• Title/Summary/Keyword: 율속반응

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Kinetic and Equilibrium Studies on Complex Formation Between Ni(II) and D-Penicillamine in Aqueous Media (Ni(II)와 D-Penicillamine과의 착물형성반응에 대한 속도론적 및 평형에 관한 연구)

  • Yong-Kyu Kim;Sung-Nak Choi
    • Journal of the Korean Chemical Society
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    • v.30 no.5
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    • pp.475-482
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    • 1986
  • Rates and equilibriurn of complex formation between $Ni^{2+}$ and D-penicillamine have been investigated in aqueous solutions. Kinetic study on the complex formation were performed in the pH range of 8∼9 by the use of pressure-jump technique. D-Penicillamine coordinates to the nickel(II) ion utilizing sulfur and nitrogen as donor atoms in the high pH condition (pH 9.2). However, in the pH range of 8.25∼9.07, the stepwise stability constant becomes drastically reduced and the undissociated mercapto group does not participate in bonding. The rate-determining step of the complexation reaction is found to be the release of a water molecule from the inner-coordination sphere of $Ni^{2+}$ ion.

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Kinetics and Mechanism of the Oxidation of Carbon Monoxide on $ZnCe_{1+y}O_2$ ($ZnCe_{1+y}O_2$상에서 일산화탄소의 산화반응 메카니즘)

  • Kim Keu Hong;Jae Shi Choi
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.102-108
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    • 1984
  • The catalytic oxidation of CO has been investigated on $ZnCe_{1+y}O_2$ at temperatures from 300 to $500^{\circ}C$ under various P_{CO} and PO_2 conditions. The oxidation rates have been correlated with 1.5-order kinetics: first order with respect to CO and 0.5 order with respect to O2. CO appears to be absorbed essentially on the O lattice of $ZnCe_{1+y}O_2$ as a molecular species, while $O_2$ adsorbs on an O vacancy as an ionic species. The conductivity data show that CO adsorption contributes electron to the conduction band and the adsorption process of $O_2$ withdraws it from an O vacancy. The oxidation mechanism and the defect model of $ZnCe_{1+y}O_2$ are inferred at given temperature and $PO_2'$s from the agreement between the conductivities and kinetic data. It is suggested that CO absorption is the rate-controlling.

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Cathodic Polarization Measurements on La0.9Sr0.1MnO3 Electrode for Solid Oxide Fuel Cells

  • Lee, H.Y.;Oh, S.M.
    • Applied Chemistry for Engineering
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    • v.4 no.1
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    • pp.153-161
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    • 1993
  • Cathodic oxygen reduction kinetics on $La_{0.9}Sr_{0.1}MnO_3$ electrode have been examined at $700-900^{\circ}C$ under various oxygen partial pressures. AC impedance and current interruption techniques were employed for the determination of charge transfer resistances for electrochemical oxygen reduction. The $R_{ct}$ values obtained from two different methods were very close each other for $La_{0.9}Sr_{0.1}MnO_3$ electrode. Activation energy for the electrochemical oxygen reduction was found to be 174kJ/mol under atmospheric oxygen pressure. $R_{ct}$ measurements as a function of oxygen partial pressure indicate that the rate-determining step for the electrochemical oxygen reduction on $La_{0.9}Sr_{0.1}MnO_3$ electrode is the charge transfer process.

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Effect of Temperature on the Deposition Rate and Bending Strength Characteristics of Chemical Vapor Deposited Silicon Carbide Using Methyltrichlorosilane (메틸트리클로로실란을 이용한 화학증착 탄화규소의 증착율 및 굽힘강도 특성에 미치는 온도의 영향)

  • Song, Jun-Baek;Im, Hangjoon;Kim, Young-Ju;Jung, Youn-Woong;Ryu, Hee-Beom;Lee, Ju-Ho
    • Composites Research
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    • v.31 no.2
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    • pp.43-50
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    • 2018
  • The effects of deposition temperature on chemical vapor deposited silicon carbide (CVD-SiC) were studied to obtain high deposition rates and excellent bending strength characteristics. Silicon carbide prepared at $1250{\sim}1400^{\circ}C$ using methyltrichlorosilane(MTS : $CH_3SiCl_3$) by hot-wall CVD showed deposition rates of $95.7{\sim}117.2{\mu}m/hr$. The rate-limiting reaction showed the surface reaction at less than $1300^{\circ}C$, and the mass transfer dominant region at higher temperature. The activation energies calculated by Arrhenius plot were 11.26 kcal/mole and 4.47 kcal/mole, respectively. The surface morphology by the deposition temperature changed from $1250^{\circ}C$ pebble to $1300^{\circ}C$ facet structure and multi-facet structure at above $1350^{\circ}C$. The cross sectional microstructures were columnar at below $1300^{\circ}C$ and isometric at above $1350^{\circ}C$. The crystal phases were all identified as ${\beta}$-SiC, but (220) peak was observed from $1300^{\circ}C$ or higher at $1250^{\circ}C$ (111) and completely changed to (220) at $1400^{\circ}C$. The bending strength showed the maximum value at $1350^{\circ}C$ as densification increased at high temperatures and the microstructure changed from columnar to isometric. On the other hand, at $1400^{\circ}C$, the increasing of grain size and the direction of crystal growth were completely changed from (111) to (220), which is the closest packing face, so the bending strength value seems to have decreased.

Tetramethyl orthosilicate(TMOS) Synthesis by the Copper-Catalyzed Reaction of the Metallic Silicon with Methanol (II) - The Kinetics of the Copper-Catalyzed Reaction of Silicon with Methanol - (구리 촉매하에서 규소와 메탄올의 반응에 의한 Tetramethyl orthosilicate(TMOS) 합성(제2보) - 구리촉매하에서 규소와 메탄올과의 반응의 반응속도론 -)

  • Soh, Soon-Young;Won, Ho-Youn;Chun, Yong-Jin;Lee, Bum-Jae;Yang, Hyun-Soo
    • Applied Chemistry for Engineering
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    • v.10 no.2
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    • pp.259-262
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    • 1999
  • The copper-catalyzed reaction of silicon with methanol was carried out in a mixed bed reactor to obtain tetramethyl orthosilicate (TMOS). In order to determine the kinetics of the reaction per active site on the silicon surface, a flow rate transition technique was employed. A kinetic study showed the reaction was in Linear relationship with the amount of contact mass and independent on the concentration of methanol. This result indicated that the rate-determining step was not the chemical process involving methanol, but the formation of silicon intermediate on the contact mass. On the basis of optimum experimental conditions, the maximum TMOS formation rate per g-silicon is 0.030 (g/min) at $210^{\circ}C$, in which activation energy was 8.5 kcal/mol and reaction rate equation was $k=4.09{\times}10^4\;exp$ ($-4.73{\times}10^3/T$).

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Study on the Reduction Kinetics of In2O3 with Hydrogen (수소에 의한 In2O3의 환원반응속도론 연구)

  • Nahm, Kee-Suk;Kim, Youn-Sop;Lee, Wha-Young
    • Applied Chemistry for Engineering
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    • v.3 no.2
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    • pp.305-311
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    • 1992
  • The experimental study on the reduction of $In_2O_3$ was performed by using thermogravimetric analyzer. The reduction of $In_2O_3$ was occurred at above $300^{\circ}C$. The reduction rates were rapidly increased with the reaction temperature, whilehardly affectedby the flow rate of hydrogen gas. It was found that the unreacted core model could be applied for the analysis of the reduction data and the rate control step was the chemical reaction of $In_2O_3$ with hydrogen on the surface of unreacted $In_2O_3$. The apparent activation energy for this reaction was 20kcal/g-mol $H_2$ and the rate equation of $In_2O_3$ reduction with hydrogen could be expressed in the following equation. ${\frac{dX}{dt}}=1.6{\times}10^5e^{-20000/RT}(1-X)^{2/3}$

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Synthesis of High Purity p-Phenylenediamine from p-Nitroaniline by Catalytic Hydrogenation (Pd/C촉매하 파라니트로아닐린 수소첨가에 의한 고순도 파라페닐렌디아민의 합성공정)

  • Cho, Chul Kun;Chung, Kwang Bo
    • Applied Chemistry for Engineering
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    • v.10 no.8
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    • pp.1210-1215
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    • 1999
  • Optimum conditions of the hydrogenation of PNA to pure PPD were determined in a three-phase slurry reactor with suspended Pd/C catalyst particles. Minimization of mass transfer resistances at the interfaces of both gas-liquid and liquid-catalyst particles and control of overall reaction rate on catalyst surface leaded to decrease the hydrogen starvation on reaction active sites and to reduce the side reactions during hydrogenation. The optimum temperature, pressure, and catalysst concentration were confirmed to be in the range of $60^{\circ}C$, 60~70 psig, and 1~2 g-cat/L, respectively. Reaction rate was zero order with respect to the concentration of PNA and 1st order with respect to the pressure of hydrogen(P). Overall rate expression of the reaction was $R_A=6.44{\times}10^6{\cdot}H{\cdot}P{\cdot}m{\cdot}$exp(-4659/T) where H is constant, m is concentration of catalyst, and T is temperature.

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Formation of amorphous and crystalline phase, phase sequence by solid state reaction in Zr/Si multilayer thin films (Zr/Si 다층박막에서의 고상반응에 의한 비정질상과 결정상의 생성 및 상전이)

  • Sim, Jae-Yeop;Ji, Eung-Jun;Gwak, Jun-Seop;Choe, Jeong-Dong;Baek, Hong-Gu
    • Korean Journal of Materials Research
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    • v.4 no.5
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    • pp.493-501
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    • 1994
  • DSC와 XRD를 사용하여 Zr/Si 다층박막의 고상반응에 의한 비정질상과 결정상 생성 및 상전이를 확인하고 이를 유효구동력 개념과 유효생성열 개념 및 phase determining factor(PDF)모델을 이용하여 예측한 결과와 비교하였다. Zr/Si 다층박막은 비정질호 반응이 잘 일어났으며 이는 유효구동력 개념으로 예측한 바와 일치하였다. Zr/Si 계에서 생성되는 최초의 결정상은 ZrSi 였으며 유효생성열과 PDF모델로부터 예측된 최초의 결정상은 PDF 모델의 예측 결과와 일치하였다. Zr/Si 다층박막의 원자조성비가 1대 1일경우와 1대 2일 경우의상전이는 ZrSi$\longrightarrow$$ZrSi_{2}$로 되었으며 이러한 상전이 과정은 유효생성열 다이아그램으로 해석되었다. ZrSi의 생성기구는 핵생성이 율속임을 규명하였고 ZrSi와 $ZrSi_{2}$의 생성에 필요한 활성화에너지는 1.64$\pm$0.19eV와 2.28$\pm$0.36eV이었다.

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Removal of Iron from Ilmenite through Selective Chlorination Using PVC (PVC에 의한 일메나이트 광석 중 선택염화에 의한 Fe의 제거)

  • Son, Yongik;Ring, Rie;Sohn, Ho-Sang
    • Resources Recycling
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    • v.25 no.3
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    • pp.74-81
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    • 2016
  • Study on chlorination of ilmenite ore were carried out by using PVC(polyvinyl chloride) as the chlorinating agent in a static bed reactor for selective removal of iron. The effect of amount of PVC and reaction temperature were investigated. It was found that the removal ratio of iron increased with amount of PVC and temperature. After reaction with HCl gas generated from PVC, porous surface of the specimens were observed. As a result, HCl gas could react with iron in the central portion of ilmenite particle through these pores. Examination of data using kinetic model suggest that the selective chlorination rate is controlled by chemical reaction at the interface of particles. The activation energy for the selective chlorination of ilmenite using PVC was calculated as 20.47 kJ/mol.

Enhanced Anaerobic Degradation of Food Waste by Employing Rumen Microorganisms (Rumen 미생물을 이용한 주방폐기물 혐기성소화의 효율증진 방안)

  • Shin, Hang-Sik;Song, Young-Chae;Son, Sung-Sub;Bae, Byung-Uk
    • Journal of the Korea Organic Resources Recycling Association
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    • v.1 no.1
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    • pp.103-113
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    • 1993
  • Every year, over $3.37{\times}10^7$ ton of municipal solid waste is generated in Korea, of which about 28% is organic food waste from restaurant, dining halls and households etc. Methane conversion of the food waste by anaerobic digestion could be a viable approach for energy recovery as well as safe disposal of the waste. However, as food waste is composed of highmolecular complex polymers such as cellulose, lignin and protein, anaerobic digestion of food waste has not been efficient in terms of volumetric loading rate, solid retention time and extent of anaerobic degradation. In this research, the improved anaerobic degradation of food waste was attemped by applying rumen microorganisms to anaerobic digestion. Acidification efficiency of food waste by rumen microorganisms was compared with that of conventional acidogenesis. And optimum acidification conditions by rumen microorganisms were also determined. For the experiments, anaerobic batch reactors of 600 mL was fed with the processed (dried and milled) food waste obtained from a restaurant. Ultimate volatile fatty acid (VFA) yield produced by rumen microorganisms was about 8.4 meq VFA/g volatile solid (VS) that is 95% of the theoretical value. This yield was not much different from that of conventional acidogenesis, but hydrolysis rate was about twice faster. Cumulative VFA concentration increased from 66 meq/L to 480 meq/L, when the initial TS was increased from 1% to 15%. But VFA yield at 15% TS was half of that at 1% TS. This inhibition on the acidification might be caused by the rapid drop of pH and higher concentration of nonionized VFA. Optimal pH and temperature range for the acidification were about 6.0~7.5 and $35{\sim}45^{\circ}C$, respectively.

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