• Journal of the Korean Electrochemical Society
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• v.9 no.1
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• pp.19-28
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• 2006

The phase-shift method for determining the Langmuir, Frumkin, and Temkin adsorption isotherms ($\theta_H\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at a Pt/0.1 M KOH solution interface has been proposed and verified using cyclic voltammetric, differential pulse voltammetric, and electrochemical impedance techniques. At the Pt/0.1 M KOH solution interface, the Langmuir and Temkin adsorption isotherms ($\theta_H\;vs.\;E$), the equilibrium constants ($K_H=2.9X10^{-4}mol^{-1}$ for the Langmuir and $K_H=2.9X10^{-3}\exp(-4.6\theta_H)mol^{-1}$ for the Temkin adsorption isotherm), the interaction parameters (g=0 far the Langmuir and g=4.6 for the Temkin adsorption isotherm), the rate of change of the standard free energy of $\theta_H\;with\;\theta_H$ (r=11.4 kJ $mol^{-1}$ for g=4.6), and the standard free energies (${\Delta}G_{ads}^{\circ}=20.2kJ\;mol^{-1}$ for $k_H=2.9\times10^{-4}mol^{-1}$, i.e., the Langmuir adsorption isotherm, and $16.7<{\Delta}G_\theta^{\circ}<23.6kJ\;mol^{-1}$ for $K_H=2.9\times10^{-3}\exp(-4.6\theta_H)mol^{-1}$ and $0.2<\theta_H<0.8$, i.e., the Temkin adsorption isotherm) of H for the cathodic HER are determined using the phase-shift method. At intermediate values of $\theta_H$, i.e., $0.2<\theta_H<0.8$, the Temkin adsorption isotherm ($\theta_H\;vs.\;E$) corresponding to the Langmuir adsorption isotherm ($\theta_H\;vs.\;E$), and vice versa, is readily determined using the constant conversion factors. The phase-shift method and constant conversion factors are useful and effective for determining the Langmuir, Frumkin, and Temkin adsorption isotherms of intermediates for sequential reactions and related electrode kinetic and thermodynamic data at electrode catalyst interfaces.

• Environmental Engineering Research
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• v.20 no.1
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• pp.73-78
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• 2015

The aim of this study was to examine the phosphate (P) removal by quintinite from aqueous solutions. Batch experiments were performed to examine the effects of reaction time, temperature, initial phosphate concentration, initial solution pH and stream water on the phosphate adsorption to quintinite. Kinetic, thermodynamic and equilibrium isotherm models were used to analyze the experimental data. Results showed that the maximum P adsorption capacity was 4.77 mgP/g under given conditions (initial P concentration = 2-20 mgP/L; adsorbent dose = 1.2 g/L; reaction time = 4 hr). Kinetic model analysis showed that the pseudo second-order model was the most suitable for describing the kinetic data. Thermodynamic analysis indicated that phosphate sorption to quintinite increased with increasing temperature from 15 to $45^{\circ}C$, indicating the spontaneous and endothermic nature of sorption process (${\Delta}H^0=487.08\;kJ/mol$; ${\Delta}S^0=1,696.12\;J/(K{\cdot}mol)$; ${\Delta}G^0=-1.67$ to -52.56 kJ/mol). Equilibrium isotherm analysis demonstrated that both Freundlich and Redlich-Peterson models were suitable for describing the equilibrium data. In the pH experiments, the phosphate adsorption to quintinite was not varied at pH 3.0-7.1 (1.50-1.55 mgP/g) but decreased considerably at a highly alkaline solution (0.70 mgP/g at pH 11.0). Results also indicated that under given conditions (initial P concentration=2 mgP/L; adsorbent dose=0.8 g/L; reaction time=4 hr), phosphate removal in the stream water (1.88 mgP/g) was lower than that in the synthetic solution (2.07 mgP/g), possibly due to the presence of anions such as (bi)carbonate and sulfate in the stream water.

• Applied Chemistry for Engineering
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• v.25 no.1
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• pp.96-102
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• 2014

Adsorption of metanil yellow onto granular activated carbon were studied in a batch system. Various operation parameters such as adsorbent dosage, pH, initial concentration, contact time and temperature were optimized. Experimental equilibrium adsorption data were analyzed by Langmuir and Freundlich adsorption isotherm. The equilibrium process was described well by Freundlich isotherm model. From determined separation factor (1/n), adsorption of metanil yellow by granular activated carbon could be employed as effective treatment method. By analysis of kinetic experimental data, the adsorption process were found to confirm to the pseudo second order model with good correlation and the adsorption rate constant ($k^2$) decreased with increasing initial concentration. Thermodynamic parameters like activation energy, change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorption in the temperature range of 298~318 K. The activation energy was determined as 23.90 kJ/mol. It was found that the adsortpion of metanil yellow on the granular activated carbon was physical process. The negative Gibbs free energy change (${\Delta}G=-2.16{\sim}-6.55kJ/mol$) and the positive enthalpy change (${\Delta}H=+23.29kJ/mol$) indicated the spontaneous and endothermic nature of the adsorption process, respectively.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.15 no.4
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• pp.2029-2035
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• 2014

In this study, we conducted the adsorption equilibrium and batch experiments of dissolved organic carbon (DOC) in the wastewater by granular activated carbon (GAC). The components of organic compound were Beef extract (1.8 mg/L), Peptone (2.7 mg/L), Humic acid (4.2 mg/L), Tannic acid (4.2 mg/L), Sodium lignin sulfonate (2.4 mg/L), Sodium lauryle sulfate (0.94 mg/L), Arabic gum powder (4.7 mg/L), Arabic acid (polysaccharide) (5.0 mg/L), $(NH_4)_2SO_4$ (7.1 mg/L), $K_2HPO_4$ (7.0 mg/L), $NH_4HCO_3$ (19.8 mg/L), $MgSO_4{\cdot}7H_2O$ (0.71 mg/L), The adsorption characteristics of DOC in synthetic wastewater was described using the mathematical model through a series of isotherm and batch experiments. It showed that there was linear adsorption region in the low DOC concentration (0~2.5 mg/L) and favorable adsorption region in high concentration (2.5~6 mg/L). The synthetic wastewater used was prepared using known quantities of organic and/or inorganic compounds. Adsorption modelling isotherms were predicted by the Freundlich, Langmuir, Sips and hybrid isotherm equations. Especially, hybrid isotherm of Linear and Sips equation was a good adsorption equilibrium in the region of the both the low concentration and high concentration. In applying carbon adsorption for treating water and wastewater, hybrid adsorption equation plus linear equation with Sips equation will be a good new adsorption equilibrium model. Linear driving force approximation (LDFA) kinetic equation with Hybrid (linear+Sips) adsorption isotherm model was successfully applied to predict the adsorption kinetics data in various GAC adsorbent amounts.

• Bulletin of the Korean Chemical Society
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• v.34 no.9
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• pp.2753-2759
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• 2013

The aim of the present study is to explore the possibility of utilizing fly ash and loess, as alternative to activated carbon, for the adsorption of diazinon in water. Batch adsorption experiment was performed to evaluate the influences of various factors like initial concentration, contact time and temperature on the adsorption of diazinon. The adsorption data shows that fly ash is not effective for the adsorption of diazinon. The equilibrium data for both activated carbon and loess were fitted well to the Freundlich isotherm model. The pseudo-second-order kinetic model appeared to be the better-fitting model because it has higher $R^2$ compared to the pseudo-first-order kinetic model. The thermodynamic parameters such as free energy (${\Delta}G$), the enthalpy (${\Delta}H$) and the entropy (${\Delta}S$) were calculated. Contrary to loess, the ${\Delta}G$ values of activated carbon were negative at the studied temperatures. It indicates that the adsorption of diazinon by activated carbon is a favorable and spontaneous process. The positive ${\Delta}H$ values of activated carbon and loess suggest that the diazinon adsorption process is endothermic in nature. In addition, the positive ${\Delta}S$ values show that increased randomness occurs at the solid/solution surface during the adsorption of diazinon.

• Carbon letters
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• v.14 no.1
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• pp.27-33
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• 2013

An increase in population initiating rapid industrialization was found to consequently increase the effluents and domestic wastewater into the aquatic ecosystem. In this research the potentialities of Sambucus nigra L. (SNL) plant in the remediation of water, contaminated with methylene blue (MB), a basic dye were investigated. SNL was chemically impregnated with $KHCO_3$. Operating variables studied were pH, amount of adsorbent and contact time. In general, pH did not have any significant effect on colour removal and the highest adsorption capacity was obtained in 0.035 g MB/g-activated carbon. The Langmuir, Freundlich, Temkin and Dubinin-Radushkevich adsorption models were applied to describe the equilibrium isotherms. The adsorption isotherm data were fitted to the Temkin isotherm. The mass transfer property of the sorption process was studied using Lagergren pseudo-first-order and chemisorption pseudo-second-order kinetic models. The sorption process obeyed the pseudo-second-order kinetic model. The surface area, pores volume and diameter were assessed by the Brunauer-Emmett-Teller and Barrett-Joyner-Halenda methods. The results were compared to those from activated carbon (Merck) and an actual sample. The results indicate that SNL can be employed as a natural and eco-friendly adsorbent material for the removal of dye MB from aqueous solutions.

• Carbon letters
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• v.11 no.3
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• pp.224-234
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• 2010

Four activated carbons were produced by two-stage process as followings; semi-carbonization of indigenous biomass waste, i.e. cotton stalks, followed by chemical activation with KOH under various activation temperatures and chemical ratios of KOH to semi-carbonized cotton stalks (CCS). The surface area, total pore volume and average pore diameter were evaluated by $N_2$-adsorption at 77 K. The surface morphology and oxygen functional groups were determined by SEM and FTIR, respectively. Batch equilibrium and kinetic studies were carried out by using a basic dye, methylene blue as a probe molecule to evaluate the adsorption capacity and mechanism over the produced carbons. The obtained activated carbon (CCS-1K800) exhibited highly microporous structure with high surface area of 950 $m^2/g$, total pore volume of 0.423 $cm^3/g$ and average pore diameter of 17.8 ${\AA}$. The isotherm data fitted well to the Langmuir isotherm with monolayer adsorption capacity of 222 mg/g for CCS-1K800. The kinetic data obtained at different concentrations were analyzed using a pseudo-first-order, pseudo-second-order and intraparticle diffusion equations. The pseudo-second-order model fitted better for kinetic removal of MB dye. The results indicate that such laboratory carbons could be employed as low cost alternative to commercial carbons in wastewater treatment.

• Journal of Environmental Science International
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• v.14 no.12
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• pp.1195-1201
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• 2005

In order to develop a dye coloring technology on Conchiolin layer in cultured pearls, appropriate dyes were selected, their solubilities in various solvents were studied, and adsorption and desorption experiments were performed. Solubilities of several basic dyes known to suitable for the pearl coloring, i.e., Rhodamine 6G(R6), Rhodamine B(RB) and Methylene Blue(MB), in several solvents (distilled water, methanol, ethanol, and acetone) were investigated. Among these dyes, R6 was chosen as a dye for single component adsorption and desorption experiment due to the relatively good solubility in various solvents tested. Solubilities of dyes were judged to be enough to color the pearls since dye concentrations in pearl coloring are, in general, not so high. The internal surface area of the pearl layer is believed to be directly related to the dye adsorption, the single-point internal surface area of the pearl layer measured at the nitrogen relative pressure of 0.3 was found to be $0.913m^2/g$, and the BET internal surface area, $1.01m^2/g$ The most probable diameters of micropores and macropores were found to be $40{\AA}$and $5000{\AA}$ respectively, from the pore size distribution data. Adsorption isotherm was well fitted to the Langmuir isotherm model, resulting in q=$\frac{1.62C}{1+1.09C^{.}}$

• Environmental Engineering Research
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• v.17 no.3
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• pp.125-132
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• 2012

The removal of Cd(II) and Cu(II) from aqueous solution by an agricultural solid waste biomass prepared from Moringa oleifera bark (MOB) was investigated. The biosorbent was characterized by Fourier transform infrared spectroscopy and elemental analysis. Furthermore, the effect of initial pH, contact time, biosorbent dosage, initial metal ion concentration and temperature on the biosorption of Cd(II) and Cu(II) were studied using the batch sorption technique. Kinetic studies indicated that the biosorption process of the metal ions followed the pseudo-second order model. The biosorption data was analyzed by the Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin isotherm models. Based on the Langmuir isotherm, the maximum biosorption capacities for Cd(II) and Cu(II) onto MOB were 39.41 and 36.59 mg/g at 323 K, respectively. The thermodynamic parameters, Gibbs free energy (${\Delta}G^o$), enthalpy (${\Delta}H^o$), and entropy (${\Delta}S^o$) changes, were also calculated, and the values indicated that the biosorption process was endothermic, spontaneous and feasible in the temperature range of 303-323 K. It was concluded that MOB powder can be used as an effective, low cost, and environmentally friendly biosorbent for the removal of Cd(II) and Cu(II) ions from aqueous solution.

• Environmental Engineering Research
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• v.20 no.4
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• pp.342-346
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• 2015

Haloacetonitriles (HANs) are nitrogenous disinfection by-products (DBPs) that have been reported to have a higher toxicity than the other groups of DBPs. The adsorption process is mostly used to remove HANs in aqueous solutions. Functionalized composite materials tend to be effective adsorbents due to their hydrophobicity and specific adsorptive mechanism. In this study, the removal of dichloroacetonitrile (DCAN) from tap water by adsorption on thiol-functionalized mesoporous composites made from natural rubber (NR) and hexagonal mesoporous silica (HMS-SH) was investigated. Fourier-transform infrared spectroscopy (FTIR) results revealed that the thiol group of NR/HMS was covered with NR molecules. X-ray diffraction (XRD) analysis indicated an expansion of the hexagonal unit cell. Adsorption kinetic and isotherm models were used to determine the adsorption mechanisms and the experiments revealed that NR/HMS-SH had a higher DCAN adsorption capacity than powered activated carbon (PAC). NR/HMS-SH adsorption reached equilibrium after 12 hours and its adsorption kinetics fit well with a pseudo-second-order model. A linear model was found to fit well with the DCAN adsorption isotherm at a low concentration level.