• Bulletin of the Korean Chemical Society
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• 제27권12호
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• pp.1976-1980
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• 2006

We have calculated the reaction probability and the reaction cross-section of the $N(^4S)+O_2(X^3\sum_{g}^{-})\;\rightarrow\;NO(X^2\Pi)+O(^3P)$ reaction by the quasiclassical trajectory method with the 6th-order explicit symplectic algorithm, based on a new ground potential energy surface. The advantage of the 6th-order explicit symplectic algorithm, conserving both the total energy and the total angular momentum of the reaction system during the numerical integration of canonical equations, has firstly analyzed in this work, which make the calculation of the reaction probability more reliable. The variation of the reaction probability with the impact parameter and the influence of the relative translational energy on the reaction cross-section of the reaction have been discussed in detail. And the fact is found by the comparison that the reaction probability and the reaction cross-section of the reaction estimated in this work are more reasonable than the theoretical ones determined by Gilibert et al.

• Bulletin of the Korean Chemical Society
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• 제3권4호
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• pp.144-148
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• 1982

The kinetic study on the bromine-exchange reaction of antimony tribromide with t-butyl bromide in nitrobenzene or 1,2,4-trichlorobenzene has been carried out, using Br-82 labelled antimony tribromide. The results show that the exchange reaction is first order with respect to t-butyl bromide and 1.5th order with respect to antimony tribromide. It is assumed that the 1.5th order indicates the coexistance of first- and second-order kinetics. Reaction mechanisms for the exchange reaction are proposed.

• Elastomers and Composites
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• 제50권2호
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• pp.92-97
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• 2015

A study on reaction kinetics for a PTMG/TDI prepolymer with 2,2'-dichloro-4,4'-methylenedianiline (MOCA), of which formulations may be generally used for fabricating high performance polyurethane elastomers, was peformed using non-isothermal differential scanning calorimetry (DSC). A number of thermograms were obtained at several constant heating rates, and analysed using Flynn-Wall-Ozawa (FWO) isoconversional method for activation energy, $E_a$ and extended-Avrami equation for reaction order, n. Urea formation reaction of the present system was observed to occur through the simple exothermic reaction process in the temperature range of $100{\sim}130^{\circ}C$ for the heating rate of $3{\sim}7^{\circ}C/min$. and could be well-fitted with generalized sigmoid function. Though activation energy was nearly constant as $53.0{\pm}0.5kJ/mol$, it tended to increase a little at initial stage, but it decreases at later stage by the transformation into diffusion-controlled reaction due to the increased viscosity. Reaction order was evaluated as about 2.8, which was somewhat higher than the generally well-known $2^{nd}$ order values for the various urea reactions. Both the reaction order and reaction rate explicitly increased with temperature, which was considered as the indication of occurring the side reactions such as allophanate or biuret formation.

• Bulletin of the Korean Chemical Society
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• 제11권4호
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• pp.303-306
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• 1990

Kinetic studies were carried out for the redox reaction of $[Co(NH_3)_4(C_2O_4)]^+$ with aqueous $[Fe(H_2O)_6]^{2+}$ solution in the present of $H^+$ by UV/VIS-spectrophotometric method. It was found that the order of $H^+$ for the reaction is first one in the higher $H^+$ concentration range of $1.67×10^{-1} M{\sim}1.00 M,$ while second order in the lower range of $6.30×10^{-2} M{\sim}1.67{\times}10^{-1} M.$ Reaction order of the substrates was found to be first order with respect to each of them. Accordingly overall reactions are third or fourth order. The results of calculation for the Extended Huckel Molecular Orbital theory contribute to estimate the preferred intermediates, bridging form of binuclear complex. On the basis of these results, we propose that this redox reaction proceed via inner-sphere reaction mechanism.

• Bulletin of the Korean Chemical Society
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• 제3권2호
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• pp.55-60
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• 1982

The rate of the bromine-exchange reaction of antimony tribromide with benzyl bromide in nitrobenzene or 1,2,4-trichlorobenzene has been measured, using Br-82 labelled antimony tribromide. The result of the study indicates that the exchange reaction is first order with respect to benzyl bromide, and either second or first order with respect to antimony tribromide depending on its concentrations. The second-order kinetics with respect to antimony tribromide have been observed at relatively high $[SbBr_3]$ concentrations, and the first-order kinetics at lower $[SbBr_3]$ concentrations. Reaction mechanisms are proposed for the exchange reaction.

• Bulletin of the Korean Chemical Society
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• 제17권3호
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• pp.269-273
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• 1996

Alkyl halides were reduced to the corresponding alkanes by the homonuclear bridging hydride, (μ-H)[(η5-MeCp)Mn(CO)2]2-PPN+ in THF at the elevated temperatures (40-60 ℃) under the pseudo first order reaction conditions where excess of alkyl halide was employed under nitrogen atmosphere. The reaction is of overall second order; first order with respect to [bridging hydride] and first order with respect to [alkyl halide] with the activation parameters, ΔH≠=28.93 kcal/mol and ΔS≠=17.95 e.u. The kinetic data, the ESR evidence and the reaction with cyclopropyl canbinyl bromide ensure that two possible reaction pathways are operable in this reaction: (1) concerted mechanism, and (2) single electron transfer pathway are in competition leading to the same product, the corresponding alkane.

• 한국환경과학회지
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• 제26권7호
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• pp.859-868
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• 2017

In this study, the reductive dechlorination of triclosan using zero-valent iron (ZVI, $Fe^0$) and modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium-coated iron (Pd/Fe)) was experimentally investigated, and the reduction characteristics were evaluated by analyzing the reaction kinetics. Triclosan could be reductively decomposed using zero-valent iron. The degradation rates of triclosan were about 50% and 67% when $Fe^0$ and Aw/Fe were used as reductants, respectively, after 8 h of reaction. For the Pd/Fe system, the degradation rate was about 57% after 1 h of reaction. Thus, Pd/Fe exhibited remarkable performance in the reductive degradation of triclosan. Several dechlorinated intermediates were predicted by GC-MS spectrum, and 2-phenoxyphenol was detected as the by-product of the decomposition reaction of triclosan, indicating that reductive dechlorination occurred continuously. As the reaction proceeded, the pH of the solution increased steadily; the pH increase for the Pd/Fe system was smaller than that for the $Fe^0$ and Aw/Fe system. Further, zero-order, first-order, and second-order kinetic models were used to analyze the reaction kinetics. The first-order kinetic model was found to be the best with good correlation for the $Fe^0$ and Aw/Fe system. However, for the Pd/Fe system, the experimental data were evaluated to be well fitted to the second-order kinetic model. The reaction rate constants (k) were in the order of Pd/Fe > Aw/Fe > $Fe^0$, with the rate constant of Pd/Fe being much higher than that of the other two reductants.

• Bulletin of the Korean Chemical Society
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• 제6권3호
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• pp.124-127
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• 1985

The kinetic study on the bromine-exchange reaction of antimony tribromide with ${\alpha}$-phenylethyl bromide in nitrobenzene has been carried out, using Br-82 labelled antimony tribromide. The results show that the exchange reaction is first order with respect to ${\alpha}$-phenylethyl bromide, and either second or first order with respect to antimony tribromide depending on its concentration. It is also concluded that ${\alpha}$-phenylethyl bromide exchanges bromine atom with antimony tribromide much faster than other organic bromides previously examined. Reaction mechanisms for the exchange reaction are discussed.

• Bulletin of the Korean Chemical Society
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• 제34권6호
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• pp.1848-1852
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• 2013

6,7-Dimethoxy-2-methyl-3-(4-nitrophenoxy)quinoline was synthesized by Friedl$\ddot{a}$nder's cyclization reaction. Different bases and solvents were tested in order to optimize the reaction conditions. The highest yields were obtained using piperidine in refluxing ethanol. Further reactions were carried out in order to prepare different diarylamide and diarylurea derivatives in moderate to high yields in order to examine their anticancer activities.

• 한국응용과학기술학회지
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• 제4권1호
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• pp.67-71
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• 1987

The transesterification reaction between diethanolamine and methyl methacrylate was kinetically investigated in the presence of various metal acetate catalysts at $120^{\circ}C$. The amount of reacted methyl methacrylate was measured by gas chromatography and liquid chromatography, and the reaction rate also measured from the amount of reaction products and reactants under each catalyst. The transesterification reaction was carried out in the first order with respect to the concentration of diethanolamine and methyl methacrylate, respectively. The over-all order is 2nd. The apparent rate constant was found to obey first-order kinetics with respect to the concentration of catalyst. The maximum reaction rate was appeared at the range of 1.4 to 1.6 of electronegativity of metal ions and instability constant of metal acetates.