• Title/Summary/Keyword: Oxidation Kinetic

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Removal of Bisphenol-A using Rotating Photocatalytic Oxidation Drum Reactor (RPODR)

  • Son, Hee-Jong;Jung, Chul-Woo;Kim, Seung-Hyun
    • Environmental Engineering Research
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    • v.13 no.4
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    • pp.197-202
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    • 2008
  • This study evaluated the photocatalytic oxidation of BPA using the RPOD reactor under various conditions. This study found that the RPOD was effective for BPA degradation. It could reduce 1 mg/L of BPA by half within 5 min under the optimum conditions. According to the study results, $TiO_2$ coating was important for the BPA oxidation. As the coating thickness increased, the removal efficiency improved. The light source, the light intensity and the drum rotating speed were important for the oxidation. The UV light was more effective for the BPA degradation than the visible light. The removal efficiency improved with increasing intensity. As the drum speed increased, the removal efficiency improved. The maximum speed was 240 rpm in this study. Addition of air and nitrogen was not beneficial for the BPA degradation in this study probably due to enough oxygen in the water.

A Kinetic Study on the Electrodeposition of Zn-Fe Alloys (아연-철 합금도금에 관한 속도론적 연구)

  • 백찬영;안종관;이응조
    • Journal of the Korean institute of surface engineering
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    • v.27 no.1
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    • pp.45-53
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    • 1994
  • A kinetic study on the electrodeposition of zinc-iron alloys onto a steel in chloride solutions has been car-ried out using a rotating disc geometry. The results show that the deposition rate was increased with electropotential, disc rotation speed and temperature, and consequently the rate was partly controlled by elec-trochemical reaction and partly by mass transport. The iron content of deposit was more increased with cell voltage than with disc rotating speed and temperature. During electrodeposition process, the addition of metal-lic zinc powder retards oxidation rate of $Fe^{2+}$.

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Comparison of the Kinetic Behaviors of Fe2O3 Spherical Submicron Clusters and Fe2O3 Fine Powder Catalysts for CO Oxidation

  • Yoo, Seung-Gyun;Kim, Jin-Hoon;Kim, Un-Ho;Jung, Jin-Seung;Lee, Sung-Han
    • Bulletin of the Korean Chemical Society
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    • v.35 no.5
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    • pp.1379-1384
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    • 2014
  • ${\alpha}-Fe_2O_3$ spherical particles having an average diameter of ca. 420 nm and ${\alpha}-Fe_2O_3$ fine particles (< 10 ${\mu}m$ particle size) were prepared to examine as catalysts for CO oxidation. Kinetic studies on the catalytic reactions were performed in a flow reactor using an on-line gas chromatography system operated at 1 atm. The apparent activation energies and the partial orders with respect to CO and $O_2$ were determined from the rates of CO disappearance in the reaction stage showing a constant catalytic activity. In the temperature range of $150-275^{\circ}C$, the apparent activation energies were calculated to be 13.7 kcal/mol on the ${\alpha}-Fe_2O_3$ spherical submicron clusters and 15.0 kcal/mol on the ${\alpha}-Fe_2O_3$ fine powder. The Pco and $Po_2$ dependencies of rate were investigated at various partial pressures of CO and $O_2$ at $250^{\circ}C$. Zero-order kinetics were observed for $O_2$ on both the catalysts, but the reaction order for CO was observed as first-order on the ${\alpha}-Fe_2O_3$ fine powder and 0.75-order on the ${\alpha}-Fe_2O_3$ spherical submicron clusters. The catalytic processes including the inhibition process by $CO_2$ on the ${\alpha}-Fe_2O_3$ spherical submicron powder are discussed according to the kinetic results. The catalysts were characterized using XRD (X-ray powder diffraction), FE-SEM (field emission-scanning electron microscopy), HR-TEM (high resolution-transmission electron microscopy), and $N_2$ sorption measurements.

A Study on Oxidative Degradation of Chlorophenols by Heat Activated Persulfate (열적활성화된 과황산에 의한 염화페놀의 산화분해특성 연구)

  • Son, JiMin;Kwon, Hee-Won;Hwang, Inseong;Kim, Jeong-Jin;Kim, Young-Hun
    • Journal of Environmental Science International
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    • v.29 no.1
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    • pp.69-77
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    • 2020
  • Oxidative degradation of phenol, three monochlorophenols (2-chlorophenol, 2-CP; 3-chlorophenol, 3-CP; 4-chlorophenol, 4-CP), four dichlorophenols (2,3-dichlorophenol, 2,3-DCP; 2,4-dichlorophenol, 2,4-DCP; 2,5-dichlorophenol, 2,5-DCP; 2,6-dichlorophenol, 2,6-DCP), and two trichlorophenols (2,4,5-trichlorophenol, 2,4,5-TCP; 2,4,6-trichlorophenol, 2,4,6-TCP) was conducted with heat activated persulfate. As the number of chlorinations increased, the reaction rate also increased. The reaction rate was relatively well fitted to the zero-order kinetic model, rather than the pseudo-first order kinetic model for the reactions at 60 ℃, which can be explained by insufficient activation of the persulfate at 60 ℃, and the oxidation reaction of 2,4,6-TCP at 70 ℃ was relatively well fitted to the pseudo-first order kinetic model. The oxidation reaction rate generally increased with increase of persulfate concentration in the solution. 2,6-dichloro-2,5-cyclohexadiene-1,4-dione was found as a degradation product in a GC/MS analysis. This compound is a non-aromatic compound, and one chlorine was removed. This result is similar to the result of previous studies. The current study proved that heat activated persulfate activation could be an alternative remediation technology for phenol and chlorophenols in soil and groundwater.

N-Oxidation of Pyrazines by Bromamine-B in Perchloric Acid Medium: Kinetic and Mechanistic Approach

  • Puttaswamy;Shubha, J.P.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.9
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    • pp.1939-1945
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    • 2009
  • Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

An Experimental and Modeling Study on the Oxidation Kinetics of Nitric Oxide over Platinum-based Catalysts (백금계 촉매상에서 산화질소(NO)의 산화반응속도에 관한 실험 및 모델링 연구)

  • Kim, Young-Deuk;Jeong, Soo-Jin;Kim, Woo-Seung
    • 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 $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.

Piston Crevice Hydrocarbon Oxidation During Expansion Process in an SI Engine

  • Kyoungdoug Min;Kim, Sejun
    • Journal of Mechanical Science and Technology
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    • v.17 no.6
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    • pp.888-895
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    • 2003
  • Combustion chamber crevices in SI engines are identified as the largest contributors to the engine-out hydrocarbon emissions. The largest crevice is the piston ring-pack crevice. A numerical simulation method was developed, which would allow to predict and understand the oxidation process of piston crevice hydrocarbons. A computational mesh with a moving grid to represent the piston motion was built and a 4-step oxidation model involving seven species was used. The sixteen coefficients in the rate expressions of 4-step oxidation model are optimized based on the results from a study on the detailed chemical kinetic mechanism of oxidation in the engine combustion chamber. Propane was used as the fuel in order to eliminate oil layer absorption and the liquid fuel effect. Initial conditions of the burned gas temperature and in-cylinder pressure were obtained from the 2-zone cycle simulation model. And the simulation was carried out from the end of combustion to the exhaust valve opening for various engine speeds, loads, equivalence ratios and crevice volumes. The total hydrocarbon (THC) oxidation in the crevice during the expansion stroke was 54.9% at 1500 rpm and 0.4 bar (warmed-up condition). The oxidation rate increased at high loads, high swirl ratios, and near stoichiometric conditions. As the crevice volume increased, the amount of unburned HC left at EVO (Exhaust Valve Opening) increased slightly.

Deposition of copper oxide by reactive magnetron sputtering

  • Lee, Jun-Ho;Lee, Chi-Yeong;Lee, Jae-Gap
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2010.05a
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    • pp.49.2-49.2
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    • 2010
  • Copper oxide films have been deposited on silicon substrates by direct current magnetron sputtering of Cu in O2 / Ar gas mixtures. The target oxidation occurring as a result of either adsorption or ion-plating of reactive gases to the target has a direct effect on the discharge current and the resulting composition of the deposited films. The kinetic model which relates the target oxidation to the discharge current was proposed, showing the one-to-one relationship between discharge current characteristics and film stoichiometry of the deposited films.

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Impact of Storage Temperature on Quality Characteristics and Oxidation Kinetic of Perilla Seed (저장온도가 들깨의 품질특성 및 산화속도에 미치는 영향)

  • Lee, Kyo-Yeon;Kim, Ah-Na;Rahman, M. Shafiur;Lee, Myoung Hee;Kim, Jung In;Kwak, Doyeon;Kim, Hyun-Jin;Choi, Sung-Gil
    • The Korean Journal of Food And Nutrition
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    • v.32 no.6
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    • pp.669-677
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    • 2019
  • The impact of storage temperature on the changes in acid value(AV), peroxide value(POV), color value, total phenolic content(TPC), and antioxidant activity in perilla seed(PS) was investigated. The PS was stored at 25, 35, and 45℃ for four weeks. An increase in the storage temperature resulted in significantly increased AV, POV, redness, and yellowness of the PS. Conversely, TPC, antioxidant activity, and redness of the PS significantly decreased. The changes in the AV and POV followed a first-order kinetic model, and the kinetic parameters such as k, t1/2, Q10 and Ea were calculated. The k and t1/2 values decreased with increasing storage temperature and the Q10 values for the AV and POV were 1.56, 1.91, 4.61, and 3.43, respectively. The Ea for the changes in of the AV and POV in the PS were 70.40, 102.63 kJ/mol, respectively. The half-life values for the AV and POV of the PS at 25℃ were 169.52 and 373.18 days, respectively, while the values at 45℃ for those, were 28.47 and 27.93 days, respectively.

An Advanced Kinetic Method for HO2·/O2-· Determination by Using Terephthalate in the Aqueous Solution

  • Kwon, Bum Gun;Kim, Jong-Oh;Kwon, Joong-Keun
    • Environmental Engineering Research
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    • v.17 no.4
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    • pp.205-210
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    • 2012
  • Hydroperoxyl radical/superoxide anion radical ($HO_2{\cdot}/O_2^-{\cdot}$, $pK_a$=4.8) as an intermediate is of considerable importance in oxidation processes. Hence, the method of detecting $HO_2{\cdot}/O_2^-{\cdot}$ with high sensitivity is necessary to be developed. To achieve this objective, this study newly employed terephthalate (TA) as a probe for the measurement of $HO_2{\cdot}/O_2^-{\cdot}$ in the kinetic method presented in our previous study. This method was based on the hydroxylation of TA to produce mainly hydroxyterephthalic acid or hydroxyterephthalate (OHTA), which was analyzed by fluorescence detection (${\lambda}_{ex}$=315nm, ${\lambda}_{ex}$=425nm). The life-time of $HO_2{\cdot}/O_2^-{\cdot}$ and its concentration formed from the photolysis technique of $H_2O_2$ were reported in this study. At range of pH 2-10, the life-time of $HO_2{\cdot}/O_2^-{\cdot}$ was 51-422 sec. In particular, an increase in the life-time with pH was observed. The sensitivities of the kinetic method by using TA were always higher with 1.7-2.5 times at pH 8.0 than those by using benzoic acid. From these results, this study can contribute to understanding the basic functions of $HO_2{\cdot}/O_2^-{\cdot}$ in oxidation processes.