• Title/Summary/Keyword: 열역학적 방법

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Characteristics of Lead Anodic Films Formed in Aqueous Solutions and Reactivities of Di-iso-butylnitrosoamine in Sea Water (납 산화피막 전극의 특성과 디이소부틸니트로소아민의 전극반응성)

  • Hwang Kum-Sho
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.14 no.2
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    • pp.103-115
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    • 1981
  • The cathodic reactions of lead anodic films formed in phosphoric acid, oxalic acid and sodium hydroxide solutions and the reactivities of Di-iso-butylnitrosoamine (DBNA) in sea water at $15\sim30^{\circ}C$ were studied by means of constant current-potential method. Besides, various contants and thermodynamic quantities obtained in the experiment were also do-scribed to explain the reactivities of protons that entered in the anodic film by being transferred across the metal-oxide interface. The electrode reactions of lead anodic film formed in sodium hydroxide solution in 60mM DBNA+0.5M NaCl did not occur because of complete insulator formed on anodic film. The values of $(\partial\triangle E_{H^+}/\partial T)_{i=const}$, estimated with Bead anodic films formed in phosphoric acid in 60mM DBNA+0.5M NaCl and 60mM $DBNA+6\%_{\circ}$ sea water were $-0.006\;V/^{\circ}C\;and\;-0.005\;V/^{\circ}C$, thus being nearly coincided, but the values of $(\partial E_o/\partial T)_{i=o}$ were $0.002\;V/^{\circ}C\;and\;-0.002\;V/^{\circ}C$, being completely inversed.

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Electrochemical Study on Transfer Reaction of Ionizable Cefotiam across a Water/1,2-dichloroethane Interface and Drug Sensing Applications (물/1,2-Dichloroethane 계면에서 Cefotiam 약물 이온의 전이 반응 연구 및 약물 센서에 응용)

  • Liu, XiaoYun;Jeshycka, Shinta;Lee, Hye Jin
    • Applied Chemistry for Engineering
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    • v.29 no.5
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    • pp.581-588
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    • 2018
  • In this article, electrochemical investigation of the transfer reaction of ionizable cefotiam (CTM), an antibiotic molecule across a polarized water/1,2-dichloroethane (water/1,2-DCE) interface was studied. Ion partition diagram providing the preferred charged form of CTM in either water or 1,2-DCE phase was established via the voltammetric evaluation of the transfer process of differently charged CTM species depending upon the pH variation of aqueous solutions. Thermodynamic information including the formal transfer potential and formal Gibbs transfer energy values in addition to important pharmacokinetics including partition coefficients of ionizable CTM were also evaluated. In particular, the current associated with the transfer of CTM present at pH 3.0 aqueous solution proportionally increased with respect to the CTM concentration which was further used for developing CTM sensitive ion sensor. In order to improve the portability and convenient usage, a single microhole interface fabricated in a supportive polyethylene terephthalate film was used of which hole was filled with a polyvinylchloride-2-nitrophenyloctylether (PVC-NPOE) gel replacing 1,2-DCE, a toxic organic solvent. A dynamic range of $1-10{\mu}M$ CTM was obtained.

Miscibility and Properties of Ethyl-Branched Polyethylene/Ethylene-Propylene Rubber Blends (II) (에틸 가지화된 폴리에틸렌과 에틸렌-프로필렌 고무 블렌드의 혼화성과 물성(II))

  • Cho, Ur-Ryong
    • Elastomers and Composites
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    • v.37 no.2
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    • pp.79-85
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    • 2002
  • Ethyl-branched polyethylene [PE(2)] containing 2mole% ethyl branch and three ethylene-propylene rubbers (EPR's) having the same ethylene(E)-propylene(P) molar ratio(E/P=50/50) with different stereoregularity, that is, random EPR (r-EPR), alternating-EPR (alt-EPR) and isotactic-alternating-EPR (iso-alt-EPR) were mixed for the investigation or their properties depending on the stereoregularity. Crystallinity of the prepared blends decreased with increasing content of amorphous EPR because of a decrease in both the degree of annealing and kinetics of diffusion of the crystallizable polymer content. With blend composition, crystallinity was reduced with the stereoregularity in EPR. The thermodynamic interaction parameter(x) for the three blend systems approximately equals to zero near the melting point. These systems were determined to be miscible on a molecular scale near or above the crystalline melting point or the crystalline PE(2). From the measurement of $T_m$ vs. $T_c$, the behavior of PE(2) is mainly due to a diluent effect of EPR component. The spherulite size measured by small angle light scattering (SALS) technique depended upon blend composition, and stereoregularity of EPR. The size of spherulite was enlarged with the content of rubbery EPR and the decrease of stereoregularity in EPR.

Effect of Addition of Cosolvent γ-Butyrolactone on Morphology of Polysulfone Hollow Fiber Membranes (폴리설폰 중공사막 구조에 대한 조용매 γ-Butyrolactone 첨가 영향)

  • Yun, Sukbok;Lee, Yongtaek
    • Applied Chemistry for Engineering
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    • v.25 no.3
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    • pp.274-280
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    • 2014
  • Polysulfone (PSf) hollow fiber membranes were prepared via the nonsolvent induced phase separation technique. The cosolvent of ${\gamma}$-butyrolactone (GBL) was added to the polymer solution containing a mixture of PSf and N,N-dimethylacetamide (DMAc). Water was utilized as a precipitation nonsolvent. The morphology of prepared membranes was investigated using a field emission scanning electron microscopy. The fabricated membrane showed a typical asymmetric structure such as the dense layer on the porous support layer by the addition of GBL to the polymer solution. As the concentration of GBL increased, the asymmetric porous structure was shown to be more intensified. It was thought that the added GBL played a role of enhancing the liquid-liquid phase separation of the polymer solution, since the cosolvent of GBL might change the thermodynamic solubility parameter of the doping solution. Permeation properties through the prepared hollow fiber membranes were characterized by measuring the pure water flux and the solute rejection using $0.05{\mu}m$ polystyrene latex (PSL) beads. Experimental results revealed that the use of PEG as the internal coagulant enhanced the pure water flux up to 130 times compared to the use of EG while the rejection of the PSL beads decreased only 5%.

Design and Analysis of Hydrogen Production and Liquefaction Process by Using Liquefied Natural Gas (액화천연가스(LNG)를 사용한 수소 생산 및 액화 공정 개발)

  • Noh, Wonjun;Park, Sihwan;Lee, Inkyu
    • Korean Chemical Engineering Research
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    • v.59 no.2
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    • pp.200-208
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    • 2021
  • Compare to the gaseous hydrogen, liquid hydrogen has various advantages: easy to transport, high energy density, and low risk of explosion. However, the hydrogen liquefaction process is highly energy intensive because it requires lots of energy for refrigeration. On the other hand, the cold energy of the liquefied natural gas (LNG) is wasted during the regasification. It means there are opportunities to improve the energy efficiency of the hydrogen liquefaction process by recovering wasted LNG cold energy. In addition, hydrogen production by natural gas reforming is one of the most economical ways, thus LNG can be used as a raw material for hydrogen production. In this study, a novel hydrogen production and liquefaction process is proposed by using LNG as a raw material as well as a cold source. To develop this process, the hydrogen liquefaction process using hydrocarbon mixed refrigerant and the helium-neon refrigerant is selected as a base case design. The proposed design is developed by applying LNG as a cold source for the hydrogen precooling. The performance of the proposed process is analyzed in terms of energy consumption and exergy efficiency, and it is compared with the base case design. As the result, the proposed design shows 17.9% of energy reduction and 11.2% of exergy efficiency improvement compare to the base case design.

Liposome Formation and Active Ingredient Capsulation on the Supercritical Condition (초임계 상태에서 리포좀의 생성 및 약물봉입)

  • Mun, Yong-Jun;Cha, Joo-Hwan;Kim, In-Young
    • Journal of the Korean Applied Science and Technology
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    • v.38 no.6
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    • pp.1687-1698
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    • 2021
  • This study is to produce multiple layers of liposomes in a supercritical state and encapsulates active ingredients in order to stably encapsulate thermodynamically unstable active ingredients. In order to form a liposome in a supercritical state, a mixed surfactant development including vegetable-derived hydrogenated phosphatidyl choline and their delivative, hydrogenated sucrose distearate was synthesized as high purity. It describes a manufacturing method of injecting liquid carbon dioxide into a reactor to create a supercritical state and stirring to produce a giant liposome, and adding and loading genistein and quercetin. The HLB of the mixed lipid complex (SC-Lipid Complex) was 12.50, and multiple layers of liposome vesicles were formed even at very low concentrations. This surfactant had a specific odor with a pale yellow flake, the specific gravity was 0.972, and the acid value was 0.12, indicating that it was synthesized with high purity. As a result of the emulsifying capacity experiment using 20 wt% capric/capric triglyceride and triethylhexanoin using SC-Lipid Complex, it was found to have 96.2% emulsifying power. SC LIPOSOME GENISTEIN was confirmed that a multi-layer liposome vesicle was formed through a transmission electron microscope (Cryo-TEM) for the supercritical liposome encapsulated with genistein. The primary liposome particle size in which genistein was encapsulated was 253.9 nm, and the secondary capsule size was 18.2 ㎛. Using genistein as the standard substance, the encapsulation efficiency of supercritical liposomes was 99.5%, and general liposomes were found to have an efficiency of 93.6%. In addition, the antioxidant activity experiment in which quercetin was sealed was confirmed by the DPPH method, and it was found that the supercritical liposome significantly maintained excellent antioxidant activity. In this study, thermodynamically unstable raw materials were sealed into liposomes without organic solvents in a supercritical state. Based on these results, it is expected that it can be applied to various forms such as highly functional skincare cosmetics, makeup cosmetics, and scalp protection cosmetics.

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.

Theoretical Investigation for the Adsorption of Various Gases (COx, NOx, SOx) on the BN and AlN Sheets (N과 AlN 시트에 다양한 기체(COx, NOx, SOx)의 흡착에 관한 이론 연구)

  • Kim, Sung-Hyun;Kim, Baek-Jin;Shin, Chang-Ho;Kim, Seung-Joon
    • Journal of the Korean Chemical Society
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    • v.61 no.1
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    • pp.16-24
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    • 2017
  • The adsorption of various atmospheric harmful gases ($CO_x$, $NO_x$, $SO_x$) on graphene-like boron nitride(BN) and aluminum nitride(AlN) sheets was theoretically investigated using density functional theory (DFT) and MP2 methods. The structures were fully optimized at the $B3LYP/6-31G^{**}$ and $CAM-B3LYP/6-31G^{**}$ levels of theory and confirmed to be a local minimum by the calculation of the harmonic vibrational frequencies. The MP2 single-point binding energies were computed at the $CAM-B3LYP/6-31G^{**}$ optimized geometries. Also the zero-point vibrational energy (ZPVE) and 50%-basis set superposition error (BSSE) corrections were included. The adsorptions of gases on the BN sheet were predicted to be a physisorption process and the adsorptions of gases on the AlN sheet were predicted to be a physisorption process for $CO_x$ and $NO_x$ but to be a chemisorption process for $SO_x$.

Core-hole Effect on Partial Electronic Density of State and O K-edge x-ray Raman Scattering Spectra of High-Pressure SiO2 Phases (전자-정공 효과(Core-Hole Effect) 적용에 따른 SiO2 고압상들의 전자구조 및 O K-edge X-선 Raman 산란 스펙트럼 계산 결과 분석)

  • Khim, Hoon;Yi, Yoo Soo;Lee, Sung Keun
    • Journal of the Mineralogical Society of Korea
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    • v.30 no.2
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    • pp.59-70
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    • 2017
  • $SiO_2$ is one of the most abundant constituents of the Earth's crust and mantle. Probing its electronic structures at high pressures is essential to understand their elastic and thermodynamic properties in the Earth's interior. The in situ high-pressure x-ray Raman scattering (XRS) experiment has been effective in providing detailed bonding transitions of the low-z materials under extreme compression. However, the relationship between the local atomic structures and XRS features at high pressure has not been fully established. The ab initio calculations have been used to overcome such experimental difficulties. Here we report the partial density of states (PDOS) of O atoms and the O K-edge XRS spectra of ${\alpha}-quartz$, ${\alpha}-cristobalite$, and $CaCl_2$-type $SiO_2$ phases calculated using ab initio calculations based on the full-potential linearized augmented plane wave (FP-LAPW) method. The unoccupied O PDOSs of the $CaCl_2$-type $SiO_2$ calculated with and without applying the core-hole effects present significantly distinctive features. The unoccupied O p states of the ${\alpha}-quartz$, ${\alpha}-cristobalite$ and $CaCl_2$-type $SiO_2$ calculated with considering the core-hole effect present similar features to their calculated O K-edge XRS spectra. This confirms that characteristic features in the O K-edge XRS stem from the electronic transition from 1s to unoccupied 2p states. The current results indicate that the core-hole effects should be taken in to consideration to calculate the precise O K-edge XRS features of the $SiO_2$ polymorphs at high pressure. Furthermore, we also calculated O K-edge XRS spectrum for $CaCl_2$-type $SiO_2$ at ~63 GPa. As the experimental spectra for these high pressure phases are not currently available, the current results for the $CaCl_2$-type $SiO_2$ provide useful prospect to predict in situ high-pressure XRS spectra.

Characterization of metal-containing activated carbon derived from phenolic resin (페놀 수지로부터 유도된 금속이 함유된 활성탄의 특성화)

  • Oh, Won-Chun;Jang, Won-Cheoul;Kim, Bum-Soo
    • Analytical Science and Technology
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    • v.14 no.4
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    • pp.349-355
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    • 2001
  • A series of micro- and mesoporous activated carbons were prepared from phenolic resin using a metal treated chemical activation methodology. $N_2$-adsorption data were used to characterize the surface properties of the produced activated carbons. Results of the surface properties and pore distribution analysis showed that phenolic resin can be successfully converted to micro- and mesoporous activated carbons with specific surface areas higher than $962.3m^2/g$. Activated carbons with porous structure were produced by controlling the amount of metal chlorides($CdCl_2$, $CuCl_2$). Pore evolvement was shown to be most effected by the incremental addition of metal chloride. From the thermodynamic DSC data, enthalpy formations(${\Delta}H$) of first endothermic reaction were increase with the incremental addition of metal chloride.

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