• Title/Summary/Keyword: Oxidation Rate Constant

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Oxidation Rates of TiAlLaN Thin Films Deposited by Ion Plating (이온플레이팅법으로 제조된 TiAlLaN계 박막의 산화속도)

  • Seo Sung Man;Lee Kee Sun;Lee Kee-Ahn
    • Korean Journal of Materials Research
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    • v.14 no.3
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    • pp.163-167
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    • 2004
  • TiAl(La)N thin films were oxidized in vacuum of about 7 Pa to reduce the oxidation of WC-Co as a substrate. The oxidation rate constants of the thin films were quantified by an assumption of parabolic oxidation. Increasing AI content significantly decreased the parabolic oxidation rate constant. A simultaneous addition of AI and La was more effective to reduce the oxidation rate. The parabolic oxidation rate constant of $Ti_{0.66}$ $Al_{0.32}$ $La_{ 0.02}$N thin film at 1273 K showed about ten times lower than that of TiN. The addition of a small amount of La with Al induced the preferential formation of dense $\alpha$ $-Al_2$$O_3$ film in oxide film, leading to the abrupt reduction of oxidation rate.

Theoretical Calculation of Parabolic Rate Constant for High-Temperature Oxidation of Metals (금속의 고온 산화동안 포물선 속도상수의 이론적 계산)

  • Kim, Insoo;Cho, Weol Dong
    • Journal of the Korean Society for Heat Treatment
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    • v.14 no.5
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    • pp.282-285
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    • 2001
  • Based on the mass balance of anion and cation fluxes, the parabolic rate constant ($K_p$) of oxide grown during the high-temperature oxidation of metal is theoretically calculated. It is assumed that the diffusion of oxygen anion and metal cation through oxide scale obeys the Fick's 1st law, the growth of oxide is controlled by the diffusion of ions, electrical potential gradient as driving force for diffusion of ions is ignored, and oxidation occurs within an existing oxide layer. Then, the parabolic rate constant can be expressed by $K_p=[2{\rho}_{MmOn}{M^2}_{MmOn}(mD_oC_o{^e}+nD_MC_M{^e})/nm]$.

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Voltammetric Studies of Guanine and Its Derivatives by (TEX)$Ru(bpy)^{2+/3+}$(/TEX) Mediator on Indium Tin Oxide Electrode

  • Kim, Jin Hyeong
    • Bulletin of the Korean Chemical Society
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    • v.21 no.7
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    • pp.709-711
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    • 2000
  • Oxidizing metal complex mediates the electrochemical oxidation of guanine nucleotides. This catalysis results in an enhancement in cyclic voltammograms that yield the rate constant for the oxidation of guanine by the metal complex via digital simulation. The rate constant of oxidation of guanine by Ru(bpy)3(3+) is 6.4 x 10(5)M(-1)s(-l). The rate constant and the enhanced current depend on the number of phosphate groups on the sugar of nucleotidc. Also the modified guanine bases show different oxidation rate constants following the trend guanine-5'- monophosphatc (GMP) > 8-bromo-guanine-5'-monophosphate (8-Br-GMP) > xanthosine -5'-monophosphate (XMP) > inosinc-5'-monophosphate (IMP). The guanine bases derivatized differently are all distinguishable from one another, providing a basis for studying electrochemistry of DNA and RNA and developing electrochemical biosensors.

Methyl Linoleate Oxidation via Electron Transfer in Competition with $^1O_2$ Formation Photosensitized N-Acetyl-L-Tryptophan 3-Methyl Indole

  • Yoon, Min-Joong;Song, Moon-Young;Cho, Dae-Won
    • Bulletin of the Korean Chemical Society
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    • v.6 no.5
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    • pp.291-295
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    • 1985
  • The efficiency of photosensitization of methyl linoleate (ML) oxidation by N-acetyl-L-trypophan(NAT) and 3-methyl indole(scatole) was markedly enhanced by increased concentration of ML in ethanol solution. The fluorescence intensities of sensitizers were observed to be quenched by ML, indicating that ML interacts with the indole excited singlet state. The inhibition of photosensitization by azide demonstrated a possible role of singlet oxygen in the photosensitization. The steady state kinetic treatment of azide inhibition of photosensitization was expected to show linear increase of reciprocal yield of ML oxidation product vs. reciprocal ML concentration at constant azide concentration, but the actual slope was nonlinear. This indicates another competing reaction involved in the photosensitization, As a possible competing reaction, electron transfer from ML to the excited sensitizer was proposed, since the measured fluorescence quenching rate constant closely resembled electron transfer rate constant determined from ML concentration dependence of oxidation product formation.

Thermal Oxidation Behavior and Electrical Characteristics of Silicon depending on the Crystal Orientation (결정 배향에 따른 Si의 열산화 거동 및 전기적 특성)

  • 우현정;최두진;양두영
    • Journal of the Korean Ceramic Society
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    • v.31 no.7
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    • pp.753-758
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    • 1994
  • (100) Si and 4$^{\circ}$off (100) Si were oxidized in dry oxygen, and the differences in thermal oxidation behavior and electrical characteristics between two specimens were investigated. Ellipsometer measurements of the oxide thickness produced by oxidation in dry oxygen from 1000 to 120$0^{\circ}C$ showed that the oxidation rates of the 5$^{\circ}$ off (100) Si were more rapid than those of the (100) Si and the differences between them decreased as the oxidation temperature increased. The activation energies based on the parabolic rate constant, B for (100) and 4$^{\circ}$off (100) Si were 25.8, 28.6 kcal/mol and those on the linear rate constant, B/A were 56.8, 54.9 kcal/mol, respectively. Variation of C-V characteristics with the oxidation temperature showed that the flat band voltages were shifted positively and surface state charge densities decreased as the oxidation temperature increased, and the surface state charge density of the 4$^{\circ}$off (100) Si was lower than that of the (100) Si. Also considerable decrease in the density of oxidation induced stacking faults (OSF) for the 4$^{\circ}$off (100) Si was observed through optical microscopy after preferentially etching off the oxide layer.

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CRDS Study of Tropospheric Ozone Production Kinetics : Isoprene Oxidation by Hydroxyl Radical

  • Park, Ji-Ho
    • Journal of Environmental Health Sciences
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    • v.35 no.6
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    • pp.532-537
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    • 2009
  • The tropospheric ozone production mechanism for the gas phase additive oxidation reaction of hydroxyl radical (OH) with isoprene (2-methyl-1,3-butadiene) has been studied using cavity ring-down spectroscopy (CRDS) at total pressure of 50 Torr and 298 K. The applicability of CRDS was confirmed by monitoring the shorter (~4%) ringdown time in the presence of hydroxyl radical than the ring-down time without the photolysis of hydrogen peroxide. The reaction rate constant, $(9.8{\pm}0.1){\times}10^{-11}molecule^{-1}cm^3s^{-1}$, for the addition of OH to isoprene is in good agreement with previous studies. In the presence of $O_2$ and NO, hydroxyl radical cycling has been monitored and the simulation using the recommended elementary reaction rate constants as the basis to OH cycling curve gives reasonable fit to the data.

과망간산을 이용한 지하수내 TCE 제거효과 평가

  • Yang Seung-Gwan;Go Seok-O
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2005.04a
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    • pp.53-56
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    • 2005
  • A Laboratory study was conducted to evaluate the kinetics of oxidation of trichloroethylene (TCE) in groundwater by potassium permanganate $(KMnO_4)$, Consumption of permanganate by TCE and aquifer materials was also evaluated to obtain an appropriate injection rate of $KMnO_4$. TCE degradation by $KMnO_4$ in the absence of aquifer material showed effective with pseudo-first order rate constant, $k_{obs}=1.8110^{-3}\;s^{-1}\;at\;KMnO_4=500mg/L$. TCE oxidation by $KMnO_4$ was found to be second order reaction and the rate constant, $k=0.65{\pm}0.08\;M^{-1}s^{-1}$, was independent of pH changes. $KMnO_4$ consumption rate by groundwater sampled from field site was not significant, indicating that groundwater containing negligible amount of dissolved organic matter does not have any influence on the $KMnO_4$ degradation. Meanwhile, aquifer materials from field site were actively reacted with permanganate, resulting in the significant consumption of $KMnO_4$. It might be attributed to the existence of metal oxides in aquifer materials, Based on the rate constants obtained from this study, appropriate injection rate of permanganate and TCE removal rate in groundwater could be estimated.

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FERRATE(VI) FOR WASTE WATER TREATMENT : OXIDATION OF CYANIDE IN AQUEOUS MEDIUM

  • Tiwari, Diwakar;Kim, Hyoung-Uk;Lee, Seung-Mok;Yang, Jae-Kyu;Kim, Hyun-Ook
    • Environmental Engineering Research
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    • v.11 no.6
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    • pp.318-324
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    • 2006
  • The higher valence state of iron i.e., Fe(VI) was employed for the oxidation of one of an important toxic ion, cyanide in the aqueous medium. Cyanide was oxidized into cyanate, which is 1,000 times less toxic to cyanide and often accepted for its ultimate disposal. It was to be noted that Fe(VI) is a very powerful oxidizing agent and can oxidize most of the cyanide within few minutes i.e., ca 5 mins of contact. The data was obtained by the UV-Visible measurements for the Fe(VI) decomposition. The UV-Visible data was used to evaluate the overall rate constant for second order redox reaction between ferrate(VI) and cyanide. Also the pseudo first order rate constant was calculated as keeping the cyanide concentration in excess.

Degradation of residual pharmaceuticals in water by UV/H2O2 advanced oxidation process (UV/H2O2 고도산화기술을 이용한 수중 잔류의약물질 제거)

  • Park, Chinyoung;Seo, Sangwon;Cho, Ikhwan;Jun, Yongsung;Ha, Hyunsup;Hwang, Tae-Mun
    • Journal of Korean Society of Water and Wastewater
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    • v.33 no.6
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    • pp.469-480
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    • 2019
  • This study was conducted to evaluate the degradation and mineralization of PPCPs (Pharmaceuticals and Personal Care Products) using a CBD(Collimated Beam Device) of UV/H2O2 advanced oxidation process. The decomposition rate of each substance was regarded as the first reaction rate to the ultraviolet irradiation dose. The decomposition rate constants for PPCPs were determined by the concentration of hydrogen peroxide and ultraviolet irradiation intensity. If the decomposition rate constant is large, the PPCPs concentration decreases rapidly. According to the decomposition rate constant, chlortetracycline and sulfamethoxazole are expected to be sufficiently removed by UV irradiation only without the addition of hydrogen peroxide. In the case of carbamazepine, however, very high UV dose was required in the absence of hydrogen peroxide. Other PPCPs required an appropriate concentration of hydrogen peroxide and ultraviolet irradiation intensity. The UV dose required to remove 90% of each PPCPs using the degradation rate constant can be calculated according to the concentration of hydrogen peroxide in each sample. Using this reaction rate, the optimum UV dose and hydrogen peroxide concentration for achieving the target removal rate can be obtained by the target PPCPs and water properties. It can be a necessary data to establish design and operating conditions such as UV lamp type, quantity and hydrogen peroxide concentration depending on the residence time for the most economical operation.

The Effects of Reaction Conditions and NOM on Persulfate Oxidation of RDX (Persulfate에 의한 RDX 산화시 반응조건과 NOM의 영향)

  • Wu, Dabo;Bae, Bum-Han
    • Journal of Korean Society of Environmental Engineers
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    • v.33 no.10
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    • pp.723-730
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    • 2011
  • In this experiment, persulfate, a strong oxidant for ISCO (In-Situ Chemical Oxidation) was used to degraded RDX in artificial ground water at ambient temperature. Results of RDX degradation by persulfate in a batch reactor showed that the oxidation reaction was pseudo first order with estimated Ea (activation energy) of $1.14{\times}10^2kJ/mol$ and the rate was increased with the increase of reaction temperature. The oxidation of RDX by persulfate increased slightly with the increase of initial solution pH from 4 to 8. The RDX oxidation rate increased 13 times at pH 10 compared with that at pH 4, however, alkaline hydrolysis was found to be the main reaction of RDX degradation rather than oxidation. The study also showed that the oxidation rate of RDX by persulfate was linearly dependent upon the molar ratios of persulfate to RDX from 5 : 1 up to 100 : 1, with a proportion constant of $4{\times}10^{-4}$ ($min^{-1}$/molar ratio) at $70^{\circ}C$. While NOM (Natural Organic Matter) exerted negative effects on the oxidation rate of RDX by persulfate, with a proportion constant of $1.21{\times}10^{-4}$ ($min^{-1}{\cdot}L/mg-NOM$) at $70^{\circ}C$ and persulfate/NOM molar ratio of 10/1. The decrease in RDX oxidation rate was linearly dependent upon the added NOM concentration. However, the estimated activation energy in the presence of 20 mg-NOM/L was within 3.3% error compared to that without NOM, which implies the addition of NOM does not alter intrinsic oxidation reaction.