• Title/Summary/Keyword: Rate-Controlling Reaction

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Synthesis of Silicon Carbide Whiskers (I) : Reaction Mechanism and Rate-Controlling Reaction (탄화규소 휘스커의 합성(I) : 반응기구의 율속반응)

  • 최헌진;이준근
    • Journal of the Korean Ceramic Society
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    • v.35 no.12
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    • pp.1329-1336
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    • 1998
  • A twt -step carbothermal reduction scheme has been employed for the synthesis of SiC whiskers in an Ar or a H2 atmosphere via vapor-solid two-stage and vapor-liquid-solid growth mechanism respectively. It has been shown that the whisker growth proceed through the following reaction mechanism in an Ar at-mosphere : SiO2(S)+C(s)-SiO(v)+CO(v) SiO(v)3CO(v)=SiC(s)whisker+2CO2(v) 2C(s)+2CO2(v)=4CO(v) the third reaction appears to be the rate-controlling reaction since the overall reaction rates are dominated by the carbon which is participated in this reaction. The whisker growth proceeded through the following reaction mechaism in a H2 atmosphere : SiO2(s)+C(s)=SiO(v)+CO(v) 2C(s)+4H2(v)=2CH4(v) SiO(v)+2CH4(v)=SiC(s)whisker+CO(v)+4H2(v) The first reaction appears to be the rate-controlling reaction since the overall reaction rates are enhanced byincreasing the SiO vapor generation rate.

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Synthesis of Silicon Carbide Whiskers (I) : Reaction Mechanism and Rate-Controlling Reaction (탄화규소 휘스커의 합성(I) : 반응기구의 율속반응)

  • 최헌진;이준근
    • Journal of the Korean Ceramic Society
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    • v.35 no.12
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    • pp.1336-1336
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    • 1998
  • A twt -step carbothermal reduction scheme has been employed for the synthesis of SiC whiskers in an Ar or a H2 atmosphere via vapor-solid two-stage and vapor-liquid-solid growth mechanism respectively. It has been shown that the whisker growth proceed through the following reaction mechanism in an Ar at-mosphere : SiO2(S)+C(s)-SiO(v)+CO(v) SiO(v)3CO(v)=SiC(s)whisker+2CO2(v) 2C(s)+2CO2(v)=4CO(v) the third reaction appears to be the rate-controlling reaction since the overall reaction rates are dominated by the carbon which is participated in this reaction. The whisker growth proceeded through the following reaction mechaism in a H2 atmosphere : SiO2(s)+C(s)=SiO(v)+CO(v) 2C(s)+4H2(v)=2CH4(v) SiO(v)+2CH4(v)=SiC(s)whisker+CO(v)+4H2(v) The first reaction appears to be the rate-controlling reaction since the overall reaction rates are enhanced byincreasing the SiO vapor generation rate.

Kinetics of the Formation of Metalloporphyrins and the Catalytic Effect of Lead Ions and Hydrogen Ions

  • Qi, Yong;Pan, Ji Gang
    • Bulletin of the Korean Chemical Society
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    • v.35 no.11
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    • pp.3313-3318
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    • 2014
  • The reaction mechanism of Lead ions catalyzing complexation reactions between TIPP and metal ions was investigated by researching the kinetics of the formation of metalloporphyrins by UV/Vis-spectra, and verified by exploring the formation of metalloporphyrins catalyzed by acetic acid. Kinetics studies suggested that the fluctuations of reaction rate indicated the formation of metalloporphyrin was step-wise, including the pre-equilibrium step (the coordination of the pyrrolenine nitrogens to $Mn^+$) and the rate-controlling step (the deprotonation of the pyrrole proton). In the pre-equalization step, a sitting-atop (SAT) structure formed first with the complexation between larger radius of $Pb^{2+}$ and TIPP, changed the activation, then $Pb^{2+}$ left with the smaller radius of metal ions attacking from the back of the porphyrin ring center. In the rate-controlling step, two pyrrole protons dissociated to restore a stable structure. This was verified by adding acetic acid at different reaction times.

The Changes of the Hydrogenation Properties of Zr0.9Ti0.1Cr0.7Fe1.3 Alloy Upon the Pressure Induced Hydriding-Dehydriding Cycling (수소흡수-방출 사이클에 의한 Zr0.9Ti0.1Cr0.7Fe1.3 합금의 수소화 반응 특성의 변화)

  • Lee, Jon-Ha;Lee, Jai-Young
    • Transactions of the Korean hydrogen and new energy society
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    • v.2 no.1
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    • pp.29-37
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    • 1990
  • The effect of pressure cycling of $Zr_{0.9}Ti_{0.1}Cr_{0.7}Fe_{1.3}$ on the hydrogenation properties was investigated using the P-C-Isotherm curves and hydrogen absorption rate curves in the isotherm condition. The reversible hydrogen absorption capacity was decreased about 45 % after 3300 cycles. In the case of activated sample, the rate controlling steps of hydriding reaction changed from the surface reaction to the hydrogen diffusion process through hydride phase sequentially as reaction proceeded. After 3300 cycles, the sequential change of rate controlling step was same as activated one. However, the hydrogen absorption rate significantly decreased. It is suggested that the degradation of $Zr_{0.9}Ti_{0.1}Cr_{0.7}Fe_{1.3}$ can be interpreted with the formation of $ZrFe_3$ phase at the particle surface.

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The Treatment of Flue SO$_2$ Gas by Cu Powder (I) (구리 분말을 이용한 $SO_2$ 배기가스의 처리(I))

  • 정국삼;김학성;신창섭
    • Journal of the Korean Society of Safety
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    • v.1 no.1
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    • pp.27-32
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    • 1986
  • To remove sulfur dioxide from flue gas by the method of metal oxide, copper powder of average diameter $2.4\mu\textrm{m}$and $51\mu\textrm{m}$ were used in a fixed bed reactor over a, temperature range of $300^{\circ}C-500^{\circ}C$. Copper oxide reacts with sulfur dioxide producing cupric sulfate and it can be regenerated from the latter by using hydrogen or methane. Experimental results showed that the reaction rate was increased by the increase of reaction temperature in the range of $300^{\circ}C-422^{\circ}C$ and the removal efficiency of sulfur dioxide was high in case of small size copper particle. However the removal efficiency was decreased at higher temperature due to decomposition of cupric sulfate. The rate controlling step of this reaction was chemical reaction and deactivating catalysts model can be applied to this reaction. The rate constants for this reaction and deactivation are as follows : k=8,367exp(-10,298/RT) Kd=2.23exp(-8,485/RT)

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A Study on the Hydriding and Dehydriding Kinetics of a Mechanically-Alloyed Mg-25wt.%Ni Mixture (기계적 합금처리된 Mg-25wt.%Ni 혼합물의 수소화물 형성 및 분해에 대한 반응속도론적 연구)

  • Song, Myoung Youp
    • Transactions of the Korean hydrogen and new energy society
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    • v.10 no.1
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    • pp.9-17
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    • 1999
  • The hydriding and dehydriding kinetics were studied for a Mg-25wt.%Ni mixture which has the most excellent hydrogen-storage characteristics among many mechanically-alloyed mixtures. The hydriding and dehydriding rates were measured and the rate-controlling steps were determined by comparing the hydriding and dehydriding rates with the theoretical rate equations. The rate-controlling step in the hydriding reaction is the Knudsen flow and the ordinary gaseous diffusion of hydrogen molecules through interparticle channels, cracks, etc. in the various ranges of weight percentage of absorbed hydrogen $H_a$ below $H_a$=4.0. In the $H_a$ range 4.0 < $H_a{\leq}4.25$, the diffusion of hydrogen atoms through the growing hydride layer is considered the rate-controlling step. The rate-controlling step in the dehydriding reaction is the Knudsen flow and the ordinary gaseous diffusion of hydrogen molecules for all the ranges of weight percentage of desorbed hydrogen $H_d$.

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The Effects of Environmental Conditions on the Reduction Rate of TNT by $Fe^0$ (환경요인이 $Fe^0$ 에 의한 TNT의 환원 반응속도에 미치는 영향)

  • 배범한
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2000.05a
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    • pp.52-55
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    • 2000
  • The effects of environmental conditions, initial dissolved oxygen concentrations, pH, and the presence of electron carrier vitamin B$_{12}$ , on the reduction rate of TNT by Fe$^{0}$ was Quantitatively analyzed using a batch reactor. In all experiments, TNT reduction was best described with a first order reaction and the reduction rate decreased with the increase in the initial DO concentration. However, the specific reaction rate did not decrease linearly with the increase in the initial DO concentration. In the presence of HEPES buffer 0.2 and 2.0 mM(pH 5.7$\pm$0.2), the specific reaction rate increased more than 5.8 times, which showed reduction rate is rather significantly influenced by the pH of the solution. To test the possibility of reaction rate enhancement, well-known electron carrier(or mediator), vitamin B$_{12}$ has augmented besides Fe$^{0}$ . In the presence of 8.0 $\mu\textrm{g}$/L of vitamin B$_{12}$ , the specific reaction rate increased as much as 14.6 times. The results indicate that the addition of trace amount of vitamin B$_{12}$ can be a promising rate controlling option for the removal of organics using a Fe$^{0}$ filled permeable reactive barrier.

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Studies on the Kinetics for the Formation Reaction $Ti_3AI$ by SHS (Self-propagating High-temperatuer Synthesis) Method (자체반응열 고온합성법에 의한 $Ti_3AI$ 생상반응의 동력학적 연구)

  • 전광식
    • Journal of the Korean Ceramic Society
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    • v.35 no.6
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    • pp.569-574
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    • 1998
  • The thickness of flame zone reaction rate and apparent activation energy in the formation reaction of $Ti_3AI$ intermetallic compound were investigated using SHS method which sustains the reaction spontaneously and utilizes the heat generated by thye exothermic reaction itself. In this reaction the thickness of flame zone was 1.4 mm and the reaction rate was $0.4g/\textrm{cm}^2{\cdot}sec$. Also the apparent activation energy calculated using from the experimental data obtained by controlling the realtive green density was 40kJ/mol.

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Removal of Sulfur Dioxide by Cupric Oxide and Reduction of Cupric Sulfate by Hydrogen (산화구리에 의한 이산화황의 제거와 수소에 의한 황산구리의 환원)

  • 노용우;이명철;이재훈;이태희
    • Journal of Korean Society for Atmospheric Environment
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    • v.10 no.2
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    • pp.83-89
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    • 1994
  • The reaction of sulfur dioxide with cupric oxide was investigated over a temperature range of 300-50$0^{\circ}C$, and the regenaration reaction was studied using cupric sulfate and hydrogen over a temperature range of 240-35$0^{\circ}C$ in a fixed bed reactor. The experimental results showed that the efficiencies for elimination and regenaration reactions were maximum at 45$0^{\circ}C$ and at 30$0^{\circ}C$ respectively. In both cases the experimental data could be interpreted properly by shrinking unreacted core model while the chemical reaction is rate controlling step. The reaction rate constants were determined to be 24.88 exp(-6724/RT) (cm/min) for elimination reaction, and 0.0165 exp(-2047/RT)(cm/min ) for regeneration reaction.

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Decarbonization Kinetics of Molten Iron by Ar+O2 Gas Bubbling (Ar+O2 혼합가스 취입에 의한 용철의 탈탄 반응속도)

  • Sohn, Ho-Sang;Jung, Kwang-Hyun
    • Korean Journal of Metals and Materials
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    • v.47 no.2
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    • pp.107-113
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    • 2009
  • Molten iron with 2 mass % carbon content was decarbonized at 1823 K~1923 K by bubbling $Ar+O_2$ gas through a submerged nozzle. The reaction rate was significantly influenced by the oxygen partial pressure and the gas flow rate. Little evolution of CO gas was observed in the initial 5 seconds of the oxidation; however, this was followed by a period of high evolution rate of CO gas. The partial pressure of CO gas decreased with further progress of the decarbonization. The overall reaction is decomposed to two elementary reactions: the decarbonization and the dissolution rate of oxygen. The assumptions were made that these reactions are at equilibrium and that the reaction rates are controlled by mass transfer rates within and around the gas bubble. The time variations of carbon and oxygen contents in the melt and the CO partial pressure in the off-gas under various bubbling conditions were well explained by the mathematical model. Based on the present model, it was explained that the decarbonization rate of molten iron was controlled by gas-phase mass transfer at the first stage of reaction, but the rate controlling step was transferred to liquid-phase mass transfer from one third of reaction time.