• Title/Summary/Keyword: reaction intermediates

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The Effect of $H^+$ on Reduction of $[Co(NH_3)_4(C_2O_4)]^+$ with $[Fe(H_2O)_6]^{2+}$

  • Lim, Joo-Sang;Lee, Jae-Weon;Kang, Seung-Gu;Park, Byung-Kak
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.303-306
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    • 1990
  • Kinetic studies were carried out for the redox reaction of $[Co(NH_3)_4(C_2O_4)]^+$ with aqueous $[Fe(H_2O)_6]^{2+}$ solution in the present of $H^+$ by UV/VIS-spectrophotometric method. It was found that the order of $H^+$ for the reaction is first one in the higher $H^+$ concentration range of $1.67×10^{-1} M{\sim}1.00 M,$ while second order in the lower range of $6.30×10^{-2} M{\sim}1.67{\times}10^{-1} M.$ Reaction order of the substrates was found to be first order with respect to each of them. Accordingly overall reactions are third or fourth order. The results of calculation for the Extended Huckel Molecular Orbital theory contribute to estimate the preferred intermediates, bridging form of binuclear complex. On the basis of these results, we propose that this redox reaction proceed via inner-sphere reaction mechanism.

Gas phase Photocatalytic Oxidation of PCE with $TiO_2$ ($TiO_2$를 이용한 PCE의 기상 광산화처리)

  • 조인철;변종환;변은숙;이동근;김성우
    • Journal of Korean Society for Atmospheric Environment
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    • v.17 no.1
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    • pp.57-66
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    • 2001
  • Gas phase photocatalytic oxidation of tetrachloroethylene (PCE) under 370 nm ultra-violet irradiation was investigated with TiO$_2$ catalyst. During the photocatalytic oxidation of PCE vapor several kinds of intermediate were produced, and the reaction pathways were proposed on the basis of the production sequency of the intermediates. The intermediates in the pathways of PCE oxidation were hexachloroethane, pentachlotoethane, 1, 1, 2-trichloroethane, carbon tetrachl-oride, dichloroacetylchloride, chloroform, 1,1-dichloroethane, phosgene, CO, $CO_2$, HCl, Cl$_2$.

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Analogue Substrate Cometabolism by Chemical Oxidation of Recalcitrant PAHs (난분해 PAHs의 화학적산화에 의한 유사기질동시대사)

  • 류선정;박갑성
    • Journal of Korea Soil Environment Society
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    • v.3 no.3
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    • pp.87-92
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    • 1998
  • The effect of chemically oxidized intermediates of Polynuclear Aromatic Hydrocarbon (PAH) compounds on the degradation of the parent PAHs was characterized and evaluated for the context of cooxidation. Anthracene and pyrene exhibited extensive degradation (mean percent removal of 57.5%) after 28 days of incubation by introducing the Fenton oxidation intermediate of the PAH compounds, while unoxidized anthracene and pyrene exhibited 12.5% removal The chemical oxidation products can serve as a structually similar analogue substrates for a consortia of soil microorganisms and as a metabolic intermediates in the biodegradation sequence of the parent PAH compounds. These results may be interpreted in the context of cooxidation mechanism whereby high recalcitrant PAH compounds are biodegraded in the soil and suggest a potential tool for bioremediation of PAHs contaminated soils and protection of groundwater.

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Continuous Cell-Free Protein Synthesis Using Glycolytic Intermediates as Energy Sources

  • Kim, Ho-Cheol;Kim, Tae-Wan;Park, Chang-Gil;Oh, In-Seok;Park, Kyung-Moon;Kim, Dong-Myung
    • Journal of Microbiology and Biotechnology
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    • v.18 no.5
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    • pp.885-888
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    • 2008
  • In this work, we demonstrate that glycolytic intermediates can serve as efficient energy sources to regenerate ATP during continuous-exchange cell-free (CECF) protein synthesis reactions. Through the use of an optimal energy source, approximately 10 mg/ml of protein was generated from a CECF protein synthesis reaction at greatly reduced reagent costs. Compared with the conventional reactions utilizing phosphoenol pyruvate as an energy source, the described method yields 10-fold higher productivity per unit reagent cost, making the techniques of CECF protein synthesis a more realistic alternative for rapid protein production.

Interaction of Hydrosilanes with the Surface of Rhodium

  • Boo Bong Hyun;Hong Seung Ki;Lee Sun Sook;Kim Hyun Sook
    • Bulletin of the Korean Chemical Society
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    • v.15 no.12
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    • pp.1103-1107
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    • 1994
  • Interaction of triethylsilane and diphenylsilane ($Ph_2$$SiH_2$, $Ph_2$$SiD_2$) with the surfaces of rhodium has been examined by trapping the reaction intermediates with 2,3-dimethyl-l,3-butadiene. 1,4-Hydrosilylation of the diene is predominantly observed to occur under mild condition over the rhodium catalyst. It is inferred from the product analyses that silylene and silyl radicals bonded to rhodium surfaces are the intermediates for addition of silylene to the diene, and for 1,4-hydrosilylation, respectively.

Characteristics of Transesterification Reaction of Soy Bean Oil by Acid Catalysts (산촉매에 의한 대두유의 전이에스테르화 반응 특성)

  • Shin, Yong-Seop
    • Journal of Environmental Science International
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    • v.18 no.2
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    • pp.231-238
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    • 2009
  • Characteristics of the transesterification reaction between triglycerides in soy bean oil and methanol were investigated in the presence of acid catalysts. such as sulfuric acid and PTS (p-toluene sulfonic acid). Concentrations of diglyceride and monoglyceride which were intermediates in the reaction mixtures, were far below 10% of triglyceride under any reaction conditions. Thus, conversion of the reaction could be determined from the concentration of triglyceride. Dried PTS had more superior catalytic power than sulfuric acid for transesterification reaction between soy bean oil and methanol. When transesterification reaction of soy bean oil was catalyzed by 1 wt% of PTS at methanol stoichiometric mole ratio of 2 and $65^{\circ}C$, final conversion reached 95% within 48 hours. If FAME (fatty acid methyl ester) was added into reaction mixture of soy bean oil, methanol and PTS catalyst, it converted reaction mixture into homogeneous phase, and substantially increased reaction rate. When reaction mixture was freely boiling which had equal volumetric amount of FAME to soy bean oil, methanol stoichiometric mole ratio of 2 and 1 wt% of PTS, final conversion achieved value of 94% and temperature approached to $110^{\circ}C$ within 2 hours.

Substitution Reaction of Fe(CO)$_5$ by Ethylene

  • Ko, Jae-Jung
    • Bulletin of the Korean Chemical Society
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    • v.9 no.2
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    • pp.87-94
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    • 1988
  • The substitution reaction of Fe$(CO)_5$ by ethylene has been studied for plausible intermediates by means of extended Huckel calculations. Among various reaction mechanisms the favorable reaction pathway is via a dissociative mechanism in which ethylene approaches to Fe$(CO)_4$ unit. For Fe$(CO)_4$ fragment, the square planar conformation is found to be the most stable form by the extended Huckel calculations. Our calculations show that ethylene attacks square planar intermediate formed by removing one carbonyl from Fe$(CO)_5$ and then the unstable species thus formed is distored to the most stable trigonal bipyramid with the ethylene lying in the equatorial plane.

Mechanistic Aspects in the Grignard Coupling Reaction of Bis(chloromethyl)dimethylsilane with Trimethylchlorosilane

  • 조연석;유복렬;안삼영;정일남
    • Bulletin of the Korean Chemical Society
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    • v.20 no.4
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    • pp.422-426
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    • 1999
  • The Grignard reactions of bis(chloromethyl)dimethylsilane (1) with trimethylchlorosilane (2) in THF give both the intermolecular C-Si coupling and intramolecular C-C coupling products. At beginning stage, 1 reacts with Mg to give the mono-Grignard reagent ClCH2Me2SiCH2MgCl (1) which undergoes the C-Si coupling reaction to give MC2Si(CH2SiMe3)2 3, or C-C coupling to a mixture of formula Me3SiCH2(SiMe2CH2CH2)nR1 (n = 1, 2, 3, ..; 4a, R1I = H: 4b, R1 = SiMe3). In the reaction, two reaction pathways are involved: a) Ⅰ reacts with 2 to give Me3SiCH2SiMe2CH2Cl 6 which further reacts with Mg to afford a Me2SiCH2Mel-SiCH2MgCl (Ⅱ) or b) I cyclizes intramolecularly to a silacyclopropane intermediate A, which undergoes a ring-opening polymerization by the nucleophilic attack of the intermediates I or Ⅱ, followed by the termination reaction with H2O and 2, to give 4a and 4b, respectively. As the mole ratio of 2/1 increased from 2 to 16 folds, the formation of product 3 increased from 16% to 47% while the formation of polymeric products 4 was reduced from 60% to 40%. The intermolecular C-Si coupling reaction of the pathway a becomes more favorable than the intramolecular C-C coupling reaction of the pathways b at the higher mole ratio of 2/1.

The Investigation of Diesel Spray Combustion in DME HCCI Combustion (DME 예혼합 자기착화 연소중의 디젤분무연소에 관한 연구)

  • Lim, Ock-Taeck
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.32 no.4
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    • pp.241-248
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    • 2008
  • The purpose of the research is to investigate of diesel spray combustion for simultaneously reduction way of NOx and PM. The diesel injection were done into intermediates that are generated by very lean DME HCCI combustion using a RCM. The concentration of intermediate could not be directly measured, so we estimated it by CHEMKIN calculation. Two dimensional spontaneous luminescence images which are created by chemical species reaction at low temperature reaction (LTR) and high temperature reaction (HTR) are captured by using a framing streak camera. Also, combustion events were observed by high-speed direct photography. The ignition and combustion events were analyzed by pressure profiles and the KL values and flame temperatures were analyzed by the two-color method.

A Study on the Synthesis of Cationic Fiber-Softener HEC-2-HP-AC Ether Derivatives (양이온성 섬유유연제 HEC-2-HP-AC Ether 유도체의 합성에 관한 연구)

  • Kang, Ik Joong
    • Applied Chemistry for Engineering
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    • v.9 no.4
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    • pp.603-607
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    • 1998
  • Cellulose was reacted with ethylene oxide to get hydroxyethylcellulose. Quaternary ammonium salt was produced by reaction of epichlorohydrin and trialkylamine. The epoxide ring was opened by acid addition to 3-chloro-2-hydroxypropyltrialkylammonium chloride. Previously unreported two compounds, hydroxyethylcellulose-2-hydroxypropylammonium chloride ether and hydroxyethylcellulose-2-hydroxypropyltriethylammonium chloride ether were synthesized by substitution reaction of hydroxyethylcellulose with glycidyltrialkylammonium chloride or 3-chloro-2-hydroxypropyl-glycidyltrialkylammonium trialkylammonium chloride. All of the compounds including starting materials and reaction intermediates were characterized by $^1H$-NMR and FT-IR spectroscopy.

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