• Title/Summary/Keyword: O-O bond formation

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Selective Separation of Amino Acid Mixture Using H2O-CH2Cl2-H2O Liquid Membrane containing p-Dimethylaminobenzaldehyde, 1-Napthol and Sulfosalicylic acid as a Carrier (II) (p-Dimethylaminobenzaldehyde, 1-Naphtol, Sulfosalicylic acid 등의 Carrier를 함유하는 H2O-CH2Cl2-H2O Liquid Membrane을 이용한 아미노산의 선택적 분리(II))

  • Park, Chung Oh;Hong, Jae Jin
    • Korean Journal of Clinical Laboratory Science
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    • v.36 no.2
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    • pp.115-120
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    • 2004
  • A bulk liquid membrane system was introduced for selective separation of an amino acid mixture. We confirmed p-diamethylaminobenzaldehyde (DAB), sulfosalicylic acid (SSA) and 1-naphtol were very useful carriers for selective separation of an amino acid mixture. As a result, Ala, Leu, Val, Phe and Ile were successfully separated by SSA, 1-naphtol in basic condition, 1-naphtol in weak acidic condition, DAB in strong acidic condition and DAB in strong basic condition. The separation mechanism was proposed by ion pair mechanism in the case of SSA and 1-naphtol and Imine bond formation mechanism was also introduced for DAB.

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Kinetics and Mechanism of Nucleophilic Displacement Reactions of Y-Substituted Phenyl Benzoates with Z-Substituted Phenoxides

  • Min, Se-Won;Seo, Jin-A;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2403-2407
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    • 2009
  • Second-order rate constants have been measured for two series of nucleophilic displacement reactions, i.e., reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides and those of Y-substituted phenyl benzoates (1a-h) with 4-chlorophenoxide (4-ClPhO–) in 80 mol% $H_2O$/20 mol% DMSO at 25.0 ${\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot for reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.72. Reactions of 1a-h with 4-chlorophenoxide result in also a linear Br$\phi$nsted-type plot with ${\beta}_{lg}$ = –0.62, a typical ${\beta}_{lg}$ value for a concerted mechanism. The Hammett plots correlated with ${\sigma}^o\;and\;{\sigma}^-$ constants show many scattered points for reactions of 1a-h with 4-chlorophenoxide. In contrast, the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with $\rho_Y$ = 2.26 and r = 0.53, indicating that expulsion of the leaving group occurs at the rate-determining step (RDS) either in a concerted mechanism or in a stepwise pathway. However, a stepwise mechanism with leaving group departure being the RDS is excluded since the leaving Y-substituted phenoxide is less basic and a better nucleofuge than the incoming 4-ClPh$O^-$. Thus, the reactions have been concluded to proceed through a concerted mechanism, in which bond formation between the nucleophile and electrophilic center is more advanced than expulsion of the leaving group in the transition state on the basis of the magnitude of ${\beta}_{nuc}\;and\;{\beta}_{lg}$ values.

A Study on Optimization of Alumina and Catalysts Coating on Tube Reactor for Endothermic Reaction of n-Dodecane Under Supercritical Conditions (고온, 고압 조건에서 n-dodecane 액체연료의 흡열분해를 위한 관벽 내 알루미나 및 촉매 코팅 최적화 연구)

  • Kim, Sung Su;Lee, Sang Moon;Lee, Ye Hwan;Lee, Dong Yoon;Gwak, Ji-Yeong
    • Journal of the Korean Society of Propulsion Engineers
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    • v.25 no.3
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    • pp.56-61
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    • 2021
  • In this study, Al2O3 and H-ZSM-5 were coated on the inner wall of the stainless steel tube for the stable use of liquid hydrocarbon fuel and an endothermic catalyst used as coolant for hypersonic flying vehicles. Coke production is inevitable by the endothermic decomposition reaction of the liquid hydrocarbon fuel, and Fe, Ni metals induce the production of the filamentous coke by using a stainless steel tube reactor as a cooling channel. By coating the stainless steel with H-ZSM-5, Fe and Ni metals are prevented from being directly exposed to the liquid hydrocarbon fuel, and the formation of the filamentous coke is inhibited. In addition, Al2O3 is coated between the stainless steel and H-ZSM-5 to enhance adhesion bond strength.

Surface modifiers on the waterglass aerogels prepared by ambient drying process (상압건조 물유리 에어로젤에 대한 표면개질제의 영향)

  • Kim, Tae-Jung;Nahm, Sahn;Oh, Young-Jei
    • Journal of Sensor Science and Technology
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    • v.15 no.3
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    • pp.173-178
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    • 2006
  • Silica aerogel with ultra low density and high porosity has been focused on versatile application due to its fascinating properties. Ambient drying process of waterglass, in this study was researched to fabricate a crack-free monolith body in the point view of cost effective way. Wet gel was obtained by removing of $Na^{+}$ ions in waterglass, which contains 8 wt% of $SiO_{2}$. Xylene, which has a low vapor pressure, was used as a solution substitutor to prevent the formation a cracks during drying. Various surface modifiers like as hexamethyldisilazane (HMDSZ), trimethylchlorosilane (TMCS), methyltriethoxylsilane (MTES), methyltrimethoxysilane (MTMS) and phenyltriethoxysilane (PTES) were used in order to improve hydrophobicity of the waterglass Silica aerogel. Some physical properties of the surface modified aerogels were investigated by FT-IR, TGA, BET and SEM. Hydrophobicity and hydrophilicity of Silica aerogel is attributed to the Si-OH bond and the non-polar C-H bond groups on the surface of aerogel. Crack-free waterglass aerogel with >90 % of porosity, 17 nm of pore size and <0.15 $g/cm^{3}$ of density was prepared. HMDSZ and TMCS are effective as a surface modifier

Influence of Oxyfluorination on Properties of Polyacrylonitrile (PAN)- Based Carbon Fibers

  • Lim, In-Seub;Yoo, Seung-Hwa;Park, Il-Nam;Lee, Young-Seak
    • Carbon letters
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    • v.5 no.1
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    • pp.12-17
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    • 2004
  • In this study, the oxyfluorination of PAN-based carbon fibers was undertaken at room temperature using fluorine-oxygen mixtures, and the influence of oxyfluorination on properties was investigated. The surface characteristics of the modified fiber were determined by using X-ray photoelectron spectroscopy (XPS) and dynamic contact angle analyzer. The oxyfluorination of carbon fibers was one of the more effective methods to increase surface wettability by the formation of semicovalent C-F bond and C-O bond depending on reaction conditions. When oxygen mole fraction is increased from 0.5 to 0.9, it is probable that attached fluorine atoms at the surface of the fibers reacted with other components. As increased oxyfluorination time and decreased its pressures, semi-covalent peak is increased at 0.5 of oxygen mole fraction. The total surface free energy of oxyfluorinated carbon fibers decreased with increasing oxygen mole fraction over 0.5. These results indicate that the surface of carbon fibers became much more hydrophilic after the short oxyfluorination. The surface free energy of oxyfluorinated carbon fibers progressively decreased after 10 min treatment. The polar components of surface free energies were however, significantly higher for all oxyfluorinated samples than that for the untreated carbon fiber.

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Density Functional Theory Studies on the Electrophilic versus Electron Transfer Mechanisms of Aryl Vinyl Ethers

  • 김왕기;손창국;임선희;이순기;김창곤;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.20 no.10
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    • pp.1177-1180
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    • 1999
  • The ab initio SCF MO and density functional theory (DFT) studies are carried out on the electrophilic (1a) and electron transfer (1b) addition reactions to the vinyl double bond of aryl vinyl sulfides and ethers. In the electrophilic addition processes, a double bond shift from C3 = C4 to X = C3 occurs with occupation number (1.97) close to the normal two. Due to this shift direct conjugation between the cationic center, X = S or O, and the para electron-donor substituent becomes impossible so that the reaction energies (or log K) are correlated with σ rather than σ+. By contrast, radical cation formation leads to delocalization of the SOMO, a lone-pair πorbital on X, with four major resonance structures in which cationic charge as well as spin density is delocalized over C4 , X and C7 atoms. As a result, partial πbonds are formed over C1 -X and C3 - C4 with occupation numbers (0.82) lower than one. In two of the cannonical structures, III(Ⅹ) and III(X+), direct conjugation between the cationic center, X, and the para substituent is achieved so that a better correlation with σ+ rather than σis obtained. The SCF MO energies at the HF/3-21G* and HF/6-31G* levels lead to very much inferior Hammett correlations in the σ/ σ+ diagnostic criterion. In contrast, the ρvalues evaluated with the DFT energies can give reliable diagnostic distinction between the two addition mechanisms.

Brazing of Aluminium Nitride(AlN) to Copper with Ag-based Active Filler Metals (은(Ag)계 활성금속을 사용한 질화 알미늄(AlN)과 Cu의 브레이징)

  • Huh, D.;Kim, D.H.;Chun, B.S.
    • Journal of Welding and Joining
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    • v.13 no.3
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    • pp.134-146
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    • 1995
  • Aluminium nitride(AlN) is currently under investigation as potential candidate for replacing alumium oxide(Al$_{2}$ $O_{3}$) as a substrate material for for electronic circuit packaging. Brazing of aluminium nitride(AlN) to Cu with Ag base active alloy containing Ti has been investigated in vacuum. Binary Ag$_{98}$ $Ti_{2}$(AT) and ternary At-1wt.%Al(ATA), AT-1wt.%Ni(ATN), AT-1wt.% Mn(ATM) alloys showed good wettability to AlN and led to the development of strong bond between brate alloy and AlN ceramic. The reaction between AlN and the melted brazing alloys resulted in the formation of continuous TiN layers at the AlN side iterface. This reaction layer was found to increase by increase by increasing brazing time and temperature for all filler metals. The bond strength, measured by 4-point bend test, was increased with bonding temperature and showed maximum value and then decreased with temperature. It might be concluded that optimum thickness of the reaction layer was existed for maximum bond strength. The joint brazed at 900.deg.C for 1800sec using binary AT alloy fractured at the maximum load of 35kgf which is the highest value measured in this work. The failure of this joint was initiated at the interface between AlN and TiN layer and then proceeded alternately through the interior of the reaction layer and AlN ceramic itself.

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Simultaneous Oxidation of NO, CO, and CH4 over Mn-Cu/Al2O3 Catalyst (Mn-Cu/Al2O3 촉매 상에서 NO, CO 및 CH4 동시 산화)

  • Ji Eun Jeong;Chang-Yong Lee
    • Applied Chemistry for Engineering
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    • v.35 no.1
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    • pp.1-7
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    • 2024
  • Mn-M/Al2O3 (M = Cu, Fe, Co, and Ce) catalysts were prepared for simultaneous oxidation of NO, CO, and CH4, and their oxidation activities were compared. The Mn-Cu/ Al2O3 catalyst with the best simultaneous oxidation activity was characterized by XRD, Raman, XPS, and O2-TPD analysis. The result of XRD indicated that Mn and Cu existed as complex oxides in the Mn-Cu/Al2O3 catalyst. Raman and XPS results showed that electron transfer between Mn ions and Cu ions occurred during the formation of the Mn-O-Cu bond in the Mn-Cu/Al2O3 catalyst. The XPS O 1s and O2-TPD analyses showed that the Mn-Cu/Al2O3 catalyst has more adsorbed oxygen species with high mobility than the Mn/Al2O3 catalyst. The high simultaneous oxidation activity of the Mn-Cu/Al2O3 catalyst is attributed to these results. Gas-phase NO promotes the oxidation reactions of CO and CH4 in the Mn-Cu/Al2O3 catalyst while suppressing the NO oxidation reaction. These results were presumed to be because the oxidized NO was used as an oxidizing agent for CO and CH4. On the other hand, the oxidation reactions of CO and CH4 competed on the Mn-Cu/Al2O3 catalyst, but the effect was not noticeable because the catalyst activation temperature was different.

Surface energy change and hydrophilic formation of PE, PS and PTFE films modification by hydrogen ion assisted reaction

  • Jung Cho;Ki Hyun;Koh, Seok-Keun
    • Proceedings of the Korean Vacuum Society Conference
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    • 1999.07a
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    • pp.202-202
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    • 1999
  • The Polyethylene (PE), Polystyrene (PS) and Polytetrafluoroethylene (PTFE) surface modification was investigated by hydrogen io assisted reaction (H-IAR) in oxygen environment. The IAR is a kind of surface modification techniques using ion beam irradiation in reactive gas environment. The energy of hydrogen ion beam was fixed at 1keV, io dose was varied from 5$\times$1014 to 1$\times$1017 ions/$\textrm{cm}^2$, and amount of oxygen blowing gas was fixed 4ml/min. Wettability was measured by water contact angles measurement, and the surface functionality was analyzed by x-ray photoelectron spectroscopy. The contact angle of water on PE modified by argon ion beam only decrease from 95$^{\circ}$ to 52$^{\circ}$, and surface energy was not changed significantly. But, the contact angle using hydrogen ion beam with flowing 4ml/min oxygen stiffly decreased to 8$^{\circ}$ and surface energy to 65 ergs/cm. In case of PS, the contact angle and surface energy changes were similar results of PE, but the contact angle of PTEE samples decreased with ion dose up to 1$\times$1015 ions/$\textrm{cm}^2$, increased at higher dose, and finally increased to the extent that no wetting was appeared at 1$\times$1017 ions/$\textrm{cm}^2$. These results must be due to the hydrogen ion beam that cleans the surface removing the impurities on polymer surfaces, then hydrogen ion beam was activated with C-H bonding to make some functional groups in order to react with the oxygen gases. Finally, unstable polymer surface can be changed from hydrophobic to hydrophilic formation such as C-O and C=O that were confirmed by the XPS analysis, conclusionally, the ion assisted reaction is very effective tools to attach reactive ion species to form functional groups on C-C bond chains of PE, PS and PTFE.

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The Study of Alumina Ceramic to Metal Bonding (알루미나 소결체와 금속간의 접합에 관한 연구)

  • 김종희;김형준
    • Journal of the Korean Ceramic Society
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    • v.15 no.2
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    • pp.89-97
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    • 1978
  • The basic mechanism of adherence in sintered high purity alumina ceramic-to-metal bonding was studied. Emphasis was placed on flux composition, porosity of the fired ceramics, and metallizing mixtures. The study was conducted on 95 and 99.5% alumina, using molydbenum-manganese, molybdenum-manganese-silicon dioxide metallizing compositions. Metallizing was performed in wet hydrogen (dew point, +17$^{\circ}C$) at 145$0^{\circ}C$ for 45min. This experiment indicated that adhernece mechanism of ultra high purity alumina ceramic was attributed to formation of $MnAl_2O_$4, and in the case of 95% alumina containing glass, the migration of glass from the interface into the void of the metal coating was the main role to the adhrence. It showed also that greater the bond-strength was resulted as porosity was increased.

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