• Title/Summary/Keyword: 화학적 확산계수

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Retention Behavior of Poly(Ethylene-co-Vinyl Acetate)s in Thermal Field-Flow Fractionation (열장 흐름 분획법에서 에틸렌-아세트산 비닐 혼성중합체들의 머무름거동에 관한 연구)

  • Jeon, Seon Ju;Jo, Gyeong Ho;Lee, Dae Un;Mun, Myeong Hui
    • Journal of the Korean Chemical Society
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    • v.38 no.6
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    • pp.427-434
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    • 1994
  • The retention behaviors of poly(ethylene-co-vinyl acetate)s have been studied by thermal field-flow fractionation(ThFFF) with respect to effective separation and characterization of thermal diffusion coefficients($D_{\tau}$) as one of the physicochemical properties of polymers. The eight copolymers are different in vinyl acetate composition ranging from 25% to 70% and in molecular weight ranging from 110,000 to 285,000. The carrier solvents are THF, toluene and chlorobenzene which have different viscosities and thermal conductivities. It is shown that the retention of a copolymer is dependent on the type of the carrier, the molecular weight and chemical composition of the copolymer. The results show that the retention of a copolymer increases when either vinyl acetate composition or the molecular weight increase. $D_{\tau}$ values measured by experiments vary from 1.36∼5.97 $\cm^2/(s.K)$ depending on the copolymer composition and the type of the carrier solvent. These values increase $(r^2{\geq}0.928)$ with increase of weight % of vinyl acetate. THF is found to be the proper carrier solvent for separation of copolymers employed in this study due to the fact that a $D_{\tau}$ value greatly changes with variation of copolymer composition. From the above results, ThFFF can be used for separation of copolymers with similar molecular sizes but different compositions.

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Electrochemical Reduction of Iodine in Non-aqueous Solvents (물아닌 용매속에서의 요오드의 전기화학적 환원)

  • Park Doo Won;Choi Won Hyung
    • Journal of the Korean Chemical Society
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    • v.19 no.2
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    • pp.104-115
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    • 1975
  • The electrochemical reduction of iodine in non-aqueous media have been studied by polarography, chronopotentiometry, cyclic voltammetry and controlled potential coulometry at dropping mercury electrode and platinum, gold and amalgamated platium electrodes. In amphiprotic solvents such as methanol, ethanol, isopropanol and pyridine, iodine were reduced to iodide ions via one step reduction involving 1 electron and in aprotic solvents such as acetonitrile, dimethylformamide and dimethylsulfoxide via two step reduction involving all 3 electrons. The reductions of iodine give well defined polarograms at dropping mercury electrode and irreversible chronopotentiograms at platinum electrode, but less defined irreversible chronopotentiograms at gold and amalgamated platinum electrodes, those are all diffusion controlled. The diffusion coefficients of iodine in various solvents were estimated from the chronopotentiometric data and Sand equation.

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Electrochemical Behavior of Lithium-Iron Oxide Electrode and Measurement of Chemical Diffusion Coefficient of Lithium (리튬-철계 산화물 전극의 전기화학 거동 및 리튬의 화학확산 계수 측정)

  • Lee Joung-Jun;Chong Won-Jung;Ju Jeh-Beck;Sohn Tai-Won;Cho Won-Il;Cho Byung-Won;Kim Hyung-Sun
    • Journal of the Korean Electrochemical Society
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    • v.4 no.4
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    • pp.139-145
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    • 2001
  • Various compositions of iron oxide based materials as a cathode of lithium secondary battery have been fabricated and tested with electrochemical method. A layered form of $LiFeO_2$ was synthesized by mixing and heating the initial materials of $FeCl_3\;6H_2O,\;LiOH$ and NaOH at low temperature. The effect of changing the precursors composition was investigated. As a result, when increasing the additive amount of NaOH, the capacity of the electrode is decreased but the performance and declining rate of capacity became smaller. $LiFeO_2$ synthesized with the weight ratio of $NaOH/FeCl_3/LiOH,\;2/1/7$ showed the largest capacity, but the discharging efficiency was sharply decreased after 30 cycles. Charge-discharge tests of lithium cells with $LiFeO_2$ cathode having the layer structure were performed. This cell showed the reversibility in the range of 1.5-4.5V of cell voltage. By using CPR method, chemical diffusion coefficients were measured in 1M $LiPF_6/EC/DEC$ solution. The value of chemical diffusion coefficient decreased with increasing the lithium content x, In 0.5$10^{-11}^cm^2/s$.

A Study on Electrochemical Behaviors of Samarium Ions in the Molten LiCl-KCl Eutectic Using Optically Transparent Electrode (LiCl-KCl 용융염에서 광학적으로 투명한 전극을 이용한 사마륨 이온의 전기화학적 거동에 관한 연구)

  • Lee, Ae-Ri;Park, Byung Gi
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.15 no.4
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    • pp.313-320
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    • 2017
  • A spectroelectrochemical method has been applied to investigate the electrochemical behaviors and identify the kinds of samarium ions dissolved in high temperature molten LiCl-KCl eutectic. An optically transparent electrode (OTE) fabricated with a tungsten gauze as a working electrode has been used to conduct cyclic voltammetry and potential step chronoabsorptometry. Based on the reversibility of the redox reaction of $Sm^{3+}/Sm^{2+}$, which was determined from the cyclic voltammograms, the formal potential and the diffusion coefficient were calculated to be -1.99 V vs. $Cl_2/Cl^-$ and $2.53{\times}10^{-6}cm^2{\cdot}s^{-1}$, respectively. From the chronoabsorptometry results at the applied potential of -1.5 V vs. Ag/AgCl (1wt%), the characteristic peaks of absorption for samarium ions were determined to be 408.08 nm for $Sm^{3+}$ and 545.62 nm for $Sm^{2+}$. Potential step chronoabsorptometry was conducted using the anodic and the cathodic peak potentials from the voltammograms. Absorbance analysis at 545.63 nm shows that the diffusion coefficient of $Sm^{3+}$ is $2.15{\times}10^{-6}cm^2{\cdot}s^{-1}$, which is comparable to the value determined by cyclic voltammetry at the same temperature.

Chemical Characteristics of Liguid Crystals and Its Applicability (액정의 화학적성질과 응용의 가능성)

  • 김준용
    • Journal of the Korean Institute of Telematics and Electronics
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    • v.10 no.3
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    • pp.10-22
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    • 1973
  • Recently, nematic and nematic-cholesteric mixtures of substances have been discovered which have stimulated progress in electronics research and industry. In the liquid crystalline state, compounds with nematic mesopheses possess the ability to scatter light, depending on the strength of an applied electric field. The rewaking of interest in this fascinating but long-neglected area has occasioned the introduction of the subjects at the situation of the chemists. Since 1888 year, approximately 2000 compounds have been found to possess the unusual properties of what are commonly referred to as liquid crystals. In this paper, a comprehensive review will not be attempthed here. Nevertheless, some general information necessary to familarize the reader with rather exotic field will facilitate an understanding of the new effect and its application.

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Analysis of Parameter Sensitivity of 2D Numerical Model for Simulation of Toxic Contaminants Transport in Stream (하천에서 독성물질의 혼합거동모의를 위한 2차원 수치모형의 매개변수 민감도 분석)

  • Shin, Dongbin;Seo, Il Won
    • Proceedings of the Korea Water Resources Association Conference
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    • 2019.05a
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    • pp.106-106
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    • 2019
  • 많은 도심의 하천들은 오염물질의 유입에 취약하다. 최근 신소재 공학 등 첨단산업이 발전하게 되면서 유해화학물질의 유입문제는 더욱 대두되고 있으며, 실제로 최근 유해화학물질 유입사고 발생건수가 늘어나고 있다. 특히 국내 취수량의 90%는 지표수에서 취수하고 있어, 하천오염사고는 직접적인 피해로 이어지게 된다. 따라서 이러한 사고에 대응하기 위하여 수환경에 유입된 유해물질의 거동 매커니즘을 반영한 수질해석이 필요하다. 수체 내에 유입된 유해화학물질은 기본적으로 흐름에 따른 이송 확산을 하며 흡 탈착, 휘발, 침전 부유, 생화학 반응과 같은 다양한 반응과 함께 혼합거동을 한다. 특히 소수성물질의 경우 용해된 상태뿐만 아니라, 유사에 흡착된 상태로 수체에 존재하게 된다. 결국 유해화학물질의 거동을 해석하기 위해서는 유체의 흐름 해석뿐만 아니라 수체에 존재하는 유사의 이송 또한 해석해야한다. 본 연구에서는 흐름해석을 위하여 서울대에서 개발한 흐름모형(HDM-2D)을 사용하였으며, 부유사 거동모의를 위해 부유사거동모형(STM-2D)을 개발하였다. 또한 유해화학물질의 거동모의를 위해 서울대에서 개발한 수질모형(CTM-2D)에 생성/소멸항을 추가하였으며 흐름모형과 부유사모형과의 연계를 통해 유해화학물질의 혼합거동 수치모형을 개발하였다. 각 반응항(흡 탈착, 휘발, 침전 부유, 생화학 반응)을 수치모형에 반영 시에는 보통 두 계(물-토양, 물-공기) 사이의 선형 물질교환으로 이해된다. 따라서 물질의 각 반응 별 평형농도와 물질교환속도계수를 추정식을 통해 산정하여 사용하게 된다. 하지만 각 기작이 반영유무에 따라 계산시간 및 필요입력변수가 늘어나게 되므로, 유해화학물질 유입사고와 같은 빠른 대처가 필요한 경우 각 반응 텀의 유의성을 판단하여 모형에 반영여부를 결정을 통해 경제적인 모의를 할 수 있어야 한다. 이에 따라 본 연구에서는 개발된 모형의 각 매개변수들의 민감도를 분석하고, 흐름조건 및 물질의 특성에 따른 반응항의 유의성을 판단하였다. 본 연구에서는 개발된 모형(부유사거동모형, 유해화학물질의 혼합거동모형)은 해석해 및 현장 데이터와 비교검증을 통해 개발을 완료하였으며, 각 반응항의 민감도 분석을 통해 매개변수의 임계값을 결정하였다.

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Electrochemical Properties of Cu(I)hexafluoroacetylacetonate (Cu(I)hexafluoroacetylacetonate 착화합물들의 전기화학적 성질)

  • Choi, Yong-Kook;Jeong, Byeong-Goo;Shin, Hyun-Kook
    • Journal of the Korean Chemical Society
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    • v.37 no.9
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    • pp.806-812
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    • 1993
  • Complexes of $Cu(I)(hfac)PR_3$(P: phosphine and R: Me, Et and Bu) as Cu(I)(${\beta}$-diketonate) compounds have been synthesized and their electrochemical properties have been investigated using glassy carbon and carbon microelectrode in aprotic solvent. Reduction process of $Cu(I)(hfac)PR_3$ compounds carried out one electron pathway to Cu(0) by cyclic voltammetry in acetonitrile solution. Chronoamperometric curve using carbon microelectrode shows that these complexes are one electron process and diffusion coefficients are $4.5{\sim}6.7{\times}10^{-6}cm^2$/sec.

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Electrochemical Reduction of Thionyl Chloride : Catalytic Effects of Metalomacrocyclic Compounds (SOCl$_2$의 전기화학적 환원 : 금속-거대고리 화합물의 촉매효과)

  • Woo-Seong Kim;Yong-Kook Choi;Chjo Ki-Hyung
    • Journal of the Korean Chemical Society
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    • v.37 no.8
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    • pp.744-752
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    • 1993
  • Electrochemical reduction of thionyl chloride has been carried out at glassy carbon and microelectrode that modified by macrocyclic compounds. The catalyst molecules of macrocyclic compounds were adsorbed on the electrode surface and reduced thionyl chloride resulting in a generation of oxidized catalyst molecules. The concentration of catalysts and electrode immersion time were found to affect the catalyst performance strongly. Significant improvements in cell performance have been noted in terms of both exchange rate constants of up to 10 times and power densities of up to 220% at glassy carbon electrode. The diffusion coefficients obtained at carbon microelectrode were slightly different from that determined at glassy carbon electrode.

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Influence of Temperature and Affinity of Disperse Dye on Dyeing of PET(Polyethylene Terephthalate) Microfiber (PET 초극세사 염색에서 분산염료의 친화력과 온도 의존성)

  • Lee, Hun
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.20 no.9
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    • pp.532-540
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    • 2019
  • PET microfibers with various diameters (0.5, 0.2, 0.06, and 0.01 dpf) were dyed with a dispersed dye (C.I. Disperse Blue 56) at various temperatures. The dyeing process was conducted under infinite dyebath conditions at constant temperatures. The effects of the dyeing temperature and diameter on the partition coefficient, affinity, and diffusion coefficient of disperse dyes were studied. The curve of isotherms was fitted well to Nernst-type model in a large range of initial dye concentrations. At the same temperature, the partition coefficient and affinity decreased with increasing sample diameter due to the increase in surface area. At all deniers, the partition coefficient and affinity decreased with increasing temperature because the dyeing process is an exothermic reaction. In addition, the decrease in radius of the sample gives rise to a decrease in the heat of dyeing. The fine diameter of the sample resulted in an increased surface area but decreased space between the microfibers. Consequently, decreasing the diameter of the microfibers leads to a decrease in the diffusion coefficient. At the same diameter, the diffusion coefficient increased with increasing temperature because of rapid dye movement and the large free volume of the sample inside. In addition, thermal dependence of the diffusion coefficient increased when the diameter of the sample increased.

Redox Reaction Mechanisms of Thorium (IV) Complexes with Crown Ethers in Dimethylsulfoxide (디메틸술폭시드용매중에서 Thorium (IV)-Crown Ether 착물의 산화-환원 반응메카니즘)

  • Jung, Hak-Jin;Jung, Oh-Jin;Suh, Hyouck-Choon
    • Journal of the Korean Chemical Society
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    • v.31 no.3
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    • pp.250-257
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    • 1987
  • The electrical conductances for the thorium (IV) complexes with crown ethers have been measured in DMSO, and water solvents, and the oxidation-reduction reaction mechanisms, electron number and diffusion coefficients in the reversible reduction process have been examined by polarography and cyclic voltammography. The dissociation mole ratio of $Th^{4+}$ and nitrate ion are 1:1 and in aprotic solvent, and 1:4 in protic solvent like as water. The limiting molar conductances of all complexes in aprotic solvent have been found to be in the range of $92.2{\times}159$ $ohm^{-1}cm^2mol^{-1}$. In aprotic solvent, DMSO, the reduction of each complex is reversible by one electron reduction of one step, and the range of diffusion coefficients is obserbed to be $5.83\;10^{-6}{\sim}6.90{\times}10^{-6}$. The complexes which have reduction step were hydrolyzed above at 1.8volt with reference saturated calomel electrode, generating the hydrogen gas. The reaction mechanisms of thorium (IV)-crown ether complexes appear as follows. ${Th_m(IV)L_n(H_2O)_x(NO_3)_{4y}}_=^{DMSO} {\overline{{Th_m(IV)L_n(H_2O)_x(NO_3)_{4y-1}}}^+ + NO_3-$

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