• Title/Summary/Keyword: Kinetics and mechanism

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Spectrophotometric Investigation of Oxidation of Cefpodoxime Proxetil by Permanganate in Alkaline Medium: A Kinetic Study (알칼리성 용매에서 과망간에 의한 세프포독심 프록세틸의 산화의 분광광도법적 조사: 속도론적 연구)

  • Khan, Aftab Aslam Parwaz;Mohd, Ayaz;Bano, Shaista;Siddiqi, K. S.
    • Journal of the Korean Chemical Society
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    • v.53 no.6
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    • pp.709-716
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    • 2009
  • A Kinetics pathway of oxidation of Cefpodoxime Proxetil by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically. The reaction showed first order kinetics in permanganate ion concentration and an order less than unity in cefpodoxime acid and alkali concentrations. Increasing ionic strength of the medium increase the rate. The oxidation reaction proceeds via an alkali-permanganate species which forms a complex with cefpodoxime acid. The latter decomposes slowly, followed by a fast reaction between a free radical of cefpodoxime acid and another molecule of permanganate to give the products. Investigations of the reaction at different temperatures allowed the determination of activation parameters with respect to the slow step of proposed mechanism and fallows first order kinetics. The proposed mechanism and the derived rate laws are consistent with the observed kinetics.

Folding Mechanism of WT* Ubiquitin Variant Studied by Stopped-flow Fluorescence Spectroscopy

  • Park, Soon-Ho
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2877-2883
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    • 2010
  • The folding kinetics of $WT^*$ ubiquitin variant with valine to alanine mutation at sequence position 26 (HubWA) was studied by stopped-flow fluorescence spectroscopy. While unfolding kinetics showed a single exponential phase, refolding reaction showed three exponential phases. The semi-logarithmic plot of urea concentration vs. rate constant for the first phase showed v-shape pattern while the second phase showed v-shape with roll-over effect at low urea concentration. The rate constant and the amplitude of the third phase were constant throughout the urea concentrations, suggesting that this phase represents parallel process due to the configurational isomerization. Interestingly, the first and second phases appeared to be coupled since the amplitude of the second phase increased at the expense of the amplitude of the first phase in increasing urea concentrations. This observation together with the roll-over effect in the second folding phase indicates the presence of intermediate state during the folding reaction of HubWA. Quantitative analysis of Hub-WA folding kinetics indicated that this intermediate state is on the folding pathway. Folding kinetics measurement of a mutant HubWA with hydrophobic core residue mutation, Val to Ala at residue position 17, suggested that the intermediate state has significant amount of native interactions, supporting the interpretation that the intermediate is on the folding pathway. It is considered that HubWA is a useful model protein to study the contribution of residues to protein folding process using folding kinetics measurements in conjunction with protein engineering.

Detonation Wave Simulation of Thermally Cracked JP-7 Fuel/Oxygen Mixture using Induction Parameter Modeling (Induction Parameter Modeling을 이용한 열 분해된 JP-7 연료 /산소 혼합기의 데토네이션 파 해석)

  • Cho, Deok-Rae;Shin, Jae-Ryul;Choi, Jeong-Yeol;Yang, Vigor
    • Journal of the Korean Society for Aeronautical & Space Sciences
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    • v.37 no.4
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    • pp.383-391
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    • 2009
  • The detonation wave characteristics of JP-7 and oxygen mixture is investigated by one-step induction parameter model (IPM) obtained from a detailed chemistry mechanism. A general procedure of obtaining reliable one-step kinetics IPM for hydrocarbon mixture from the fully detailed chemistry is described in this study. The IPM is obtained by the reconstruction of the induction time database obtained from a detailed kinetics library. The IPM was confirmed by the comparison of the induction time calculations with that from detailed kinetics. The IPM is later implemented to a fluid dynamics code and applied for the numerical simulation of detonation wave propagation. The numerical results show the detailed characteristics of the detonation wave propagation in JP-7 and oxygen mixture at affordable computing time, which is not be possible by the direct application of the detailed chemical kinetics mechanism of hydrocarbon fuel combustion.

Oxidation Kinetics of Pitch Based Carbon Fibers

  • Roh, Jae-Seung
    • Carbon letters
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    • v.9 no.2
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    • pp.121-126
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    • 2008
  • High modulus pitch based carbon fibers (HM) were exposed to isothermal oxidation using tube furnace in carbon dioxide gas to study the oxidation 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 1.02~1.42. The oxidation kinetics were evaluated by the reaction-controlling regime (RCR) depending upon the apparent activation energies with the conversion increasing from 0.2 to 0.8. The activation energies decrease from 24.7 to 21.0 kcal/mole with the conversion increasing from 0.2 to 0.8, respectively. According to the RCR, the reaction was limited by more diffusion controlling regime for the HM fibers with the conversion increasing. Therefore, it seems that the oxidation which is under the diffusion controlling regime takes place continuously from the skin to the core of the fiber.

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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