• Title/Summary/Keyword: thermodynamic solution

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The Extraction of Ca in Electric arc Furnace Slag for CO2 Sequestration (CO2고정화(固定化)를 위한 전기로제강(電氣爐製鋼)슬래그의 칼슘성분(成分) 침출(浸出))

  • Youn, Ki-Byoung
    • Resources Recycling
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    • v.22 no.1
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    • pp.64-71
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    • 2013
  • Mineral carbonation has been proposed as a possible way for $CO_2$ sequestration. The electric arc furnace slags consist of calcium, magnesium and aluminum silicates in various combinations. If they could be used instead of natural mineral silicates for carbonation, considerable energy savings and $CO_2$ emissions reductions could be achieved. Indirect aqueous carbonation of the slags consists of two steps, extraction of calcium and carbonation. Acetic acid leaching of electric arc furnace slags had been already studied to extract Ca in them, but it was reported that the carbonation of the extracted $Ca^{2+}$ in the leached solution would suffer from too slow kinetics, even at high pressure of $CO_2$. In this work, to develop more efficient extraction of the electric arc furnace slags, hydrochloric acid leaching to separate calcium from them was studied, and the results were compared with the acetic acid ones. The phase boundary between $Ca^{2+}$ and $CaCO_3$ in the solution with pH was determined by thermodynamic calculations. Hydrochloric acid was more effective than acetic acid for the extraction of Ca in electric arc furnace slag, and there is a possibility to recycle an unreacted hydrochloric acid in the leached solution by electrolysis or evaporation.

Determination of the Langmuir and Temkin Adsorption Isotherms of H for the Cathodic H2 Evolution Reaction at a Pt/KOH Solution Interface Using the Phase-Shift Method

  • Chun Jang-H.;Jeon Sang-K.;Chun Jin-Y.
    • 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.

Thermodynamics of Hydrogen-Induced Phase Separation on Pd-Co Alloys (수소유기에 따른 Pd-Co합금들의 상 분리 현상에 대한 열역학적 고찰)

  • Song, D.M.;Park, C.N.;Choi, J.
    • Journal of Hydrogen and New Energy
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    • v.16 no.3
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    • pp.244-252
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    • 2005
  • It is very interesting and important in the academic point of view and in practical use the hydrogen-induced phase separation(HIPS) which appears during hydrogen heat treatment. Since hydrogen can be removed very fast by pumping it out the hydrogen-induced new lattice phase which can not be obtained without hydrogen can be preserved as meta-stable state. In this study it has been investigated whether the HIPS appear in Pd-Al, Pd-Co, Pd-Cr, Pd-Ti, Pd-V and Pd-Zr alloys and discussed thermodynamic representation of the HIPS. The Pd alloys were arc-melted under argon atmosphere and remelted 4 or 5 times for homogenization. The alloys were annealed at 600$^{\circ}C$ under vacuum for 24 hrs and then subjected to pressure-composition isotherm measurements at 100$^{\circ}C$. The hydrogen heat treatment(HHT) of samples was carried out at 600$^{\circ}C$ under hydrogen pressure of 70 bar for 6 days and PC isotherms at 100$^{\circ}C$ were measured. By comparing the PC isotherms measured before and after HHT, occurrence of phase separation was determined. The experimental results showed that the HIPS appeared only in Pd-0.05Co alloy. For Pd-Co alloys with various composition the PC isotherms were measured. By adopting Park-Flanagan model for ternary thermodynamics the Gibbs free energy change for Pd-Co-H solid solution was calculated and subsequently with this the HIPS in Pd-Co alloy was explained fairly.

Solubilization of 4-Alkylbenzoic Acid Isomers by the Aqueous Solution of Tetradecyltrimethylammonium Bromide (테트라데실트리메틸암모늄 브로마이드의 수용액에서 4-알킬벤조산 이성질체들의 가용화에 대한 연구)

  • Lee, Nam-Min;Lee, Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.56 no.2
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    • pp.188-194
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    • 2012
  • The interaction of 4-alkylbenzoic acid isomers with the micellar system of TTAB (tetradecyltrimethylammonium bromide) was studied by the UV/Vis spectrophotometric method. The solubilization constants ($K_s$) of 4-alkylbenzoic acid isomers into the TTAB micellar system and the critical micelle concentration (CMC) of TTAB have been measured with the change of temperature. Various thermodynamic parameters have been calculated and analyzed from those measurements. The results show that the values of ${\Delta}G^o{_s}$ for the solubilization of all the isomers are negative and the values of ${\Delta}H^o{_s}$ and ${\Delta}S^o{_s}$ are all positive within the measured temperature range. The effects of additives (n-butanol and NaCl) on the solubilization of 4-alkylbenzoic acid isomers have been also measured. There was a great change on the values of $K_s$ and CMC simultaneously with these additives. From these changes we can postulate that the solubilization sites of 4-alkylbenzoic acids are the core or deep palisade region of the TTAB micelle.

Phosphate Adsorption on Metal-Impregnated Activated Carbon (금속담지 활성탄의 인산염 흡착특성)

  • Hwang, Min-Jin;Hwang, Yu Sik;Lee, Wontae
    • Journal of Korean Society of Environmental Engineers
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    • v.37 no.11
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    • pp.642-648
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    • 2015
  • Oak wood based activated carbon was modified with surface impregnation of $Fe^{3+}$ and $Al^{3+}$ metal ions mixture for enhancements of phosphate adsorption capacity in aqueous solution. The phosphate adsorption capacity of the prepared metal impregnated carbon (MC) was about 8 times higher than that of the original activated carbon (OC). Adsorption equilibrium capacities of the phosphate increased with increasing system temperature. The adsorption equilibrium isotherm of phosphate on the prepared MC could be represented by the Langmuir equation. Thermodynamic parameters also indicated that adsorption system was spontaneous and endothermic reaction. The internal diffusion coefficient was measured to analyze the adsorption behavior and kinetic rate. To determine the internal diffusion coefficient, pore diffusion model (PDM) was employed and the result was in good agreement with experimental data.

Effects of Structural Difference of Ionic Liquids on the Catalysis of Horseradish Peroxidase

  • Hong, Eun-Sik;Park, Jung-Hee;Yoo, Ik-Keun;Ryu, Keun-Garp
    • Journal of Microbiology and Biotechnology
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    • v.19 no.7
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    • pp.713-717
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    • 2009
  • The dependence of the catalytic properties of horseradish peroxidase on the structural changes of ionic liquids was investigated with two water-miscible ionic liquids, N-butyl-3methypyridinium tetraftuoroborate ([$BMP_y$][$BF_4$]) and 1-butyl-3-methylimidazolium methylsulfate ([BMIM][$MeSO_4$]), each of which shares an anion ($BF_4^-$) or a cation ($BMIM^+$) with 1-butyl-3-methylimidazolium tetraftuoroborate ([BMIM][$BF_4$]), respectively. The oxidation of guaiacol (2-methoxyphenol) with $H_2O_2$was used as a model reaction. In order to minimize the effect of solution viscosity on the kinetic constants of the enzymatic catalysis, the enzymatic reactions for the kinetic study were performed in water-ionic liquid mixtures containing 25% (v/v) ionic liquid at maximum. Similarly to the previously reported results for [BMIM][$BF_4$], as the concentration of [$BMP_y$][$BF_4$] increased, the $K_m$value increased with a decrease in the $k_{cat}$value: the $K_m$value increased markedly from 2.8 mM in 100% water to 12.6 mM in 25% (v/v) ionic liquid, indicating that ionic liquid significantly weakens the binding affinity of guaiacol to the enzyme. On the contrary, [BMIM][$MeSO_4$] decreased the Km value to 1.4 mM in 25% (v/v) ionic liquid. [BMIM][$MeSO_4$] also decreased $k_{cat}$more than 3-folds [from 13.8 $s^{-1}$in 100% water to 4.1 $s^{-1}$in 25% (v/v) ionic liquid]. These results indicate that the ionic liquids interact with the enzyme at the molecular level as well as at a macroscopic thermodynamic scale. Specifically, the anionic component of the ionic liquids influenced the catalysis of horseradish peroxidase in different ways.

Phase Equilibria and Formation Behaviors of Methane Hydrate with Ethylene Glycol and Salts (에틸렌글리콜과 염이 포함된 메탄 하이드레이트의 상평형과 형성 거동)

  • Kim, Dong Hyun;Park, Ki Hun;Cha, Minjun
    • Korean Chemical Engineering Research
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    • v.58 no.4
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    • pp.635-641
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    • 2020
  • In this study, phase equilibria and formation behaviors of methane hydrate containing mono-ethylene glycol (MEG) and salts (sodium chloride, NaCl; sodium bromide, NaBr; sodium iodide, NaI) are investigated. Equilibrium conditions of methane hydrate containing MEG and salts are measured in a temperature range 272~283 K and a pressure range 3.5~11 MPa. Hydrate inhibition performance in the presence of additives can be summarized as follows: methane hydrate containing (5 wt% NaCl + 10 wt% MEG) > (5 wt% NaBr + 10 wt% MEG) > (5 wt% NaI + 10 wt% MEG). Formation behaviors of methane hydrate with MEG and salts are investigated for analyzing the induction time, gas consumption amount and growth rate of methane hydrates. There are no significant changes in the induction time during methane hydrate formation, but the addition of MEG and salts solution during hydrate formation can affect the gas consumption amount and growth rate.

Effect of Propionic Acid Additive on Preparation of Phase Inversion Polysulfone Membrane (폴리설폰 상전환막의 제조에 있어 프로피오닉산 첨가제의 영향)

  • Han, Myeong-Jin;Choi, Seung-Rag;Park, So-Jin;Seo, Bum-Kyoung;Lee, Kune-Woo;Nam, Suk-Tae
    • Membrane Journal
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    • v.18 no.4
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    • pp.317-324
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    • 2008
  • Polysulfone membranes were prepared via the phase inversion process. With propionic acid as a nonsolvent additive, polysulfone casting solutions were solidified in an isopropanol bath. Propionic acid (PA) worked as a thermodynamic enhancer for phase separation and as a rheological suppressor for kinetic hindrance. Morphology of the prepared membranes significantly varied with propionic acid content in the casting solution. The dense skin layer, which was identified in the membrane prepared without PA, almost disappeared in the membrane prepared trom PA 10wt%. With 30wt% PA, the membrane revealed the morphological gradient from a nodular skin structure to a sponge-like substructure, including the finger-like cavity. Water permeability increased with PA content, and polyethylene glycol rejection decreased with the nonsolvent content.

Equilibrium and kinetic studies of an electro-assisted lithium recovery system using lithium manganese oxide adsorbent material

  • Lee, Dong-Hee;Ryu, Taegong;Shin, Junho;Kim, Young Ho
    • Carbon letters
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    • v.28
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    • pp.87-95
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    • 2018
  • This study examined the influence of operating parameters on the electrosorptive recovery system of lithium ions from aqueous solutions using a spinel-type lithium manganese oxide adsorbent electrode and investigated the electrosorption kinetics and isotherms. The results revealed that the electrosorption data of lithium ions from the lithium containing aqueous solution were well-fitted to the Langmuir isotherm at electrical potentials lower than -0.4 V and to the Freundlich isotherm at electrical potentials higher than -0.4 V. This result may due to the formation of a thicker electrical double layer on the surface of the electrode at higher electrical potentials. The results showed that the electrosorption reached equilibrium within 200 min under an electrical potential of -1.0 V, and the pseudo-second-order kinetic model was correlated with the experimental data. Moreover, the adsorption of lithium ions was dependent on pH and temperature, and the results indicate that higher pH values and lower temperatures are more suitable for the electrosorptive adsorption of lithium ions from aqueous solutions. Thermodynamic results showed that the calculated activation energy of $22.61kJ\;mol^{-1}$ during the electrosorption of lithium ions onto the adsorbent electrode was primarily controlled by a physical adsorption process. The recovery of adsorbed lithium ions from the adsorbent electrode reached the desorption equilibrium within 200 min under reverse electrical potential of 3.5 V.

Isotherm, Kinetic and Thermodynamic Characteristics for Adsorption of Congo Red by Activated Carbon (활성탄에 의한 Congo Red의 흡착에 대한 등온선, 동력학 및 열역학적 특성)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.53 no.1
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    • pp.64-70
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    • 2015
  • Batch experiment studies were carried out for adsorption of congo red using granular activated carbon with various parameters such as activated carbon dose, pH, initial dye concentration, temperature and contact time. Equilibrium experimental data are fitted to the Langmuir, Freundlich, Temkin and Dubin-Radushkevich isotherm equations. From Freundlich's separation factor (1/n) estimated, adsorption could be employed as effective treatment method for adsorption of congo red from aqueous solution. Base on Temkin constant (B) and Dubinin-Radushkevich constant (E), this adsorption process is physical adsorption. Adsorption kinetics has been tested using pseudo-first order and pseudo second order models. The results followed pseudo second order model with good correlation. Adsorption process of congo red on granular activated carbon was endothermic (${\Delta}H$=42.036 kJ/mol) and was accompanied by decrease in Gibbs free energy (${\Delta}G$=-2.414 to -4.596 kJ/mol) with increasing adsorption temperature.