• Title/Summary/Keyword: First-order kinetics

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Dependence of an Interfacial Diels-Alder Reaction Kinetics on the Density of the Immobilized Dienophile: An Example of Phase-Separation

  • Min, Kyoung-Mi;Jung, Deok-Ho;Chae, Su-In;Kwon, Young-Eun
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1679-1684
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    • 2011
  • Interfacial reactions kinetics often differ from kinetics of bulk reactions. Here, we describe how the density change of an immobilized reactant influences the kinetics of interfacial reactions. Self-assembled monolayers (SAMs) of alkanethiolates on gold were used as a model interface and the Diels-Alder reaction between immobilized quinones and soluble cyclopentadiene was used as a model reaction. The kinetic behavior was studied using varying concentrations of quinones. An unusual threshold density of quinones (${\Gamma}_c$ = 5.2-7.2%), at which the pseudo-first order rate constant started to vary as the reaction progressed, was observed. This unexpected kinetic behavior was attributed to the phase-separation phenomena of multi-component SAMs. Additional experiments using more phase-separated two-component SAMs supported this explanation by revealing a significant decrease in ${\Gamma}_c$ values. When the background hydroxyl group was replaced with carboxylic or phosphoric acid groups, ${\Gamma}_c$ was observed at below 1%. Also, more phase-separated thermodynamically controlled SAMs produced a lower critical density (3% < ${\Gamma}_c$ < 4.9%) than that of the less phaseseparated kinetically controlled SAMs (6.5% < ${\Gamma}_c$ < 8.9%).

Comparison of Bioleaching Kinetics of Spent Catalyst by Adapted and Unadapted Iron & Sulfur Oxidizing Bacteria - Effect of Pulp Density; Particle Size; Temperature

  • Pradhan, Debabrata;Kim, Dong-Jin;Ahn, Jong-Gwan;Gahan, Chandra Sekhar;Chung, Hun-Saeng;Lee, Seoung-Won
    • Korean Journal of Metals and Materials
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    • v.49 no.12
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    • pp.956-966
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    • 2011
  • Bioleaching studies of metals from a spent catalyst were conducted using both adapted and unadapted bacterial cultures. The bacterium used in this experiment was Acidithiobacillus ferrooxidans. A comparison of the kinetics of leaching was made between the two cultures by varying the leaching parameters, including the pulp density, particle size and temperature. Both cultures showed similar effects with respect to the above parameters, but the leaching rates of all metals were higher with the adapted compared to the unadapted bacterial cultures. The leaching reactions were continued for 240 h in the case of the unadapted bacterial culture, but only for 40 h in the case of the adapted bacterial culture. The leaching reactions followed first order kinetics. In addition, the kinetics of leaching was concluded to be a diffusion control model; therefore, the product layers were impervious.

Oxidative Degradation Kinetics of Tocopherols during Heating

  • Chung, Hae-Young
    • Preventive Nutrition and Food Science
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    • v.12 no.2
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    • pp.115-118
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    • 2007
  • Tocopherols are important lipid-phase antioxidants that are subject to heat degradation. Therefore, kinetic analyses for oxidative degradation of tocopherols as a function of temperatures and times were performed. Alpha-, gamma- and delta-tocopherols dissolved in glycerol were heated at 100${\sim}$250$^{\circ}C$ for 5~60 min. Oxidized tocopherols were analyzed by HPLC using a reversed phase ${\mu}$-Bondapak C$_{18}$-column with two kinds of elution solvent systems in a gradient mode. The degradation kinetics for tocopherols followed a first-order kinetic model. The rate of tocopherol degradation was dependent on heating temperatures. The degradation rate constants for ${\gamma}$- and ${\delta}$-tocopherols were higher than those for ${\alpha}$-tocopherol. The experimental activation energies of ${\alpha}$-, ${\gamma}$- and ${\delta}$- tocopherols were 2.51, 6.05 and 5.34 kcal/mole, respectively. The experimental activation energies for the oxidative degradation of ${\gamma}$- and ${\delta}$-tocopherols were higher than that of ${\alpha}$-tocopherol.

Reaction Mechanisms and Kinetics of Antioxidant Using Arrhenius Equation in Soybean Oil Oxdation

  • Cho, Hyung-Young
    • Preventive Nutrition and Food Science
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    • v.2 no.1
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    • pp.6-10
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    • 1997
  • The reaction mechanisms and kinetics of tertiary butylhydroquinone(TBHQ) as an antioxidant in soybean oil oxidation were studied. The oxidation reaction of soybean oil at 55, 60 and $65^{\circ}C$ was a first order. The activation energies of soybean oil containing 0, 25, 50, and 75ppm TBHQ were 12.15, 6.05, 6.15 and 6.17kcal/mole. respectively. The addition of THQ to soybean oil containing 0, 25, 50, and 75ppm TBHQ were 1.88$\times${TEX}$10^{7}${/TEX}, 4.10$\times${TEX}$10^{2}${/TEX}, 4.32 $\times${TEX}$10^{2}$p/TEX} and 3.97$\times${TEX}$10^{2}${/TEX}, respectively. The decrease of frequency factor rather than the activation energy. The effects of antioxidants on the temperature dependecy of lipid oxidation could be effectively evaluated by measuring their effects on the activation energy of lipid oxidation.

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Biosorption and Flotation of Lead and Chromium using Waste Activated Sludge (폐 활성슬러지를 이용한 납과 크롬의 생체흡착 및 부상)

  • Lee, Chang-Han
    • The Journal of the Korea Contents Association
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    • v.9 no.10
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    • pp.444-450
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    • 2009
  • We have investigated biosorption kinetics and equilibrium of $Pb^2+$ and $Cr^2+$ using waste sludge, and separation efficiency of waste sludge by dissolved air flotation was evaluated in the various A/S ratio. The biosorption capacity and contact time were shown as a simulation of biosorption equilibrium and kinetics models. Biosorption equilibrium of the $Pb^2+$ and $Cr^2+$ onto the waste sludge could be fitted by the Langmuir, Freundlich, Redlich-Peterson, and Koble-Corrigan equation. The kinetics could be fitted by a pseudo-second-order rate equation more than a pseudo-first-order rate equation. The separation efficiency of waste sludge using DAF was kept above 90%.

The Nature of Acid-Catalyzed Acetalization Reaction of 1,2-Propylene Glycol and Acetaldehyde

  • Cheng, Chen;Chen, Hui;Li, Xia;Hu, Jianli;Liang, Baochen
    • Korean Chemical Engineering Research
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    • v.53 no.4
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    • pp.463-467
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    • 2015
  • We investigated catalytic activity of ion-exchange resins in acetalization of 1,2-propylene glycol with acetaldehyde. The impacts of reaction variables, such as temperature, reaction time, catalyst loading and feedstock composition, on the conversion of 1,2-propylene glycol were measured. The life of the catalyst was also studied. Furthermore, the reaction kinetics of 1,2-propylene glycol acetalization was studied. It was found that reaction rate followed the first-order kinetics to acetaldehyde and 1,2-propylene glycol, respectively. Therefore, overall acetalization reaction should follow the second-order reaction kinetics, expressed as. Key words: 1,2-propylene Glycol, 2,4-dimethyl-1,3-dioxolane, Ion-exchange Resin, Polyhydroxy Compounds, Acetalization $r=kC^{nA}_AC^{nB}_B=19.74e^{\frac{-6650}{T}}C^1_AC^1_B$.

Coconut husk as a biosorbent for methylene blue removal and its kinetics study

  • Dave, Shailesh R.;Dave, Vaishali A.;Tipre, Devayani R.
    • Advances in environmental research
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    • v.1 no.3
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    • pp.223-236
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    • 2012
  • Biosorption of methylene blue (MB) from aqueous solution was studied with respect to the point of zero charge of coconut husk, dye concentration, particle size, pH, temperature, as well as adsorbent and NaCl concentration using coconut husk biomass. Amongst Langmuir and Freundlich adsorption isotherms studied, Langmuir adsorption isotherm showed better agreement. Pseudo second order kinetics model was found to be more suitable for data presentation as compared to pseudo first order kinetics model. Also, involvement of diffusion process was studied using intraparticle diffusion, external mass transfer and Boyd kinetic model. Involvement of intraparticle diffusion model was found to be more relevant (prominent) as compared to external mass transfer (in) for methylene blue biosorption by the coconut husk. Moreover, thermodynamic properties of MB biosorption by coconut husk were studied. Desorption of methylene blue from biomass was studied with different desorbing agents, and the highest desorption achieved was as low as 7.18% with acetone, which indicate stable immobilization. Under the experimental conditions MB sorption was not significantly affected by pH, temperature and adsorbent concentration but low sorption was observed at higher NaCl concentrations.

Kimchi Quality Kinetics during Isothermal and Nonisothermal Fermentation Conditions

  • Kim, Myung-Hwan;Chang, Moon-Jeong
    • Preventive Nutrition and Food Science
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    • v.4 no.4
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    • pp.246-250
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    • 1999
  • This study was conducted to develop the fermentation kinetic modeling for the prediction of pH and acidity changes in kimchi at isothermal and nonisothermal fermentation temperatures(0~15$^{\circ}C$) and salt concentrations(1.5~4.0%) using the traditional two-step method and alternative one-step method. The calculations of the two-step method of pH and acidity change during fermentation followed the pattern of the first order and zero order, respectively. The reaction rate constant of pH by the first order was increased from 0.008 {TEX}$day^{-1}${/TEX} to 0.017 {TEX}$day^{-1}${/TEX} by increasing the temperature from $0^{\circ}C$ to 15$^{\circ}C$ at 2.75% of salt concentration, and was decreased from 0.013 {TEX}$day^{-1}${/TEX} to 0.010 {TEX}$day^{-1}${/TEX} by increasing the salt concentration from 1.5% to 4.0% at 5$^{\circ}C$. For the pH and acidity of Kimchi, the zero order had a higher correlation than the first order to the estimate of the kinetics parameters by the one-step method. The {TEX}$E_{a}${/TEX} ranges of pH and acidity were 61.057~66.086 and 62.417~68.772 kJ/mole with different temperatures and salt concentrations. This one-step method had smaller and more realistic estimates of error(p〈0.05). The effective temperatures, {TEX}$T_{eff}${/TEX}, with 0~15$^{\circ}C$ of square function type of 12 hr intervals were 12.85, 11.48 and 12.46$^{\circ}C$ as increasing the salt concentration, 1.50, 2.75 and 4.00%, respectively. The {TEX}$T_{eff}${/TEX} were higher values than the mean temperature(7.5$^{\circ}C$).

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Biosorption of Rhodamine B onto Waste Activated Sludge: Equilibrium and Kinetic Modelling (폐 활성슬러지를 이용한 Rhodamine B의 생체흡착:흡착평혀여 및 흡착속도 모델링)

  • Lee Chang-Han;Ahn Kab-Hwan
    • Journal of Environmental Science International
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    • v.14 no.9
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    • pp.881-888
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    • 2005
  • The biosorption of dye, Rhodamine B(Rh-B), onto waste activated sludge was investigated. The biosorption capacity and contact time were shown as a simulation of dye adsorption equilibrium and kinetics models. We observed that biosorption of Rh-B occurred rapidly less than 4 hr. These experimental data could be better fitted by a pseudo-second-order rate equation than a pseudo-first-order rate equation. The equilibrium dependence between biosorption capacity and initial concentration of Rh-B was estimated and it was found that the equilibrium data of biosorption were fitted by four kinds of model such as Langmuir, Freundlich, Redlich-Peterson, and Koble-Corrigan model. The average percentage errors, $\varepsilon(\%)$, observed between experimental and predicted values by above each model were $21.19\%,\;9.97\%,\;10.10\%\;and\;11.76\%$, respectively, indicating that Freundlich and Redlich-Peterson model could be fitted more accrately than other models.

Equilibrium modeling for adsorption of NO3- from aqueous solution on activated carbon produced from pomegranate peel

  • Rouabeh, I.;Amrani, M.
    • Advances in environmental research
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    • v.1 no.2
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    • pp.143-151
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    • 2012
  • Nitrate removal from aqueous solution was investigated using $ZnCl_2$ and phosphoric acid activated carbon developed from pomegranate peel with particle size 0.4 mm. Potassium nitrate solution was used in batch adsorption experiments for nitrate removal from water. The effects of activated carbon dosage, time of contact, and pH were studied. The equilibrium time was fond to be 45 min. Two theoretical adsorption isotherms namely Langmuir and Freundlich were used to describe the experimental results. The Langmuir fit the isotherm with the theoretical adsorption capacity ($q_t$) was fond 78.125 mg g-1. Adsorption kinetics data were modeled using the pseudo-first, pseudo-second order, and intraparticle diffusion models. The results indicate that the second-order model best describes adsorption kinetic data. Results show activated carbon produced from pomegranate is effective for removal of nitrate from aqueous solution.