• Title/Summary/Keyword: pseudo-first-order reaction

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Characteristics of Toluene Destruction by Non-thermal Plasma in Packed with Catalyst Reactor (촉매가 충진된 플라즈마 반응기에서의 Toluene 제거특성)

  • 한소영;송영훈;차민석;김석준;최경일;신동준
    • Journal of Korean Society for Atmospheric Environment
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    • v.18 no.1
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    • pp.51-58
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    • 2002
  • Destruction process of toluene using a wire-cylindrical BBD (Dielectric Barrier Discharge) reactor packed with catalysts was investigated to characterize the synergetic effects of non-thermal plasma and catalyst process. The catalysts used in the present study were ${\gamma}$-Al$_2$BO$_3$ and Pt/${\gamma}$-Al$_2$O$_3$. Under the numerous test conditions, specific energy density (SED (J/L)) and the conversion of toluene, defined as (1 -[C$_{f}$]/[C$_{i}$]), were measured. The test results showed that toluene decomposition efficiency followed the pseudo-first order in the case of plasma only process. The pseudo-first order process, however, was modified to pseudo-zeroth order reaction in the case of catalyst-assisted plasma process. This modification of the reaction order was verified based on a simple kinetic model proposed in the present study. Owing to the modification of reaction order, which resulted from the catalytic process, the specific energy to achieve the high removal efficiencies, i.e. 80~90%, was reduced significantly.y.y.

Kinetics of Reversible Consecutive Reactions

  • Park, Tae Jun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.243-245
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    • 2013
  • Rate equations are exactly solved for the reversible consecutive reaction of the first-order and the time-dependence of concentrations is analytically determined for species in the reaction. With the assumption of pseudo first-order reaction, the calculation applies and determines the concentration of product accurately and explicitly as a function of time in the unimolecular decomposition of Lindemann and in the enzyme catalysis of Michaelis-Menten whose rate laws have been approximated in terms of reactant concentrations by the steady-state approximation.

Decolorization Characteristics of Acid and Basic Dyes Using Modified Zero-valent Iron (개질 영가철을 이용한 산성 및 염기성 염료의 탈색 특성)

  • Choi, Jeong-Hak;Kim, Young-Hun
    • Journal of Environmental Science International
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    • v.25 no.12
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    • pp.1717-1726
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    • 2016
  • In this study, the reductive decolorization of three acid and basic dyes using modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium coated iron (Pd/Fe)) at various pH conditions (pH 3~5) was experimentally investigated and the decolorization characteristics were evaluated by analyzing the absorbance spectra and reaction kinetics. In the case of acid dyes such as methyl orange and eriochrome black T, color removal efficiencies increased as initial pH of the dye solution decreased. However, the color removal of methylene blue, a basic dye, was not affected much by the initial pH and more than 70% of color was removed within 10 min. During the decolorization reaction, the absorbance of methyl orange (${\lambda}_{max}=464nm$) and eriochrome black T (${\lambda}_{max}=528nm$) decreased in the visible range but increased in the UV range. The absorbance of methylene blue (${\lambda}_{max}=664nm$) also decreased gradually in the visible range. Pseudo-zero order, pseudo-first order, and pseudo-second order kinetic models were used to analyze the reaction kinetics. The pseudo-second order kinetic model was found to be the best with good correlation. The decolorization reaction rate constants ($k_2$) of methylene blue were relatively higher than those of methyl orange and eriochrome black T. The reaction rate constants of methyl orange and eriochrome black T increased with a decrease in the initial pH.

Reduction of Alkyl Halides by Homonuclear Bridging Hydride, (μ-H)[(η$^5-MeCp)$Mn(CO)₂]₂-ppn+

  • 박용광;김영웅
    • Bulletin of the Korean Chemical Society
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    • v.17 no.3
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    • pp.269-273
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    • 1996
  • Alkyl halides were reduced to the corresponding alkanes by the homonuclear bridging hydride, (μ-H)[(η5-MeCp)Mn(CO)2]2-PPN+ in THF at the elevated temperatures (40-60 ℃) under the pseudo first order reaction conditions where excess of alkyl halide was employed under nitrogen atmosphere. The reaction is of overall second order; first order with respect to [bridging hydride] and first order with respect to [alkyl halide] with the activation parameters, ΔH≠=28.93 kcal/mol and ΔS≠=17.95 e.u. The kinetic data, the ESR evidence and the reaction with cyclopropyl canbinyl bromide ensure that two possible reaction pathways are operable in this reaction: (1) concerted mechanism, and (2) single electron transfer pathway are in competition leading to the same product, the corresponding alkane.

Innovative Remediation of Arsenic in Groundwater by Nano Scale Zero-Valent Iron

  • Kanel, Sushil-Raj;Kim, Ju-Yong;Park, Heechul
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2003.09a
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    • pp.87-90
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    • 2003
  • This research examines the feasibility of using laboratory-synthesized nano scale zero-valent iron particles to remove arsenic from aqueous phase. Batch experiments were performed to determine arsenic sorption rates as a function of the nano scale zero-valent iron solution concentration. Rapid adsorption of arsenic was achieved with the nano scale zero-valent iron. Typically 1 mg $L^{-1}$ arsenic (III) was adsorbed by 5 g $L^{-1}$ nano scale zero-valent iron below the 0.01 g $L^{-1}$ concentration within 7min. The kinetics of the arsenic sorption followed pseudo-first-order reaction kinetics. Observed reaction rate constants ( $K_{obs}$) varied between 11.4 to 129.0 $h^{-1}$ with respect to different concentrations of nano scale zero-valent iron. A variety of analytical techniques were used to study the reaction products including HGAAS (hydride generator atomic adsorption spectrophotometer), SEM (scanning electron microscopy) and TEM (transmission electron microscopy). Our experimental results suggest novel method for efficient removal of arsenic Iron groundwater.r.

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The Reactions of O(3P) Atom with Halomethanes: Discharge Flow-Chemiluminescence Imaging Method

  • Lee, Jee-Yon;Yoo, Hee-Soo
    • Bulletin of the Korean Chemical Society
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    • v.23 no.2
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    • pp.291-294
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    • 2002
  • The reactions of triplet oxygen atom with halomethanes as a potential fire extinguisher were studied by a discharge flow-chemiluminescence imaging method. The experiments were carried out under second order conditions. The bimolecular atom-molecule reaction rate constants were determined in terms of the initial rate method. The initial concentration of oxygen atom was also determined under second order rate law instead of the pseudo-first order conditions with $[O(^3P)]_0{\ll}[sample]_0$. The second order conditions were more reliable than pseudo-first order conditions for the determinations of rate constants. The rate constants of the reactions $CF_3I\;+\;O(^3P)$, $CH_3PI\;+\'O(^3P)$, and $CHBrCl_2\;+\;O(^3P)$ were determined to be $5.0\;{\times}\;10^{-12}$ , $1.1\;×\;0^{-11}$ , and $1.9\;{\times}\;10^{-14}cm^3molecule^{-1}s^{-1}$, respectively.

Chemical Modification of the $\beta$-D-Xylosidase from Bacillus stearothermophilus (화학적 수식에 의한 Bacillus stearothermophilus $\beta$-D-Xylosidase 의 연구)

  • 서정한;최용진
    • Microbiology and Biotechnology Letters
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    • v.22 no.6
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    • pp.636-642
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    • 1994
  • Essential amino acids involving in the catalytic mechanism of the $\beta$-D-xylosidase of Bacillus stearothermophilus were determined by chemical modification studies. Among various che- mical modifiers tested N-bromosuccinimide (NBS), $\rho$-hydroxymercurybenzoate (PHMB), N-ethylma- leimide, 1-[3-(di-ethylamino)-propyl]$-3-ethylcarbodi-imide (EDC), and Woodward's Reagent K(WRK)inactivated the enzyme, resulting in the residual activity of less than 20%. WRK reduced the enzyme activity by modifying carboxylic amino acids, and the inactivation reacion proceeded in the form of pseudo-first-order kinetics. The double-lagarithmic plot of the observed pseudo-first- order rate constant against the modifier concentration yielded a reaction order of 2, indicating that two carboxylic amino acids were essential for the enzyme activity. The $\beta$-D-xylosidase was also inactivated by N-ethylmaleimide which specifically modified a cysteine residue with a reaction order of 1, implying that one cysteine residue was important for the enzyme activity. Xylobiose protected the enzyme against inactivation by WRK and N-ethylmaleimide, revealing that carboxylic amino acids and a cysteine residue were present at the substrate-binding site of the enzyme molecule.

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The Removal Kinetics of Mn and Co from the Contaminated Solutions by Various Calcium Carbonate Surfaces (다양한 방해석 표면에 대한 Mn과 Co 흡착 기작)

  • H., Yoon;Ko, K.S.;Kim, S.J.
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.09a
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    • pp.219-222
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    • 2004
  • Removal characteristics of Mn and Co was studied from the contaminated solutions via surface reaction with various calcium carbonate (calcite). Synthetic calcium carbonates which has different surface morphology as well as surface areas were prepared by a spontaneous precipitation method and used. Mn and Co removal behavior by the different solid surface demonstrate characteristic sorption behaviors depend on the type of calcite used, such as surface area or surface morphology. Calcium carbonate crystals (mostly calcite) which exhibit complicated surface morphology (c-type) shows strong sorption affinity for Mn and Co removal via sorption than on the a-type or b-type calcite crystals of less complicated surfaces. The applicability of two kinetic models, the pseudo-first-order kinetic equation and the Elovich kinetic model was examined on these sorption behavior. Elovich kinetic model was found more suitable to explain the very early stage adsorption kinetics, while the pseudo-first-order kinetic equation was successfully fitted for the adsorption kinetics after 50 hours.

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Degradation of Humic Acid Using N-Doped TiO2 (질소를 도핑한 TiO2를 이용한 부식산 분해)

  • So, Ji-Yang;Rhee, Dong-Seock
    • Journal of Industrial Technology
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    • v.31 no.B
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    • pp.119-125
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    • 2011
  • N-doped Titanium oxides were prepared by using urea as a source of nitrogen. The photoactivities of the doped $TiO_2$ were evaluated on the basis of degradation of humic acid in aqueous solutions with different light sources, ultraviolet lamp, fluorescent lamp and solar light. XRD analysis was conducted to identify the crystal structure of the synthesized photocatalysts. N-doped $TiO_2$ and $pure-TiO_2$ was anatase type. SEM results showed that spherical particles were formed, which are the characteristics of the anatase form. N doped $TiO_2$ showed higher $UV_{254}$ decrease ratio and DOC removal ratio compared to $pure-TiO_2$. The humic acid degradation reaction using the UV-A lamp and UV-C lamp was assigned to pseudo-first order reaction. For solar light, only $pure-TiO_2$ and $N-TiO_2$ exhibited the pseudo-first order reaction.

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Kinetics and Mechanism of Substitution Reaction of $PPN^+(\eta^n-MeCp)Mn(CO)_2\;Cl^-$ with $PR_3$(R=Me, Et, OEt, $C_6H_5$)

  • Park, Yong Gwang;Lee, Yong Gu;Kim, Gyu Sik
    • Bulletin of the Korean Chemical Society
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    • v.17 no.2
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    • pp.138-142
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    • 1996
  • The transition metal carbonylate, PPN+(${\eta}^5-MeCp)Mn(CO)_2Cl^-$ undergoes a novel ligand substitution reaction with PR3 (R=Me, Et, OEt, $C_6H_5$ in THF at elevated temperatures (40 $^{\circ}C$ up to 60 $^{\circ}C)$ under the pseudo-first-order reaction conditions (usually 20-fold excess of PR3 with respect to metal carbonylate concentrations) where chloride is displaced by PR3. The reaction follows overall first order dependence on [(${\eta}^5-MeCp)Mn(CO)_2Cl^-$]; however, the negative entropy changes of activation (${\Delta}S^{\neq}$=-19.3 e.u. for $P(OEt)_3$; ${\Delta}S^{\neq}$=-16.4 e.u. for $PPh_3$) suggest the existence of the intermediate, ((η3-MeCp)Mn(CO)2(THF)Cl-, which eventually transforms to the product (${\eta}^5-MeCp)Mn(CO)_2(PR_3)$.