• Bulletin of the Korean Chemical Society
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• v.26 no.1
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• pp.139-145
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• 2005

Artificial neural networks (ANNs), for a first time, were successfully developed for the modeling and prediction of solvent effects on rate constant of [2+2] cycloaddition reaction of diethyl azodicarboxylate with ethyl vinyl ether in various solvents with diverse chemical structures using quantitative structure-activity relationship. The most positive charge of hydrogen atom (q$^+$), dipole moment ($\mu$), the Hildebrand solubility parameter (${\delta}_H^2$) and total charges in molecule (q$_t$) are inputs and output of ANN is log k$_2$ . For evaluation of the predictive power of the generated ANN, the optimized network with 68 various solvents as training set was used to predict log k$_2$ of the reaction in 16 solvents in the prediction set. The results obtained using ANN was compared with the experimental values as well as with those obtained using multi-parameter linear regression (MLR) model and showed superiority of the ANN model over the regression model. Mean square error (MSE) of 0.0806 for the prediction set by MLR model should be compared with the value of 0.0275 for ANN model. These improvements are due to the fact that the reaction rate constant shows non-linear correlations with the descriptors.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2473-2479
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• 2013

The kinetics of the radical-polar molecule reaction $CH_3+HBr{\rightarrow}CH_4+Br$ has been studied at temperatures between 150 and 1000 K using classical dynamics procedures. Potential energy surfaces constructed using analytical forms of inter- and intramolecular interaction energies show a shallow well and barrier in the entrance channel, which affect the collision dynamics at low temperatures. Different collision models are used to distinguish the reaction occurring at low- and high-temperature regions. The reaction proceeds rapidly via a complex-mode mechanism below room temperature showing strong negative temperature dependence, where the effects of molecular attraction, H-atom tunneling and recrossing of collision complexes are found to be important. The temperature dependence of the rate constant between 400 and 1000 K is positive, the values increasing in accordance with the increase of the mean speed of collision. The rate constant varies from $7.6{\times}10^{-12}$ at 150 K to $3.7{\times}10^{-12}$ at 1000 K via a minimum value of $2.5{\times}10^{-12}\;cm^3\;molecule^{-1}\;s^{-1}$ at 400 K.

• Korean Chemical Engineering Research
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• v.47 no.3
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• pp.380-385
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• 2009

The absorption rate of carbon dioxide with 2-amino-2-methyl-1-propanol(AMP) was measured in such non-aqueous solvents as methanol, ethanol, n-propanol, n-butanol, ethylene glycol, propylene glycol, and propylene carbonate, and in water at 298 K and 101.3 kPa using a semi-batch stirred tank with a plane gas-liquid interface. The overall reaction rate constant, obtained under the condition of fast reaction regime, from the measured rate of absorption was used to get the elementary reaction rate constants in complicated reactions represented by reaction mechanism of carbamate formation and the order of overall reaction of $CO_2$ with amine. The correlation between the elementary reaction rate constant and the solubility parameter of the solvent was also presented.

• 제어로봇시스템학회:학술대회논문집
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• 1991.10b
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• pp.1873-1878
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• 1991

An high-speed isothermal calorimeter which can trace the progress of a liquid phase reversible reaction was constructed using analog and digital computer. By means of a set point change of the calorimeter, the thermal energy capacity and the heat of reaction in reversible reaction mixture can be measured. The heat of reaction between 2-methyl furan and maleic anhydride and the heat capacities of the adduct were 61,200 J/mol and 2.38 J/ g K, respectively. Also reaction equilibrium constant and reaction rate constants can be estimated from the response curves of the calorimeter.

• Journal of the Korean Applied Science and Technology
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• v.26 no.3
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• pp.370-378
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• 2009

Kinetic studies on the ligand substitution reactions of cyanocomplexes were performed in several micellar solutions. It showed the observed rate constants was found to be independent of the entering ligand concentration at high concentration of cyanopyridine and pyrazinecarboxylate. We could see also that in nonionic and anionic micellar solutions no influence of changes in the surfactant concentration on the observed rate constants was found. Taking into account the hydrophilic nature of the cobalt complex, the cobalt complex molecule was expected to be located in the aqueous phase of the micellar systems, where the reaction would take place. In cationic micellar solutions, a small increase in the observed rate constant was found when the cationic surfactant concentration increased. After reaching a maximum, the rate constant decreased on increasing surfactant concentration and subsequently it reached a plateau, where the observed rate constant was independent of changes in the surfactant concentration.

• Journal of the Korean Society of Combustion
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• v.20 no.3
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• pp.35-42
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• 2015

Investigating coal combustion in a large-scale boiler using computational fluid dynamics (CFD) requires a combination of flow and reaction models. These models include a number of rate constants which are often difficult to determine or validate for particular coals or furnaces. Nonetheless, CFD plays an important role in developing new combustion technologies and improving the operation. In this study, the model selection and rate constants for coal devolatilization, char conversion, and turbulent reaction were evaluated for a commercial wall-firing boiler. The influence of devolatilization and char reaction models was found not significant on the overall temperature distribution and heat transfer rate. However, the difference in the flame shapes near the burners were noticeable. Compared to the coal conversion models, the rate constant used for the eddy dissipation rate of gaseous reactions had a larger influence on the temperature and heat transfer rate. Based on the operation data, a value for the rate constant was recommended.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.692-698
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• 1991

The reaction path Smoluchowski equation approach developed in a recent work to calculate the rate constant for a diffusive multidimensional barrier crossing process is extended to incorporate the configuration-dependent diffusion matrix. The resulting formalism is then applied to the investigation of stilbene photoisomerization dynamics. Adapting a model two-dimensional potential and a model diffusion matrix proposed by Agmon and Kosloff [J. Phys. Chem.,91 (1987) 1988], we derive an eigenvalue equlation for the relaxation rate constant of the stilbene photoisomerization. This eigenvalue equation is solved numerically by using the finite element method. The advantages and limitations of the present method are discussed.

• Journal of the Korean Applied Science and Technology
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• v.9 no.2
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• pp.141-148
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• 1992

Transesterification reactions (methyl methacrylate with diethanolamine, ethylene glycol with dimethylphthalate) were kinetically investigated in the presence of zinc compound catalysts at $120{\sim}170^{\circ}C$ The amount of reactants was measured by gas chromatography. and the reaction rates also measured from the amount of reaction products and reactants upon each catalyst. The transesterification reactions were carried out under the first order conditions respect to the concentration of reactants, respectively, The overall reaction order was 2nd. The apparent rate constant (k') was found to obey first kinetics with respect to the concentration of catalyst. It shows that according to an increase in basicity of anionic species the rate constant increase, and that a linear relationship exists between ln k and pKa in transesterification reaction of methyl methacrylate with diethanolamine.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.151-157
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• 2014

We have reported the reaction probability, integral reaction cross section, and rate constant for the title system calculated with the aid of a time-dependent wave packet approach. The ab initio potential energy surface (PES) of Prudente et al. (Chem. Phys. Lett. 2009, 474, 18) is employed for the purpose. The calculations are carried out over the collision energy range of 0.05-1.4 eV for the two reaction channels of H + LiH ${\rightarrow}$ Li + $H_2$ and $H_b$ + $LiH_a$ ${\rightarrow}$ $LiH_b$ + $H_a$. The Coriolis coupling (CC) effect are taken into account. The importance of including the Coriolis coupling quantum scattering calculations are revealed by the comparison between the Coriolis coupling and the centrifugal sudden (CS) approximation calculations.

• Journal of the Korean Chemical Society
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• v.35 no.2
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• pp.111-118
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• 1991

The kinetic of the gas phase reactions of ozone(0.5 torr) with sulfur dioxide was studied. The SO2 reaction was conducted in the 7∼22 torr range at 90∼155$^{\circ}$C. The reaction rate was faster than the reaction rate of O$_3$ in the presence of CO$_2$ alone. The reaction of O$_3$ with SO$_2$ follows the rate law: -d(O$_3)/dt=k_0(SO_2)(M)(O_3)+2k _1(SO_2)(O_3$). The first term of this rate law arises from a third order molecular reaction predominating in the lower temperature range and gave a rate constant k$_0$ = (9.35 $\pm$ 8.6) ${\times}$ 10$^9$e$^{-(11.05{\pm}2.04)kcal/RT}(M^{-2}s^{-1}$). The second term of the above rate law derived from a second order thermal decomposition reaction which was the major part of the reaction and gave a rate constant k$_0 =(9.35{\pm}8.6){\times}10^9e^{-(11.05{\pm}2.04)kcal/RT}(M^{-2}s^{-1}$). The overall reaction proceeds with kinetics of complex order composed mainly of second order and third order components.