• Title/Summary/Keyword: Charge Exchange

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Theoretical Studies of Substituent Effects on S$_N$2 Transition States$^\dag$

  • Lee, Ik-Choon;Song, Chang-Hyun
    • Bulletin of the Korean Chemical Society
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    • v.7 no.3
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    • pp.186-190
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    • 1986
  • Effects of substituents in the nucleophile(X), the substrate(Y) and the leaving group(Z) on the structure of $S_N2$ transition states have been analyzed by considering effects of four components, electrostatic($E_{es}$), exchange repulsion ($E_{ex}$), polarization($E)_{pl}$) and charge transfer($E_{ct}$) terms, of interaction between the reactants on the degree of bond making and bond breaking. Prediction of net effects of all substituents(X, Y and Z) on the degree of bond making were found to be clearcut whereas the effect of an electron withdrawing group on the substrate (Y = EWG) on the degree of bond breaking was complex; the substituent(Y = EWG) is normally carbon-leaving group($C^{\ast}$-L) bond tightening($E_{pl}$ dominance) but becomes $C^{\ast}$-L bond loosening when the bond is strongly antibonding ($E_{ct}$ dominance). Our model calculations on the reaction of $CH_2XNH_2$ with $YCH_2COOCH_2Z$ using energy decomposition scheme have confirmed that predictions based on our analysis are correct.

Electrocatalytic Reduction of Thionyl Chloride by Schiff Base Metal(II) Complexes (1)

  • Sin, Mi Suk;Kim, U Seong;Jo, Gi Hyeong;Choe, Yong Guk
    • Bulletin of the Korean Chemical Society
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    • v.16 no.3
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    • pp.205-210
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    • 1995
  • Catalytic effects of various Schiff base metal(II) complexes on the reduction of thionyl chloride at glassy carbon electrode are evaluated by determining the kinetic parameters from cyclic voltammetry technique. The charge transfer process is affected strongly by the concentration of catalysts during the reduction of thionyl chloride. The catalytic effects are shown by both a shift of the reduction potential for thionyl chloride toward more positive direction and an increase in peak current. The diffusion coefficient value, Do, of the 8.17 ${\times}$ 10-9 $cm^2/s$ was observed at the bare glassy carbon electrode, whereas larger values (0.9-1.09 ${\times}$ 10-8 $cm^2/s$) were observed at the catalyst supported glassy carbon electrode. Significant improvements in the cell performance have been noted in terms of both exchange rate constants and current densities at glassy carbon electrode.

Effect of Transition Metal(II)-N,N-Bis(salicylaldehyde)phenylenediimines on the Electrochemical Reduction of Thionyl Chloride

  • 김현수;최용국;조기형;국성근;우희권
    • Bulletin of the Korean Chemical Society
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    • v.17 no.3
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    • pp.223-227
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    • 1996
  • Catalytic effects of transition metal (Co2+, Ni2+) complexes of N,N-bis(salicylaldehyde)-o-phenylenediimine (SOPD), N,N-bis(salicylaldehyde)-m-phenylenediimine (SMPD), and N,N-bis(salicylaldehyde)-p-phenylenediimine (SPPD), on the reduction of thionyl chloride at glassy carbon electrode, are evaluated by determining the kinetic parameters with cyclic voltammetric technique. The charge transfer process for the reduction of thionyl chloride is strongly affected by the concentration of the catalysts. Some quadridentate Schiff base-M(Ⅱ) complexes show sizable catalytic activities for the reduction of thionyl chloride. Catalytic effects of [M(Ⅱ)(SOPD)] complexes are slightly larger compared to [M(Ⅱ)2(SMPD)2] and [M(Ⅱ)2(SPPD)2] complexes. On those electrodes deposited with the catalysts, the observed exchange rate constants (ko) are in the range of 0.89-2.28 × 10-7 cm/s, while it is 1.24 × 10-7 cm/s on the bare glassy carbon electrode.

Development of a Continuous Electrolytic System for pH-control with Only One Discharge of Electrolytic Solution by Using Non-equilibrium Steady State Transfer of Ions across Ion Exchange Membranes (이온 교환막에서 이온의 비 평형 정상상태 이동을 이용한 단일 전해액의 배출만을 가지는 pH 조절용 연속식 전해 반응기 개발)

  • Kim Kwang-Wook;Lyu Je-Wook;Kim In-Tae;Park Geun-Il;Lee Eil-Hee
    • Proceedings of the Korean Radioactive Waste Society Conference
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    • 2005.06a
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    • pp.101-109
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    • 2005
  • In order to produce only a pH-controlled solution without discharging any unused solution, this work has developed a continuous electrolytic system with a pH-adjustment reservoir being placed before an ion exchange membrane-equipped electrolyzer, where as a target solution was fed into the pH-adjustment reservoir, some portion of the solution in the pH-adjustment reservoir was circulated through the cathodic or anodic chamber of the electrolyzer depending on the type of the ion exchange membrane used, and some other portion of the solution in the pH-adjustment reservoir was discharged from the electrolytic system through other counter chamber with its pH being controlled as acid or base. The phenomena of the pH being controlled in the system could be explained by the electro-migration of the ion species in the solution through the ion exchange membrane under a cell potential difference between anode and cathode and its consequently-occurring non-charge equilibriums and electrolytic water- split reactions in the anodic and cathodic chambers.

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Effects of Immobilized Bipolar Interface Formed by Multivalent and Large Molecular Ions on Electrodialytic Water Splitting at Cation-Exchange Membrane Surface (양이온교환막 표면의 전기투석 물분해에서 다가의 큰 이온성분자에 의해 형성된 고정층 바이폴라 계면의 영향)

  • Seung-Hyeon Moon;Moon-Sung Kang;Yong-Jin Choi
    • Membrane Journal
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    • v.13 no.3
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    • pp.143-153
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    • 2003
  • The effects of bipolar interface formed on the surface of cation-exchange membrane on water splitting phenomena were investigated. Results showed that the formation of immobilized bipolar interface resulted in significant water splitting during electrodialysis. In particular, the immobilized bipolar interface was easily created on the cation-exchange membrane surface in the electrodialytic systems where multivalent cations served as an electrolyte. Multivalent cations with low solubility product resulted in violent water splitting because they were easily precipitated on the membrane surface in hydroxide form. Therefore, the bipolar interface consisting of H- and OH-affinity groups were formed on the membrane-solution interface. Apparently, water splitting was largely activated with the help of strong electric fields generated between the metal hydroxide layer and fixed charge groups on the membrane surface. Likewise, the accumulation of large molecular counter ions on the membrane surface led to the formation of a fixed bipolar structure that could cause significant water splitting in the over-limiting current region. Therefore, the prevention of the immobilization of bipolar interface on the membrane surface is very essential in improving the process efficiency in a high-current operation.

The effects of a Leader's organizational citizenship behavior(OCB) on subordinates' interpersonal citizenship behavior(ICB) and job stress: Leader-Member Exchange(LMX) as a mediating variable (리더의 조직시민행동이 조직구성원들의 사람중심 시민행동과 스트레스에 미치는 영향: 리더-구성원 교환관계의 매개효과를 중심으로)

  • Moon, JeeYoung;Lee, JungHun
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.21 no.5
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    • pp.230-239
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    • 2020
  • The purpose of this study was to examine how a leader's organizational citizenship behavior (OCB) affects subordinates' interpersonal citizenship behavior (ICB) and job stress levels. A leader's OCB involves taking-charge behavior, loyal boosterism, and the industry. We hypothesized that leader-member exchange (LMX) would mediate the relationship between leader's OCB and subordinates' ICB and job stress level. We tested the model using a sample of 293 employees from different organizations from September 2019 until November 2019. We conducted confirmatory factor analyses of the variables and analyzed the data by using structural equation modeling. We also conducted a CFA to assess the fit of a three-factor model for the leader's OCB items. Empirical findings show that LMX fully mediated the effect of leader's OCB on employees' ICB and job stress level. Leader's OCB had a positive effect on LMX. Moreover, LMX had a positive effect on employees' ICB but had a negative effect on job stress. We found support for our hypotheses that leader's OCB is positively related to ICB but negatively related to job stress, and this relationship is mediated by LMX. We discuss limitations, implications for practice, and future research.

A Numerical Modeling of the Temperature Dependence on Electrochemical Properties for Solid Oxide Electrolysis Cell(SOEC) (고체 산화물 수전해 시스템(SOEC)에서 전기화학적 특성의 온도 의존성에 대한 수치 모델링)

  • Han, Kyoung Ho;Jung, Jung Yul;Yoon, Do Young
    • Journal of Energy Engineering
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    • v.29 no.2
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    • pp.1-9
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    • 2020
  • In recent days, fuel cell has received attention from the world as an alternative power source to hydrocarbon used in automobile engines. With the industrial advances of fuel cell, There have been a lot of researches actively conducted to find a way of generating hydrogen. Among many hydrogen production methods, Solid Oxide Electrolysis Cell(SOEC) is not only a basic way but also environment-friendly method to produce hydrogen gas. Solid Oxide Electrolysis Cell has lower electrical energy demands and high thermal efficiency since it is possible to operate under high temperature and high pressure conditions. For these reasons, experimental researches as well as studies on numerical modeling for Solid Oxide Electrolysis Cell have been under way. However, studies on numerical modeling are relatively less enough than experimental accomplishments and have limited performance prediction, which mostly is considered as a result from inadequate effects of electrochemical properties by temperature and pressure. In this study, various experimental studies of commercial Membrane Electrode Assembly (MEA) composed of Ni-YSZ (40wt%, Ni-60 wt% YSZ)/8-YSZ (TOSOH, TZ8Y)/LSM (La0.9Sr0.1MnO3) was utilized for improving effectiveness of SOEC model. After numerically analyzing effects of electrochemical properties according to operating temperature, causing the largest deviation between experiments and simulation are that Charge Transfer Coefficient (CTC), exchange current density, diffusion coefficient, electrical conductivity in SOEC. Analyzing temperature effect on parameter used in overpotential model is conducted for modeling of SOEC. cross-validation method is adopted for application of various MEA and evaluating feasibility of model. As a result, the study confirm that the numerical model of SOEC based on structured process of effectiveness evaluation makes performance prediction better.

Electrochemical Characteristics of Supercapacitor Using Ionic Liquid Electrolyte (Supercapacitor용 이온성 액체 전해질의 전기화학적 특성)

  • Kim, Sang-Gil;Hwang, Gab-Jin;Kim, Jae-Chul;Ryu, Cheol-Hwi
    • Journal of the Korean Electrochemical Society
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    • v.14 no.4
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    • pp.201-207
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    • 2011
  • Supercapacitor has been studied actively as one of the most promising electrochemical energy storage system for a wide range of applications. To increase the energy density of supercapacitor, the introduction of ionic liquids is required. In this study, two types of EMI-$BF_4$ based on quaternary imidazolium salt were prepared with quaternary reaction and anion exchange. The structural characterization and thermal stability were analyzed by nuclear magnetic resonance($^1H$-NMR) and thermogravimetric analysis(TGA), respectively. Thermal stability of the EMI-$BF_4$ using TGA confirmed that, after heat treatment, the decomposition temperature of EMI-$BF_4$ was increased. Supercapacitors were fabricated with synthesized and commercial ionic liquids, and charge/discharge characteristics were also investigated. The capacity of supercapacitor, for synthesized and commercial EMI-$BF_4$ were determined to be 0.067 F and 0.073 F respectively, by means of charge/discharge test.

The characteristics of premeability and formation of clay cake by electrophoresis technique (전기영동기법에 의한 점토케이크의 형성과 투수특성)

  • Kim, Jong-Yun;Kim, Tae-Ho;Kim, Dae-Ra;Han, Sang-Jae;Kim, Soo-Sam
    • Proceedings of the Korean Geotechical Society Conference
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    • 2008.03a
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    • pp.938-946
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    • 2008
  • This study is on sealing leakage holes where are in landfills to make clay cakes with clay particles, which have a negative surface charge using the method of electrophoresis. Generally, electrophoresis is the motion of charged particles in a colloid under the influence of an electric field; particles with a positive charge go to the cathode and negative to the anode. In this study in order to develop the prevention system of leakages of the leachate in landfills, one-dimensional electrophoresis tests were conducted for determining the properties of the motion of the electrophoresis and cutoff using the method of electrophoresis depending on various the effect factors such as types of clays, concentrations of the clays, and applied electric field. In case of the experiments of determining the optimum clays, Na and Ca-Bentonite, Na and Ca-Montmorillonite, which have greater zeta-potential, cation, exchange capacity as well as ability of cutoff, and Micro-cement inducing cementation were chosen and then the effect of those clays was investigated. Moreover, the properties of the motion and settling of the clays were investigated following electric field varied from 0 to 1V/cm at different concentration of the clays in order to determine both the properties of the motion of the clays and the efficiency of electric field when applying different direct current. Ultimately, the ability of cutoff was examined through measuring the permeability of the clay cakes derived from the one-dimensional electrophoresis tests.

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The design and fabricationt for ion fraction measurement of plasma generator (플라즈마발생기의 이온분율 측정 장치 설계 및 제작)

  • Lee, Chan-Young
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.11a
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    • pp.368-368
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    • 2008
  • Ion implantation has been widely developed during the past decades to become a standard industrial tool. To comply with the growing needs in ion implantation, innovative technology for the control of ion beam parameters is required. Beam current, beam profile, ion fractions are of great interest when uniformity of the implant is an issue. Especially, it is important to measure the spatial distribution of beam power and also the energy distribution of accelerated ions. This energy distribution is influenced by the proportion of mass for ion in the plasma generator(ion source) and by charge exchange and dissociation within the accelerator structure and also by possible collective effects in the neutralizer which may affect the energy and divergence of ions. Hydrogen atom has been the object of a good study to investigate the energy distribution. Hydrogen ion sources typically produce multi-momentum beams consisting of atomic ion ($H^+$) and molecular ion ($H_2^+$ and $H_3^+$). In the beam injector, the molecular ions pass through a charge-exchanges gas cell and break up into atomic with one-half (from $H_2^+$) or one-third (from $H_3^+$) according to their accelerated energy. Burrell et al. have observed the Doppler shifted lines from incident $H^+$, $H_2^+$, and $H_3^+$ using a Doppler shift spectroscopy. Several authors have measured the proportion of mass for hydrogen ion and deuterium using an ion source equipped with a magnetic dipole filter. We developed an ion implanter with 50-KeV and 20-mA ion source and 100-keV accelerator tube, aiming at commercial uses. In order to measure the proportion of mass for ions, we designed a filter system which can be used to measure the ion fraction in any type of ion source. The hydrogen and helium ion species compositions are used a filter system with the two magnets configurations.

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