• Title/Summary/Keyword: reduction kinetics

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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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Fabrication and Characterization of Nano-sized Fe-50 wt% Co Powder from Fe- and Co-nitrate (Fe- 및 Co-질산염을 이용한 Fe-50 wt% Co 나노분말의 합성 및 특성 평가)

  • Riu, Doh-Hyung;Oh, Sung-Tag
    • Korean Journal of Materials Research
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    • v.20 no.10
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    • pp.508-512
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    • 2010
  • The optimum route to fabricate nano-sized Fe-50 wt% Co and hydrogen-reduction behavior of calcined Fe-/Conitrate was investigated. The powder mixture of metal oxides was prepared by solution mixing and calcination of Fe-/Co-nitrate. A DTA-TG and microstructural analysis revealed that the nitrates mixture by the calcination at $300^{\circ}C$ for 2 h was changed to Fe-oxide/$Co_3O_4$ composite powders with an average particle size of 100 nm. The reduction behavior of the calcined powders was analyzed by DTA-TG in a hydrogen atmosphere. The composite powders of Fe-oxide and Co3O4 changed to a Fe-Co phase with an average particle size of 40 nm in the temperature range of $260-420^{\circ}C$. In the TG analysis, a two-step reduction process relating to the presence of Fe3O4 and a CoO phase as the intermediate phase was observed. The hydrogen-reduction kinetics of the Fe-oxide/Co3O4 composite powders was evaluated by the amount of peak shift with heating rates in TG. The activation energies for the reduction, estimated by the slope of the Kissinger plot, were 96 kJ/mol in the peak temperature range of $231-297^{\circ}C$ and 83 kJ/mol of $290-390^{\circ}C$, respectively. The reported activation energy of 70.4-94.4 kJ/mol for the reduction of Fe- and Co-oxides is in reasonable agreement with the measured value in this study.

Kinetics of 2, 4, 6-Trinitrotoluene reduction by zero valent iron (금속 철을 이용한 TNT 환원시의 동역학 산정)

  • 배범한
    • Journal of Korea Soil Environment Society
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    • v.4 no.1
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    • pp.97-108
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    • 1999
  • Reduction 2, 4, 6-trinitrotoluene by zero valent iron was studied in a batch reactor under anoxic conditions. Results showed that the removal of trinitrotoluene (TNT)followed a pseudo-first order reaction and the rate was linearly dependent on the available reactive surfau area of the zero valent iron surface area, resulting a rate constant of 0.0981min$^{1}m$$^{-2}m$. High concentrations of the final product, presumably triaminotoluene which needs to be treated by other means, accumulated in the solution. However , little amount of TAT was extracted from the metal surface by using acetonitrile or phosphate buffered water (pH 7.0). Other common major intermediate in biological TNT degradation, a group of aminodinitrotoluenes, was not detected in the solution. Therefore, it is postulated that the reduction of nitro group by $Fe^0$ occurs simultaneously in all three positions and a TNT reduction model by zero valent iron was suggested.

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Effect of Catalyst on the Hydrogenation of Rapeseed Oil (채종유 수소첨가반응에 미치는 촉매의 영향)

  • Cha, Ik-Soo;Park, Ki-Moon
    • Korean Journal of Food Science and Technology
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    • v.29 no.4
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    • pp.687-692
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    • 1997
  • During the hydrogenation of rapeseed oil, reaction kinetics and physicochemical characteristics with catalysts (UP9900, DM3, Nysosel 222) were determined. Hydrogenation reaction rates for the UP 9900, Nysel DM3 and Nysosel 222 were $1.6{\pm}0.1\;({\times}10^{-2}),\;1.2{\pm}0.1\;(10^{-2}),\;1.2{\pm}0.1\;(10^{-2})$, respectively. The selectivities for the linoleic acid and oleic acid were determined to be $0.9{\sim}1.5\;and\;39{\sim}44$ at 20 min. From these results, the use of catalysts was shown to be non-selective. Trans isomer content in Nysosel 222 was 32% when the reduction rate of iodine value was 38%, that in Nysel DM3 was 28% at the reduction rate of 45%. UP9900 showed no influence on the trans isomer content. Below the melting point of $35^{\circ}C$, oleic acid and trans isomer acid were increased. On the other side, over the melting point of $35^{\circ}C$, oleic acid was decreased and trans isomer acid was constant. And this tendency was also appeared at the reduction rate of iodine value of 38%.

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Kinetics and mechanism of chromate reduction by biotite and pyrite (흑운모 및 황철석에 의한 6가 크롬의 환원 반응속도와 반응기작)

  • 전철민;김재곤;문희수
    • Economic and Environmental Geology
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    • v.36 no.1
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    • pp.39-48
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    • 2003
  • The removal of chromate from aqueous solution using finely ground pyrite and biotite was investigated by batch experiments and the kinetics and the mechanism of chromate reduction were discussed. The chromate reduction by pyrite was about hundred times faster than that by biotite and was also faster at pH 3 than at pH 4. When pyrite was used, more than 90% of initial chromate was reduced within four hours at pH 4 and within 40 min. at pH 3. However, more than 400 hours was taken for the reduction of 90% of initial chromate by biotite. The results indicate that the rate of chromate reduction was strongly depending on the amount of Fe(II) in the minerals and on the dissolution rate of Fe(II) from the minerals. The reduction of chromate at pH 4 resulted in the precipitation of (Cr, Fe)(OH))$_3$$_{ (s)}$, which is believed to have limited the concentrations of dissolved Cr(III) and Fe(III) to less than expected values. When biotite was used, amounts of decreased Fe(II) and reduced Cr(Ⅵ) did not show stoichiometric relationship, which implying there was not only chromate reduction by ferrous ions in the acidic solution but also heterogeneous reduction of ferric ions by the structural ferrous iron in biotite. However, the results from a series of the experiments using Pyrite showed that concentrations of the decreased Fe(II) and the reduced Cr(Ⅵ) were close to the stoichiometric ratio of 3:1. It was because the oxidation of pyrite rapidly created ferrous ions even in oxygenated solutions and the chromate reduction by the ferrous ions was significantly faster than ferrous ion oxygenation.

Reduction of High Explosives (HMX, RDX, and TNT) Using Micro- and Nano- Size Zero Valent Iron: Comparison of Kinetic Constants and Intermediates Behavior (마이크로와 나노 철을 이용한 고성능 화약물질(HMX, RDX 및 TNT)의 환원처리: 중간산물의 거동과 도역학 상수의 비교)

  • Bae, Bum-Han
    • Journal of Soil and Groundwater Environment
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    • v.11 no.6
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    • pp.83-91
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    • 2006
  • Reduction kinetics and the behaviour of intermediate of three high explosives (HMX, RDX, and TNT) were studies in batch reactors using nano- or micro- size zero valent iron(nZVI or mZVI) as reducing agent. The kinetic constants normalized by the mass of iron ($k_M$) or by the surface area ($k_{SA}$) were measured and compared along with the changes in the concentrations of intermediates. Results showed that $k_M$ and $k_{SA}$ values were not suitable to fully explain the behaviour of mother compounds and reduced intermediates in the batch reactor. The concentrations of initial explosives degradation products, such as nitroso-RDXs, nitroso-HMXs, and hydroxylamino-TNTs, were higher in mZVI treated reactor than in nZVI treated reactor, whereas more reduced polar intermediates such as TAT were accumulated in the nZVI reactor. Therefore, a new parameter, which accounted for the intermediates reduction, needs to be developed.

The Flavin-Containing Reductase Domain of Cytochrome P450 BM3 Acts as a Surrogate for Mammalian NADPH-P450 Reductase

  • Park, Seon-Ha;Kang, Ji-Yeon;Kim, Dong-Hyun;Ahn, Taeho;Yun, Chul-Ho
    • Biomolecules & Therapeutics
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    • v.20 no.6
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    • pp.562-568
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    • 2012
  • Cytochrome P450 BM3 (CYP102A1) from Bacillus megaterium is a self-sufficient monooxygenase that consists of a heme domain and FAD/FMN-containing reductase domain (BMR). In this report, the reduction of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and 5-cyano-2,3-ditolyl tetrazolium chloride (CTC) by BMR was evaluated as a method for monitoring BMR activity. The electron transfer proceeds from NADPH to BMR and then to BMR substrates, MTT and CTC. MTT and CTC are monotetrazolium salts that form formazans upon reduction. The reduction of MTT and CTC followed classical Michaelis-Menten kinetics ($k_{cat}=4120\;min^{-1}$, $K_m=77{\mu}M$ for MTT and $k_{cat}=6580\;min^{-1}$, $K_m=51{\mu}M$ for CTC). Our continuous assay using MTT and CTC allows the simple, rapid measurement of BMR activity. The BMR was able to metabolize mitomycin C and doxorubicin, which are anticancer drug substrates for CPR, producing the same metabolites as those produced by CPR. Moreover, the BMR was able to interact with CYP1A2 and transfer electrons to promote the oxidation reactions of substrates by CYP1A2 and CYP2E1 in humans. The results of this study suggest the possibility of the utilization of BMR as a surrogate for mammalian CPR.

Biomimetic Copper Complex Containing Polymer Modified Electrode for Electrocatalytic Reduction of Oxygen

  • Saravanakumar, D.;Nagarale, Rajaram Krishna;Jirimali, Harish Chandra;Lee, Jong Myung;Song, Jieun;Lee, Junghyun;Shin, Woonsup
    • Journal of Electrochemical Science and Technology
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    • v.7 no.4
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    • pp.298-305
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    • 2016
  • The development of non-precious metal based electrocatalysts is highly desired for the oxygen reduction reaction (ORR) as alternates to noble metal based ORR electrocatalysts. Herein, we report mononulcear copper(II) complex $[CuLbpy]ClO_4$ (L=4-[(2-hydroxyphenylimino)methyl]benzoic acid) containing poly(allylamine.HCl) polymer (PAlACuLbpy) as an electrocatalyst for oxygen reduction reaction (ORR). PAlACuLbpy was mixed with poly(acrylic acid) and tetraethylortho silicate to prepare a composite and then deposited on the screen printed electrode surface. The modified electrode (PAlACuLbpy/PCE) is highly stable and showed a quasi-reversible redox behavior with $E_{1/2}=-0.2V$ vs. Ag/AgCl(3 M KCl) in 0.1 M phosphate buffer at pH 7 under argon atmosphere. PAlACuLbpy/PCE exhibited a remarkable ORR activity with an onset potential of -0.1 V vs Ag/AgCl in 0.1 M PB (pH 7) in the presence of oxygen. The kinetics for ORR was studied by rotating disk voltammetry in neutral aqueous medium and the results indicated that the number of electrons involving in the ORR is four and the conversion products are water and hydrogen peroxide.

Modeling of the effect of current density and contact time on membrane fouling reduction in EC-MBR at different MLSS concentration (EC-MBR 공정의 MLSS, 전류밀도 및 접촉시간이 막 오염 감소에 미치는 영향 모델링)

  • Kim, Wan-Kyu;Chang, In-Soung
    • Journal of Korean Society of Water and Wastewater
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    • v.33 no.2
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    • pp.111-119
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    • 2019
  • Electro-coagulation process has been gained an attention recently because it could overcome the membrane fouling problems in MBR(Membrane bio-reactor). Effect of the key operational parameters in electro-coagulation, current density(${\rho}_i$) and contact time(t) on membrane fouling reduction was investigated in this study. A kinetic model for ${\rho}_i$ and t required to reduce the membrane fouling was suggested under different MLSS(mixed liquor suspended solids) concentration. Total 48 batch type experiments of electro-coagulations under different sets of current densities(2.5, 6, 12 and $24A/m^2$), contact times(0, 2, 6 and 12 hr) and MLSS concentration(4500, 6500 and 8500mg/L) were carried out. After each electro-coagulation under different conditions, a series of membrane filtration was performed to get information on how much of membrane fouling was reduced. The membrane fouling decreased as the ${\rho}_i$ and t increased but as MLSS decreased. Total fouling resistances, Rt (=Rc+Rf) were calculated and compared to those of the controls (Ro), which were obtained from the experiments without electro-coagulation. A kinetic approach for the fouling reduction rate (Rt/Ro) was carried out and three equations under different MLSS concentration were suggested: i) ${\rho}_i^{0.39}t=3.5$ (MLSS=4500 mg/L), ii) ${\rho}_i^{0.46}t=7.0$ (MLSS=6500 mg/L), iii) ${\rho}_i^{0.74}t=10.5$ (MLSS=8500 mg/L). These equations state that the product of ${\rho}_i$ and t needed to reduce the fouling in certain amounts (in this study, 10% of fouling reduction) is always constant.

Combined Effect of Catholyte Gap and Cell Voltage on Syngas Ratio in Continuous CO2/H2O Co-electrolysis

  • Ha, Min Gwan;Na, Youngseung;Park, Hee Young;Kim, Hyoung-Juhn;Song, Juhun;Yoo, Sung Jong;Kim, Yong-Tae;Park, Hyun S.;Jang, Jong Hyun
    • Journal of Electrochemical Science and Technology
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    • v.12 no.4
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    • pp.406-414
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    • 2021
  • Electrochemical devices are constructed for continuous syngas (CO + H2) production with controlled selectivity between CO2 and proton reduction reactions. The ratio of CO to H2, or the faradaic efficiency toward CO generation, was mechanically manipulated by adjusting the space volume between the cathode and the polymer gas separator in the device. In particular, the area added between the cathode and the ion-conducting polymer using 0.5 M KHCO3 catholyte regulated the solution acidity and proton reduction kinetics in the flow cell. The faradaic efficiency of CO production was controlled as a function of the distance between the polymer separator and cathode in addition to that manipulated by the electrode potential. Further, the electrochemical CO2 reduction device using Au NPs presented a stable operation for more than 23 h at different H2:CO production levels, demonstrating the functional stability of the flow cell utilizing the mechanical variable as an important operational factor.