• 대한화학회지
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• 제56권1호
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• pp.28-33
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• 2012

The kinetics of ruthenium(III) chloride catalyzed oxidation of butanone and uncatalyzed oxidation of cyclohexanone by cerium(IV) in sulphuric acid medium have been studied. The kinetic rate law(I) in case of butanone conforms to the proposed mechanism. $$-\frac{1}{2}\frac{d[Ce^{IV}]}{dt}=\frac{kK[Ru^{III}][butanone]}{1+K[butanone]}$$ (1). However, oxidation of cyclohexanone in absence of catalyst accounts for the rate eqn. (2). $$-\frac{1}{2}\frac{[Ce^{IV}]}{dt}=\frac{(k_1+k_1K^'[H^+])[Ce^{IV}][Cyclohexanone]}{1+K_3[HSO_4^-]}$$ (2) Kinetics and activation parameters have been evaluated conventionally. Kinetically preferred mode of reaction is via ketonic and not the enolic forms.

• Carbon letters
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• 제9권2호
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• pp.121-126
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• 2008

High modulus pitch based carbon fibers (HM) were exposed to isothermal oxidation using tube furnace in carbon dioxide gas to study the oxidation kinetics under the temperature of $800-1100^{\circ}C$. The kinetic equation $f=1-{\exp}(-at^b)$ was introduced and the constant b was obtained in the range of 1.02~1.42. The oxidation kinetics were evaluated by the reaction-controlling regime (RCR) depending upon the apparent activation energies with the conversion increasing from 0.2 to 0.8. The activation energies decrease from 24.7 to 21.0 kcal/mole with the conversion increasing from 0.2 to 0.8, respectively. According to the RCR, the reaction was limited by more diffusion controlling regime for the HM fibers with the conversion increasing. Therefore, it seems that the oxidation which is under the diffusion controlling regime takes place continuously from the skin to the core of the fiber.

• 환경위생공학
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• 제16권1호
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• pp.66-71
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• 2001

The objective of this study was to depict the kinetic behavior of the platinum catalyst for the deep oxidation of aromatic solvents and their binary mixtures. The oxidation kinetics of aromatic solvents, which were benzene, toluene and m-xylene, was studied on a 0.5% $Pt/{\gamma}-Al_2O_3$ catalyst. Deep oxidation of binary mixtures, which were 1:1 in volume, was carried out and the inlet concentration was controlled in the range of 133 and 333ppmv. An approach based on the two-stage redox model was used to analysis the results. The deep oxidation conversion of aromatic solvents was inversely proportional to inlet concentration in plug flow reactor. This trend is due to the zeroth-order kinetics with respect to inlet concentration. The kinetic parameters of multicomponent model were independently evaluated from the single compound oxidation experiments. A simple multicomponent model based on two-stage redox rate model made reasonably good predictions of conversion over the range of parameters studied.

• 대한금속재료학회지
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• 제46권7호
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• pp.427-436
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• 2008

The effect of dewpoints on annealing behavior and coating characteristics such as wettability and galvannealing kinetics was studied by annealing 0.3wt%Si - 0.1~0.4wt% Mn added interstitial-free high strength steels(IF-HSS). The 0.3wt%Si-0.1wt%Mn steel exhibited good wettability with molten zinc and galvannealing kinetics after annealing when the dewpoint of $H_2-N_2$ mixed gas was above $-20^{\circ}C$. It is shown that the wettability and galvannealing kinetics are directly related to the coverage of the external(surface) oxide formed by selective oxidation during annealing. At $N_2-15%H_2$ annealing atmosphere, the increase of dewpoint results in a gradual transition from external to internal selective oxidation. The decrease of external oxidation of alloying elements with a concurrent increase of their subsurface enrichment in the substrate, showing a larger surface area that was free of oxide particles, contributed to the improved wettability and galvannealing kinetics. On the other hand, the corresponding wettability and galvannealing kinetics were deteriorated with the dewpoints below $-20^{\circ}C$. The continuous oxide layer of network and/or film type was formed on the steel surface, leading to the poor wettability and galvannealing kinetics. It causes a high contact angle between annealed surface and molten zinc and plays an interrupting role in interdiffusion of Zn and Fe during galvannealing process.

• Corrosion Science and Technology
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• 제19권1호
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• pp.43-50
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• 2020

In this study, the effects of KCl(s) and K₂SO₄(s) on the oxidation characteristics of 2.25Cr-1Mo steel were investigated for 500 h in 10O₂ + 10CO₂ (vol%) gas environmen at 650 ℃. Oxidation kinetics were characterized by weight gain, oxide layer thickness, and fitted models for the experiment data were proposed. The fitted models presented considerable agreement with the experimental data. The oxide layer was analyzed using the scanning electron microscope, optical microscope, and energy dispersive X-ray spectroscopy. The oxidation kinetics of 2.25Cr-1Mo steel with KCl and K₂SO₄ coatings showed significantly different oxidation kinetics. KCl accelerated the oxidation rate very much and had linear oxidation behavior. In contrast, K₂SO₄ had no significant effect, which had parabolic kinetics. The oxide layer was commonly composed of Fe₂O₃, Fe₃O₄, and FeCr₂O₄ spinel. KCl strongly accelerated the oxidation rates of 2.25Cr-1Mo steel in the high-temperature oxidation environment. Conversely, K₂SO₄ had little effect on the oxidation rates.

• Preventive Nutrition and Food Science
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• 제2권1호
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• pp.6-10
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• 1997

The reaction mechanisms and kinetics of tertiary butylhydroquinone(TBHQ) as an antioxidant in soybean oil oxidation were studied. The oxidation reaction of soybean oil at 55, 60 and $65^{\circ}C$ was a first order. The activation energies of soybean oil containing 0, 25, 50, and 75ppm TBHQ were 12.15, 6.05, 6.15 and 6.17kcal/mole. respectively. The addition of THQ to soybean oil containing 0, 25, 50, and 75ppm TBHQ were 1.88$\times${TEX}$10^{7}${/TEX}, 4.10$\times${TEX}$10^{2}${/TEX}, 4.32 $\times${TEX}$10^{2}$p/TEX} and 3.97$\times${TEX}$10^{2}${/TEX}, respectively. The decrease of frequency factor rather than the activation energy. The effects of antioxidants on the temperature dependecy of lipid oxidation could be effectively evaluated by measuring their effects on the activation energy of lipid oxidation.

• 한국환경보건학회지
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• 제30권2호
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• pp.133-139
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• 2004

The objective of this study was to investigate the destruction efficiency and to determine the fundamental parameters of oxidation kinetics under the supercritical water(SCW) condition. Target material was cephradine, toxic and antibiotic material, in the pharmaceutical wastewater. For this purpose, the effect of reaction temperature and oxidant were investigated on the destruction efficiency of cephradine. And the oxidation kinetics of cephradine was derived by using a empirical power-law model. The experiment was carried out in a cylindrical batch reactor made of Hastelloy C-276 which was endurable high temperature and pressure. The destruction efficiency of cephradine increased with increment of the temperature and reaction time. Also the type of oxidants was effected and oxidants(Air and $H_2O$$_2$) were enhanced the destruction efficiency. The global oxidation kinetics for cephradine has led to two rate expressions according to type of oxidant. - In the presence of air oxidant: Rate=k. $e^{-Ea}$RT/(Ceph.)$^{1.0}$ ( $O_2$)$^{0.51}$$\pm$0.05(k=3.27${\times}$$10^{5}$ sec. Ea=63.25 kJ/mole) - In the presence of $H_2O$$_2$ oxidant : Rate=kㆍ $e^{-Ea}$RT/(Ceph.)$^{1.0}$ ($H_2O$$_2$)$^{0.62}$$\pm$0.02(k=2.76${\times}$$10^4$/sec. Ea=47.65 kJ/mole)ole))

• 한국자동차공학회논문집
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• 제20권5호
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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 $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.

• 대한화학회지
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• 제56권2호
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• pp.212-216
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• 2012

The kinetics of oxidation of nicotinic acid by peroxomonosulfate (PMS) has been studied in acetate buffers. Stoichiometry of the reaction corresponds to the reaction of one mole of the oxidant with a mole of nicotinic acid. N${\rightarrow}$O product has been confirmed both by UV visible and IR spectroscopy. The reaction is second order viz. first order with respect to each reactant. Activation parameters have also been evaluated. A plausible reaction mechanism is mentioned and the derived kinetic rate law accounts for experimental observations.

• 한국정보디스플레이학회:학술대회논문집
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• 한국정보디스플레이학회 2000년도 제1회 학술대회 논문집
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• pp.63-64
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• 2000

The low-temperature Si oxidation kinetics by inductively coupled oxygen plasma has been studied. Linear rate constants had negative values when the oxide growth rate was described by linear-parabolic growth law. The analysis of transverse-optical mode frequencies and etch rates indicated that the density of surface oxide was lower than that of bulk oxide. The oxidation kinetics could be explained qualitatively by assuming a surface layer with larger diffusion coefficient and a bulk layer with smaller diffusion coefficient.