• Title/Summary/Keyword: Oxidation kinetics

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Kinetics and Mechanism of Electron Transfer Reaction: Oxidation of Sulfanilic Acid by N-Chloro-p-Toluene Sulfonamide in Acid Perchlorate Medium

  • Sailani, Riya;Bhasin, Meneka;Khandelwal, C.L.;Sharma, P.D.
    • Bulletin of the Korean Chemical Society
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    • v.35 no.1
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    • pp.111-116
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    • 2014
  • The kinetics and mechanism of oxidation of sulfanilic acid by N-chloro-p-toluene sulfonamide (chloramine-T) have been studied in acid medium. The species of chloramine-T were analysed on the basis of experimental observations and predominantly reactive species was taken into account for proposition of most plausible reaction mechanism. The derived rate law (1) conforms to such a mechanism. $$-\frac{d[CAT]}{dt}=\frac{kK_1[RNHCl][SA]}{K_1+[H^+]}$$ (1) All kinetic parameters were evaluated. Activation parameters such as energy and entropy of activation were calculated to be $(61.67{\pm}0.47)kJmol^{-1}$ and $(-62.71{\pm}2.48)kJmol^{-1}$ respectively employing Eyring equation.

Kinetics Study on the Reduction with Methane, Oxidation with Water and Oxidation with Air of Fe2O3/ZrO2 Using TGA (TGA를 이용한 Fe2O3/ZrO2의 환원/물 분해/공기산화 kinetic 연구)

  • Nam, Hyun-Woo;Kang, Kyoung-Soo;Bae, Ki-Kwang;Kim, Chang-Hee;Cho, Won-Chul;Kim, Young-Ho;Park, Chu-Sik
    • Transactions of the Korean hydrogen and new energy society
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    • v.22 no.2
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    • pp.168-177
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    • 2011
  • A set of kinetics study on the reduction with $CH_4$, oxidation with steam and oxidation with air was performed for $Fe_2O_3/ZrO_2$. $Fe_2O_3/ZrO_2$ was prepared by aerial oxidation method. The reactivity experiments were performed in a thermogravimetric analyzer (TGA) with different reacting gas concentrations and temperatures. The obtained activation energy of reduction by methane, oxidation by water and oxidation by air are 219 kJ/mol, 238 and 20 respectively.

Oxidation Kinetics of Carbon Fibers

  • Roh, Jae-Seung
    • Carbon letters
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    • v.6 no.1
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    • pp.1-5
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    • 2005
  • Isotropic pitch based carbon fibers were exposed to isothermal oxidation in carbon dioxide gas to study the activation kinetics under the temperature of 800~$1100^{\circ}C$. The kinetic equation $f=1-{\exp}(-at^b)$ was introduced and the constant b was obtained in the range of 0.92~1.25. It was shown that the activated carbon fiber shows the highly specific surface area (SSA) when the constant b comes close to 1. The activation kinetics were evaluated by the reaction-controlling regime (RCR) according to changes of the apparent activation energy with changes of the conversion. It was observed that the activation energies increase from 47.6 to 51.2 kcal/mole with the conversion increasing from 0.2 to 0.8. It was found that the pores of the activated carbon fiber under the chemical reaction were developed well through the fiber.

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Experimental Verification of a Kinetic Model of Zr-Oxidation

  • Yoo, Han-Ill;Park, Sang-Hyun
    • Journal of the Korean Ceramic Society
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    • v.43 no.11 s.294
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    • pp.724-727
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    • 2006
  • It has long been known that the oxidation kinetics of Zr-based alloys undergoes a crossover from parabolic to cubic in the pretransition period (before breakaway of the oxide scale). This kinetic crossover, however, is not fully understood yet. We have earlier proposed a model for the Zr-oxidation kinetics, in a closed form for the first time, by taking into account a compressive strain energy gradient as a diffusional driving force in addition to a chemical potential gradient of component oxygen across the ZrO$_2$ scale upon Zr [J. Nucl. Mater., 299 (2001) 235]. In this paper, we experimentally reconfirm the validity of the proposed model by using the thermogravimetric data on mass gain of Zr in a plate and wire form, respectively, in air atmosphere at different temperatures in the range of 500$^{\circ}$ to 800$^{\circ}C$, and subsequently report on the numerical values for oxygen chemical diffusivity and strain energy gradient across the oxide scale.

Kinetics of Oxidation, and Effects of TiC on Oxidation Resistance in MgO-Carbon Refractory (MgO-Carbon 내화물의 산화반응기구와 TiC첨가에 의한 산화방지 효과)

  • Cheon, Sungho;Kong, Hyunsik;Jun, Byungsei
    • Journal of the Korean Ceramic Society
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    • v.41 no.9
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    • pp.657-662
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    • 2004
  • The kinetics of oxidation and disappearance of graphite in MgO-C refractories containing TiC were, in the temperature range from 1000 to 1200$^{\circ}C$, investigated to enhance the oxdation resistance of MgO-C refractproes. The air was blown into the furnace at flow rate of 0.2 litters per minute, and then weight decrease was measured with a thermo balance at 30 seconds intervals until the value of weight became unchanged. The value of effective diffusion coefficient (De) for the specimen of MgO-C was 1.39${\times}$10$\^$-4/ ㎡/sec. The diffusion of oxygen through decarburized layer was the rate deforming step in the overall oxidation process under present experimental conditions. The TiC additions enhanced the oxidation resistance of the MgO-C refractories.

High-temperature Oxidation of Nano-multilayered TiAlSiN Filems (나노 다층 TiAlSiN 박막의 고온 산화)

  • Lee, Dong-Bok;Kim, Min-Jeong
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2016.11a
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    • pp.189-189
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    • 2016
  • In this study, the Al-rich AlTiSiN thin films that consisted of TiN/AlSiN nano-multilayers were deposited on the steel substrate by magnetron sputtering, and their high-temperature oxidation behavior was investigated, which has not yet been adequately studied to date. Since the oxidation behavior of the films depends sensitively on the deposition method and deposition parameters which affect their crystallinity, composition, stoichiometry, thickness, surface roughness, grain size and orientation, the oxidation studies under various conditions are imperative. AlTiSiN nano-multilayer thin films were deposited on a tool steel substrate, and their oxidation behavior of was investigated between 600 and $1000^{\circ}C$ in air. Since the amount of Al which had a high affinity for oxygen was the largest in the film, an ${\alpha}-Al_2O_3-rich$ scale formed, which provided good oxidation resistance. The outer surface scale consisted of ${\alpha}-Al_2O_3$ incoporated with a small amount of Ti, Si, and Fe. Below this outer surface scale, a thin ($Al_2O_3$, $TiO_2$, $SiO_2$)-intermixed scale formed by the inwardly diffusing oxygen. The film oxidized slower than the $TiO_2-forming$ kinetics and TiN films, but faster than ${\alpha}-Al_2O_3-forming$ kinetics. During oxidation, oxygen from the atmosphere diffused inwardly toward the reaction front, whereas nitrogen and the substrate element of iron diffused outwardly to a certain extent.

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Quenching Mechanisms and Kinetics of $\alpha$-, $\beta$-, $\gamma$-, and $\delta$-Tocopherol in Photosensitized Oxidation of Lard

  • King, Robert;Lee, Hyung-Ok;Min, David B.
    • Food Science and Biotechnology
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    • v.18 no.2
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    • pp.526-532
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    • 2009
  • Quenching mechanisms and kinetics of $\alpha$-, $\beta$-, $\gamma$-, and $\delta$-tocopherol in photosensitized oxidation of lard were studied. Lard at 0.03, 0.07, 0.11, and 0.3 M in methylene chloride containing $4.4{\times}10^{-6}\;M$ chlorophyll and 0, 0.1, 0.3, and 0.6 mM $\alpha$-, $\beta$-, $\gamma$-, and $\delta$-tocopherol were stored under light for 4 hr, respectively. Oxidation was determined by headspace oxygen and peroxide value. Tocopherols prevented the photosensitized oxidation of lard (p<0.05). Steady state kinetic study showed that $\alpha$-, $\beta$-, $\gamma$-, and $\delta$-tocopherol prevented the photosensitized oxidation of lard by quenching singlet oxygen. Singlet oxygen quenching rates of $\alpha$-, $\beta$-, $\gamma$-, and $\delta$-tocopherol by headspace oxygen depletion were 1.86, 2.39, 2.47, and $2.11{\times}10^7/M/sec$, respectively. The quenching rates of $\alpha$-, $\beta$-, $\gamma$-, and $\delta$-tocopherol by peroxide value were 1.42, 1.11, 0.97, and $0.42{\times}10^7/M/sec$, respectively. The quenching rates of tocopherols were slightly different depending on the measurements of oxidation.

Oxidation Kinetics of $UO_2$ Pellets in Defective Fuel Rods and Its Effect on Fission Gas Release (노내 손상 핵연료의 산화거동 및 핵연료 산화가 핵분열기체 방출에 미치는 효과)

  • Koo, Yang-Hyun;Sohn, Dong-Seong;Yoon, Young-Ku
    • Nuclear Engineering and Technology
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    • v.26 no.1
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    • pp.90-99
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    • 1994
  • One of the major phenomena occurring in defective fuel rods is the oxidation of UO$_2$ fuel pellets from UO$_2$ to UO$_{2+}$x/ by the oxygen Produced from the dissociation of the steam in the Pellet-to-clad gap, which leads to the enhancement of fission gas release. In this paper, the oxidation kinetics of defective fuel rods was analyzed on the basis of operating conditions of the reactor and defective fuel rod itself. Oxidation kinetics of the fuel pellet was determined under the assumption that the gap is filled with the saturated steam of 150 atm and an enhancement factor for fission gas release was introduced to take into account the effect of fuel oxidation on fission gas release. Comparison with experimental data shows that the enhancement factor predicts well the increased fission gas release due to the oxidation of UO$_2$fuel pellets.

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High-Temperature Oxidation Behavior of Fe-22%Cr-5.8%Al Alloy (Fe-22%Cr-5.8%Al 합금의 고온 산화 거동)

  • Kim, Song-Yi;Choi, Sung-Hwan;Yun, Jung-Yeul;Kong, Young-Min;Kim, Byoung-Kee;Lee, Kee-Ahn
    • Journal of the Korean institute of surface engineering
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    • v.44 no.1
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    • pp.13-20
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    • 2011
  • This study investigated the high temperature oxidation behavior of Fe-22%Cr-5.8%Al alloy and the oxidation kinetics of the alloy were discussed. Bulk samples were prepared by VAM (vacuum arc melting) and hot forging. High temperature oxidation testes were isothermally conducted up to 100 hours in 79%$N_2$+21%$O_2$ environment at three different temperatures ($900^{\circ}C$, $1000^{\circ}C$, $1100^{\circ}C$). The weight gain was measured after oxidation according to oxidation time (2, 4, 6, 8, 10, 15, 20, 25, 30, 60, 80, 100 hours). The weight gain significantly increased with increasing oxidation temperature. As the temperature increased, the oxidized samples showed sequential formation of $Al_2O_3$, Cr-rich oxide, Fe-rich oxide. The activation energy of high temperature oxidation was obtained as 306.63 KJ/mol. $Al_2O_3$ were developed on the surface in the early stage of oxidation, representing protective role of oxidation. However, Fe-based and Cr-based oxides leaded to breakaway of oxide layer, thus resulted in the significant increase of additional oxidation.

Synthesis of Vertically Aligned CuO Nanorods by Thermal Oxidation (열산화법을 이용한 산화구리 나노선 수직성장)

  • Kim, Jimin;Jung, Hyuck;Kim, Dojin
    • Korean Journal of Materials Research
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    • v.23 no.1
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    • pp.1-6
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    • 2013
  • A simple thermal oxidation of Cu thin films deposited on planar substrates established a growth of vertically aligned copper oxide (CuO) nanorods. DC sputter-deposited Cu thin films with various thicknesses were oxidized in environments of various oxygen partial pressures to control the kinetics of oxidation. This is a method to synthesize vertically aligned CuO nanorods in a relatively shorter time and at a lower cost than those of other methods such as the popular hydrothermal synthesis. Also, this is a method that does not require a catalyst to synthesize CuO nanorods. The grown CuO nanorods had diameters of ~100 nm and lengths of $1{\sim}25{\mu}m$. We examined the morphology of the synthesized CuO nanorods as a function of the thickness of the Cu films, the gas environment, the oxidation time, the oxidation temperature, the oxygen gas flow rate, etc. The parameters all influence the kinetics of the oxidation, and consequently, the volume expansion in the films. Patterned growth was also carried out to confirm the hypothesis of the CuO nanorod protrusion and growth mechanism. It was found that the compressive stress built up in the Cu film while oxygen molecules incorporated into the film drove CuO nanorods out of the film.