of the Korean Chemical Society
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• v.9 no.1
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• pp.1-7
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• 1965

Reaction of monochloroacetic acid with zinc in presence of toluene, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, and dioxane solvents showed the solvent effect in order of dimethylformamide, dioxane, dimethyl sulfoxide, toluene, acetonitrile, and tetrahydrofuran. The increasing reactivity of the reagents was observed in order of the polarity and hydrophilicity of the solvent. The same reaction of ethyl monochloroacetate in the same series of solvents showed also the solvent effect, but the difference was not large as compared to that of the acid. The reaction of the acid, ester, zinc, and carbonyl precursors such as benzaldehyde and 4-heptanone gave the Reformatsky reaction product in the case of the aldehyde, but the reactivity with 4-heptanone was slight. The yield of the product was varied by the method of addition of reagents. The best yield observed in case of the acid reaction was 38.5% of the hydroxy acid and 0.8g of the salt in presence of acetonitrile and in case of the ester reaction 19.3% of ethyl cinnamate and 21.6% of polymer. The variation of the reactivity of reagents due to the reaction temperature was observed in case of carbonyl reaction. The result was discussed in terms of the solvent effect and the procedures were described.

• Bulletin of the Korean Chemical Society
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• v.7 no.3
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• pp.166-169
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• 1986

In order to synthesize conformationally rigid etorphine analogues having potentially interesting pharmacological activities, synthesis of compound 3 by the reaction of compound 4 and compound 5 via intramolecular Diels-Alder reaction has been attempted. However, the reaction did not go well and the compound 3 would not be isolated. Therefore, intermolecular Diels-Alder reaction using dimethyl acetylene dicarboxylate was attempted. As shown in scheme 2, Diels-Alder adduct 9 was converted into the target molecule 14 containing the new [2.2.2] bicyclo octane ring in good yields.