• Title/Summary/Keyword: ion transfer reaction

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Synthesis of Aniline from Nitrobenzene and Fe(CO)5 with PEG/γ-Al2O3 as Phase Transfer Catalyst (PEG/γ-Al2O3 상이동 촉매상에서 니트로벤젠과 Fe(CO)5로부터의 아닐린 합성)

  • Oh, So-Young;Lee, Hwa-Su;Park, Dae-Won;Park, Sang-Wook;Shin, Jung-Ho
    • Applied Chemistry for Engineering
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    • v.4 no.1
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    • pp.144-152
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    • 1993
  • Immobilized polyethylene glycols onto metal oxides such as ${\gamma}-Al_2O_3$, ${\alpha}-Al_2O_3$, $SiO_2$ and $TiO_2$ were used as phase transfer catalysts for the room temperature synthesis of aniline from nitrobenzene and ironpentacarbonyl. The amount of attached PEG molecules increased with specific surface area of metal oxides. Among the immobilized catalysts tested PEG/${\gamma}-Al_2O_3$ showed the highest activity. The reaction rate increased with the chain length of PEG mole-cules and the aqueous NaOH concentration. Mechanistic study carried out using infrared spectrometer revealed that the role of PEG was to increase the formation of $HFe(CO)_4{^-}$ ion, which is known as active species, and its movement from aqueous to organic phase.

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A Study on the Computational Simulation of Cyclic Voltammetry using Semi-infinite Diffusion Model (반무한 확산모델을 이용한 순환전위법의 전산모사에 관한 연구)

  • Cho, Ha-Na;Kim, Tae-Yong;Yoon, Do-Young
    • Journal of the Korean Electrochemical Society
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    • v.14 no.3
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    • pp.138-144
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    • 2011
  • The transport phenomena of electron and ion around the electrode have been analyzed, herein the computational program to simulate the electrochemical signal of cyclic voltammetry has been implemented. For the dominant mass-transfer system, the governing equation and its boundary conditions are confined to the semi-infinite diffusion model and the reversible reaction at the electrode. In order to obtain the numerical solutions of cyclic voltammetry, MATLAB was used for the explicit finite difference method. Experimental results from the cyclic voltammetry of electrochemical system(10 mM $K_3Fe(CN)_6$ and 0.1M KCl) upon the ITO glass substrate were compared with the numerical solutions. Present program explains the experimental results fairly well, where they approached the simulated ones closely with deceasing the scan rate. Furthermore, the effects of electrode area, electrochemical reaction constants and transfering coefficients in the cyclic voltammetry were discussed quantitatively.

Er(III)-chelated Prototype Complexes Based on Benzoate and Pentafluorobenzoate Ligands : Synthesis and Key Parameters for Near IR Emission Enhancement

  • Roh, Soo-Gyun;Oh, Jae-Buem;Nah, Min-Kook;Baek, Nam-Seob;Lee, Young-Il;Kim, Hwan-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.25 no.10
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    • pp.1503-1507
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    • 2004
  • New synthetic methodology of the saturated and unsaturated Er(III)-chelated prototype complexes based on benzoate and pentafluorobenzoate ligands was developed through ligand-exchange reaction. The saturated 8-coordinated Er(III) complexes exhibit stronger near-IR emission than those of the unsaturated 6-coordinated Er(III) complexes, obtained from the direct photoexcitation of Er ions with 488 nm. Three $H_2O$ molecules coordinated in the unsaturated 6-coordinated complexes seriously quenched the near IR emission by the harmonic vibration relaxation decay of O-H bonds. Also, the stronger emission of the Er(III) complexes was obtained by the indirect photoexcitation of ligands than by the direct photoexcitation of the Er(III) ions, due to the energy transfer between the excited ligand and the erbium ion. Furthermore, the saturated Er(III)-chelated complex with C-F bonds shows much stronger near IR emission than that of the saturated Er(III)-chelated complex with C-H bonds. It is attributed to the influence of C-F bonds on near IR emission.

Principles of Simulated Moving Bed Reactor(SMBR) (Simulated Moving Bed Reactor(SMBR)의 원리)

  • Song, Jae-Ryong;Kim, Jin-Il;Koo, Yoon-Mo
    • Korean Chemical Engineering Research
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    • v.49 no.2
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    • pp.129-136
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    • 2011
  • Simulated Moving Bed(SMB) process consists of multiple chromatographic columns, which are usually partitioned into four zones. Such a process characteristic allows a continuous binary separations those are impracticable in conventional batch chromatographic processes. Compared with batch chromatography, SMB has advantages of continuity, high purity and productivity. Various researches have been reported for the integration of reaction and recovery during process operation on the purpose of economics and effectiveness. Simulated Moving Bed Reactor(SMBR) is introduced to combine SMB as a continuous separation process and reactor. Several cases of SMBR have been reported for diverse reactions with catalytic, enzymatic and chemical reaction on ion exchange resin as main streams. With an early type of fixed bed using catalyst, SMBR has been developed as SMB using fluidized enzyme, SMB with immobilized enzyme and SMB with discrete reaction region. For simple modeling and optimization of SMBR, a method considering convection only is possible. A complex method considering axial dispersion and mass transfer resistance is needed to explain the real behavior of solutes in SMBR. By combining reaction and separation, SMBR has benefits of lower installation cost by minimizing equipment use, higher purity and yield by avoiding the equilibrium restriction in case of reversible reaction.

Kinetics and Mechanism of the Oxidation of Alcohols by C9H7NHCrO3Cl (C9H7NHCrO3Cl에 의한 알코올류의 산화반응에서 속도론과 메카니즘)

  • Park, Young-Cho;Kim, Young-Sik;Kim, Soo-Jong
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.19 no.8
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    • pp.378-384
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    • 2018
  • $C_9H_7NHCrO_3Cl$ was synthesized by reacting $C_9H_7NH$ with chromium (VI) trioxide. The structure of the product was characterized by FT-IR (Fourier transform infrared) spectroscopy and elemental analysis. The oxidation of benzyl alcohol by $C_9H_7NHCrO_3Cl$ in various solvents showed that the reactivity increased with increasing dielectric constant(${\varepsilon}$) in the following order: DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. The oxidation of alcohols was examined by $C_9H_7NHCrO_3Cl$ in DMF. As a result, $C_9H_7NHCrO_3Cl$ was found to be an efficient oxidizing agent that converts benzyl alcohol, allyl alcohol, primary alcohols, and secondary alcohols to the corresponding aldehydes or ketones (75%-95%). The selective oxidation of alcohols was also examined by $C_9H_7NHCrO_3Cl$ in DMF. $C_9H_7NHCrO_3Cl$ was the selective oxidizing agent of benzyl, allyl and primary alcohol in the presence of secondary ones. In the presence of DMF with an acidic catalyst, such as $H_2SO_4$, $C_9H_7NHCrO_3Cl$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, and $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308K). The observed experimental data were used to rationalize hydride ion transfer in the rate-determining step.

Electrochemistry for Redox Polymer Film of N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium Ion (N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium이온의 산화-환원 고분자 피막에 대한 전기화학)

  • Cha, Seong-Keuck
    • Polymer(Korea)
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    • v.25 no.1
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    • pp.6-14
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    • 2001
  • The monomer N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium$(PF_6)_2$ was electrochemically polymerized on glassy carbon electrode surface. This polymer film electrode has electroactive sites on its bipyridinium ions distributed at the polymer strands. The formal potentials of the electrodes were -0.41V and -0.81V(vs. SSCE) for each step at phosphate buffer(pH=5.70). The diffusion coefficients of the dopants ions into the polymer matrix were $1.57{\times}10^{-4}$ and $4.35{\times}10^{-5}cm^2s^{-1}$ for first and second redox couple, respectively. The rate constants of electron transfer at $V^{2+/+}$ of the first step was a $57.53s^{-1}$, which was 22 times higher than $V^{+/0}$ one having $2.63s^{-1}$ in the solution. The charge transfer resistance of the polymer film was influenced by the dopant ion of the electrolyte. Thus the resistances were 22.63, 16.81, 12.44 and $11.36k{\Omega}$ for $LiClO_4,\;NaClO_4,\;KClO_4$, and phosphate buffer, respectively. The reaction order of the electropolymerization was first order and the rate constant of the polymerization was $1.31{\times}10^{-1}s^{-1}$ as determined by EQCM method. The G.C./p-BPB type electrode doped with phosphate ions showed a stability and reproducibility in CV procedure over 20 cycles.

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Property of Optical Spectroscopy on the Lanthanum Tungstate doped Eu3+ Ion (Eu3+ 이온이 첨가된 란타넘텅스텐산화물의 분광학 특성)

  • Seo, Hyojin;Park, Cheolwoo
    • Journal of the Korean Society of Radiology
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    • v.9 no.1
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    • pp.39-45
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    • 2015
  • $La_2W_3O_{12}:Eu^{3+}$ phosphors were prepared by solid state reaction method. The crystal structure was characterized by XRD pattern and ICSD card (78180). Luminescence properties of $La_2W_3O_{12}:Eu^{3+}$ are investigated by optical and laser-excitation spectroscopy in which emission and excitation spectra and time-resolved spectra are measured. The 1 mol % $Eu^{3+}$-doped $La_2W_3O_{12}$ phosphor exhibits broad excitation band peaking at 286 nm due to the ligand-to-metal charge transfer transition. The excitation lines due to the $^7F_0{\rightarrow}{^5D_4},{^5D_4},{^5L_6},{^5G_4},{^5D_3},{^5D_2}$ transitions of $Eu^{3+}$ are observed in the wavelength region 350-500 nm. The strong line emission is observed at 618 nm corresponding to the due to the $^5D_0{\rightarrow}^7F_2$ transition. The lifetime of 618 nm emission decreases with increasing temperature as 7 K ($114{\mu}s$), 100 K ($94{\mu}s$), 200 K ($10{\mu}s$) and 300 K ($0.5{\mu}s$).

A study on the Optimization of Activated carbon Adsorbent Preparation condition and Evaluation of Application Supporting of K-Fe-Li ternary metal ions for Improving Adsorption Capacity of Hydrogen Sulfide (H2S) (황화수소(H2S) 흡착성능 증진을 위한 K-Fe-Li 3원계 금속이온물질이 담지된 활성탄 흡착제 제조조건 최적화 및 적용성 평가 연구)

  • Choi, Sung Yeol;Han, Dong hee;Kim, Sung Su
    • Clean Technology
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    • v.25 no.3
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    • pp.189-197
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    • 2019
  • In this study an optimization of the preparation conditions of activated carbon with a ternary metal ion material to treat $H_2S$, which is classified as a representative odor substance, was carried out. For a metal ion material for enhancing the adsorption performance of hydrogen sulfide, performance enhancement was confirmed by combining Li and Fe or a ternary combination (K, Li, Fe) based on KI, which is a substance promoting hydrogen sulfide adsorption performance. Also, it was determined by XRD analysis that the reaction of each active substance with $H_2S$ was because of binding. The adsorption performance increased more than 3 times with heat treatment of the adsorbent with nitrogen compared with heat treatment with air. The maximum adsorption constant ($q_m$) value of the optimum adsorbent was 97.07, which is 6 times higher than that of the existing K-based impregnated activated carbon. It was confirmed that the objective adsorption amount ($0.3g\;g^{-1}$) was secured by an equilibrium between the mass transfer rate and adsorption rate. From the results, it was confirmed that the performance improvement was noticeable even when activated carbon with a reagent grade activated carbon particle size was modified. It was confirmed that the adsorption performance exists at high relative humidity levels of 60 and 100%, and the optimized preparation can be applied to a wet process such as a scrubber downstream.

A Study for Kinetics and Oxidation Reaction of Alcohols using (C10H8N2H)2Cr2O7 ((C10H8N2H)2Cr2O7를 이용한 알코올들의 산화반응과 반응속도에 관한 연구)

  • Park, Young-Cho;Kim, Soo-Jong
    • The Journal of the Convergence on Culture Technology
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    • v.8 no.6
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    • pp.927-933
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    • 2022
  • We synthesized (C10H8N2H)2Cr2O7, The structure of the product was characterized with FT-IR(infrared) and elemental analysis. The oxidation of benzyl alcohol by (C10H8N2H)2Cr2O7 in organic solvents showed that the reactivity increased with the increase of the dielectric constant. The oxidation of alcohols was examined by (C10H8N2H)2Cr2O7 in DMF, acetone. As a resuit, (C10H8N2H)2Cr2O7 was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones(65%~95%). The selective oxidation of alcohols was also examined by (C10H8N2H)2Cr2O7 in DMF, acetone. (C10H8N2H)2Cr2O7 was selective oxidizing agent(15%~95%) of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary ones. In the presence of DMF solvent with acidic catalyst such as H2SO4. (C10H8N2H)2Cr2O7 oxidized benzyl alcohol(H) and its derivatives. The Hammett reaction constant(ρ) was -0.69(308K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

Effect of Cathode Porosity on the Cathodic Polarization Behavior of Mixed Conducting LSCF(La0.6Sr0.4Co0.2Fe0.8O3) (혼합전도체 LSCF(La0.6Sr0.4Co0.2Fe0.8O3) 양극의 기공률에 따른 양극분극 특성)

  • Yun, Joong-Cheul;Lee, Jong-Ho;Kim, Joosun;Lee, Hae-Weon;Kim, Byong-Ho
    • Journal of the Korean Ceramic Society
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    • v.42 no.4
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    • pp.251-259
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    • 2005
  • In order to characterize the influence of the reaction-site density on the cathodic polarization property of LSCF, we chose the porosity of LSCF as a main controlling variable, which is supposed to be closely related with active sites for the cathode reaction. To control the porosity of cathodes, we changed the mixing ratio of fine and coarse LSCF powders. The porosity and pore perimeter of cathodes were quantitatively analyzed by image analysis. The electrochemical half cell test for the cathodic polarization was performed via 3-probe AC-impedance spectroscopy. According to the investigation, the reduction of oxygen at LSCF cathode was mainly controlled by following two rate determining steps; i) surface diffusion and/or ionic conduction of ionized oxygen through bulk LSCF phase, ii) charge transfer of oxygen ion at cathode/electrolyte interface. Moreover, the overall cathode polarization was diminished as the cathode porosity increased due to the increase of the active reaction sites in cathode layer.