• Korean Chemical Engineering Research
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• v.46 no.3
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• pp.535-539
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• 2008

Conversion to oil, yield of styrene and formation of side products such as ${\alpha}-methyl$ styrene, ethyl benzene, benzene, toluene, dimer and trimer were affected by residue formed during thermal degradation. Also, control of reaction temperature had a difficulty at the first stage. Thus, new reaction system using wetted-wall type reactor was proposed and examined on various parameters such as reaction temperature, feeding rate and removal velocity of formed vapor. Optimun condition was obtained from continuous thermal degradation using wetted-wall type reactor and reaction kinetic study was carried out at new type reactor.

• Applied Chemistry for Engineering
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• v.24 no.4
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• pp.375-381
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• 2013

Kinetics data were obtained for steam reforming of methane and natural gas over the commercial nickel catalyst. Variables for the steam reforming were the reaction temperature and partial pressure of reactants. Parameters for the Power law rate model and the Langmuir-Hinshelwood model were obtained from the kinetic data. As a result of the reforming reaction using pure methane as a reactant, the reaction rate could be determined by the Power law rate model as well as the Langmuir-Hinshelwood model. In the case of methane in natural gas, however, the Langmuir-Hinshelwood model is much more suitable than the Power law rate model in terms of explaining methane reforming reaction. This behavior can be attributed to the competitive adsorption of methane, ethane, propane and butane in natural gas over the same catalyst sites.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2081-2085
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• 2014

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of phenyl 2- pyridyl carbonate (6) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot for the reaction of 6 is linear with ${\beta}_{nuc}$ = 0.54, which is typical for reactions reported previously to proceed through a concerted mechanism. Substrate 6 is over $10^3$ times more reactive than 2-pyridyl benzoate (5), although the reactions of 6 and 5 proceed through the same mechanism. A combination of steric hindrance, inductive effect and resonance contribution is responsible for the kinetic results. The reactions of 6 and 5 proceed through a cyclic transition state (TS) in which H-bonding interactions increase the nucleofugality of the leaving group (i.e., 2-pyridiniumoxide). The enhanced nucleofugality forces the reactions of 6 and 5 to proceed through a concerted mechanism. In contrast, the corresponding reaction of 4-nitrophenyl 2-pyridyl carbonate (7) proceeds through a stepwise mechanism with quantitative liberation of 4-nitrophenoxide ion as the leaving group, indicating that replacement of the 4-nitrophenoxy group in 7 by the PhO group in 6 changes the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as the leaving group (i.e., from 4-nitrophenoxide to 2-pyridiniumoxide). The strong electron-withdrawing ability of the 4-nitrophenoxy group in 7 inhibits formation of a H-bonded cyclic TS. The presence or absence of a H-bonded cyclic TS governs the reaction mechanism (i.e., a concerted or stepwise mechanism) as well as the leaving group (i.e., 2-pyridiniumoxide or 4-nitrophenoxide).

• Transactions of the Korean Society of Automotive Engineers
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• v.20 no.5
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• pp.71-80
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• 2012

To improve the $NO_X$ conversion over a SCR (selective catalytic reduction) catalyst, the DOC (diesel oxidation catalyst) is usually placed upstream of the SCR catalyst to enhance the fast SCR reaction ($4NH_3+2NO+2NO_2{\rightarrow}4N_2+6H_2O$) using equimolar amounts of NO and $NO_2$. Here, a ratio of $NO_2/NO_X$ above 50% should be avoided, because the reaction with $NO_2$ only ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$) is slower than the standard SCR reaction ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$). In order to accurately predict the performance characteristics of SCR catalysts, it is therefore desired to develop a more simple and reliable mathematical and kinetic models on the oxidation kinetics of nitric oxide over a DOC. In the present work, the prediction accuracy and limit of three different chemical reaction kinetics models are presented to describe the chemicophysical characteristics and conversion performance of DOCs. Steady-state experiments with DOCs mounted on a light-duty four-cylinder 2.0-L turbocharged diesel engine then are performed, using an engine-dynamometer system to calibrate the kinetic parameters such as activation energies and preexponential factors of heterogeneous reactions. The reaction kinetics for NO oxidation over Pt-based catalysts is determined in conjunction with a transient one-dimensional (1D) heterogeneous plug flow reactor (PFR) model with diesel exhaust gas temperatures in the range of 115~$525^{\circ}C$ and space velocities in the range of $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.

• Journal of the Korean Chemical Society
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• v.33 no.3
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• pp.309-314
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• 1989

A kinetic study was carried out for the redox reaction of cis-$[Co(en)_2(N_3)_2]^+$ with Fe(II) in acidic solution by spectrophotometric methods. This redox reaction system have been found to show a third order for overall reaction as the respective first order with respect to reactant cis-$[Co(en)_2(N_3)_2]^+$, Fe(II), and $H^+$ catalyst. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were obtained as 14.2Kcal/mol and -16.7 e.u., respectively. On the basis of the kinetic data, we suggest that the redox reaction system proceeds via inner sphere mechanism. The rate equation derived from the proposed mechanism is in agreement with the observed rate equation.

• Journal of the Korean Chemical Society
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• v.10 no.1
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• pp.25-31
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• 1966

It is well known that the coloration and structural changes in thermal treatment of polyacrylonitrile are due to the formation of partly hydrogenated naphthylidine-type ring involving the pendant nitrile groups. Any quantitative study of the reaction, in the sense of kinetics and/or statistics, however, has never been reported. This paper presents that, at first, the disappearance of the nitrile groups follows the first order kinetics, which indicates clearly that nitrile groups do not disappear by a long chain reaction-the kinetic chain length is very short. This observation rules out the long intramolecular and intermolecular propagation chain through which most of the nitrile groups disappear. From the evidence that a similar reaction occurs in propylene carbonate solutions without gel formation, one may conclude that the coloration and structural changes are not necessarily intermolecular reaction. Secondly, a finite amount of nitrile groups remains unreacted at the extrem of reaction-not contributed to the formation of naphthylidine-type ring. The concentration of this unreacted nitrile groups is 19∼22% which is good agreement with the statistically calculated value of 19.2%.

• KSBB Journal
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• v.11 no.6
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• pp.712-717
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• 1996

Cellulase was modified with synthetic copolymers of polyoxyethylene derivative and maleic acid anhydride. The saccharification characteristics and enzymatic reaction kinetic mechanism of modified and native cellulases were observed. In modification reaction of cellulase, degree of modification(DM) increased, as mass ratio of copolymers to enzyme increased. Maximum DM was 55% at mass ratio of 4 and remained activity was 75%. In saccharification experiment modified enzyme had maintained higher stability than native enzyme over all the reaction and the final conversion yield of modified enzyme was greater than that of native enzyme. Numerical simulation based on the reaction mechanism considering enzymatic deactivation was performed. Modified enzyme had kept higher free enzyme concentration over all the reaction than that of native enzyme. Comparing calculation values with experimental data, calculation values were in accordance with experimental data.

• Microbiology and Biotechnology Letters
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• v.17 no.6
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• pp.552-555
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• 1989

A 150-fold purified preparation of NADPH-specific glutamate dehydrogenase of Corynebacterium glutamicum (1) was used for the determination of kinetic parameters of the substrates, NADPH, NH$_4$Cl, and $\alpha$-ketoglutarate in the direction of glutamate synthesis. The kinetic constants determined from this study suggest a biosynthetic role for the enzyme, Based on the analysis of the result derived from initial velocity, the reaction mechanism was postulated to be ordered addition with NADPH as a first substrate to bind in the forward direction. Of the several metabolites tested for a possible function in the regulation of glutamate dehydrogenase activity, only malate and citrate were appeared to have an appreciable influence on the enzyme, Potassium chloride showed to be the most effective for the enzyme activity.

• Journal of Environmental Science International
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• v.9 no.3
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• pp.261-266
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• 2000

A kinetic study for nitrate removal by anion exchange resin was performed using continuous column reactors. Kinetic approach from the packed bed showed the reaction rate constant k$_1$ was 0.07~0.17 $\ell$/mgㆍhr and maximum exchange quantity q$_{o}$ was 27.75~31.81 mg/g. The results from the continuous column well agreed with that from the batch reactor. An economic analysis of the water treatment plant by anion exchange resin with a regenerating system was performed to design plant and process. Based on the treatment of 20 mg/$\ell$ nitrate-contained wastewater of 10,000 gallons per day to 2 mg/$\ell$, total capital cost and total annual cost are estimated to be 836 million wons and 211 million wons, respectively.y.

• Journal of Korean Society for Atmospheric Environment
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• v.18 no.E3
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• pp.165-174
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• 2002

A dual -column biofilter system with two different composts was used to investigate the macro-kinetics of dim-ethyl disulfide (DMDS) degradation. The biofilter columns were filled with compost mixtures up to one meter, The gas How rate and DMDS concentration to the biofilters were varied to study their effect on the removal characteris-tics of DMDS. It was found that the biodegradation of DMDS was governed by zero-order reaction -limited macro-kinetics for inlet DMDS concentrations between 10 and 55 ppmv. The overall average zero-order kinetic coeffi-cient for DMDS removal by compost was 0.50 ($\pm$0.1) ppm/sec for both compost mixtures studied. Variations in individual kinetic coefficients were observed due to varying environmental conditions, such as pH and temperature. The kinetic coefficients determined are specific to the system discussed in this work. During high acidity conditions in the filter beds, methyl mercaptan (MM) was observed in the gas samples collected. Appearance of MM was pro-bably due to decreased microbial activity in the lower portions of the biofilter. Considering the neutral pH range required and the presence of methyl mercaptan, it is likely that the microorganisms present in the biofilters used in this research are similar to the T. thioparus (strain E6) species.