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

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Characteristics of the sonolytic reaction of refractory aromatic compounds in aqueous solution by ultrasound (초음파에 의한 수중의 난분해성 방향족화합물의 반응특성)

  • Sohn, Jong-Ryueul;Mo, Se-Young
    • Journal of Korean Society on Water Environment
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    • v.18 no.4
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    • pp.411-419
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    • 2002
  • In this study, the series of ultrasonic irradiation for removal of refractory aromatic compounds has been selected as a model reaction in the batch reactor system in order to obtain the reaction kinetics. The products obtained from the ultrasonic irradiation were analysed by GC and GC/MSD. The decomposition of benzene produced toluene, phenol, and C1-C4 compounds, while the intermediates during the ultrasonic irradiation of 2,4-Dichlorophenol(DCP) were phenol, HCl, catechol, hydroquinone, and benzoquinone. It was found that more than 80% of benzene, and 2,4-DCP solutions were removed within 2 hours in all reaction conditions. The reaction order in the degradation of these three compounds was verified as pseudo-zero or first order. From the fore-mentioned results, it can be concluded that the refractory organic compounds could be removed by the ultrasonic irradiation with radicals, such as $H{\cdot}$ and $OH{\cdot}$ radical causing the high increase of pressure and temperature. Finally, it appeared that the technology using ultrasonic irradiation can be applied to the treatment of refractory compounds which are difficult to be decomposed by the conventional methods.

Adsorption Characteristics of Methylene Blue and Phenol from Aqueous Solution using Coal-based Activated Carbon (석탄계 활성탄에 의한 수중의 메틸렌블루와 페놀 흡착 특성)

  • Lee, Song-Woo;Kam, Sang-Kyu;Lee, Min-Gyu
    • Journal of Environmental Science International
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    • v.22 no.9
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    • pp.1161-1170
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    • 2013
  • The efficiency of coal-based activated carbon in removing methylene blue (MB) and phenol from aqueous solution was investigated in batch experiments. The batch adsorption kinetics were described by applying pseudo-first-order, pseudo-second-order, and first order reversible reaction. The results showed that the adsorption of MB and phenol occurs complexed process including external mass transfer and intraparticle diffusion. The maximum adsorption capacity obtained from Langmuir isotherm was 461.0 mg/g for MB and 194.6 mg/g for phenol, respectively. The values of activation parameters such as free energy (${\Delta}G^0$), enthalpy (${\Delta}H^0$), and entropy (${\Delta}S^0$) were also determined as -19.0~-14.9 kJ/mol, 25.4 kJ/mol, and 135.2 J/mol K for MB and 51.8~54.1 kJ/mol, -29.0 kJ/mol, and -76.4 kJ/mol K for phenol, respectively. The MB adsorption was found to be endothermic and spontaneous process. However, the CV adsorption was found to be exothermic and non-spontaneous process.

Effects of EBCT and Water Temperature on HAA Removal using BAC Process (BAC 공정에서 EBCT와 수온에 따른 HAA 제거 특성)

  • Son, Hee-Jong;Yoo, Soo-Jeon;Yoo, Pyung-Jong;Jung, Chul-Woo
    • Journal of Korean Society of Environmental Engineers
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    • v.30 no.12
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    • pp.1255-1261
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    • 2008
  • In this study, The effects of three different biological activated carbon (BAC) materials (each coal, coconut and wood based activated carbons), empty bed contact time (EBCT) and water temperature on the removal of haloacetic acid (HAA) 5 species in BAC filters were investigated. Experiments were conducted at three water temperatures (5, 10 and 20$^{\circ}C$) and four EBCTs (5, 10, 15 and 20 min). The results indicated that coal based BAC retained more attached bacterial biomass on the surface of the activated carbon than the other BAC, increasing EBCT or increasing water temperature increased the HAA 5 species removal in BAC columns. To achieve an HAA removal efficiency 50% or higher in a BAC filter, the authors suggest 10 min EBCT or longer for 5$^{\circ}C$ waters and 5 min EBCT for waters at 10$^{\circ}C$ or higher. The kinetic analysis suggested a first-order reaction model for HAA 5 species removal at various water temperatures (5, 10 and 20$^{\circ}C$). The pseudo-first-order reaction rate constants and half-lives were also calculated for HAA removal at 5, 10 and 20$^{\circ}C$. The pseudo-first-order reaction rate constants and half-lives were also calculated for HAA 5 species removal at 5$\sim$ 20$^{\circ}C$. The half-lives of HAA 5 species ranging from 0.75 to 18.58 min could be used to assist water utilities in designing and operating BAC filters for HAA removal.

Applicability of Theoretical Adsorption Models for Studies on Adsorption Properties of Adsorbents(II) (흡착제의 흡착특성 규명을 위한 흡착모델의 적용성 평가(II)-흡착속도론을 중심으로)

  • Na, Choon-Ki;Park, Hyun-Ju
    • Journal of Korean Society of Environmental Engineers
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    • v.33 no.11
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    • pp.804-811
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    • 2011
  • The aim of this study is to evaluate the applicability of adsorption models for understanding adsorption properties of adsorbents. For this study, the adsorption charateristics of $NO_3^-$ by commercial anion exchange resin, PA-308, were investigated in bach process. The adsorption kinetic data for $NO_3^-$ by anion exchange resin showed two stage process comprising a fast initial adsorption process and a slower second adsorption process. Both the pseudo-first-order kinetic model and the pseudo-second-order kinetic model could not be used to predict the adsorption kinetics of $NO_3^-$ onto anion exchange resin for the entire sorption period. Only the fast initial portion ($t{\leq}20min$) of adsorption kinetics was found to follow pseudo-first-order kinetic model and controlled mainly by external diffusion that is very fast and high, whereas, the slower second portion (t > 20 min) of adsorption kinetics seems to be controlled by a second-order chemical reaction and by intraparticle diffusion.

Solvolysis of 3-Chloro-1,2-benzisothiazole-1,1-dioxide (pseudosaccharin chloride (3-Chloro-1,2-benzisothiazole-1,1-dioxide (pseudosaccharin chloride)의 가용매 분해반응)

  • In-Sun Koo;Jeong-Ja Kim;Yong-Jin Yoon;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.30 no.3
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    • pp.296-300
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    • 1986
  • The pseudo-first order rate constants have been obtained for the solvolysis of pseudo-saccharinechloride in MeOH-$H_2O$, EtOH-$H_2O$, MeOH-MeCN and MeOH-$(Me)_2$CO solvents mixtures at various temperatures. Values of n and m in the Kivinen and Grunwald-Winstein plots, respectively, have been determined and the Taft's solvatochromic parameters were obtained; based on these solvent effect parameters as well as on the activation parameters it was concluded that reaction proceeds via an $S_N2$ mechanism.

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Kinetics and Mechanism of $N_2H_4-KBrO_3$ Reaction in the Presence of Allyl Alcohol$^\dag$

  • Choi, Q.-Won;Chung, Keun-Ho
    • Bulletin of the Korean Chemical Society
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    • v.7 no.6
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    • pp.462-465
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    • 1986
  • Kinetics and Mechanism of $N_2H_4-KBrO_3$ reaction in the presence of allyl alcohol have been studied. The pseudo-first order rate constant for gas evolution was found to be $10^{-4}{\sim}10^{-2}\;sec^{-1}\;at\;25.0{\pm}0.1^{\circ}C$, increasing with concentration of hydrogen ion. When concentrations of sulfuric acid and allyl alcohol are both sufficiently high, the following overall reaction explains experimental results reasonably well: $N_2H_4\;+\;BrO_3^-\;+\;H^+\;{\to}\;N_2\;+\;HOBr\;+\;2H_2O,\;CH_2\;=\;CHCH_2OH\;+\;HOBr\;{\to}\;CH_2-OHCHBrCH_2OH$. More complicated reaction mechanisms at lower acidity conditions have been contemplated.

Reaction Mechanism and Kinetics of Degradation for Refractory Organic Pollutants in Water by Ultrasonic Irradiation

  • Sohn, Jong-Ryeul;Moon, Kyung-Hwan
    • Proceedings of the Korean Environmental Health Society Conference
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    • 2003.06a
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    • pp.123-127
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    • 2003
  • This experiment was performed to investigate the characteristics of sonolytic reaction as the basic data for development of the ultrasonic AOP(Advanced Oxidation Process) process from which the refractory organic compounds in aqueous solution which are not readily removed by the existing conventional wastewater treatment processes can be destructed and removed. Trichloroethylene (TCE), benzene, and 2,4-dichlorophenol(DCP) were used as the samples, and their destruction efficiency were measured in terms of experimental parameters of the initial solution concentration, initial solution pH, reaction temperature, acoustic frequencies and intensities. Results showed that the destruction efficiencies of all of the sample materials were above 80% within 120 minutes of sonolytic reaction in all reaction condition. The reaction order of these three compounds was verified as Pseudo first order. From the fore-mentioned results, it can be concluded that the refractory organic compounds could be removed by the ultrasonic irradiation with radicals, such as H$.$and OH$.$causing the high increase of pressure and temperature. Finally, it appears that the new AOP technology using ultrasonic irradiation can be applied to the treatment of refractory substances which are difficult to be decomposed by the conventional methods.

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Chemical Modification of 5-Lipoxygenase from the Korean Red Potato

  • Kim, Kyoung-Ja
    • BMB Reports
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    • v.33 no.2
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    • pp.172-178
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    • 2000
  • The lipoxygenase was purified 35 fold to homogeneity from the Korean red potato by an ammonium sulfate precipitation and DEAE-cellulose column chromatography. The simple purification method is useful for the preparation of pure lipoxygenase. The molecular weight of the enzyme was estimated to be 38,000 by SDS-polyacrylamide gel electrophoreses and Sepharose 6B column chromatography. The purified enzyme with 2 M $(NH_4)_2SO_4$ in a potassium phosphate buffer, pH 7.0, was very stable for 5 months at $-20^{\circ}C$. Because the purified lipoxygenase is very stable, it could be useful for the screening of a lipoxygenase inhibitor. The optimal pH and temperature for lipoxygenase purified from the red potato were found to be pH 9.0. and $30^{\circ}C$, respectively. The Km and Vmax values for linoleic acid of the lipoxygenase purified from the red potato were $48\;{\mu}M$ and $0.03\;{\mu}M$ per minute per milligram of protein, respectively. The enzyme was insensitive to the metal chelating agents tested (2 mM KCN, 1 and 10mM EDTA, and 1 mM $NaN_3$), but was inhibited by several divalent cations, such as $Cu^{++}$, $Co^{++}$ and $Ni^{++}$. The essential amino acids that were involved in the catalytic mechanism of the 5-lipoxygenase from the Korean red potato were determined by chemical modification studies. The catalytic activity of lipoxygenase from the red potato was seriously reduced after treatment with a diethylpyrocarbonate (DEPC) modifying histidine residue and Woodward's reagent (WRK) modifying aspartic/glutamic acid. The inactivation reaction of DEPC (WRK) processed in the form of pseudo-first-order kinetics. The double-logarithmic plot of the observed pseudo-first-order rate constant against the modifier concentration yielded a reaction order 2, indicating that two histidine residues (carboxylic acids) were essential for the lipoxygenase activity from the red potato. The linoleic acid protected the enzyme against inactivation by DEPC(WRK), revealing that histidine and carboxylic amino acids residues were present at the substrate binding site of the enzyme molecules.

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Kinetics and Reaction Mechanism for Aminolysis of Benzyl 4-Pyridyl Carbonate in H2O: Effect of Modification of Nucleofuge from 2-Pyridyloxide to 4-Pyridyloxide on Reactivity and Reaction Mechanism

  • Kang, Ji-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2269-2273
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    • 2012
  • Pseudo-first-order rate constants $k_{amine}$ have been measured spectrophotometrically for the reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{amine}$ vs. [amine] curve upward, indicating that the reactions proceed through a stepwise mechanism with two intermediates, a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$. This contrasts to the report that the corresponding reactions of benzyl 2-pyridyl carbonate 5 proceed through a forced concerted pathway. The $k_{amine}$ values for the reactions of 6 have been dissected into the second-order rate constant $Kk_2$ and the thirdorder rate constant $Kk_3$. The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}=0.94$ and 1.18 for $Kk_2$ and $Kk_3$, respectively. The $Kk_2$ for the reaction of 6 is smaller than the second-order rate constant $k_N$ for the corresponding reaction of 5, although 4-pyridyloxide in 6 is less basic and a better nucleofuge than 2-pyridyloxide in 5.

Verification of Kinetic Theoretical Prediction of Diffusion-influenced Reversible

  • Yang, Min O;Sin, Guk Jae
    • Bulletin of the Korean Chemical Society
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    • v.21 no.1
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    • pp.93-96
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    • 2000
  • A diffusion-influenced pseudo-first order reversible reaction A + B ⇔C + B is investigated by the molecular dynamics (MD) simulation method. Theoretical finding that the temporal evolution of reactants [conditional probabilities] in the reversible system can be expressed by the irreversible survival probability with an effective rate parameter is confirmed even in the presence of solvent particles. We carry out molecular dynamics simulations for both the irreversible and the reversible cases to evaluate the survival and the conditional probabilities for each cases. When the resultant irreversible survival probability is inserted into the proposed relation, the conditional probabilities given by the simulation are exactly reproduced.