• Title/Summary/Keyword: oxidation rate

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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.

N-Oxidation of Pyrazines by Bromamine-B in Perchloric Acid Medium: Kinetic and Mechanistic Approach

  • Puttaswamy;Shubha, J.P.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.9
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    • pp.1939-1945
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    • 2009
  • Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

Effects of Dietary Supplementation with a Compound Composed of Caffeine, Capsaicin, Sesamine, L-Carnitine, Banaba and Lotus on Human Autonomic Nervous System Activity and Lipid Oxidation

  • Kang, Sung-Hwun;Shin, Ki-Ok
    • Preventive Nutrition and Food Science
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    • v.14 no.3
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    • pp.173-178
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    • 2009
  • This study was conducted to determine if supplementation with a compound composed of caffeine (50 mg), capsaicin (75 mg), sesamine (30 mg), L-carnitine (300 mg), banaba (50 mg) and lotus (10 mg) enhanced human autonomic nervous activities (ANS) associated with thermogenic sympathetic activity and fat utilization. Ten healthy college males (21.2$\pm$1.0 yr) volunteered for this experiment. Autonomic nervous activities associated with energy metabolism were examined at 30 min intervals for a total of 120-min while at rest and every 5-min during exercise at 50% of the ventilation threshold before and after intake of the compound or placebo with 100 ml of water for 10 days. In addition, heart rate variability power spectral analysis was used to assess human autonomic nervous activities. The results indicated that there were no significant differences in heart rate during rest and exercise among trials. Furthermore, the autonomic nervous activity tended to increase after 10-days of consumption of the test compounds during the experimental period, but the differences did not reach statistical significance. However, before and after the compound test trial there was a significantly higher respiratory gas exchange ratio (rest 0: 0.83$\pm$0.01 vs. rest 3: 0.89$\pm$0.02, p<0.05), carbohydrate oxidation (CHO) rate (rest 0: 44.57$\pm$5.83 vs. rest 2: 63.86$\pm$5.91%, p<0.05) and a lower fat oxidation rate (rest 0: 55.43$\pm$5.83 vs. rest 2: 36.14$\pm$5.91%, p<0.05. In conclusion, the results of the present study suggested that the compound composed of caffeine, capsaicin, sesamine, L-carnitine, banaba and lotus components that was evaluated in this study did not induce a significant increase in human autonomic nervous activities or lipolysis, even though the individual components have been reported to induce increased fat oxidation.

Control of Persulfate Activation Rate and Improvement of Active Species Transfer Rate Using Selenium-modified ZVI (셀레늄으로 개질된 영가철을 이용한 과황산 활성화 속도 조절 및 활성종 전달율 향상에 관한 연구)

  • Hee-won Kwon;Hae-Seong Park;In-seong Hwang;Jeong-Jin Kim;Young-Hun Kim
    • Journal of Environmental Science International
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    • v.32 no.1
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    • pp.57-65
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    • 2023
  • The advanced oxidation treatment using persulfate and zero-valent iron (ZVI) has been evaluated as a very effective technology for remediation of soil and groundwater contamination. However, the high rate of the initial reaction of persulfate with ZVI causes over-consumption of an injected persulfate, and the excessively generated active species show a low transfer rate to the target pollutant. In this study, ZVI was modified using selenium with very low reactivity in the water environment with the aim of controlling the persulfate activation rate by controlling the reactivity of ZVI. Selenium-modified ZVI (Se/ZVI) was confirmed to have a selenium coating on the surface through SEM/EDS analysis, and low reductive reactivity to trichlroethylene (TCE) was observed. As a result of inducing the persulfate activation using the synthesized Se/ZVI, the persulfated consumption rate was greatly reduced, and the decomposition rate of the model contaminant, anisole, was also reduced in proportion. However, the final decomposition efficiency was rather increased, which seems to be the result of preventing persulfate over-consumption. This is because the transfer efficiency of the active species (SO4-∙) of persulfate to the target contaminant has been improved. Selenium on the surface of Se/ZVI was not significantly dissolved even under oxidation conditions by persulfate, and most of it was present in the form of Se/ZVI. It was confirmed that the persulfate activation rate could be controlled by controlling the reactivity of ZVI, which could greatly contribute to the improvement of the persulfate oxidation efficiency.

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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Oxidation behavior of CaO added Mg and Mg-Al alloys (CaO을 첨가한 Mg 및 Mg-Al 합금의 산화거동)

  • Ha, Seong-Ho;Lee, Jin-Kyu;Jung, Seung-Boo;Kim, Young-Jig;Jo, Hyung-Ho;Kim, Shae-K.
    • Journal of Korea Foundry Society
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    • v.27 no.3
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    • pp.126-130
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    • 2007
  • Oxidation behavior of CaO added Mg and Mg-5Al alloys was investigated. At $500^{\circ}C$, oxidation rate of pure Mg was abruptly increased, while that of CaO added Mg was remarkably reduced with increasing CaO content. As a result of surface analysis by AES, there was the thin oxide layer mixed with MgO and CaO in CaO added Mg. Oxidation behavior of CaO added Mg was similar to that of Ca added Mg. Oxidation rate of 0.6CaO added Mg-5Al alloy was much lower than that of Mg-5Al alloy at $500^{\circ}C$ and both alloys showed the linear weight change at $400^{\circ}C$.

The effect of Rh/Ce/Zr additives on the redox cycling of iron oxide for hydrogen storage (산화철의 환원-산화 반응을 이용한 수소저장에 미치는 Rh/Ce/Zr의 효과)

  • Lee, Dong-Hee;Cha, Kwang-Seo;Park, Chu-Sik;Kang, Kung-Soo;Kim, Young-Ho
    • 한국신재생에너지학회:학술대회논문집
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    • 2007.06a
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    • pp.49-52
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    • 2007
  • We investigated hydrogen storage and production properties using redox system of iron oxide($Fe_{3}O_{4}$ + $4H_{2}$ ${\leftrightarrows}$ 3Fe + $4H_{2}O$) modified with rhodium, ceria and zirconia under atmospheric pressure. Reduction of iron oxide with hydrogen(hydrogen storage) and re-oxidation of reduced iron oxide with steam(hydrogen evolution) was carried out using a temperature programmed reaction(TPR) technique. On the temperature programmed studies, the effects of amounts of cerium and zirconium on the re-oxidation rate of partial reduced iron oxides were increased with increasing metal additives amount, but the rhodium amount showed little effect on the re-oxidation rate. On the thermal studies, the re-oxidation rates were enhanced with increasing temperature(300 $^{\circ}C$ < 350 $^{\circ}C$).

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A Study on the Oxidation Characteristics of p-Cresol on Pt Anode (백금전극(白金電極)에 의한 파라크레졸의 양극전해(陽極電解) 산화특성(酸化特性))

  • Kim, Hong-Soo;Nam, Jeong-Woo
    • Journal of the Korean Applied Science and Technology
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    • v.7 no.2
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    • pp.47-53
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    • 1990
  • The electrochemical oxidation behavior of p-cresol on platinum anode had been investigated by cyclic voltammetric method for the variation of concentration, scan rate of potential, temperature and pH of electrolyte. The oxidation potential of p-cresol was dependent on the electrolyte until the pH=11.5, but in basic solution over its, it was held at o.40V(vs. SCE). A diffusion was rate determining step of oxidation as irreversible reaction by the transfer atone electron. The current of peak was proportional to concentration of p-cresol until the 0.1N and optimum concentration was found to be about 0.1N. The activation energy was calculated for 5.8kcal/mol from the plot of log $I_l$ vs. 1/T.

Growth and Properties of Ultra-thin SiO2 Films by Rapid Thermal Dry Oxidation Technique (급속 건식 열산화 방법에 의한 초박막 SiO2의 성장과 특성)

  • 정상현;김광호;김용성;이수홍
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.17 no.1
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    • pp.21-26
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    • 2004
  • Ultra-thin silicon dioxides were grown on p-type(100) oriented silicon employing rapid thermal dry oxidation technique at the temperature range of 850∼1050 $^{\circ}C$. The growth rate of the ultra-thin film was fitted well with tile model which was proposed recently by da Silva & Stosic. The capacitance-voltage, current-voltage, characteristics were used to study the electrical properties of these thin oxides. The minimum interface state density around the midgap of the MOS capacitor having oxide thickness of 111.6 $\AA$ derived from the C-V curve was ranged from 6 to 10${\times}$10$^{10}$ /$\textrm{cm}^2$eV.

Decomposition of Ethylene Glycol by Catalytic Wet Air Oxidation (촉매습식산화에 의한 Ethylene Glycol의 분해)

  • 안상준;최장승;이동근
    • Textile Coloration and Finishing
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    • v.13 no.4
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    • pp.264-271
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    • 2001
  • Catalytic wet oxidation of ethylene glycol as refractory compound was studied in a batch slurry reactor using lwt% $Pt/A1_2O_3$, lwt% $Pt/TiO_2,\;Mn/CeO_2$(1:1) and 5wt% $Mn/Al_2O_3$. Experiments were conducted to investigate theeffects of temperature, initial ethylene glycol concentration, catalyst dosage and PH on the ethylene glycol decomposition. When compared with the uncatalyzed reaction, the use of catalysts could increase the rate of ethylene glycol decomposition. The lwt% $Pt/A1_2O_3$ catalyst was preferable to the other catalysts for the destructive oxidation of ethylene glycol. The reaction rate was first order with respect to initial concentration of ethylene glycol. In acidic condition the removal efficiency of ethylene glycol was good, but there was a significant leaching of platinum. Small amount of acetic acid, oxalic acid, masonic acid and formic acid as intermediates were detected during catalytic wet air oxidation of ethylene glycol.

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