• 제목/요약/키워드: chloride reduction

검색결과 477건 처리시간 0.024초

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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    • 제35권2호
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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

  • 김우성;정광일;김신국;전성원;김연희;성용은;최용국
    • Bulletin of the Korean Chemical Society
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    • 제21권6호
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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.

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

  • 최혁순
    • 한국지하수토양환경학회지:지하수토양환경
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    • 제14권6호
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    • pp.29-34
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    • 2009
  • 본 연구에서는 질산염(${NO_3}^-$)과 용존산소(DO)에 의한 생물학적 퍼클로레이트 환원의 저해 그리고 전자공여체를 차지하기 위한 이러한 전자수용체들의 경쟁적 관계를 조사하고자 염소이온프로브(chloride ion probe)를 직접적인 측정방법으로 사용하였다. 퍼클로레이트 환원미생물을 포함하는 플라스크에서 염소이온프로브를 이용하여 염소생성 (=퍼클로레이트 환원)을 모니터링하였다. 2 mM 퍼클로레이트의 생물학적 환원은 2 mM의 질산염에 의해 저해를 받았으며, 염소이온 생성율이 퍼클로레이트가 단독으로 존재하는 경우에 비해 30% 정도 감소하였고, 아세테이트가 제한된 상태이며 질산염과 퍼클로레이트가 공존하는 경우는 염소이온의 생성율이 약 70% 정도 감소하였다. 7-8 mg/L의 용존산소와 2 mM의 퍼클로레이트가 공존하는 조건에서 아세테이트의 공급정도와 상관없이 퍼클로레이트의 생물학적 환원작용이 완벽하게 저해를 받았다.

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

  • 신기돈;고산;이건철
    • 한국건축시공학회:학술대회논문집
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    • 한국건축시공학회 2017년도 추계 학술논문 발표대회
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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)

  • 신미숙;김우성;조기형;최용국
    • Bulletin of the Korean Chemical Society
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    • 제16권3호
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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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    • 제17권3호
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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.

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

  • 전상훈
    • Journal of Chest Surgery
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    • 제21권2호
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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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    • 제31권10호
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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.

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

  • 김우성;최용국;김찬영;조기형;김종순
    • 대한화학회지
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    • 제37권8호
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    • pp.702-710
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    • 1993
  • 이핵성 네자리 schiff base Co(II), Ni(II), Cu(II) alc Fe(II) 착물들을 촉매로 사용하여 몰리브데늄 전극과 유리질 탄소 전극에서 SOCl2의 전기화학적 환원반응을 조사하였다. 이들 전이금속(II) 착물들은 먼저 전극 표면에 흡착된 후 촉매로 작용하였으며, 각각의 전이금속(II) 착물들의 촉매 화합물은 SOCl$_2$ 를 환원시킬 수 있는 최적 조건의 농도를 나타냈다. SOCl$_2$의 환원반응에 대한 촉매 효과는 몰리브데늄 전극에서보다 유리질 탄소전극에서 더 크게 나타났고, 환원 전류는 최고 120% 정도 증가하였다. 주사속도 증가에 따른 SOCl$_2$의 환원 전류는 증가하였고 환원 전위는 음전위쪽으로 이동되었으며, SOCl$_2$의 환원과정은 확산지배적인 반응으로 진행되었다.

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

  • 윤지희;권현우;유연태;김병규;김광수
    • 한국재료학회지
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    • 제15권4호
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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 $Na_4P_2O_7{\cdot}10H_2O$.