• Journal of the Korean Chemical Society
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• v.24 no.4
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• pp.315-321
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• 1980

A steady-state kinetic study on a dye-coupled cytoplasmic polyol dehydrogenase from G. melanogenus was carried by the initial velocity measurements in the direction of the polyol oxidation and the product inhibition by D-fructose. For the initial rate experiments, D-mannitol and D-sorbitol were employed as the specific polyol substrates and 2,6-dichlorophenolin-dophenol (DPIP) as the specific cofactor substrate for the enzyme. When the polyol and DPIP were examined by varying one of substrates and by fixing the second, the corresponding reciprocal plots showed the typical parallel pattern. This suggests that the enzyme from G. melanogenus proceeds by a Ping Pong Bi-Bi mechanism in which the polyol may account as the first reactant-in, and the ketose formed as the first product-out, respectively. The product inhibition patterns obtained by D-fructose (one no-inhibition, one non-competitive, and two competitive) may also provide an additional conformatory evidence for the above mechanism. Based on the kinetic parameters obtained, it was also suggested that the rate-limiting step in the direction of polyol oxidation is associated with the release of the ketose from the Enzyme${\cdot}$Polyol complex.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.7
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• pp.746-752
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• 2005

In this study, the effect of reaction parameters including reaction temperature, time, and pressure on sludge degradation and conversion to intermediates such as organic acids were investigated at low critical wet air oxidation(LC-WAO) conditions. Degradation pathways and a modified kinetic model in LC-WAO were proposed and the kinetics model predictions were compared with experimental data under various conditions. Results in the batch experiments showed that reaction temperature directly affected the thermal hydrolysis reaction rather than oxidation reaction. The efficiencies of sludge degradation and organic acid formation increased with the increase of the reaction temperature and time. The removal of SS at $180^{\circ}C$, $200^{\circ}C$, $220^{\circ}C$ and $240^{\circ}C$ of reaction temperatures and 10 min of reaction time were 52.6%, 68.3%, 72.6%, and 74.4%, respectively, indicating that most organic suspended solids were liquified at early stage of reaction. At $180^{\circ}C$, $200^{\circ}C$, $220^{\circ}C$ and $240^{\circ}C$ of reaction temperatures and 40 min of reaction time, the amounts of organic acids formed from 1 g of sludge were 93.5 mg/g SS, 116.4 mg/g SS, 113.6 mg/g SS, and 123.8 mg/g SS, respectively, and the amounts of acetic acid from 1 g of sludge were 24.5 mg/g SS, 65.5 mg/g SS, 88.1 mg/g SS, and 121.5 mg/g SS, respectively. This suggested that the formation of sludge to organic acids as well as the conversion of organic acids to acetic acid increased with reaction temperature. Based on the experimental results, a modified kinetic model was suggested for the liquefaction reaction of sludge and the formation of organic acids. The kinetic model predicted an increase in kinetic parameters $k_1$ (liquefaction of organic compounds), $k_2$ (formation of organic acids to intermediate), $k_3$ (final degradation of intermediate), and $k_4$ (final degradation of organic acids) with reaction temperature. This indicated that the liquefaction of organic solid materials and the formation of organic acids increase according to reaction temperature. The calculated activation energy for reaction kinetic constants were 20.7 kJ/mol, 12.3 kJ/mol, 28.4 kJ/mol, and 54.4 kJ/mol, respectively, leading to a conclusion that not thermal hydrolysis but oxidation reaction is the rate-limiting step.

• Journal of the Korean Chemical Society
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• v.50 no.1
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• pp.46-52
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• 2006

studies of olefin oxidation using Al(III)-porphyrin complexes as catalyst are investigated in CH2Cl2, in which NaClO is used as terminal oxidant. Porphyrins are TPP(5,10,15,20-Tetraphenylporphyrin) and (p-X)TPP(X=CH3O, CH3, F, Cl). Olefins are styrene and (p-X)styrene (X=CH3O, CH3, Cl, Br). The values of Km and Vmax are calculated from the Michaelis-Menten equation. According to the substituents of substrate and catalyst, kinetic parameters will be measured. Investigating the correlation between the Michaelis-Menten rate parameters and the substituent constants, we were able to analyze the influence on the changes of catalytic activity or the rate determining step during the process of the formation and the dissociation of the M-oxo-olefin.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.2
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• pp.168-177
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• 2011

A set of kinetics study on the reduction with $CH_4$, oxidation with steam and oxidation with air was performed for $Fe_2O_3/ZrO_2$. $Fe_2O_3/ZrO_2$ was prepared by aerial oxidation method. The reactivity experiments were performed in a thermogravimetric analyzer (TGA) with different reacting gas concentrations and temperatures. The obtained activation energy of reduction by methane, oxidation by water and oxidation by air are 219 kJ/mol, 238 and 20 respectively.

• Journal of the Korean Chemical Society
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• v.28 no.2
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• pp.102-108
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• 1984

The catalytic oxidation of CO has been investigated on $ZnCe_{1+y}O_2$ at temperatures from 300 to $500^{\circ}C$ under various P_{CO} and PO_2 conditions. The oxidation rates have been correlated with 1.5-order kinetics: first order with respect to CO and 0.5 order with respect to O2. CO appears to be absorbed essentially on the O lattice of $ZnCe_{1+y}O_2$ as a molecular species, while $O_2$ adsorbs on an O vacancy as an ionic species. The conductivity data show that CO adsorption contributes electron to the conduction band and the adsorption process of $O_2$ withdraws it from an O vacancy. The oxidation mechanism and the defect model of $ZnCe_{1+y}O_2$ are inferred at given temperature and $PO_2'$s from the agreement between the conductivities and kinetic data. It is suggested that CO absorption is the rate-controlling.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.9 no.1
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• pp.119-125
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• 1999

This research has been studied in terms of investigating the reaction behavior of pyrite with a cyclone reactor. The Mathematical model has developed pyrite oxidation and lime sulfation in this reactor. The model assumes a chemical control shrinking core behavior for the pyrite and a fluid film control shrinking core behavior for the lime. The model was solved and characterized numerically. Experiments have been performed to study the influence of reaction parameters such as reactor temperatures, pyrite particle sizes, air flow rates, feeding rates, and mixing ratio of pyrite and lime. The oxidation and sulfation products were characterized chemically and physically.

• Journal of Environmental Health Sciences
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• v.32 no.5 s.92
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• pp.446-450
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• 2006

In order to treat the wastewater containing organic compound, pre-treatment system connected with MSP(molecular separation process) was investigated. With the aim of selecting an optimum process of Fenton's oxidation, removal efficiency of each process in the optimum reaction condition was recommended. The $Fe/H_{2}O_{2}$(ferric sulfate to hydrogen peroxide)reagent is referred to as the Fenton's regent, which produces hydroxyl radicals by the interaction of Fe with $H_{2}O_{2}$. The powerful oxidizing ability and extreme kinetic reactively of the hydroxyl radical was well established. Increasing dosage of $Fe/H_{2}O_{2}$ increased removal efficiency as molar ratio of $Fe/H_{2}O_{2}$ between 0.2 and 2.5. Optimum dosage of molar ratio was 1. The removal efficiency for reaction condition was increased as pH decreased when the molar ratio of $Fe/H_{2}O_{2}$ was 1.7. Fenton's oxidation was most efficient in the reaction time 35 min for complex wastewater. Also, coagulation aid experiments using kaolin resulted in 3% of kaolin dosage.

• Journal of the Korean Society of Combustion
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• v.5 no.2
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• pp.37-50
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• 2000

In the present study, a systematic chemical kinetic calculations were made to investigate the augmentation of $NO-NO_2$ conversion due to the addition of various hydrocarbons (methane, ethylene, ethane, propylene, propane) in the nonthermal plasma treatment. It is included in the present conclusion that the reaction between hydrocarbon and oxygen radicals induced by electron collision, is believed to be a primarily process for triggering the overall NO oxidation and the eventual NOx reduction. Upon the completion of the initiating step, various radicals (OH, $HO_2$ etc.) successively are produced by hydrocarbon decomposition form the primary path of $NO-NO_2$ conversion. When the initiating step is not activated, hydrocarbon consumption rate appeared to be very low, thereby the targeted level of NO conversion can only be achieved by the addition of more input energy. Present study showed ethylene and propylene to have higher affinity with O radical under all conditions, thereby both of these hydrocarbons show very fast and efficient $NO-NO_2$ oxidation. It was also shown that propylene is superior to ethylene in the aspect of NOx removal.

• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3539-3543
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• 2012

Butacaine sulfate is an ester of p-aminobenzoic acid which has been widely used as a local anaesthetic and it is a long standing agent particularly for spinal anaesthesia. For this reason, a kinetic study of oxidation of butacaine sulfate by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried out in $HClO_4$ medium at 303 K in order to explore this redox system mechanistic chemistry. The rate shows a first-order dependence on both $[CAB]_o$, and $[substrate]_o$, and a fractional-order dependence on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increases the rate of the reaction. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction has been found to be 1:2 and the oxidation products have been identified by spectral analysis. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

• Journal of the Korean Chemical Society
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• v.57 no.3
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• pp.322-328
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• 2013

Copper iodide was employed as a modifier for preparation of a new carbon ceramic electrode. For the first time, the catalytic oxidation of amoxicillin (AMX) was demonstrated by cyclic voltammetry, chronoamperometry and amperometry methods at the surface of this modified carbon ceramic electrode. The copper iodide modified sol-gel derived carbon ceramic (CIM-SGD-CC) electrode has very high catalytic ability for electrooxidation of amoxicillin. The catalytic oxidation peak current was linearly dependent on the amoxicillin concentration and the linearity range obtained was 100 to 1000 ${\mu}mol\;L^{-1}$ with a detection limit of 0.53 ${\mu}mol\;L^{-1}$. The diffusion coefficient ($D=(1.67{\pm}0.102){\times}10^{-3}\;cm^2\;s^{-1}$), and the kinetic parameter such as the electron transfer coefficient (${\alpha}$) and exchange current density ($j_0$) for the modified electrode were calculated. The advantages of the modified CCE are its good stability and reproducibility of surface renewal by simple polishing, excellent catalytic activity and simplicity of preparation.