• 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.

• Korean Chemical Engineering Research
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• v.54 no.6
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• pp.734-745
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• 2016

This review article described the electrochemical Frumkin, Langmuir, and Temkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) and deuterium (OPD D) for the cathodic $H_2$ and $D_2$ evolution reactions (HER, DER) at Pt, Ir, Pt-Ir alloy, Pd, Au, and Re/normal ($H_2O$) and heavy water ($D_2O$) solution interfaces. The Frumkin, Langmuir, and Temkin adsorption isotherms of intermediates (OPD H, OPD D, etc.) for sequential reactions (HER, DER, etc.) at electrode/solution interfaces are determined using the phase-shift method and correlation constants, which have been suggested and developed by Chun et al. The basic procedure of the phase-shift method, the Frumkin, Langmuir, and Temkin adsorption isotherms of OPD H and OPD D and related electrode kinetic and thermodynamic parameters, i.e., the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. potential (E) behavior (${\theta}$ vs. E), equilibrium constant (K), interaction parameter (g), standard Gibbs energy (${\Delta}G_{\theta}{^{\circ}}$) of adsorption, and rate (r) of change of ${\Delta}G_{\theta}{^{\circ}}$ with ${\theta}$ ($0{\leq}{\theta}{\leq}1$), at the interfaces are briefly interpreted and summarized. The phase-shift method and correlation constants are useful and effective techniques to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and related electrode kinetic and thermodynamic parameters (${\theta}$ vs. E, K, g, ${\Delta}G_{\theta}{^{\circ}}$, r) at electrode/solution interfaces.

• Membrane and Water Treatment
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• v.7 no.6
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• pp.555-571
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• 2016

Heavy metal contamination has attracted considerable attention during recent decades due to the potential risk brought about for human beings and the environment. Several adsorbent materials are utilized for the purification of contaminated water resources among which chitosan is considered as an appropriate alternative. Copper is a heavy metal contaminants found in several industrial wastewaters and its adsorption on porous and macroporous chitosan membranes is investigated in this study. Membranes are prepared by phase inversion and particulate leaching method and their morphology is characterized using SEM analysis. Batch adsorption experiments are performed and it is found that copper adsorption on macroporous chitosan membrane is higher than porous membrane. The iso-steric heat of adsorption was determined by analyzing the variations of temperature to investigate its effect on adsorption characteristics of macroporous chitosan membranes. Furthermore, desorption experiments were studied using NaCl and EDTA as eluants. The mechanism of copper adsorption was also investigated using XPS spectroscopy which confirms simultaneous occurrence of chelation and electrostatic adsorption mechanisms.

• Journal of the Korean Geosynthetics Society
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• v.10 no.1
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• pp.53-61
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• 2011

This study was conducted to confirm the adsorption capacity of CFW(Carbonized Foods Waste), which is produced by the process of recycling waste, in PRB method that Electrokinetic(E/K) method was applied. The batch test was carried out to analyze the adsorption characteristics of CFW for adsorbing the organic compounds. The organic compounds used in the batch test were Phenanthrene and Trichloroethylene(TCE), and the anionic surfactant(SDS) and the nonionic surfactant(Brij$^{(R)}$30) were used for the surfactants. The results of the batch test confirmed that the adsorption efficiency of Phenanthrene was 99% and TCE was 26%. The each compounds compared with the adsorption isotherms, which is calculated by the Langmuir and Freundlich models. The results indicated that Phenanthrene is fitted to the linear Langmuir model, whereas the distribution of TCE is unclear. The results of the batch test used in surfactants confirmed that the adsorption efficiency of CFW using Phenanthrene was reduced to 6~8%. However, the adsorption efficiency of CFW in TCE was increased up to 81% by surfactants. Especially, the nonionic surfactant was excellent in the adsorption of CFW using TCE. Nevertheless, the adsorption efficiency of CFW in Phenanthrene was still higher than TCE. Therefore, the adsorption efficiency of CFW in Phenanthrene was better than in TCE. In PRB method using E/K method, the adsorption of CFW used nonionic surfactant is better to use than the anion surfactants on the organic compounds.

• Journal of Environmental Science International
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• v.20 no.12
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• pp.1607-1615
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• 2011

The adsorption performance of cupper and zinc ions($Cu^{2+}$ and $Zn^{2+}$) in aqueous solution was investigated by an adsorption process on reagent grade Na-A zeolite(Z-WK) and Na-A zeolite (Z-C1) prepared from coal fly ash. Z-C1 was synthesized by a fusion method with coal fly ash from a thermal power plant. Batch adsorption experiment with Z-C1 was employed to study the kinetics and equilibrium parameters such as initial metal ions concentration and adsorption time of the solution on the adsorption process. Adsorption rate of metal ions occurred rapidly and adsorption equilibrium reached at less than 120 minutes. The kinetics data of $Cu^{2+}$ and $Zn^{2+}$ ions were well fitted by a pseudo-second-order kinetics model more than a pseudo-first-order kinetics model. The equilibrium data were well fitted by a Langmuir model and this result showed $Cu^{2+}$ and $Zn^{2+}$ adsorption on Z-C1 would be occupied by a monolayer adsorption. The maximum adsorption capacity($q_{max}$) by the Langmuir model was determined as $Cu^{2+}$ 99.8 mg/g and $Zn^{2+}$ 108.3 mg/g, respectively. It appeared that the synthetic zeolite, Z-C1, has potential application as absorbents in metal ion recovery and mining wastewater.

• Journal of Korean Society of Water and Wastewater
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• v.29 no.6
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• pp.609-615
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• 2015

This study was carried out for characterization of MIO synthesized in our laboratory by co-precipitation method and applied isotherm and kinetic models for adsorption properties. XRD analysis were conducted to find crystal structure of synthesized MIO. Further SEM and XPS analysis was performed before and after phosphate adsorption, and BET analysis for surface characterization. Phosphate stock solution was prepared by KH2PO4 for characterization of phosphate adsorption, and batch experiment was conducted using 50 ml conical tube. Langmuir and Freundlich models were applied based on adsorption equilibrium test of MIO by initial phosphate solution. Pseudo first order and pseudo second order models were applied for interpretation of kinetic model by temperature. Surface area and pore size of MIO were found $89.6m^2/g$ and 16 nm respectively. And, the determination coefficient ($R^2$) value of Langmuir model was 0.9779, which was comparatively higher than that of Freundlich isotherm model 0.9340.

• Journal of the Korean Ceramic Society
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• v.46 no.6
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• pp.627-632
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• 2009

Formaldehyde emissions from the construct was harmful to human. Diatomite, bentonite and zeolite were used as porous materials for fabricating panels. Formaldehyde adsorption and physical characteristics of porous materials were investigated and hydrothermal method was applied to fabricate panels. Formaldehyde adsorption contents of panels with porous materials were higher than that of panel without porous materials. The panels with Cheolwon diatomite and Pohang zeolite showed excellent characteristics of Formaldehyde adsorption. These characteristics were caused by higher surface area and pore volume of porous materials. Formaldehyde adsorption contents were influenced by surface area and pore volume of panels. Correlation coefficient between surface area and Formaldehyde adsorption content of panels was 0.87. The panels with porous materials had higher strength than that without porous materials because of bridging role particles.

• Bulletin of the Korean Chemical Society
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• v.26 no.7
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• pp.1075-1078
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• 2005

Hydrogen adsorption on various porous materials have been studied with a volumetric method at low temperature in the pressure of 0-760 torr. Their hydrogen uptakes depend at least partly on microporosity rather than total porosity. However, it is also necessary to consider other parameters such as pore size and pore architecture to explain the adsorption capacity. The heat of adsorption and adsorption-desorption-readsorption experiments show that the hydrogen adsorption over the porous materials are composed of physisorption with negligible contribution of chemisorption. Among the porous materials studied in this work, SAPO-34 has the highest adsorption capacity of 160 mL/g at 77 K and 1 atm probably due to high micropore surface area, micropore volume and narrow pore diameter.

• 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.

• Applied Chemistry for Engineering
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• v.10 no.5
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• pp.672-676
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• 1999

Adsorption isotherm is the most fundamental information in adsorption separation-process. Directly from the elution profile of a peak, the elution-curve method and frontal analysis(FA) were utilized to measure the adsorption isotherm in this work. Using RP-HPLC, sample and the buffer added in mobile phase were 5'-GMP and sodium phosphate, respectively. In this experimental condition, the retention time was decreased with increase in the injected mass of sample. And the front part of a peak was very stiff, so Langmuir adsorption isotherm might be applied. By the elution-curve method, the parameters used in the isotherm were obtained by optimization method, while by the FA, the concentrations of stationary phase were measured from the elution curve and the isotherm was determined by regression analysis. Compared to FA, the consumption of sample was less, and only one or two injections were needed by the elution-curve method. Finally, the effect of concentration of sodium phosphate in mobile phase on the parameters of the isotherm was investigated.