• Title/Summary/Keyword: chloride reduction

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MPV-Reduction of C=O bond with Al-substituted-dialkylalan; A Theoretical Study on Relative Reactivity of Various Carbonyl Substrates

  • Nahm, Keepyung
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.546-550
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    • 2014
  • Relative reactivity of various carbonyl and acid derivatives in MPV-type (Meerwein-Ponndorf-Verley) reduction with an DIBAL(F) model has been studied via DFT and MP2 methods. Free energies of initial adduct formation (-Gadd) of DIBAL(F) model and carbonyls are in the order of amide < ester < aldehyde < ketone < acid chloride; in the alan-amide adduct, the developed positive charge at carbonyl carbon is expected to be stabilized by amide resonance, but in the acid chloride adduct it is destabilized by inductive effect of chloride. However the TS barrier energies (${\Delta}G_{TS}$) for the MPV-type hydride reduction of the carbonyl adducts are in the order of aldehyde < ketone < acid chloride << ester < amide; presumably decreasing order of electrophilicity of carbonyl carbon at adducts, which is well correlated with experimental data. It is noted that the relative reactivity of carbonyl derivatives in MPV-type reduction with DIBAL(X) is not governed by the alan-adduct formation energies, but follows the order of electrophilicity of carbonyl carbon of transition states.

Electrocatalytic Effects for the Reduction of Thionyl Chloride in $Li/SOCl_2$ Cell Containing Schiff Base Metal(II) Complexes

  • Kim, Woo-Seong;Chung, Kwang-Il;Kim, Shin-Kook;Jeon, Seung-Won;Kim, Yeon-Hee;Sung, Yung-Eun;Choi, Yong-Kook
    • Bulletin of the Korean Chemical Society
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    • v.21 no.6
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    • pp.571-576
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    • 2000
  • Electrocatalytic effects for the reduction of thionyl chloride in $LiAICI_4/SOCl_2$ electrolyte solution containing Schiff base M(II) (M; Co and Fe) complexes are evaluated by determining kinetic parameters with cyclic voltammetry and chronoamperometry at a glassy carbon electrode. The charge transfer process during the reduction of thionyl chloride is affected by the concentration of the catalyst. The catalytic effects are demonstrated from both a shift of the reduction potential for the thionyl chloride toward a more positive direction and an increase in peak currents. Catalytic effects are larger in thionyl chloride solutions containing the binuclear [M(II) $_2$ (TSBP)] complex rather than mononuclear [M(II)(BSDT)] complexes. Significant improvements in the cell performance have been noted in terms of both thermodynamics and activation energy for the thionyl chloride reduction. The activation energy calculated from the Arrhenius plots is 4.5-5.9 kcal/mole at bare glassy carbon electrodes. The activation energy calculated for the catalyst containing solution is 3.3-4.9 kcalmole, depending on whether the temperature is lowered or rasied.

Inhibition of Biological Perchlorate Reduction by Nitrate and Oxygen (질산염과 산소에 의한 생물학적 퍼클로레이트 환원의 저해)

  • Choi, Hyeok-Sun
    • Journal of Soil and Groundwater Environment
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    • v.14 no.6
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    • pp.29-34
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    • 2009
  • In this study, a chloride ion probe as a direct measurement for perchlorate reduction was used to determine whether biological perchlorate reduction was inhibited by other electron acceptors ($O_2$ and ${NO_3}^-$) and to investigate competition of electron acceptors for using electron donors. Profiles of chloride production (= perchlorate reduction) in flasks containing perchlorate reducing populations were monitored by a chloride ion probe. Biological reduction of 2 mM perchlorate was inhibited by 2 mM nitrate that chloride production rate was decreased by 30% compared to perchlorate used as the only electron acceptor and chloride production rate was decreased by 70% when acetate was limited. Reduction of 2mM perchlorate was completely inhibited by oxygen at 7~8 mg/L, regardless of acetate excess / limitation.

Study on the Reactivity of Sodium Phosphate Ammonium Chloride pH Reduction Agents (인산나트륨계 염화암모늄 pH저감제의 반응성 검토)

  • Shin, Ki-Don;Gao, San;Lee, Gun-Cheol
    • Proceedings of the Korean Institute of Building Construction Conference
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    • 2017.11a
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    • pp.105-106
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    • 2017
  • Previous studies have confirmed the performance of pH reduction agents using liquid sodium phosphate based ammonium chloride as a pH reduction agent. In this study, the pH reduction performance considering economical and applicability as a practical stage and the property change analysis for the identification of the reaction mechanism of the pH reduction agent were carried out. As a result, the pH reduction performance at a low rate of the pH reducing agent was confirmed. The specific gravity of CaO decreased significantly after XRF analysis. It is also believed that this reduces the amount of Ca(OH)2 produced and contributes to pH reduction.

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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.

Changes of Total and Ionized Calcium following Cardiopulmonary Bypass (심폐관류에 따른 혈청칼슘의 변동)

  • 전상훈
    • Journal of Chest Surgery
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    • v.21 no.2
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    • pp.240-245
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    • 1988
  • This study was prospectively planned to realize the reduction of calcium ion in serum along with the cardiopulmonary bypass[CPB], to find out the cause of the reduction, and to verify the justification of the classical methods of calcium replacement. Nine patients with various open heart surgeries by CPB in 1987 wee selected at random. Calcium chloride was added as follows:: For each unit of ACD blood transfusion, 600mg of calcium chloride was added. In case of massive transfusion, 600 mg of calcium chloride was injected every 2 or 3 units of transfusion. On occasions such as weaning from CPB, or following defibrillation, or hypotension, weak myocardial contractility of the heart, calcium chloride was needed in an amount of 10 mg / kg. In ICU, calcium chloride was limited to use in low serum level or in emergency use. Total calcium decreased early bypass and progressively increased above the preoperative value during late bypass and three hours thereafter, Ionized calcium increased during late bypass and three hours following. Total and ionized calcium depicted similar patterns of change during open heart surgery. Decrease of the calcium at the early bypass was thought from reduction of total protein and alkalosis during bypass. Meanwhile, increase of both calciums during the end of surgery was presumably attributable to addition of calcium chloride in priming solution, injections of calcium chloride in the process of termination of bypass. We conclude that enough calcium was replaced by the classical methods of calcium supplement.

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Facile Synthesis of Silver Chloride Nanocubes and Their Derivatives

  • Kim, Seung-Wook;Chung, Haeg-Eun;Kwon, Jong-Hwa;Yoon, Ho-Gyu;Kim, Woong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2918-2922
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    • 2010
  • We demonstrate a facile route to synthesize silver chloride nanocubes and derivative nanomaterials. For the synthesis of silver chloride nanocubes, silver nitrate and hydrochloric acid were used as precursors in ethylene glycol, and poly (vinyl pyrrolidone) as a surfactant. Molar ratio of the two precursors greatly influenced the morphology and composition of the final products. As-synthesized silver chloride nanocubes showed size-dependent optical properties in the visible region of light, which is likely due to a small amount of silver clusters formed on the surface of silver chloride nanocubes. Moreover, we show for the first time that simple reduction of silver chloride nanocubes with different reducing reagents leads to the formation of delicate nanostructures such as cube-shaped silver-nanoparticle aggregates, and silver chloride nanocubes with truncated corners and with silver-nanograin decorated corners. Additionally, we quantitatively investigated for the first time the evolution of silver chloride nanocubes to silver chloride nanocubes decorated with silver nanoparticles upon exposure to e-beam. Our novel and facile synthesis of silver chloride related nanoparticles with delicately controlled morphologies could be an important basis for fabricating efficient photocatalysts and antibacterial materials.

Electrochemical Reduction of Thionyl Chloride by Tetradentate Schiff Base Transition Metal(II) Complexes : Catalytic Effects (네자리 Schiff Base 전이금속(II) 착물들에 의한 SOCl$_2$의 전기화학적 환원 : 촉매 효과)

  • Woo-Seong Kim;Yong-Kook Choi;Chan-Young Kim;Ki-Hyung Chjo;Jong-Soon Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.8
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    • pp.702-710
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    • 1993
  • Electrochemical reduction of thionyl chloride has been carried out at glassy carbon and molybdenum electrodes, the surface of which is modified by binuclear tetradentate schiff base Co(II), Ni(II),Cu(II) and Fe(II) complexes. The catalyst molecules of transition metal(II) complexes were adsorbed on the electrode surface and reduced thionyl chloride resulting in a generation of oxidized catalyst molecules. There was an optimum concentration for each catalyst compound. The catalytic effects of SOCl$_2$ reduction were larger on glassy carbon electrodes compared to molybdenum electrodes and enhancements in reduction current of up to 120${\%}$ at the glassy carbon electrodes. The reduction currents of thionyl chloride were increased and the reduction potentials were shifted to the negative potential when scan rates became faster. The reduction of thionyl chloride was proceed to diffusion controlled reaction.

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Synthesis of Uniform Cu Particles from Copper Chloride Solution (염화동 수용액으로부터 Cu 미립자의 합성)

  • Yoon Ji-hee;Kwon Hyun-Woo;Yu Yeon-tae;Kim Byoung-Gyu;Kim Gwang-soo
    • Korean Journal of Materials Research
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    • v.15 no.4
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    • pp.263-270
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    • 2005
  • In order to prepare the uniform copper particles from copper chloride solution, the reduction behavior of copper particles from copper chloride and the effects of reduction agent and dispersing agent was investigated. In the case that 2.56 M of $C_6H_8O_6$ was used as a reduction agent, the highly dispersed Cu particles with sharp size distribution were generated from 0.96M of copper chloride solution, and the size of Cu particles was $6\~10\;{\mu}m$. To form $Cu(NH_3)_4Cl_2$ complex solution, $NH_4OH$ was added in the copper chloride solution before the reductive reaction of Cu ion. The generated Cu particles have a two kind of shape, spherical and rod-like. In the case that $N_2H_4{\cdot}H_2O$ was used as a reduction agent, the very fine spherical Cu particles with the size of $0.2\~0.5\;{\mu}m$ was obtained. Arabic gum as a dispersing agent was more effective than $Na_4P_2O_7{\cdot}10H_2O$.