• Title/Summary/Keyword: Thermodynamic

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Electrochemical Analysis and Applications of Tetracycline Transfer Reaction Process at Liquid/liquid Interfaces (액체/액체 계면에서 테트라사이클린 전이반응의 전기화학적 분석 및 응용)

  • Liu, XiaoYun;Han, Hye Youn;Goh, Eunseo;Lee, Hye Jin
    • Applied Chemistry for Engineering
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    • v.28 no.5
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    • pp.506-512
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    • 2017
  • The transfer reaction characteristics of tetracycline (TC) across a polarized water/1,2-dichloroethane (1,2-DCE) interface was studied via controlling both pH and ionic strength of the aqueous phase in conjunction with cyclic and differential pulse voltammetries. Formal transfer potential values of differently charged TC ionic species at the water/1,2-DCE interface were measured as a function of pH values of the aqueous solution, which led to establishing an ionic partition diagram for TC. As a result, we could identify which TC ionic species are more dominant in the aqueous or organic phase. Thermodynamic properties including the formal transfer potential, partition coefficient and Gibbs transfer energy of TC ionic species at the water/1,2-DCE interface were also estimated. In order to construct an electrochemical sensor for TC, a single microhole supported water/polyvinylchloride-2-nitrophenyloctylether (PVC-NPOE) gel interface was fabricated. A well-defined voltammetric response associated with the TC ion transfer process was achieved at pH 4.0 similar to that of using the water/1,2-DCE interface. Also the measured current increased proportionally with respect to the TC concentration. A $5{\mu}M$ of TC in pH 4.0 buffer solution with a dynamic range from $5{\mu}M$ to $30{\mu}M$ TC concentration could be analyzed when using differential pulse stripping voltammetry.

Partial Oxidation of Methane for Hydrogen Production over Co and Ni Catalysts (수소생산을 위한 메탄 부분산화용 코발트와 니켈촉매의 반응특성 연구)

  • Lee, Sang-Sik;Hong, Ju-Hwan;Ha, Ho-Jung;Kim, Byung-Kwan;Han, Jong-Dae
    • Korean Chemical Engineering Research
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    • v.48 no.6
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    • pp.776-783
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    • 2010
  • Co and Ni catalysts supported on $Al_2O_3$ for partial oxidation of methane producing hydrogen were synthesized using impregnation to incipient wetness. The activities of these catalysts for the partial oxidation of methane was investigated at 1 atm and $CH_4/O_2=2.0$ in the temperature range of $450{\sim}650^{\circ}C$. The reaction activity of $Ni/Al_2O_3$ and $Co/Al_2O_3$ catalysts with different loading was investigated. And the beneficial effects of Ni addition to $Co/Al_2O_3$ and the promotional effects of Ce and La addition to $Ni/Al_2O_3$ and $Co/Al_2O_3$ were investigated. These catalysts were characterized by XRD and SEM/EDX. Comparing catalyst loadings, 10 wt% Co and 10 wt% Ni were found to be optimal at the experimental conditions. The 10 wt% $Ni/Al_2O_3$ and 10 wt% $Co/Al_2O_3$ catalysts in partial oxidation of methane showed $CH_4$ conversions and CO selectivity close to the thermodynamic equilibrium levels, but showed lower $H_2$ selectivity than equilibrium level. The addition of Ni to $Co/Al_2O_3$ exhibited higher $H_2$ selectivity but beneficial effect was not observed in the $CH_4$ conversion. Addition of Ce to $Co/Al_2O_3$ and addition of La to $Ni/Al_2O_3$ a improved the $CH_4$ conversion level and $H_2$ selectivity.

Adsorption Characteristics of Dimetridazole Antibiotics on Activated Carbon Prepared from Agricultural Waste Citrus Peel (폐감귤박 활성탄을 이용한 항생제 Dimetridazole의 흡착특성)

  • Lee, Chang-Han;Kam, Sang-Kyu;Lee, Min-Gyu
    • Korean Chemical Engineering Research
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    • v.55 no.6
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    • pp.798-806
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    • 2017
  • A activated carbon (WCAC, waste citrus activated carbon) prepared from an agricultural waste citrus peel material generated in Jeju was utilized for the removal of dimetridazole (DMZ) antibiotics in aqueous solution. The adsorption of DMZ on WCAC was investigated with the change of various parameters such as contact time, dosage of WCAC, particle size of WCAC, temperature, pH, and DMZ concentration. The DMZ adsorption capacity increased with increasing temperature and decreasing particle size. Also it was decreased at less than pH 4 but sustained almost constantly at pH 4 or greater. Isotherm parameters were determined from the Langmuir, Freundlich, Redlich-Peterson and Duinin-Radushkevich (D-R) isotherm models. The isotherm data were best described by the Redlich-Peterson isotherm model. And the adsorption kinetics can be successfully fitted to the pseudo-second-order kinetic model. The results of the intra-particle diffusion model suggested that film diffusion and intra-particle diffusion were occurred simultaneously during the adsorption process. Meanwhile, the thermodynamic parameters indicated that the adsorption reaction of DMZ on WCAC was an endothermic and spontaneous process. The experimental results showed that WCAC is a promising and cheap adsorbent for the removal of DMZ antibiotics.

Nonstoichiometry of the Ytterbium Oxide (산화 이테르븀의 비화학양론)

  • Chul Hyun Yo;Hyung Rak Kim;Kwon Sun Roh;Kyu Hong Kim;Eung Ju Oh
    • Journal of the Korean Chemical Society
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    • v.36 no.4
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    • pp.511-516
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    • 1992
  • The x-values of the nonstoichiometric compound YbO$_x$ have been measured in a temperature range of 600 to 1150$^{\circ}C$ under oxygen partial pressure of 1.00 ${\times}$ 10$^{-2}$ atm∼atmospheric air pressure. The values are varied between 1.55453 and 1.60794 in the conditions. The enthalpy of the formation for x' in YbO$_{1.5+x'}$(${\Delta}$H$_f$) was 1.55, 1.18, and 1.05 kJ/mol under the above conditions, respectively. The electrical conductivities of the oxides or ${\sigma}$ have been measured in the temperature range from 600 to 1100$^{\circ}C$ under oxygen partial pressure of 1.00 ${\times}$ 10$^{-5}$ ∼ 2.00 ${\times}$ 10$^{-1}$ atm. They varied from 10$^{-9}$ to 10$^{-5}$ ohm$^{-1}$ cm$^{-1}$ within the semiconductor range. The Arrhenius plots of the electrical conductivities show a linearity and the activation energy for the conduction was about 1.7eV. The oxygen partial pressure dependence of the conductivity or 1/n value increases with the pressure. The nonstoichiometric conduction mechanism of the oxide was discussed in terms of the x values, ${\sigma}$ values, and the thermodynamic data.

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The Thermodynamics of the Formation of Polymethylbenzene-Halogens Charge Transfer Complexes (III) (폴리메틸벤젠과 할로겐 사이의 전하이동착물 생성에 관한 열역학적 연구 (제3보))

  • Oh Cheun Kwun;Jin Burm Kyong;Jung Sung Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.6
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    • pp.351-360
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    • 1981
  • Ultraviolet spectrophotometric investigations have been carried out on the system of durene with iodine, bromine, iodine monochloride and iodine monobromide in carbon tetrachloride. The results reveal the formation of the charge transfer complexes of the type, $C_6H_2(CH_3)_4{\cdot}X_2$ or $C_6H_2(CH_3)_4{\cdot}IX$(X denotes halogen atoms). The equilibrium constant were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperatures. The thermodynamic parameters, ${\Delta}H,\;{\Delta}G\;and\;{\Delta}S$ for the formation of the charge transfer complexes were calculated from these values. These results indicate that the relative stabilities of the durene complexes at each temperature decrease in the order, $ICl>IBr>I_2>Br_2$. This order may be a measure of their relative acidities toward durene, which is explained in terms of the relative polarizabilities of halogen molecules and the relative electronegativities of halogen atoms. These results combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order; Benzene

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Effects of Temperature and n-Alcohols (Propanol, Butanol, Pentanol and Hexanol) on the Micellization of Cetyltrimethylammonium Bromide (Cetyltrimethylammonium Bromide의 미셀화 현상에 미치는 온도 효과 및 n-알코올(프로판올, 부탄올, 펜탄올 및 헥산올) 효과)

  • Lee, Byeong Hwan
    • Journal of the Korean Chemical Society
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    • v.38 no.8
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    • pp.539-546
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    • 1994
  • The critical micelle concentration(CMC) and the counterion binding $constant(\beta)$ at the CMC of cetyltrimethylammonium bromide(CTAB) in a series of aqueous solutions containing medium chain-length n-alcohols(Propanol, Butanol, Pentanol and Hexanol) have been determined from the concentration dependence of electrical conductance at serveral temperature from $17^{\circ}C\;to\;41^{\circ}C.$ Thermodynamic parameters $({\Delta}G^o_m,\;{\Delta}H^o_m,\;{\Delta}S^o_m,\;and\;{\Delta}C_p)$ associated with micelle formation of CTAB have been also estimated from the temperature dependence of CMC and $\beta$ values, and the significance of these parameters and their relation to the theory of micelle formation have been considered. The results show that an enthalpy-entropy compensation effect is usually observed for the micellization of CTAB. The effects of n-alcohols on the micellar properties (CMC and $\beta$) of CTAB solutions have been also investigated. The addition of n-alcohol to the CTAB solution in a small quantity decreases the CMC value and the counterion binding constant $(\beta)$ at the CMC, but the addition of n-alcohol in an excessive quantity increases the CMC values on the conterary. These results have been explained in terms of the effect of the micelle-solubilized alcohol on the micellar surface charge density.

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Studies on the Coordination of Acetamide to Rare Earth Metal Ion (Ln(II) (희토류 금속이온 (Ln(III))과 Acetamide 사이의 상호작용에 대한 연구)

  • Sang-Won Lee;Jeonga Yu;Chang-Ju Yoon;Yoo-Hyek Jun;Young-Sang Choi
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.205-211
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    • 1992
  • The $2{\nu}_{C=0}$ + amide III combination band spectrum of acetamide (AA) was obtained in very dilute solutions of AA+lanthanide shift reagents (LSR) in carbon tetrachloride over the range of $15^{\circ}$ to $45^{\circ}C$. It was found that only 1 : 1 AA-LSR complex is formed by the interaction between carbonyl oxygen of AA and central metal ion(Ln(Ⅲ)) in LSR. The thermodynamic parameters for Ln(III)${\cdot}$O=C bond were determined by computer analysis of concentration and temperature dependent spectra. ${\Delta}H^{\circ}$ for the coordination of AA to Eu$(dpm)_3$, Yb$(dpm)_3$, and Pr$(dpm)_3$ have been found to be -39.1, -28.4, and -25.5 kJ/mol, respectively. It has shown that this type of ion-dipole interaction is more than twice stronger compared to the dipole-dipole interaction in the amide linkage, and largely depending on the steric hindrence effect by the bulky dpm groups around central metal ion (Ln(III)) rather than the ionic potential effect of central metal ion itself.

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Formulation of Alternative Non-Aqueous Cleaning Agents to Chlorofluorocarbon Compounds for Cleaning Flux, Solder and Grease (Flux, Solder 및 Grease 세정용 CFC 대체 비수계 세정제 배합 연구)

  • Jung, Young Woo;Lee, Ho Yeoul;Lee, Myoung Jin;Song, Ah Ram;Bae, Jae Heum
    • Clean Technology
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    • v.12 no.4
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    • pp.250-258
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    • 2006
  • CFC compounds such as CFC-113 and 1,1,1-TCE, etc. have been used in various industries due to their excellent chemical stability, thermodynamic characteristics, non-inflammability and anti-corrosiveness. However, in oder to protect the earth environment, "the Montreal Protocol on substances that deplete the ozone layer" was adopted in 1989 for prevention of production and utilization of these CFC compounds and alternative cleaning agent have been required in the industry. The objective of this study is to develop non-aqueous cleaning agents that do not require major change of cleaning system, have excellent cleaning efficiency, are favorable to the environment, are harmless to the human body, and are not generated corrosive materials. In this work, non-aqueous cleaning agents have been formulated with glycol ether series and paraffinic hydrocarbon series with siloxane, and their physical properties and cleaning efficiencies were analyzed and compared with those of regulated materials. As a result of physical properties measurement of the formulated cleaning agents, it is expected that they may have good penetration ability into contaminated materials due to their properties with low density and low surface tension. Measurement of flash point and vapor pressure of the cleaning agents will be helpful for evaluation of their safety and working environment. The experimental results of cleaning flux, solder and grease by the formulated cleaning agents show that their cleaning abilities of soils were good and that there were no residues on the substance after cleaning. Therefore, alternative cleaning agents which have equivalent cleaning ability to regulating materials, good penetration ability and low hazard to human body, have been developed in this work.

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Value-added Chemicals Derived from Propane Using Heterogeneous Catalysts (불균일계 촉매를 통한 프로판 고부가화)

  • Yoon, Ji-Sun;Suh, Dong-Jin;Park, Tae-Jin;Cho, Young-Sang;Suh, Young-Woong
    • Clean Technology
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    • v.14 no.2
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    • pp.71-86
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    • 2008
  • In this review we discussed the effective ways to catalytically derive value-added chemicals from propane which has been utilized only as an energy source so far. Among various propane-derived products, the most valuable chemicals such as propylene and acrylonitrile were mainly focused herein. Propylene could be manufactured through oxidative dehydrogenation of propane using $O_2,\;CO_2$, etc. as an oxidant for the purpose of overcoming thermodynamic limitations of propane dehydrogenation. On the other hand, propane ammoxidation would be an alternative to propylene ammoxidation for producing acrylonitrile since propane is much cheaper than propylene as a starting material. Although effective $MoVTeNbO_x$ catalysts have been developed fur propane ammoxidation in recent years, more detailed studies should be thoroughly performed. In carrying out both oxidative dehydrogenation and ammoxidation of propane fur a long period, the most critical issue is definitely considered to find out the most active and selective catalysts, which makes it possible to commercialize both reactions into economically viable processes.

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Simultaneous Removal of Mercury and NO by Metal Chloride-loaded V2O5-WO3/TiO2-based SCR catalysts (금속염화물이 담지된 V2O5-WO3/TiO2 계 SCR 촉매에 의한 수은 및 NO 동시 제거)

  • Ham, Sung-Won
    • Clean Technology
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    • v.23 no.2
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    • pp.172-180
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    • 2017
  • Thermodynamic evaluation indicates that nearly 100% conversion of elemental mercury to oxidized mercury can be attained by HCl of several tens of ppm level at the temperature window of SCR reaction. Cu-, Fe-, Mn-chloride loaded $V_2O_5-WO_3/TiO_2$ catalysts revealed good NO removal activity at the operating temperature window of SCR process. The catalysts with high desorption temperature indicating adsorption strength of $NH_3$ revealed higher NO removal activity. The HCl fed to the reaction gases promoted the oxidation of mercury. However, the activity for the oxidation of elemental mercury to oxidized mercury by HCl was suppressed by $NH_3$ inhibiting the adsorption of HCl to catalyst surface under SCR reaction condition containing $NH_3$ for NO removal. Metal chloride loaded $V_2O_5-WO_3/TiO_2$ catalysts showed much higher activity for mercury oxidation than $V_2O_5-WO_3/TiO_2$ catalyst without metal chloride under SCR reaction condition. This is primarily attributed to the participation of chloride in metal chloride on the catalyst surface promoting the oxidation of elemental mercury.