• Title/Summary/Keyword: Oxidation kinetics

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Numerical Study of the Effects of Hydrocarbon Addition and Corresponding Chemical Kinetics on the Promotion of NO Oxidation in Nonthermal Plasma DeNOx Treatment (비열 플라즈마에 의한 NO의 산화에서의 탄화수소 첨가 효과와 그 반응역학에 대한 수치적 연구)

  • Shin, Hyun-Ho;Yoon, Woong-Sup
    • Journal of the Korean Society of Combustion
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    • v.5 no.2
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    • pp.37-50
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    • 2000
  • In the present study, a systematic chemical kinetic calculations were made to investigate the augmentation of $NO-NO_2$ conversion due to the addition of various hydrocarbons (methane, ethylene, ethane, propylene, propane) in the nonthermal plasma treatment. It is included in the present conclusion that the reaction between hydrocarbon and oxygen radicals induced by electron collision, is believed to be a primarily process for triggering the overall NO oxidation and the eventual NOx reduction. Upon the completion of the initiating step, various radicals (OH, $HO_2$ etc.) successively are produced by hydrocarbon decomposition form the primary path of $NO-NO_2$ conversion. When the initiating step is not activated, hydrocarbon consumption rate appeared to be very low, thereby the targeted level of NO conversion can only be achieved by the addition of more input energy. Present study showed ethylene and propylene to have higher affinity with O radical under all conditions, thereby both of these hydrocarbons show very fast and efficient $NO-NO_2$ oxidation. It was also shown that propylene is superior to ethylene in the aspect of NOx removal.

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Kinetics and Mechanistic Chemistry of Oxidation of Butacaine Sulfate by Chloramine-B in Acid Medium

  • Shubha, Jayachamarajapura Pranesh;Kotabagi, Vinutha;Puttaswamy, Puttaswamy
    • Bulletin of the Korean Chemical Society
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    • v.33 no.11
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    • pp.3539-3543
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    • 2012
  • Butacaine sulfate is an ester of p-aminobenzoic acid which has been widely used as a local anaesthetic and it is a long standing agent particularly for spinal anaesthesia. For this reason, a kinetic study of oxidation of butacaine sulfate by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried out in $HClO_4$ medium at 303 K in order to explore this redox system mechanistic chemistry. The rate shows a first-order dependence on both $[CAB]_o$, and $[substrate]_o$, and a fractional-order dependence on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increases the rate of the reaction. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction has been found to be 1:2 and the oxidation products have been identified by spectral analysis. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

A Study on Nitridation and Oxidation Reaction of Titanium Powder (금속티타늄분말의 질화반응과 산화반응에 관한 연구)

  • Lee, Young-Ki;Sohn, Yong-Un;Cho, Young-Soo;Kim, Yong Seog;Kim, Suk-Yoon
    • Journal of the Korean Society for Heat Treatment
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    • v.8 no.2
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    • pp.137-148
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    • 1995
  • The nitridation kinetics of titanium powder were studied by isothermal and non-isothermal (dynamic) methods in high purity nitrogen under I atm pressure. For the comparison with nitridation, the oxidation kinetics of titanium powder were also studied in dry oxygen at I atm pressure. An automatic recording electrobalance was used to measure the weight gain as a function of time and temperature. For the reaction with nitrogen, the nitride was formed at over $700^{\circ}C$. The reaction with nitrogen followed the parabolic rate law, and the activation energy was calculated to be 31 kcal/mol in the isothermal method (above $900^{\circ}C$). The non-stoichiometric TiNx has been synthesized by the nitridation at a proper temperature and time, followed by the homogenizing treatment above $1100^{\circ}C$. In comparison with the stoichiometric $TiN_{1.0}$ and the non-stoichiometric TiNx ($TiN_{0.5}$ and $TiN_{0.65}$), the hot oxidation characteristics of the former is superior to that of the latter. However, both non-stoichiometric nitrides make little difference in the hot oxidation characteristics.

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Kinetics and Mechanism of the Oxidation of Carbon Monoxide on CoO-$\alpha-Fe_2O_3$ Catalysts

  • Kim, Keu Hong;Choi, Jae Shi;Kim, Young Bae
    • Bulletin of the Korean Chemical Society
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    • v.8 no.5
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    • pp.389-393
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    • 1987
  • The oxidation of carbon monoxide by gaseous oxygen on 0.53, 1.02, and 1.51 mol $\%$CoO-doped $-Fe_2O_3$ catalysts has been investigated in the temperature range from 340 to 480$^{\circ}C$ under various CO and $O_2$ partial pressures. The oxidation rates have been correlated with 1.5-order kinetics; the 0.5-order with respect to $O_2$ and the first-order with respect to CO. In the above temperature range, the activation energy is 0.34 $\pm$ 0.01 eV${\cdot}$$mol^{-1}$. The electrical conductivity of 0.53, 1.02, and 1.51 mol %CoO-doped $\alpha$-$Fe_2O_3$ has been measured at 350$^{\circ}C$ under various $P_{CO}and $P_{O_2}$. From the conductivity data it was found that $O_2$ was adsorbed on Vo formed by doping with CoO, while CO appeared essentially to be chemisorbed on the lattice oxygen of the catalyst surface. The proposed oxidation mechanism and the dominant defect were supported by the agreement between the kinetic data and conductivities.

Kinetics and Oxygen Vacancy Mechanism of the Oxidation of Carbon Monoxide on Perovskite$Nd_{1-x}Sr_xCoO_{3-y}$ Solutions as a Catalyst

  • Dong Hoon Lee;Keu Hong Kim
    • Bulletin of the Korean Chemical Society
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    • v.15 no.8
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    • pp.616-622
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    • 1994
  • The oxidation of carbon monoxide by gaseous oxygen in the presence of a powdered $Nd_{1-x}Sr_xCoO_{3-y}$ solid solution as a catalyst has been investigated in the temperature range from 150$^{\circ}$C to 300$^{\circ}$C under various CO and $O_2$ partial pressures. The site of Sr substitution, nonstoichiometry, structure, and microstructure were studied by means of powder X-ray diffraction and infrared spectroscopy. The electrical conductivity of the solid solution has been measured at 300$^{\circ}$C under various CO and $O_2$ partial pressures. The oxidation rates have been correlated with 1.5-and 1.2-order kinetics with and without a $CO_2$ trap, respectively; first-and 0.7 order with respect to CO and 0.5-order to $O_2$. For the above reaction temperature range, the activation energy is in the range from 0.25 to 0.35 eV/mol. From the infrared spectroscopic, conductivity and kinetic data, CO appears essentially to be adsorbed on the lattice oxygens of the catalyst, while $O_2$ adsorbs as ions on the oxygen vacancies formed by Sr substitution. The oxygen vacancy mechanism of the CO oxidation and the main defect of $Nd_{1-x}Sr_xCoO_{3-y}$ solid solution are supported and suggested from the agreement between IR data, conductivities, and kinetic data.

A Study on the Photodegradative Behavior of the Dibenzothiophene (DBP) in Water System (수용액중의 디벤조치오펜의 광화학적 분해반응의 연구)

  • Kim, Jae-Hyoun
    • Environmental Analysis Health and Toxicology
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    • v.14 no.3
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    • pp.121-126
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    • 1999
  • The present paper describes a study of the photochemical kinetics and its oxidation mechanism of DBT. The photolysis of DBT in aqueous solution media have shown to have significant oxidation activities for the photolytic desulfurization of DBT. The oxidation effect was more pronounced in 4 % NaCl solution. A mechanism was proposed that the desulfurization process arise from the substution of sulfur by the hydroxyl radicals in different aqueous medium.

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Kinetics of Lipid Oxidation in Dried Fish Meat Stored under Different Conditions of Water Activity and Temperature (건어육 저장중의 온도와 수분활성에 따른 지방의 산화속도)

  • YOU Beoyng-Jin;LEE Kang-Ho
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.15 no.1
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    • pp.83-93
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    • 1982
  • In this work, lipid oxidation and the kinetics of the oxidation reaction in fried file-fish meat were investigated when sun-dried file-fish was stored under the conditions of various water activities and temperature, 35, 45, 55 and $35/55^{\circ}C$. The storage stability and the development of browning by oxidative rancidity were also discussed. Monolayer coverage value of water content in dried file-fish was $8.03\%$ at $0.21\;a_w$Lipid oxidation at $35^{\circ}C$ was developed with increasing water activity but at $45^{\circ}C$and $55^{\circ}C$ it was rapidly progressed without clear differences between water activities except $0.44\;a_w$. The rate of reaction was more sensitive to storage temperature than to water activity. Browning in methanol-chloroform fraction was developed linearly by the progress of lipid oxidation which suggested that lipid oxidation was greatly influential to the development of browning in dried fish meat. In kinetical analysis the oxidation followed a zero order reaction mechanism as a function of carbonyl value. The activation energies obtained from the Arrhenius plot ranged 9.0 to 10.8 Kcal/mol and $Q_10$ values, 1.6-1.7. Shelf-lives at the storage of 35,45 and $55^{\circ}C$ ranged 58 days to 8 days. And in the fluctuating temperature storage at $35/55^{\circ}C$, shelf-lives were 17, 16, 15 and 13 days at 0.44, 0.52, 0.65 and $0.75\;a_w$, respectively. The shelf-lives for assessed from the accelerated shelf-life test were 125, 123, 120 and 106 days at 0.44, 0.52, 0.65 and $0.75\;a_w$, respectively, in the case of storage at $25^{\circ}C$.

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Kinetics of Chromium(III) Oxidation by Various Manganess Oxides (망간 산화물에 의한 3가 크롬의 산화)

  • Chung, Jong-Bae;Zasoski, Robert J.;Lim, Sun-Uk
    • Applied Biological Chemistry
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    • v.37 no.5
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    • pp.414-420
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    • 1994
  • Birnessite, pyrolusite and hausmannite were synthesized and tested for the ability to oxidize Cr(III) to Cr(VI). These oxides differed in zero point of charge, surface area, and crystallinity. The kinetic study showed that Cr(III) oxidation on the Mn-oxide surface is a first-order reaction. The reaction rate was various for different oxide at different conditions. Generally the reaction by hausmannite, containing Mn(III), was faster than the others, and oxidation by pyrolusite was much slower. Solution pH and initial Cr(III) concentration had a significant effect on the reaction. Inhibited oxidation at higher pH and initial Cr(III) concentration could be due to the chance of Cr(III) precipitation or complexing on the oxide surface. Oxidations by birnessite and hausmannite were faster at lower pH, but pyrolusite exhibited increased oxidation capacity at higher pH in the range between 3.0 and 5.0. Reactions were also temperature sensitive. Although calculated activation energies for the oxidation reactions at pH 3.0 were higher than the general activation energy for diffusion, there is no experimental evidence to suggest which reaction is the rate limiting step.

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