• Title/Summary/Keyword: pseudo second-order kinetics

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Nucleophile Effects for the Reactions of Nucleophilic Substitution by Pressure and Temperature (친핵성치환반응에서 압력과 온도변화에 따른 친핵체 효과)

  • Kim, Se-Kyong;Choi, Sung-Yong;Ko, Young-Shin
    • Journal of the Korean Chemical Society
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    • v.48 no.5
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    • pp.461-466
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    • 2004
  • Kinetics for the nucleophiles have been studied under high vacuum and high pressures in various temperatures. Pseudo-first order rate constants, second order rate constants, thermodynamic parameters and Hammett ${\rho}$-values are determined. The values of ${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq}\;and\;{\Delta}S^{\neq}$are all negative. The Hammett r-values are negative for the nucleophile (${\rho}$x) over the pressure range studied. The results of kinetic studies for pressure and nucleophilet show that these reactions proceed in typical $S_N2$ reaction mechanism and change of mechanism.

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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Efficient use of ferrate(VI) for the remediation of wastewater contaminated with metal complexes

  • Sailo, Lalsaimawia;Pachuau, Lalramnghaki;Yang, Jae Kyu;Lee, Seung Mok;Tiwari, Diwakar
    • Environmental Engineering Research
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    • v.20 no.1
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    • pp.89-97
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    • 2015
  • Remediation of wastewater contaminated with metal(II)-complexed species (Cu(II)-NTA (NTA: nitrilotriacetic acid), Cu(II)-EDTA (EDTA: ethylenediamine tetraacetic acid) and Cd(II)-EDTA is attempted using the potential applicability of ferrate(VI). Kinetics of pollutant degradation is obtained with the removal of ferrate(VI) studied at wide range of pH (8.0-10.0) and the concentration of metal(II)-complexed species (0.3 to 15.0 mmol/L) employing a constant dose of ferrate(VI) i.e., 1.0 mmol/L. Pseudo-first-order and pseudo-second-order rate constants were obtained in the reduction of ferrate(VI) which was then employed to obtain the overall rate constants of the pollutant degradation. The mineralization of NTA and EDTA was obtained with the change in TOC (total organic carbon) values collected by the ferrate(VI) treated pollutant samples. Decrease in pH and molar pollutant concentrations was greatly favored the percent mineralization of NTA or EDTA by the ferrate(VI) treatment. The treated pollutant samples were filtered and subjected for AAS (atomic absorption spectrophotometric) analysis to assess the simultaneous removal of copper and cadmium from aqueous solutions at the studied pH as well at the elevated pH 12.0. Results show that an enhanced removal of cadmium or copper was achieved at pH 12.0. Overall, ferrate(VI) possesses multifunctional application in wastewater treatment as it oxidizes the degradable impurities and removes metallic impurities by coagulation process.

Removal of Heavy Metals by Sawdust Adsorption: Equilibrium and Kinetic Studies

  • Lim, Ji-Hyun;Kang, Hee-Man;Kim, Lee-Hyung;Ko, Seok-Oh
    • Environmental Engineering Research
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    • v.13 no.2
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    • pp.79-84
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    • 2008
  • Adsorption of heavy metals by sawdust was investigated to evaluate the effectiveness of using sawdust to remove heavy metals from aqueous solutions. Kinetic and isotherm studies were carried out by considering the effects of initial concentration and pH. The adsorption isotherms of heavy metals fitted the Langmuir or Freundlich model reasonably well. The adsorption capacity of metal was in the order $Pb^{2+}$ > $Cu^{2+}$ > $Zn^{2+}$. A high concentration of co-existing ions such as $Ca^{2+}$ and $Mg^{2+}$ depressed the adsorption of heavy metal. Adsorption data showed that metal adsorption on sawdust follows a pseudo-second-order reaction. Kinetic studies also indicated that both surface adsorption and intraparticle diffusion were involved in metal adsorption on sawdust. Column studies prove that sawdust could be effective biosorbent for the removal of heavy metals from aqueous phase.

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.

Competitive Adsorption in Binary Solution with Different Mole Ratio of Sr and Cs by Zeolite A : Adsorption Isotherm and Kinetics (스트론튬과 세슘 이온의 혼합 몰비를 달리한 이성분 용액에서 제올라이트 A에 의한 경쟁 흡착: 흡착등온 및 속도해석)

  • Lee, Chang-Han;Park, Jeong-Min;Lee, Min-Gyu
    • Journal of Environmental Science International
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    • v.24 no.2
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    • pp.151-162
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    • 2015
  • The adsorption characteristics of Sr ions and Cs ions in single and binary solution by zeolite A were investigated in batch experiment. The adsorption rate of Sr ions and Cs ions by zeolite A obeyed pseudo-second-order kinetic model in single and binary solution. The initial adsorption rates (h) and adsorption capacities of both ions obtained from pseudo-second-order kinetic model, and the values were decreased with increasing concentration of the competitive ions (0~1.5 mM). Also, adsorption isotherm data in binary solution were well fitted to the extended Langmuir model, the maximum adsorption capacities of Sr and Cs calculated from the model were 1.78 mmol/g and 1.64 mmol/g, respectively. The adsorption of Sr and Cs ions by zeolite A was carried out in the presence of other cations such as $Na^+$, $K^+$, $Mg^{2+}$ and $Ca^{2+}$. The results showed that the zeolite A can maintain a relatively high adsorption capacity for Sr and Cs ions and exhibits a high selectivity in the presence of competitive cations. The effect of competition had an order of $Ca^{2+}$ > $K^+$ > $Mg^{2+}$ > $Na^+$ for Sr ions and $K^+$ > $Ca^{2+}$ > $Na^+$ > $Mg^{2+}$ for Cs ions at the same cation concentration.

Characterization of Bottom Ash as an Adsorbent of Lead from Aqueous Solutions

  • Gorme, Joan B.;Maniquiz, Marla C.;Kim, Soon-Seok;Son, Young-Gyu;Kim, Yun-Tae;Kim, Lee-Hyung
    • Environmental Engineering Research
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    • v.15 no.4
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    • pp.207-213
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    • 2010
  • This study investigated the potential of using bottom ash to be used as an adsorbent for the removal of lead (Pb) from aqueous solutions. The physical and chemical characteristics of bottom ash were determined, with a series of leaching and adsorption experiments performed to evaluate the suitability of bottom ash as an adsorbent material. Trace elements were present, such as silicon and aluminum, indicating that the material had a good adsorption capacity. All heavy metals leached during the Korea standard leaching test (KSLT) passed the regulatory limits for safe disposal, while batch adsorption experiments showed that bottom ash was capable of adsorbing Pb (experimental $q_e$ = 0.05 mg/g), wherein the adsorption rate increased with decreasing particle size. The adsorption data were then fitted to kinetic models, including Lagergren first-order and Pseudo-second order, as well as the Elovich equation, and isotherm models, including the Langmuir, Freundlich and Dubinin-Radushkevich isotherms. The results showed that pseudo-second order kinetics was the most suitable model for describing the kinetic adsorption, while the Freundlich isotherm best represented the equilibrium sorption onto bottom ash. The maximum sorption capacity and energy of adsorption of bottom ash were 0.315 mg/g and 7.01 KJ/mol, respectively.

Aqueous phase removal of ofloxacin using adsorbents from Moringa oleifera pod husks

  • Wuana, Raymond A.;Sha'Ato, Rufus;Iorhen, Shiana
    • Advances in environmental research
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    • v.4 no.1
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    • pp.49-68
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    • 2015
  • Chemically activated and carbonized adsorbents were prepared from Moringa oleifera pod husks (MOP), characterized and evaluated for their ability to remove a common antibiotic - ofloxacin (OFX) from aqueous solution. The pulverized precursor was steeped in a saturated ammonium chloride solution for a day to give the chemically activated adsorbent (AMOP). A portion of AMOP was pyrolyzed in a muffle furnace at 623 K for 30 min to furnish its carbonized analogue (CMOP). The adsorbents showed favorable physicochemical attributes. The effects of operational parameters such as initial OFX solution pH and concentration, adsorbent dosage, temperature and contact time on OFX removal were investigated. At equilibrium, optimal removal efficiencies of 90.98% and 99.84% were achieved at solution pH 5 for AMOP and CMOP, respectively. The equilibrium adsorption data fitted into both the Langmuir and Freundlich isotherms. Gibbs free energy change (${\Delta}G^o$), enthalpy change (${\Delta}H^o$) and entropy change (${\Delta}S^o$) indicated that the adsorption of OFX was feasible, spontaneous, exothermic and occurred via the physisorption mode. Adsorption kinetics obeyed the Blanchard pseudo-second-order model. The results may find applications in the adsorptive removal of micro-contaminants of pharmaceutical origin from wastewater.

Adsorption of Bisphenol A Using Dried Rice Husk: Equilibrium, Kinetic and Thermodynamic Studies

  • Balarak, Davoud;Mostafapour, Ferdos Kord;Lee, Seung Mok;Jeon, Choong
    • Applied Chemistry for Engineering
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    • v.30 no.3
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    • pp.316-323
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    • 2019
  • The adsorption of bisphenol A from an aqueous solution onto dried rice husk was investigated. Batch adsorption experiments were performed as a function of the pH, contact time, bisphenol A concentration, adsorbent dose and temperature. The concentration of Bisphenol A was measured by HPLC. The results showed that bisphenol A removal was highest at a solution pH value of 3, adsorbent dose of 4 g/L, and contact time of 75 min. The bisphenol A removal percentage decreased from 99.1 to 66.7%, when the bisphenol A concentration increased from 10 to 200 mg/L. The Langmuir isotherm and pseudo-second order kinetics provided the best fit for the experimental data. Thermodynamic parameters such as ${\Delta}G^0$, ${\Delta}H^0$ and ${\Delta}S^0$ were also evaluated and it was found that the sorption process was feasible, spontaneous and exothermic in nature. Overall, the studied absorbent can be used as an effective and low cost material to treat the industrial wastewater and aqueous solution containing phenolic compounds.

Drug adsorption and anti-microbial activity of functionalized multiwalled carbon nanotubes

  • Saxena, Megha;Mittal, Disha;Boudh, Richa;Kumar, Kapinder;Verma, Anita K.;Saxena, Reena
    • Advances in nano research
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    • v.11 no.6
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    • pp.667-678
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    • 2021
  • Multiwalled carbon nanotubes (MWCNTs) were first oxidized (O-CNTs) to introduce carboxylic group and then further functionalized (F-CNTs) with m-phenylenediamine, which was confirmed by FTIR and SEM. It was used as an effective adsorbent for the adsorptive removal of diclofenac drug from water. Under optimum conditions of pH 6, stirring speed 600 rpm, the maximum adsorption capacity obtained was 532 mg g-1 which is superior to the values reported in literature. The adsorption was quite rapid as 25 mg L-1 drug solution was adsorbed in only 3 minutes of contact time with 10 mg of adsorbent dose. The adsorption kinetics and isotherms were studied using various models to evaluate the adsorption process. The results showed that the data best fit in kinetics pseudo-second order and Langmuir isotherm model. Furthermore, the oxidized and functionalized MWCNTs were applied on gram-negative Escherichia coli and gram-positive Staphylococcus aureus using agar disc diffusion assay to validate their anti-microbial activity. Results were unique as both oxidized and functionalized MWCNTs were equally active against both E. coli and S. aureus. The newly synthesized F-CNTs have great potential in water treatment, with their dual action of removing drug and pathogens from water, makes it potential applicant to save environment.