• 제목/요약/키워드: Oxidation Rate Constant

검색결과 171건 처리시간 0.024초

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

  • 서성만;이기선;이기안
    • 한국재료학회지
    • /
    • 제14권3호
    • /
    • pp.163-167
    • /
    • 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.

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

  • 김인수;조월동
    • 열처리공학회지
    • /
    • 제14권5호
    • /
    • pp.282-285
    • /
    • 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 $K_p=[2{\rho}_{MmOn}{M^2}_{MmOn}(mD_oC_o{^e}+nD_MC_M{^e})/nm]$.

  • PDF

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

  • 김진형
    • Bulletin of the Korean Chemical Society
    • /
    • 제21권7호
    • /
    • pp.709-711
    • /
    • 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
    • /
    • 제6권5호
    • /
    • pp.291-295
    • /
    • 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.

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

  • 우현정;최두진;양두영
    • 한국세라믹학회지
    • /
    • 제31권7호
    • /
    • pp.753-758
    • /
    • 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.

  • PDF

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

  • Park, Ji-Ho
    • 한국환경보건학회지
    • /
    • 제35권6호
    • /
    • pp.532-537
    • /
    • 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

  • 양승관;고석오
    • 한국지하수토양환경학회:학술대회논문집
    • /
    • 한국지하수토양환경학회 2005년도 총회 및 춘계학술발표회
    • /
    • pp.53-56
    • /
    • 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.

  • PDF

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
    • /
    • 제11권6호
    • /
    • pp.318-324
    • /
    • 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.

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

  • 박진영;서상원;조익환;전용성;하현섭;황태문
    • 상하수도학회지
    • /
    • 제33권6호
    • /
    • pp.469-480
    • /
    • 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.

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

  • 무대박;배범한
    • 대한환경공학회지
    • /
    • 제33권10호
    • /
    • pp.723-730
    • /
    • 2011
  • 본 연구는 토양이나 지하수 원위치 화학적 산화법(In-Situ Chemical Oxidation, ISCO)에서 사용할 수 있는 산화제 Persulfate를 상온에서 활용할 수 있도록 RDX를 처리대상물질로 연구하였다. Persulfate로 RDX를 처리한 결과, 반응은 유사1차반응으로 나타났으며 온도가 증가함에 따라 분해속도도 증가하였고, 이 때 활성화에너지(Activation energy)는 $1.14{\times}10^2kJ/mol$으로 산정되었다. Persulfate에 의한 RDX의 분해반응속도는 pH에 비례하여 증가하였으며, pH값이 4, 6, 8일 때 반응속도의 변화가 크지 않았다. 그러나 pH 10에서는 13배 이상 증가하였는데, persulfate에 의한 산화가 아니라 alkaline hydrolysis로 나타났다. Persulfate에 의한 RDX의 분해반응속도는 persulfate/RDX의 몰 비율에 따라 선형적으로 증가하였으며, $70^{\circ}C$에서 측정한 비례상수는 $4{\times}10^{-4}$ ($min^{-1}$/몰 비율)이었다. 용액 내 천연유기물(NOM) 농도가 증가함에 따라 persulfate에 의한 RDX 분해속도 선형 감소하였으며 $70^{\circ}C$, persulfate/RDX 몰비 10/1에서 측정한 비례상수는 $1.21{\times}10^{-4}$ ($min^{-1}{\cdot}L/mg-NOM$)이었다. 반응속도의 감소는 NOM 첨가량에 선형적으로 비례하였다. NOM 20 mg/L을 첨가한 반응의 Ea값은, 무첨가 반응에서 산정된 Ea값과 3.3% 오차에 불과하였는데, 이는 NOM의 첨가가 본래의 산화반응을 변화시키지는 않음을 의미한다.