• Bulletin of the Korean Chemical Society
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• 제23권1호
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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.

• Bulletin of the Korean Chemical Society
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• 제9권5호
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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.

• International Journal of Automotive Technology
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• 제7권3호
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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.

• 공업화학
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• 제28권6호
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• pp.619-625
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• 2017

본 연구에서는 하이드로퍼옥시 라디칼 생성단계에서 반응 부산물로 생성되는 과산화수소를 정량하여 수산화라디칼의 생성 및 비스페놀 A (BPA)의 분해특성을 조사하였다. 라디칼 연쇄반응이 일어나지 않는 조건에서는 Criegee mechanism과 동일하게 오존에 의한 직접산화반응만이 BPA를 분해시키는 것으로 나타났다. 라디칼 연쇄반응이 일어나는 pH 6.5 및 9.5의 조건에서는 비선택적 산화반응이 일어나 수산화라디칼의 생성을 간접적으로 확인할 수 있었다. 투입된 촉매에 의한 BPA의 분해효율은 $O_3$/PAC ${\geq}$ $O_3/H_2O_2$ > $O_3$/high pH > $O_3$ alone 공정 순으로 나타났다. 오존/촉매공정들의 산화반응 동안에는 0.03~0.08 mM의 과산화수소가 지속적으로 측정되었다. $O_3$/high pH 공정의 경우, BPA가 반응시작 50 min 만에 완전히 분해되었지만, TOC (총유기탄소) 제거율은 29%로 산화반응 중 생성된 중간물질을 충분히 산화시키지 못하는 것으로 나타났다(선택적 산화반응). $O_3/H_2O_2$ 및 $O_3$/PAC 공정에서는 BPA가 반응시작 40 min 만에 완전히 분해되었으며, TOC 제거율은 각각 57% 및 66% 정도로 반응 중간체들을 산화(비선택적 산화반응)시키는 것으로 나타났다.

• 생명과학회지
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• 제5권2호
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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.

• 한국대기환경학회지
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• 제3권1호
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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 $ro_2 = 2.49 \times 10^{-7} P_O_2^{0.604}$.

• 한국응용과학기술학회지
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• 제20권2호
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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.

• BMB Reports
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• 제29권1호
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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.

• 공업화학
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• 제35권2호
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• pp.79-84
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• 2024

메탄은 풍부하고 재생 가능한 탄화수소이지만, 온실가스로서 지구 온난화를 발생시킨다. 따라서 메탄을 유용한 화학물질이나 에너지원으로의 변환이 필요하다. 메탄올은 메탄의 부분 산화 반응을 통해 합성할 수 있는 간단하고 풍부한화학물질이다. 메탄올은 화학 공급 원료나 수송 연료로 사용될 뿐만 아니라, 저온 연료 전지의 연료로도 적합하다. 그러나 메탄올의 전기화학 산화는 복잡하고 다단계의 반응이므로, 이 반응을 이해하고 최적화하기 위해서는 새로운 전기화학촉매와 반응 메커니즘의 연구가 필요하다. 본 총설에서는 메탄올 산화 반응 메커니즘 및 최근 연구 동향과 향후 연구 방향을 고찰하였다.

• Bulletin of the Korean Chemical Society
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• 제23권3호
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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.