• Journal of the Korean Chemical Society
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• v.17 no.6
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• pp.411-415
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• 1973

The reaction between cyanide ion and triphenyl methane dyes is subject to marked catalysis by cationic micelles of cetyltrimethyl ammonium bromide(CTABr) and retarded by anionic micelles of sodium lauryl sulfate(NaLS). Added salts, anions inhibit the catalysis by CTABr, and cations, especially $Zn^{++},\;Cd^{++}$ decrease the retardation of the reaction rates in the presence of NaLS. The kinetic effects of the ionic micelles are much larger in water than in ethanol-water, methanol-water, propanol-water and acetone-water, but strange solvent effects, acceleration the reaction rates, was found in the reaction with malachite green in water-methanol system.

• 한국연소학회:학술대회논문집
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• 2003.05a
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• pp.129-136
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• 2003

Numerical study with momentum-balanced boundary conditions has been conducted to grasp chemical effects of added $CO_{2}$ and $H_{2}O$ to fuel- and oxidizer-sides on flame structure and NO emission behavior in $CH_{4}$/Air counterflow diffusion flames. The dilution with $H_{2}O$ results in significantly higher flame temperatures and NO emission, but dilution with $CO_{2}$ has much more chemical effects than that with $H_{2}O$. Maximum reaction rate of principal chain branching reaction due to chemical effects decreases with added $CO_{2}$. but increases with added $H_{2}O$. The NO emission behavior is closely related to the production rate of OH, CH and N. The OH radical production rate increases with added $H_{2}O$ but those of CH, N decrease. On the other hand the production rates of OR CH and N decrease with added $CO_{2}$. It is found that NO emission behavior is considerably affected by chemical effects of added $CO_{2}$ and $H_{2}O$.

• Journal of the Korean Applied Science and Technology
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• v.10 no.1
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• pp.23-29
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• 1993

Transesterification reaction between dimethyl phthalate and ethylene glycol was kinetically investigated in the presense of various metal nitrate catalysts at $170^{\circ}C$. The reaction rates measured by the amount of distilled methanol from the reaction vessel. The transesterification reaction was carried out under the first order conditions respect to the concentration of dimethyl phthalate and catalyst, respectively. The over all order was 2nd. By Arrhenius plot, the activation energy was calculated as 17.4kcal/mole and 17.2kcal/mole on the transesterification reaction with zinc nitrate and lead nitrate, respectively. Apparent rate constant, k' was appeared linear about concentration of catalyst.

• Bulletin of the Korean Chemical Society
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• v.18 no.11
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• pp.1179-1182
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• 1997

The rates for the reaction of (Z)-phenacyl (X)-benzenesulfonates with (Y)-pyridines in acetone were measured by an electrical conductivity method at 1-2000 bars and 45 ℃. The magnitudes of the Hammett reaction constants, ρX, ρY and ρZ, represent the degree of Nu-C bond formation and that of C-L bond breaking. The magnitude of correlation interaction term ρij can be used to determine the structure of the transition state (TS) for the SN reaction. As the pressure is increased, the Hammett reaction constants, ρX, |ρY| and ρZ are increased, but correlation interaction coefficient, |ρXZ| and ρYZ, are decreased. The results indicate that the reaction of (Z)-phenacyl (X)-benzenesulfonates with (Y)-pyridines probably moves from an associative SN2 to late-type SN2 mechanism by increasing pressure.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.862-868
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• 2012

Based on the recently derived general expression for the rates of diffusion-controlled reactions, we calculate the rates of dismutation of the superoxide anion radical catalyzed by Cu/Zn superoxide dismutases (SOD). This is the first attempt to calculate the absolute rates of diffusion-controlled enzyme reactions based on the atomiclevel molecular dynamics simulations. All solvent molecules are included explicitly and the effects of the structural flexibility of enzyme, especially those of side chain motions near the active site, are included in the present calculation. In addition, the actual mobility of the substrate molecule is taken into account, which may change as the molecule approaches the active site of enzyme from the bulk solution. The absolute value of the rate constant for the wild type SOD reaction obtained from MD simulation is shown to be in good agreement with the experimental value. The calculated reactivity of a mutant SOD is also in agreement with the experimental result.

• Applied Chemistry for Engineering
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• v.19 no.4
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• pp.432-438
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• 2008

Hydrogenation reactions of p-toluidine over Ru/C were performed while varying reaction temperature, the hydrogen pressure, catalyst loading, solvent, and alkali additive and the effects on the reaction rates and product distribution were examined. 4-Methylcyclohexylamine was generated as a main product and bis(4-methyl cyclohexyl)amine was obtained as a resentative side-product for the hydrogenation reaction of p-toluidine. The selectivity of MCHA decreased with reaction temperature and the hydrogen pressure while increased with catalyst loading. IPA was the best solvent for MCHA. A mechanism of hydrogenation reaction of p-toluidine was suggested from the results. It was found that the presence of alkali salt increased MCHA by reducing BMCHA and rates of hydrogen reaction increased.

• Carbon letters
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• v.12 no.4
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• pp.229-235
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• 2011

Isotactic polyacrylonitrile (PAN) with triad isotacticity of 0.53, which was determined by $^{13}C$ NMR, using dialkylmagnesium as an initiator, was successfully synthesized. Isothermal treatment of iso-PAN was conducted in air at 200, 220, 250 and $280^{\circ}C$. Structural evolutions and chemical changes were studied with Fourier transformation infrared and wide-angle X-ray diffraction during stabilization. A new parameter $CNF={I_{2240cm}}^{-1}/ ({I_{1595cm}}^{-1}+f^*{I_{1595cm}}^{-1})$ was defined to evaluate residual nitrile groups. Crystallinity and crystal size were calculated with X-ray diffraction dates. The results indicated that the nitrile groups had partly converted into a ladder structure as stabilization proceeded. The rate of reaction increased with treatment temperature; crystallinity and crystal size decreased proportionally to pyrolysis temperature. The iso-conversional method coupled with the Kissinger and Flynn-Wall-Ozawa methods were used to determine kinetic parameters via differential scanning calorimetry analysis with different heating rates. The active energy of the reaction was 171.1 and 169.1 kJ/mol, calculated with the two methods respectively and implied the sensitivity of the reaction with temperature.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4387-4391
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• 2011

The kinetic studies on the pyridinolysis of diisopropyl thiophosphinic chloride have been carried out in acetonitrile at $55.0^{\circ}C$. The free energy correlations for substituent X variations in the X-pyridines are biphasic concave upwards with a break point at X = 3-Ph. A concerted SN2 mechanism is proposed with a change of the attacking direction of the X-pyridine from a frontside attack for the strongly basic pyridines to a backside attack for the weakly basic pyridines. The factors to determine the rates and thio effects on the rates for the pyridinolyses of thiophophinic chloride, chlorothiophosphate, phosphinic chloride, phosphonochloridothioate, and chlorophosphate systems are briefly reviewed on the basis of the magnitude of the positive charge of the reaction center P atom and steric effects of the two ligands.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1295-1300
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• 2010

The $CO_2-CH_4$ reaction catalyzed by Ni/silicon wafers was kinetically studied by using a photoacoustic technique. The catalytic reaction was performed at various partial pressures of $CO_2$ and $CH_4$ (50 Torr total pressure of $CO_2/CH_4/N_2$) in the temperature range of 500 - $650^{\circ}C$ in a static reactor system. The photoacoustic signal that varied with the $CO_2$ concentration during the catalytic reaction was recorded as a function of time. Under the reaction conditions, the $CO_2$ photoacoustic measurements showed the as-prepared Ni thin film sample to be inactive for the reaction, while the $CO_2/CH_4$ reactions carried out in the presence of the sample pre-treated in $H_2$ at $600^{\circ}C$ were associated with significant time-dependent changes in the $CO_2$ photoacoustic signal. The rate of $CO_2$ disappearance was measured from the $CO_2$ photoacoustic signal data in the early reaction period of 50 - 150 sec to obtain precise kinetic data. The apparent activation energy for $CO_2$ consumption was determined to be 6.9 kcal/mol from the $CO_2$ disappearance rates. The partial reaction orders, determined from the $CO_2$ disappearance rates measured at various $PCO{_2}'S$ and $PCH{_4}'S$ at $600^{\circ}C$, were determined to be 0.33 for $CH_4$ and 0.63 for $CO_2$, respectively. Kinetic data obtained in these measurements were compared with previous works and were discussed to construct a catalytic reaction mechanism for the $CO_2-CH_4$ reaction over Ni/silicon wafer at low pressures.

• Journal of the Korean Applied Science and Technology
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• v.21 no.1
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• pp.45-50
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• 2004

The effects of reaction temperature and flow rate of reactants on the methane conversion, product selectivity, product ratio, and carbon deposition were investigated with 13wt% Ni/MgO catalyst. Reaction temperatures were changed from 600 to $850^{\circ}C$, and reactants flow rates were changed from 100 to 200 mL/mim. There were no significant changes in the methane conversion observed in the range of temperatures used. It is possibly stemmed from the nearly total exhaustion of oxygen introduced. The selectiveties of hydrogen and carbon monoxide did not largely depend on the reaction temperature. The selectivities of hydrogen and carbon monoxide were 96 and 90%, respectively. Carbon deposition observed was the smallest at $750^{\circ}C$ and the largest at $850^{\circ}C$. It is found that the proper reaction temperature is $750^{\circ}C$. The best reactant flow rate was 150 ml/min.