• Title/Summary/Keyword: linear isotherm

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Determination of Adsorption Isotherms of Hydroxide ata Platinum Electrode Interface Using the Phase-Shift Method and Correlation Constants

  • Chun, Jin-Y.;Chun, Jang-H.
    • Journal of the Korean Electrochemical Society
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    • v.10 no.3
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    • pp.219-228
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    • 2007
  • The phase-shift method and correlation constants, i.e., the electrochemical impedance spectroscopy (EIS) techniques for studying linear relationships between the behaviors (${\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and those (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}{\theta}{\geq}0$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at noble and transition-metal/aqueous solution interfaces. At the Pt/0.1 MKOH aqueous solution interface, the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=5.6{\times}10^{-10}\;mol^{-1}\;at\;0{\leq}{\theta}<0.81$, $K=5.6{\times}10^{-9}{\exp}(-4.6{\theta})\;mol^{-1}\;at\;0.2<{\theta}<0.8$, and $K=5.6{\times}10^{-10}{\exp}(-12{\theta})\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$, interaction parameters (g = 4.6 for the Temkin and g = 12 for the Frumkin adsorption isotherm), rates of change of the standard free energy ($r=11.4\;kJ\;mol^{-1}$ for g=4.6 and $r=29.8\;kJ\;mol^{-1}$ for g=12), and standard free energies (${\Delta}G_{ads}^0=52.8\;kJ\;mol^{-1}\;at\;0{\leq}{\theta}<0.81,\;49.4<{\Delta}G_{\theta}^0<56.2\;kJ\;mol^{-1}\;at\;0.2<{\theta}<0.8$ and $80.1<{\Delta}_{\theta}^0{\leq}82.5\;kJ\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$) of OH for the anodic $O_2$ evolution reaction (OER) are also determined using the phase-shift method and correlation constants. The adsorption of OH transits from the Langmuir to the Frumkin adsorption isotherm (${\theta}\;vs.E$), and vice versa, depending on the electrode potential (E) or the fractional surface coverage (${\theta}$). At the intermediate values of ${\theta}$, i.e., $0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms and related electrode kinetic and thermodynamic parameters. They are useful and effective ways to study the adsorptions of intermediates (H, OH) for the sequential reactions (HER, OER) at the interfaces.

Determination of Adsorption Isotherms of Hydrogen on Zirconium in Sulfuric Acid Solution Using the Phase-Shift Method and Correlation Constants

  • Chun, Jang-H.;Chun, Jin-Y.
    • Journal of the Korean Electrochemical Society
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    • v.12 no.1
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    • pp.26-33
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    • 2009
  • The phase-shift method and correlation constants, i.e., the unique electrochemical impedance spectroscopy (EIS) techniques for studying the linear relationship between the behavior ($-{\varphi}$ vs. E) of the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) for the optimum intermediate frequency and that ($\theta$ vs. E) of the fractional surface coverage ($0{\leq}{\theta}{\leq}1$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at noble metal (alloy)/aqueous solution interfaces. At a Zr/0.2 M ${H_2}{SO_4}$ aqueous solution interface, the Frumkin and Temkin adsorption isotherms ($\theta$ vs. E), equilibrium constants (K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ for the Frumkin and K = $1.401{\times}10^{-16}\exp(8.1{\theta})mol^{-1}$ for the Temkin adsorption isotherm), interaction parameters (g = 3.5 for the Frumkin and g = 8.1 for the Temkin adsorption isotherm), rates of change of the standard free energy (r = $8.7\;kJ\;mol^{-1}$ for g = 3.5 and r = $20\;kJ\;mol^{-1}$ for g = 8.1) of H with $\theta$, and standard free energies ($96.13{\leq}{\Delta}G^0_{\theta}{\leq}104.8\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ and $0{\leq}{\theta}{\leq}1$ and ($94.44<{\Delta}G^0_{\theta}<106.5\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-16}\exp(-8.1{\theta})mol^{-1}$ and $0.2<{\theta}<0.8$) of H are determined using the phase-shift method and correlation constants. At 0.2 < $\theta$ < 0.8, the Temkin adsorption isotherm correlating with the Frumkin adsorption isotherm, and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are probably the most accurate, useful, and effective ways to determine the adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at highly corrosion-resistant metal/aqueous solution interfaces.

Adsorption Isotherms of Catechin Compounds on (+)Catechin-MIP

  • Jin, Yinzhe;Wan, Xiaolong;Row, Kyung-Ho
    • Bulletin of the Korean Chemical Society
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    • v.29 no.8
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    • pp.1549-1553
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    • 2008
  • A molecular imprinted polymer (MIP) using (+)catechin ((+)C) as a template and acrylamide (AM) as a functional monomer was prepared. Acetonitrile was used as the porogen with ethylene glycol dimethacrylate (EGDMA) as the crosslinker and 2,2'-azobis(isobutyronitrile) (AIBN) as the initiator. The adsorption isotherms in the MIP were measured and the parameters of the equilibrium isotherms were estimated by linear and nonlinear regression analyses. The linear equation for original concentration and adsorpted concentrations was then expressed, and the adsorption equilibrium data were correlated into Langmuir, Freundlich, quadratic, and Langmuir Extension isotherm models. The mixture compounds of (+)C and epicatechin (EC) show competitive adsorption on specific binding sites of the (+)catechin-MIP. The adsorption concentrations of (+)C, epicatechin (EC), epicatechin gallate (ECG), and epigallocatechin gallate (EGCG), on the (+)catechin-molecular imprinted polymer were compared. Through the analysis, the (+)catechin-molecular imprinted polymer showed higher adsorption ability than blank polymer which was synthesized molecular imprinted polymer without (+)catechin. Furthermore, the competitive Langmuir isotherms were applied to the mixture compounds of (+)C and EC.

Behaviors of the Fungicide Procymidone in Soils (살균제 Procymidone의 토양 중 동태)

  • Choi, Gyu-Il;Seong, Ki-Yong;Kim, Jeong-Gyu
    • Korean Journal of Environmental Agriculture
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    • v.24 no.2
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    • pp.123-131
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    • 2005
  • This study was focused on adsorption, leaching, photolysis, and hydrolysis of the fungicide procymidone in soils. Adsorption type of procymidone on three different soil were well fitted to Linear and Freundlich isotherm. Distribution coefficients (Kd) were ranged from 2.75 to 12.18 and Freundlich isotherm Kf value $1.99{\sim}9.98$, 1/n value $0.74{\sim}0.89$. Desorption rates were $20.1{\sim}34.0%$ (Namgye), $26.3{\sim}44.6%$ (Jigog) and $31.6{\sim}50.9%$ (Baegsan series) and desorption hysteresis were $0.65{\sim}0.79,\;0.55{\sim}0.73\;and\;0.49{\sim}0.68$. Procymidone seemed to be stable to photolysis in acidic and neutral solutions but hydrolyzed rapidly in alkaline solution. Considering leaching properties procymidone mobility low in soils.

Effects of activated carbon packing length in PSA process for production of high-purity hydrogen (고순도 수소제조를 위한 PSA 공정에서 활성탄 충전길이 효과)

  • Paik, Eun-gyu;Choi, Min-Ho;Suh, Sung-Sup
    • Clean Technology
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    • v.7 no.2
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    • pp.127-132
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    • 2001
  • The effects of activated-carbon (AC) packing length on the Pressure Swing Adsorption (PSA) performance was investigated for the hydrogen separation from the multicomponent mixture gas. Linear driving force model was used to describe mass transfer between two phase and coupled Langmuir isotherm was used for each component as a nonlinear adsorption isotherm. When two adsorbents with a different adsorption capacity were packed consecutively in one bed, it is very important to determine the packing ratio of zeolite to activated carbon affecting the purity and recovery of the product. The activated carbon packing length in adsorption tower of 120 cm was determinated by the ending point of $CO_2$ contration. The optimum length of an activated carbon layer was 65 cm for production of high-purity hydrogen.

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Removal of Arsenite and Arsenate by a Sand Coated with Colloidal Hematite Particl (나노 크기 적철석 입자 피복 모래를 이용한 비소 3가와 비소 5가의 제거)

  • 고일원;이상우;김주용;김경웅;이철효
    • Journal of Soil and Groundwater Environment
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    • v.9 no.1
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    • pp.63-69
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    • 2004
  • Hematite-coated sand was examined for the application of the PRB (permeable reactive barrier) to the arsenic-contaminated subsurface in the metal mining areas. The removal efficiency of As in a batch and a flow system was investigated through the adsorption isotherm, removal kinetics and column experiments. Hematite-coated sand followed a linear adsorption isotherm with high adsorption capacity at low level concentrations of As (<1.0 mg/L). In the column experiments, high content of hematite-coated sand enhanced the removal efficiency, but the amount of the As removal decreased due to the higher affinity of As (V) than As (III) and reduced adsorption kinetics in the flow system. Therefore. the amount of hematite-coated sand, the adsorption affinity of As species and removal kinetics determined the removal efficiency of As in a flow system.

Modeling of Sediment and Phosphorous Transport in a River Channel (하천 내 유사와 인 이동에 관한 모델링)

  • Kim, Kyunghyun
    • Journal of Korean Society on Water Environment
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    • v.26 no.2
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    • pp.332-342
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    • 2010
  • A model has been developed to investigate in-river sediment and phosphorus dynamics. This advective-dispersive model is coupled with hydrodynamics and sediment transport submodels to simulate suspended sediment, total dissolved phosphorus, total phosphorus, and particulate phosphorus concentrations under unsteady flow conditions. It emphasizes sediment and phosphorus dynamics in unsteady flow conditions, in which the study differs from many previous solute transport studies, conducted in relatively steady flow conditions. The diffusion wave approaximation was employed for unsteady flow simulations. The first-order adsorption and linear adsorption isotherm model was used on the basis of the three-layered riverbed submodel with riverbed sediment exchange and erosion/deposition processes. Various numerical methods were tested to select a method that had minimal numerical dispersion under unsteady flow conditions. The responses of the model to the change of model parameter values were tested as well.

Sorption and desoption behaviors of PAHs in soil and sediments

  • Wang, Qiliang;Shin, Sik;Song, Dong-Ik
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.04a
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    • pp.277-284
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    • 2004
  • Batch experiments were conducted to investigate the sorption and desorption behaviors of PAHs (naphthalene, phenanthrene and pyrene) in soils. Three different soils montmorillonite KSF (foc =0.14%), masato (foc =0.08%), and diatomite (foc =0.007%) were investigated. The results of sorption-desorption experiment indicate that the sorption affinity of PAHs was in the order of montmorillonite > masato > diatomite. The Freundlich model was well fitted to the sorption and desorption data. Sorption affinity increased as loc increased. Desorption of PAHs from soils was biphasic composed of reversible and irreversible compartments. Desorption-resistance of phenanthrene in soils was also determined. The biphasic desorption model was used to explain desorption-resistance of phenanthrene in soils. The linear term represents reversible sorption fraction and Langmuinian-type term represents desorption-resistant fraction.

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Removal of Halocarbonanted Volatile Organic Compounds by Adsorption Technology (흡착법을 이용한 염소계 휘발성 유기화합물의 제거)

  • 김승재;조성용;김태영
    • Journal of Korean Society for Atmospheric Environment
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    • v.17 no.4
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    • pp.355-362
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    • 2001
  • Adsorption isotherms of dichloromethane and 1, 1, 2-trichloro-1,2,2-trifluoroethane on an activated carbon pellet, Norit B4, were studied. For these chemicals, Sips equation gave the best fit for the single component adsorption isotherm. The adsorption affinity on activated carbon was greater for dichloromethane than that of 1, 1, 2-trichloro-1,2,2-trifluoroethane. An experimental and theoretical study was made for the adsorption of dichloromethane and 1, 1,2-trichloro-1,2,2-trifluoroethane in a fixed bed. Experimental results were used to examine the effect of operation variables, such as feed concentration, flow rate and bed height. Intraparticle diffusion was able to be explained by surface diffusion mechanism. An adsorption model baked on the linear driving force approximation (LDFA) was found to be applicable to fit the experimental data.

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Evaluation of Natural Attenuation of Petroleum Hydrocarbons in a Shallow Sand Aquifer: a Modeling Study (자연저감 모델링 연구)

  • 이진용;이명재;이강근;이민효;윤정기
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2001.04a
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    • pp.128-131
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    • 2001
  • We evaluated natural attenuation of petroleum hydrocarbons in a shallow aquifer using a modeling study. The studied shallow aquifer was severely contaminated with petroleum hydrocarbons, especially toluene, ethylbenzene and xylenes (i.e, TEX). The exact spill history was not known. Therefor we used a contaminant level in May 1999 (the first sampling date of our integrated study) as an initial contaminant concentration. we calibrated required transport parameters using the contamination levels obtained from groundwater analyses in September of 1999. For fate and transport of the petroleum contaminants, five case 2 with sorption and degradation. case 3 with sorption and degradation (half decay constant compared with case 2), case 4 with degradation but no sorption, and case 5 with sorption but no degradation. For sorption and degradation, a linear sorption isotherm and first order irreversible decay was assumed, respectively and no additional contamination source to groundwater is also assumed.

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