• Title/Summary/Keyword: Oxidation Reaction

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Liquid Phase Oxidation of Xylenes: Effects of Water Concentration and Alkali Metals

  • Jhung, Sung-Hwa;Lee, Ki-Hwa;Park, Youn-Seok
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.59-64
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    • 2002
  • A facile and precise batch oxidation reaction system allows continuous monitoring of the oxidation rate and cumulated oxygen conversion of xylenes, and the side reactions to carbon monoxide and carbon dioxide may also be studied. The oxidation reaction can be analyzed precisely with the rate and amount of oxygen consumed. The reaction reveals that 4-carboxybenzaldehyde is an unstable intermediate of p-xylene oxidation as the reaction proceeds instantaneously from p-toluic acid to TPA (terephthalic acid). The alkali metals accelerate oxidation, even though they retard the reaction initially. The oxidation rate increases with decreasing water concentration. However, in the later part of reaction, the reactivity decreases a bit if the water concentration is very low. This retarding effect of water can be overcome partly by the addition of potassium. The oxidation of o-xylene, compared with the oxidation of p-xylene and m-xylene, proceeds quite fast initially, however, the oxidation rate of xylene isomers in the later stage of reaction is in the order of p-xylene > mxylene > o-xylene.

Interaction Metal Ions with NADH Model Compounds. Cupric Ion Oxidation of Dihydronicotinamides

  • Park, Joon-Woo;Yun, Sung-Hoe;Koh Park, Kwang-Hee
    • Bulletin of the Korean Chemical Society
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    • v.9 no.5
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    • pp.298-303
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    • 1988
  • Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.

INVESTIGATION OF SOOT OXIDATION CHARACTERISTICS IN A SIMULATED DIESEL PARTICULATE FILTER

  • Lee, H.S.;Chun, K.M.
    • International Journal of Automotive Technology
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    • v.7 no.3
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    • pp.261-267
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    • 2006
  • Understanding the mechanism of carbon oxidation is important for the successful modeling of diesel particulate filter regeneration. Carbon oxidation characteristics were investigated by temperature programmed oxidation(TPO) method as well as constant temperature oxidation(CTO) with a flow reactor including porous bed. The activation energy of carbon oxidation was increasing with temperature and had two different constant values in the early and the later stage of the oxidation process respectively in TPO experiment. Kinetic constants were derived and the reaction mechanisms were assumed from the experimental results and a simple reaction scheme was proposed, which approximately predicted the overall oxidation process in TPO as well as CTO.

A Comparison between the Decomposition of Bisphenol A and the Concentration of Hydrogen Peroxide Formed during Ozone/Catalyst Oxidation Process (오존/촉매 산화공정에서 비스페놀 A의 분해와 생성된 과산화수소의 농도 비교)

  • Choi, Jae Won;Lee, Hak Sung
    • Applied Chemistry for Engineering
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    • v.28 no.6
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    • pp.619-625
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    • 2017
  • In this study, the formation of hydroxyl radical and decomposition characteristics of bisphenol A (BPA) was investigated by quantifying hydrogen peroxide formed as a reaction by-product during the formation stage of hydroperoxyl radical. The direct oxidation reaction by ozone only decomposed BPA just like the Criegee mechanism under the condition where radical chain reactions did not occur. Non-selective oxidation reactions occurred under the conditions of pH 6.5 and 9.5 where radical chain reactions do occur, confirming indirectly the formation of hydroxyl radical. The decomposition efficiency of BPA by the added catalysts appeared in the order of $O_3$/PAC ${\geq}$ $O_3/H_2O_2$ > $O_3$/high pH > $O_3$ alone. 0.03~0.08 mM of hydrogen peroxide were continuously measured during the oxidation reactions of ozone/catalyst processes. In the case of $O_3$/high pH process, BPA was completely decomposed in 50 min of the oxidation reaction, but reaction intermediates formed by oxidation reaction were not oxidized sufficiently with 29% of the removal ratio for total organic carbon (TOC, selective oxidation reaction). In the case of $O_3/H_2O_2$ and $O_3$/PAC processes, BPA was completely decomposed in 40 min of the oxidation reaction, and reaction intermediates formed by the oxidation reaction were oxidized with 57% and 66% of removal ratios for TOC, respectively (non-selective oxidation reactions).

Effect of Lipoxygenase on the Oxidation of Rainbow Trout Lipid in Model system (모델시스템에 있어서 무지개 송어 지방질의 산화에 대한 Lipoxygenase의 영향)

  • 김혜경;엄수현;최홍식
    • Journal of Life Science
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    • v.5 no.2
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    • pp.70-75
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    • 1995
  • The effect of lipoxygenase (LOX) on the oxidation and co-oxidation of lipid fraction was studied in the model system of rainbow trout. For the reaction in model system 1 g of lipid fraction and 50mL of enzyme extract(LOX, 140 unit in 50mL phosphate buffer solution at pH 7, 4)), which were obtained from rainbow trout, were homoginized in the presence of Tween 20 and kept at 23$\circ$C for 3 days. The activity of LOX was decreased to 43% of initial level during the reaction in the model system. The initial composition of rainbow trout lipid was showed to be consisted of trigliceride(TG;82%) and free fatty acid(FFA;0.1%), while this converted to 59% of TG and 20% of FIFA, respectively after reaction in model system. Change of fatty acid composition was also observed and the content of linoleic acid, one of the major fatte acids, was decreased to 13% from 54% in the content of total fatty acids after reaction. The carotenoids in rainbow trout were composed of 0.4% $\alpha$-carotene, 1.6% $\beta$ -carotene, 80% canthaxanthin, 7% lutein and 11% zeaxanthin, thus the canthaxanthin was the major component. This canthaxanthin was the most degraded carotenoid by lipoxygenase catalyzed co-oxidation during the reaction. On the other hand the tocopherol isomers found in the rainbow trout were $\alpha$ and $\beta$ -tocopherol, and $\alpha$-tocopherol had a higher degradation rate by the lipoxygenase catalyzed co-oxidation than of $\beta$-tocopherol in the reaction of model system.

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Adsorption and Oxidation Reaction Rate of $SO_2$ in Slurries of Activated Carbon (활성탄 슬러리를 이용한 $SO_2$ 가스의 흡착 및 산화반응 속도)

  • 최용택;신창섭;이태희
    • Journal of Korean Society for Atmospheric Environment
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    • v.3 no.1
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    • pp.41-46
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    • 1987
  • Adsorption and reaction studies were made for the catalytic oxidation in aqueous slurries of activated carbon at room temperature and atmospheric pressure. In order to analyze the reaction rate, the mechanism was assumed by the steps of nonhomogeneous catalytic reaction. The experimental result show that oxidation rate was controlled by the reaction between adsorbed molecular oxygen and sulfur dioxide on the catalyst surface. Ar room temperature, the equat5ion of reaction rate was given as $ro_2 = 2.49 \times 10^{-7} P_O_2^{0.604}$.

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A Study on the Synthesis of Oxidized Polyethylene Wax by Controlling Reaction Parameters (공정변수를 조절한 폴리에틸렌 산화왁스 합성에 관한 연구)

  • Yang, Chun-Hoe
    • Journal of the Korean Applied Science and Technology
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    • v.20 no.2
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    • pp.141-147
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    • 2003
  • Oxidized polyethylene wax is obtained by oxidation of polyethylene wax and it is composed of various chemicals, e.g., fatty acid, alcohol, ketone and ester. The application of oxidized polyethylene wax is determined by the composition of these chemical substances. In this basic study we observed the basic reaction parameters of time, temperature, oxygen concentration and catalysts on the oxidation reaction of low molecular weight polyethylene(PE wax) by analyzing the acid value, physical and chemical properties of oxidized PE wax to develop a new oxidation process. Acid values are increased with temperature increase in the rage of $150^{\circ}C^{\sim}180^{\circ}C$ but decreased beyond 190$^{\circ}C$. Acid values are also increased with oxygen concentration. As the oxidation reaction proceeds the molecular weight and softening points of oxidation products are decreased by cracking reaction, but the viscosities are increased. To observe the crystallinity of oxidation products SEM experiment was performed. To obtain a high acid-value product in a mild condition, we adopted free radical catalysts and the acid value of the product using catalyst was higher than the product obtained without catalyst in the same reaction condition. The effective initiators were dicumyl peroxide(DCPO), t-butylperoxy-2-ethyl hexanoate(HOPO) and benzoyl peroxide(BPO) having long half-life.

S-Thiolation and Oxidation of Glycogen Phosphorylase b and Peroxidation of Liposome Initiated by Free Radical Species

  • Lee, Kyu-Sun;Lee, Hyung-Min;Park, Young-Mee;Chang, Byeong-Doo;Chung, Tae-Young;Choi, Eun-Mi
    • BMB Reports
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    • v.29 no.1
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    • pp.81-87
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    • 1996
  • The relationship of S-thiolation and oxidation of glycogen phosphorylase b and peroxidation of phosphatidyl choline liposome by xanthine oxidase (XOD), 2,2'-azobis(2-amidinopropane) hydrochloride (AAPH), and 2,2'-azobis(dimethylvaleronitrile) (AMVN)-generated free radicals was investigated, Glycogen phosphorylase b was S-thiolated in the presence of glutathione and oxidized in the absence of it by XOD, AAPH and AMVN. In XOD-initiated reaction, the rates of S-thiolation and oxidation of phosphorylase were very similar and addition of liposome to the reaction mixture showed little inhibition of the modifications. In AAPH-initiated reaction, the rate of oxidation was higher than that of S-thiolation and addition of liposome increased oxidation of the protein but had no effect on S-thiolation. In AMVN-initiated reaction, S-thiolation was higher than oxidation and addition of liposome increased S-thiolation remarkably but showed no effect on oxidation. The effect of liposome on modifications of protein in AAPH and AMVN reaction seemed to be caused by certain reactive degradation products or intermediates of liposome by free radical attack. Peroxidation of liposome was not observed in XOD-initiated reaction. Liposome was gradually peroxidized by AAPH reaction. The peroxidation was inhibited by addition of GSH and phosphorylase. Peroxidation of liposome by AMVN was extreamly fast, and was not affected by GSH and phosphorylase.

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The Trends in Methanol Oxidation Reaction Mechanisms and Electrochemical Oxidation Catalysts (메탄올 산화 반응 메커니즘과 전기화학 산화 촉매 최신 동향)

  • Sungyool Bong
    • Applied Chemistry for Engineering
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    • v.35 no.2
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    • pp.79-84
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    • 2024
  • Methane is an abundant and renewable hydrocarbon, but it causes global warming as a greenhouse gas. Therefore, methods to convert methane into useful chemicals or energy sources are needed. Methanol is a simple and abundant chemical that can be synthesized by the partial oxidation of methane. Methanol can be used as a chemical feedstock or a transportation fuel, as well as a fuel for low-temperature fuel cells. However, the electrochemical oxidation of methanol is a complex and multi-step reaction. To understand and optimize this reaction, new electrocatalysts and reaction mechanisms are required. This review discusses the methanol oxidation reaction mechanism, recent research trends, and future research directions.

Precipitation of Manganese in the p-Xylene Oxidation with Oxygen-Enriched Gas in Liquid Phase

  • Jhung, Sung-Hwa;Park, Youn-Seok
    • Bulletin of the Korean Chemical Society
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    • v.23 no.3
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    • pp.369-373
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    • 2002
  • The liquid phase oxidation of p-xylene has been carried out with oxygen-enriched gas, and the manganese component was precipitated probably via over-oxidation to $Mn^{4+}$. The precipitation increased with rising oxygen concentration in the reaction gas and occurred mainly in the later part of the oxidation. The activity of the reaction decreased, and the blackening of the product and side reactions to carbon dioxide increased with the degree of precipitation. Precipitation can be decreased with the addition of metal ions, such as cerium, chromium and iron.