• Title/Summary/Keyword: equilibrium isotherm

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The Phase-Shift Method for the Langmuir Adsorption Isotherms of Electroadsorbed Hydrogens for the Cathodic H2 Evolution Reactions at the Poly-Pt Electrode Interfaces (다결정 Pt 전극계면에서 음극 H2 발생반응을 위한 전착된 수소의 Langmuir 흡착등온식에 관한 위상이동 방법)

  • Chun, Jang H.;Jeon, Sang K.;Lee, Jae H.
    • Journal of the Korean Electrochemical Society
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    • v.5 no.3
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    • pp.131-142
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    • 2002
  • The Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the poly-Pt/0.5M $H_2SO_4$ and 0.5 M LiOH aqueous electrolyte interfaces have been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift $(0^{\circ}{\leq}{-\phi}{\leq}90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1{\geq}{\theta}{\geq}0)$ at the interfaces. The phase-shift method, i.e., the phase-shift profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new electrochemical method to determine the Langmuir adsorption isotherms $({\theta}\;vs.\;E)$ of the UPD H and the OPD H for the cathodic $H_2$ evolution reactions at the interfaces. At the poly-Pt/0.5M $H_2SO_4$ aqueous electrolyte interface, the equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.1\times10^{-4}$ and 21.0kJ/mol, respectively. At the poly-Pt/0.5M LiOH aqueous electrolyte interface, K transits from 2.7(UPD H) to $6.2\times10^{-6}$ (OPD H) depending on the cathode potential (E) and vice versa. Similarly, ${\Delta}G_{ads}$ transits from -2.5kJ/mol (UPD H) to 29.7kJ/mol (OPD H) depending on I and vice versa. The transition of K and ${\Delta}G_{ads}$ is attributed to the two distinct adsorption sites of the UPD H and the OPD H on the poly-Pt surface. The UPD H and the OPD H on the poly-Pt surface are the independent processes depending on the H adsorption sites themselves rather than the sequential processes for the cathodic $H_2$ evolution reactions. The criterion of the UPD H and the OPD H is the H adsorption sites and processes rather than the $H_2$ evolution reactions and potentials. The poly-Pt wire electrode is more efficient and useful than the Pt(100) disc electrode for the cathodic $H_2$ evolution reactions in the aqueous electrolytes. The phase-shift method is well complementary to the thermodynamic method rather than conflicting.

Removal of Soluble Fe(II) using Reactive Media Coated with both Fe and Mn (철과 망간이 동시에 코팅된 반응성 매질을 이용한 용존 Fe(II) 제거)

  • Min, Sang-Yoon;Chang, Yoon-Young;Yang, Jae-Kyu
    • Journal of Korean Society of Environmental Engineers
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    • v.33 no.2
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    • pp.85-92
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    • 2011
  • Evaluation of the removal efficiencies of Fe(II) by reactive sand media coated with manganese (MCS), iron (ICS) and both of iron and manganese (IMCS) was investigated as functions of solution pH ranging from 2 to 9, reaction time and concentration of Fe(II) in a batch reactor using each reactive medium and additional oxidants such as $KMnO_4$ and NaOCl. When only Fe(II) was present in solution without any reactive medium, removal of Fe(II) was quite low below pH 5 due to a slow oxidation of Fe(II) and/or negligible precipitation but greatly increased above pH 5 due to a rapid oxidation of Fe(II) and subsequent precipitation of oxidized Fe species. ICS showed negligible efficiency on the removal of Fe(II) through adsorption. However, an efficient removal of Fe(II) was observed at low solution pH in the presence of IMCS or MCS through rapid oxidation and subsequent precipitation. Removal efficiency of Fe(II) by IMCS in the presence or absence of NaOCl was quite similar. Removal rate of Fe(II) by IMCS and additional oxidants gradually increased as the solution pH increased. From the kinetic experiments, removal pattern of Fe(II) was better described by pseudo-second-order equation than pseudo-first-order equation. A rapid removal of Fe(II) using IMCS in the presence of $KMnO_4$ was observed in the first 10 min. The initial removal rate of Fe(II) using $KMnO_4$ was 14,286 mg/kg hr. In case of using NaOCl, the removal of Fe(II) occurred rapidly in the first 6 hrs and then reached the near-equilibrium state. Removal of Fe(II) on IMCS was well expressed by Langmuir isotherm and the maximum removal capacity of Fe(II) was calculated as 1,088 mg/kg.

Evaluation of Adsorption Characteristics of the Media for Biofilter Design (바이오필터설계를 위한 바이오필터 담체의 흡착 특성)

  • Lee, Eun-Ju;Lim, Kwang-Hee
    • Korean Chemical Engineering Research
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    • v.46 no.5
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    • pp.994-1001
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    • 2008
  • Freundlich isothermal adsorption parameters, applicable to such biofilter-model as process-lumping model(Lim's model), for sterilized granular activated carbon(GAC), sterilized compost and sterilized equal volume mixture of GAC and compost were obtained and were compared each other, assuming that adsorbents are enclosed by water layer, in order to construct robust process-lumping biofilter model effective for wide-range of hydrophilic volatile organic compounds(VOC). In this investigation 0.04, 0.08, 0.12, 0.16, 0.2, 0.4, 0.8 and 1.0ml of ethanol were added to three kinds of adsorbent-media and were placed at $30^{\circ}{\cdots}$ under the wet condition of the media, which was the same as biofilter operating condition, until the adsorption reached the condition of equilibrium before each adsorbed amount of ethanol was obtained. Then adsorption capacity parameters(K) and adsorption exponents of Freundlich adsorption isotherm equation, which simulates the adsorbed amount of ethanol equilibrated with the ethanol concentration of the condensed water in the pore of the media, were constructed for sterilized granular activated carbon(GAC), sterilized compost and sterilized equal volume mixture of GAC and compost as (0.7566 and $5.070{\times}10^{-7}mg-ethanol/mgmedia/(mg-ethanol/m^3)^{0.7566}$), (0.8827 and $1.000{\times}10^{-8}mg-ethanol/mgmedia/(mg-ethanol/m^3)^{0.8827}$) and (0.5688 and $5.243{\times}10^{-6}mg-ethanol/mgmedia/(mg-ethanol/m^3)^{0.5688}$), respectively. These Freundlich isothermal adsorption parameters were applicable to the adsorption characteristics of biofilter media enclosed with bio-layer. The order of magnitude of the ratio of ethanol-air/water partition coefficient and toluene-air/water partition coefficient was almost consistent to that of ethanol-adsorbed amounts in this experiment with compost and in the investigation of Delhomenie et al. on toluene-adsorption to wet compost.

A Study on the Fixed Forms and Adsorption of Phosphorus in Citrus Orchard Soil Derived from Volcanic Ash (제주도(濟州道) 감귤원(柑橘園) 토양(土壤)의 인산형태(燐酸形態) 및 흡착(吸着)에 관(關)한 연구(硏究))

  • Kim, Hyeong-Ok
    • Applied Biological Chemistry
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    • v.17 no.3
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    • pp.219-234
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    • 1974
  • A series of experiments was conducted to study the behavior of the phosphorus added to the soils having the high phorphorus fixing capacity derived from volcanic ash in Cheju Island. Soil samples were taken from different depths of 0-10, 10-30, and 30-50cm in six citrus orchards where heavy application of phosphate fertilizer has been practised. Various forms of phosphorus were determined and phosphorus adsorption experiments were performed. The results obtained can be summarized as follows: 1. The content of inorganic phosphorus fractions determined by the method of Chang and Jackson was: water soluble P

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Adsorption of Arsenic onto Two-Line Ferrihydrite (비소의 Two-Line Ferrihydrite에 대한 흡착반응)

  • Jung, Young-Il;Lee, Woo-Chun;Cho, Hyen-Goo;Yun, Seong-Taek;Kim, Soon-Oh
    • Journal of the Mineralogical Society of Korea
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    • v.21 no.3
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    • pp.227-237
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    • 2008
  • Arsenic has recently become of the most serious environmental concerns, and the worldwide regulation of arsenic fur drinking water has been reinforced. Arsenic contaminated groundwater and soil have been frequently revealed as well, and arsenic contamination and its treatment and measures have been domestically raised as one of the most important environmental issues. Arsenic behavior in geo-environment is principally affected by oxides and clay minerals, and particularly iron (oxy)hydroxides have been well known to be most effective in controlling arsenic. Among a number of iron (oxy)hydroxides, for this reason, 2-line ferrihydrite was selected in this study to investigate its effect on arsenic behavior. Adsorption of 2-line ferrihydrite was characterized and compared between As(III) and As(V) which are known to be the most ubiquitous species among arsenic forms in natural environment. Two-line ferrihydrite synthesized in the lab as the adsorbent of arsenic had $10\sim200$ nm for diameter, $247m^{2}/g$ for specific surface area, and 8.2 for pH of zero charge, and those representative properties of 2-line ferrihydrite appeared to be greatly suitable to be used as adsorbent of arsenic. The experimental results on equilibrium adsorption indicate that As(III) showed much stronger adsorption affinity onto 2-line ferrihydrite than As(V). In addition, the maximum adsorptions of As(III) and As(V) were observed at pH 7.0 and 2.0, respectively. In particular, the adsorption of As(III) did not show any difference between pH conditions, except for pH 12.2. On the contrary, the As(V) adsorption was remarkably decreased with increase in pH. The results obtained from the detailed experiments investigating pH effect on arsenic adsorption show that As(III) adsorption increased up to pH 8.0 and dramatically decreased above pH 9.2. In case of As(V), its adsorption steadily decreased with increase in pH. The reason the adsorption characteristics became totally different depending on arsenic species is attributed to the fact that chemical speciation of arsenic and surface charge of 2-line ferrihydrite are significantly affected by pH, and it is speculated that those composite phenomena cause the difference in adsorption between As(III) and As(V). From the view point of adsorption kinetics, adsorption of arsenic species onto 2-line ferrihydrite was investigated to be mostly completed within the duration of 2 hours. Among the kinetic models proposed so for, power function and elovich model were evaluated to be the most suitable ones which can simulate adsorption kinetics of two kinds of arsenic species onto 2-line ferrihydrite.

Identification of Sorption Characteristics of Cesium for the Improved Coal Mine Drainage Treated Sludge (CMDS) by the Addition of Na and S (석탄광산배수처리슬러지에 Na와 S를 첨가하여 개량한 흡착제의 세슘 흡착 특성 규명)

  • Soyoung Jeon;Danu Kim;Jeonghyeon Byeon;Daehyun Shin;Minjune Yang;Minhee Lee
    • Economic and Environmental Geology
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    • v.56 no.2
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    • pp.125-138
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    • 2023
  • Most of previous cesium (Cs) sorbents have limitations on the treatment in the large-scale water system having low Cs concentration and high ion strength. In this study, the new Cs sorbent that is eco-friendly and has a high Cs removal efficiency was developed by improving the coal mine drainage treated sludge (hereafter 'CMDS') with the addition of Na and S. The sludge produced through the treatment process for the mine drainage originating from the abandoned coal mine was used as the primary material for developing the new Cs sorbent because of its high Ca and Fe contents. The CMDS was improved by adding Na and S during the heat treatment process (hereafter 'Na-S-CMDS' for the developed sorbent in this study). Laboratory experiments and the sorption model studies were performed to evaluate the Cs sorption capacity and to understand the Cs sorption mechanisms of the Na-S-CMDS. The physicochemical and mineralogical properties of the Na-S-CMDS were also investigated through various analyses, such as XRF, XRD, SEM/EDS, XPS, etc. From results of batch sorption experiments, the Na-S-CMDS showed the fast sorption rate (in equilibrium within few hours) and the very high Cs removal efficiency (> 90.0%) even at the low Cs concentration in solution (< 0.5 mg/L). The experimental results were well fitted to the Langmuir isotherm model, suggesting the mostly monolayer coverage sorption of the Cs on the Na-S-CMDS. The Cs sorption kinetic model studies supported that the Cs sorption tendency of the Na-S-CMDS was similar to the pseudo-second-order model curve and more complicated chemical sorption process could occur rather than the simple physical adsorption. Results of XRF and XRD analyses for the Na-S-CMDS after the Cs sorption showed that the Na content clearly decreased in the Na-S-CMDS and the erdite (NaFeS2·2(H2O)) was disappeared, suggesting that the active ion exchange between Na+ and Cs+ occurred on the Na-S-CMDS during the Cs sorption process. From results of the XPS analysis, the strong interaction between Cs and S in Na-S-CMDS was investigated and the high Cs sorption capacity was resulted from the binding between Cs and S (or S-complex). Results from this study supported that the Na-S-CMDS has an outstanding potential to remove the Cs from radioactive contaminated water systems such as seawater and groundwater, which have high ion strength but low Cs concentration.