• Title/Summary/Keyword: 환원반응기구

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Solution Phase Photolyses of Substituted Diphenyl Ether Herbicides under Simulated Environmental Conditions (모조(模造) 환경조건하(環境條件下)에서의 치환(置換) Diphenyl Ether 제초제(除草劑)의 광분해(光分解)에 관(關)한 연구(硏究))

  • Lee, Jae-Koo
    • Applied Biological Chemistry
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    • v.17 no.3
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    • pp.149-176
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    • 1974
  • Eight substituted diphenyl ether herbicides and some of their photoproducts were studied in terms of solution phase photolysis under simulated environmental conditions by using a Rayonet photochemical reactor. The test compounds absorbed sufficient light energy at the wavelength of 300 nm to undergo various photoreactions. All the photoproducts were confirmed by means of tlc, glc, ir, ms, and/or nmr spectrometry. The results obtained are summarized as follows: Solution phase photolysis of C-6989: An exceedingly large amount of p-nitrophenol formed strongly indicates the readiness of the ether linkage cleavage of this compound as the main reaction in all solvents used. Photoreduction of nitro to amino group(s) and photooxidation of trifluoromethyl to carboxyl group were recognized as minor reactions. Aqueous photolysis of p-nitrophenol: Quinone(0.28%), hydroquinone (0.66%), and p-aminophenol (0.42%) were confirmed as photoproducts, in addition to a relatively small amount of an unknown compound. The mechanisms of formation of these products were proposed to be the nitro-nitrite rearrangement via $n{\rightarrow}{\pi}^*$ excitation and the photoreduction through hydrogen abstractions by radicals, respectively. Solution phase photolysis of Nitrofen: Photochemical reduction leading to the p-amino derivative was the main reaction in n-hexane. In aqueous solution, the photoreduction of nitro to amino group and hydroxylation predominated over the ether linkage cleavage. Nucleophilic displacement of the nitro group by hydroxide ion and replacement of chlorine substituents by hydroxyl group or, to a lesser extent, hydrogen were also observed as minor reactoins. Solution phase photolysis of MO-338: Photoreduction of the nitro to amino group was marked in the n-hexane solution photolysis. In the aqueous solution, photoreduction of the nitro substituent and hydroxylation were the main reactions with replacement of chlorine substituents by the hydroxyl group and hydrogen, and cleavage of the ether linkage as minor reactions. Photolyses of MC-4379, MC-3761, MC-5127, MC-6063, and MC-7181 in n-hexane and cyclohexane: Photoreduction of the nitro group leading to the corresponding amino derivative and replacement of one of the halogen substituents by hydrogen from the solvent used were the key reactions in each compound. Aqueous photolysis of MC-4379: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, hydroxylation, and replacement of the nitro by hydroxy group were prominent with photoreduction and dechlorination as minor reactions. Aqueous photolysis of MC-3761: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, and photoreduction followed by hydroxylation were the main reactions. Aqueous photolysis of MC-5127: Replacement of carboxyethyl by hydrogen was predominant with ether linkage cleavage, photoreduction, and dechlorination as minor reactions. It was obvious that the decarboxyethylation proceeded more readily than decarboxymethylation occurring in the other compounds. Aqueous photolysis of MC-6063: Cleavage of the ether linkage and photodechlorination were the main reactions. Aqueous photolysis of MC-7181: Replacement of the carboxymethyl group by hydrogen and monodechlorination were the remarkable reactions. Cleavage of the ether linkage and hydroxylation were thought to be the minor reactions. Aqueous photolysis of 3-carboxymethyl-4-nitrophenol: The photo-induced Fries rearrangement common to aromatic esters did not appear to occur in the carboxymethyl group of this type of compound. Conversion of nitro to nitroso group was the main reaction.

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The Adsorption of COS with a Modified-Activated Carbon for Ultra-Cleanup of Coal Gas (석탄가스의 초정밀 정제를 위한 변형된 활성탄의 흡착특성 연구)

  • Lee, You-Jin;Park, No-Kuk;Lee, Tae-Jin
    • Clean Technology
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    • v.13 no.4
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    • pp.266-273
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    • 2007
  • The adsorption properties of the activated carbon-based adsorbents were studied to remove COS emitted from $SO_2$ catalytic reduction process on the integrated gasification combined cycle (IGCC) system in this work. Transition metal supported catalysts and mixed metal oxide catalysts were used for the $SO_2$ catalytic reduction. The mechanism of COS produced from the $SO_2$ reduction and the COS concentration s according to the reaction temperature were investigated. In this study, an activated carbon and a modified activated carbon doped with KOH were used to remove the very low concentration of COS effectively. The adsorption rate and the breakthrough time of COS were measured by a thermo gravity analyzer (TGA, Cahn Balance) and a fixed bed flow reactor equipped with GC-pulsed flammable photometric detector (PFPD), respectively. It was confirmed that the COS breakthrough time of the activated carbon doped with KOH was longer than that of an activated carbon. In conclusion, the modified-activated carbon having a high surface area showed a high adsorption rate of COS produced from the $SO_2$ reduction.

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A Study on the Reaction between Carbon Monoxide and Nitric Oxide on Platinum Catalyst (백금촉매상에서 일산화탄소와 일산화질소의 반응에 관한 연구)

  • Park, Youn-Seok;Kim, Young-Ho;Lee, Ho-In
    • Applied Chemistry for Engineering
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    • v.1 no.2
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    • pp.207-214
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    • 1990
  • The catalytic reaction between CO and NO on polycrystalline Pt surface, which is very important in the development of catalyst for automobile exhaust gas control, has been studied using thermal desorption spectrometry(TDS) and steady-state experiment under ultra-high vacuum(UHV) conditions. With the pressures of CO and NO of each $1{\times}10^{-7}Torr$, the $CO_2$ formation rate showed a maximum at 560K. At the reaction temperature of 560K and the NO pressure of $1{\times}10^{-7}Torr$, the production of $CO_2$ was first order in $CO_2$ was first order in CO pressure below $1.35{\times}10^{-7}Torr$ of CO pressure whereas at higher CO pressures the rate became minus 0.3 order in CO. But the efforts of reactant pressure on the reaction was understood in consideration of the surface concentrations of adsorbates. With the results, we proposed a new reaction mechanism for this reaction.

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A Study on the Mechanism of Micro-ECM by Use of Point Electrode Method (점 전극을 이용한 마이크로 전해가공 기구에 관한 연구)

  • Kim, Bong-Gyu;Jeon, Jong-Up;Park, Kyu-Yeol
    • Journal of the Korean Society for Precision Engineering
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    • v.19 no.8
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    • pp.77-83
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    • 2002
  • This research aimed at from the establishment of theory on micro electrochemical machining mechanism to the implementation of a practical fabrication system of micro parts. In detail, the mechanism of micro-ECM was investigated with potentiodynamic method and the optimal condition for micro-ECM was selected by voltage-current-time curve with potentiostatic method. From the experimental result, the micro part which has extremely fine surface could be fabricated by use of micro-ECM with point electrode method.

특집:녹색선박 SCR시스템 기술개발 현황 - 선박용 SCR 국내.외 현황 및 시장동향

  • Jeong, Gyeong-Yeol;Park, Chang-Dae;Im, Byeong-Ju;Bae, Jong-Uk
    • 기계와재료
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    • v.24 no.2
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    • pp.18-26
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    • 2012
  • 지구 환경오염문제가 대두되면서 세계 각국에서는 환경오염을 최소화하려는 움직임이 활발히 이루어지고 있다. 국제해사기구(IMO)에서는 해양 대기오염의 상당량이 선박에서 배출되는 배기가스에 의한 것으로 판단하고 있으며, 이에 따라 선진국을 중심으로 선박관련 환경규제 및 선박 배기가스 배출기준을 점차적으로 강화해 가고 있고, 친환경 선박 및 기자재 개발을 적극적으로 진행하고 있다. 현재 선박에 적용 가능한 NOx 제거장치로는 ECR(Exhaust Gas Recirculation), SCR(Selective, Catalytic Reduction), SAM(Scavenge Air Moistening) 등이 개발되었으며, 연소온도 조절 및 촉매 환원반응 등을 이용하여 NOx를 제거하고 있다. 현재 개발된 탈질설비 중 현실적으로 가장 적합한 것은 SCR시스템으로 인식되고 있으나, 연료효율 감소로 인하여 가스연료를 이용하거나 새로운 연료개발 등 사용연료에 변화를 주는 방법들이 미래의 대안으로 제시되고 있다.

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Desmutagenic Effects of Seaweed and Vegetable Extracts against Mutagenicity of Maillard Reaction Products (Maillard 반응생성물의 돌연변이원성에 대한 해조 및 야채추출물의 억제효과)

  • KIM In-Soo;KIM Seon-Bong;PARK Yeung-Ho
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.27 no.2
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    • pp.133-139
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    • 1994
  • The desmutagenic effects of seaweed and vegetable extracts were investigated on the mutagenicity of Maillard reaction products (MRP) obtained from equimolar amounts of glucose and amino acid (arginine and lysine${\cdot}$HCl) for Salmonella typhimurium TA 100 without S9 mix. The mutagenicities were inhibited by water-soluble extracts of seaweeds(laver, sea-straghorn, sea-mustard and tangle) and vegetables(ginger, garlic, onion, chinese-pepper, green-onion and cabbage). Cabbage, chinese-pepper, green-onion and sea-straghorn exhibited especially high desmutagenic effects. The desmutagenicities of these extracts(cabbage, green-onion and sea-straghorn) except for sea-straghorn were decreased by heat treatment at $100^{\circ}C$ for 10 min. It is assumed that the desmutagenic effect of seaweed and vegetable extract is due to the reducing power and action of enzyme such as peroxidase and catalase.

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Comparative Studies on Mechanism of Photocatalytic Degradation of Rhodamine B with Sulfide Catalysts under Visible Light Irradiation (가시광선하에서 황화물계 광촉매를 이용한 로다민 B의 광분해 반응기구에 대한 비교 연구)

  • Lee, Sung Hyun;Jeong, Young Jae;Lee, Jong Min;Kim, Dae Sung;Bae, Eun Ji;Hong, Seong Soo;Lee, Gun Dae
    • Clean Technology
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    • v.25 no.1
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    • pp.46-55
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    • 2019
  • CdS and CdZnS/ZnO materials were prepared using precipitation method and used as photocatalysts for the photocatalytic degradation of rhodamine B (RhB) under visible light irradiation. The prepared photocatalysts were also characterized by XRD and UV-vis DRS. The results indicated that the photocatalysts with intended crystalline structures were successfully obtained and both the CdS and CdZnS/ZnO can absorb visible light as well as UV. The photocatalytic activities were examined with the addition of scavenger for various active chemical species and the difference of reaction mechanisms over the catalysts were discussed. The $CH_3OH$, KI and p-benzoquinone were used as scavengers for ${\cdot}OH$ radical, photogenerated positive hole and ${\cdot}O_2{^-}$ radical, respectively. The CdS and CdZnS/ZnO showed different photocatalytic degradation mechanisms of RhB. It can be postulated that ${\cdot}O_2{^-}$ radical is the main active species for the reaction over CdS photocatalyst, while the photogenerated positive hole for CdZnS/ZnO photocatalyst. As a result, the predominant reaction pathways over CdS and CdZnS/ZnO photocatalysts were found to be the dealkylation of chromophore skeleton and the cleavage of the conjugated chromophore structure, respectively. The above results may be mainly ascribed to the difference of band edge potential of conduction and valence bands in CdS, CdZnS and ZnO semiconductors and the redox potentials for formation of active chemical species.

Synthesis of Aniline from Nitrobenzene and Fe(CO)5 with PEG/γ-Al2O3 as Phase Transfer Catalyst (PEG/γ-Al2O3 상이동 촉매상에서 니트로벤젠과 Fe(CO)5로부터의 아닐린 합성)

  • Oh, So-Young;Lee, Hwa-Su;Park, Dae-Won;Park, Sang-Wook;Shin, Jung-Ho
    • Applied Chemistry for Engineering
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    • v.4 no.1
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    • pp.144-152
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    • 1993
  • Immobilized polyethylene glycols onto metal oxides such as ${\gamma}-Al_2O_3$, ${\alpha}-Al_2O_3$, $SiO_2$ and $TiO_2$ were used as phase transfer catalysts for the room temperature synthesis of aniline from nitrobenzene and ironpentacarbonyl. The amount of attached PEG molecules increased with specific surface area of metal oxides. Among the immobilized catalysts tested PEG/${\gamma}-Al_2O_3$ showed the highest activity. The reaction rate increased with the chain length of PEG mole-cules and the aqueous NaOH concentration. Mechanistic study carried out using infrared spectrometer revealed that the role of PEG was to increase the formation of $HFe(CO)_4{^-}$ ion, which is known as active species, and its movement from aqueous to organic phase.

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A Study on the Development of Electrolysis System with Vertically Circulating Mercury Capillary Bundle Electrode and its Characteristics (수직형 순환식 수은 모세관 다발체 전극 전해계의 개발과 그 특성 연구)

  • Kim, Kwang-Wook;Lee, Eil-Hee;Shin, Young-Joon;Yoo, Jae-Hyung;Park, Hyun-Soo
    • Applied Chemistry for Engineering
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    • v.7 no.2
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    • pp.228-236
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    • 1996
  • An electrolysis system with a vertically circulating mercury capillary bundle electrode was developed with a very large electrode area in a minimum space. This system was operated by forcedly feeding mercury and aqueous solution containing metal ion into a fiber bundle packed densely within a small porous glass tube. In order to test the characteristics and stability of the electrolysis system, the reduction voltammograms of uranyl and ferric ions were measured with changes of the mercury flow rate and the aqueous flow rate. The aqueous flow rate had a large effect on the electrochemical reaction of metal ion occurring at the interface between the mercury and the aqueous solution and had to be regulated as an appropriate value to have a good limiting current shape. The limiting current was linearly proportional to the aqueous flow rate, and complete reductions of uranyl and ferric ions were rapidly and continuously accomplished at the potential showing limiting current. With a mercury flow rate high enough to keep a capillary continuum of mercury in the fiber bundle, the mercury flow rate had almost no effect on the electrochemical reaction. This system was confirmed to be effective and stable enough to control rapidly and continuously the oxidation state of metal ions fed into the system under an appropriate aqueous flow rate.

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Preparation of ZrC/SiC by Carbothermal Reduction of Zircon (지르콘의 탄소열환원에 의한 ZrC/SiC의 합성)

  • Park, Hong-Chae;Lee, Yoon-Bok;Lee, Cheol-Gyu;Oh, Ki-Dong
    • Applied Chemistry for Engineering
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    • v.5 no.6
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    • pp.1044-1055
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    • 1994
  • The preparation of ZrC/SiC mixed powders from $ZrSiO_4/C$ and $ZrSiO_4/Al/C$ systems was attempted in the temperature range below $1600^{\circ}C$ under Ar or $Ar/H_2$ gas flow(100-500ml/min). The formation mechanism and kinetics of ZrC/SiC were suggested and the resultant powders were characterized. In $ZrSiO_4/C$ system, ZrC and SiC were formed by competitive reaction of $ZrO_2(s)$ and SiO(g) with carbon at temperature higher than $1400^{\circ}C$. The apparent activation energy for the formation of ZrC was approximately 18.5kcal/mol($1400-1600^{\circ}C$). In $ZrSiO_4/Al/C$ system, ZrC was formed by reaction of ZrO(g) with Al(l, g) and carbon at temperature higher than $1200^{\circ}C$, and SiC was formed by reduction-carbonization of SiO(g) with Al(l, g) and carbon at temperature higher than $1300^{\circ}C$. The products obtained at $1600^{\circ}C$ for 5h consisted of ZrC with lattice constant of $4.679{\AA}$ and crystallite size of $640{\AA}$, and SiC with lattice constant of $4.135{\AA}$ and crystallize size of $500{\AA}$. And also, the mean particle size was about $21.8{\mu}m$.

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