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レーザー捕捉-分光-電気化学法による微小油滴/水界面物質移動過程の解析と制御

Research Project

Project/Area Number 13129202
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionUniversity of Tsukuba

Principal Investigator

中谷 清治  筑波大学, 化学系, 助教授 (00250415)

Co-Investigator(Kenkyū-buntansha) 大堺 利行  神戸大学, 理学部, 助教授 (00194118)
渡辺 寿雄  筑波大学, 化学系, 助手 (40323266)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥30,500,000 (Direct Cost: ¥30,500,000)
Fiscal Year 2003: ¥4,900,000 (Direct Cost: ¥4,900,000)
Fiscal Year 2002: ¥10,000,000 (Direct Cost: ¥10,000,000)
Fiscal Year 2001: ¥15,600,000 (Direct Cost: ¥15,600,000)
Keywords油水界面 / 液滴 / 物質移動 / 電子移動 / イオン対抽出 / 油 / 水界面 / レーザー捕捉 / 顕微分光 / 油滴 / 電荷移動
Research Abstract

レーザー捕捉-分光-電気化学装置を用いて,イオン対抽出過程のメカニズムを単一微小油滴/水系で直接測定から明らかにした。(フェロセニルメチル)トリメチルアンモニウムイオン(FcN^+)とアルキル硫酸イオン(AS^-)のイオン対抽出速度測定から,アルキル鎖長(n=11,12,13)で特徴的な挙動が観測された。n=11では抽出過程は両相で電気的中性を満たすようにFcN^+とAS^-の個々のイオン移動が進み,その律速段階偉AS^-の移動であることがわかった。n=12,13では界面に吸着したAS^-とFcN^+が電気的に中性となり,油滴中に抽出されることがわかった。また,メロシアニン540(MC^-)と有機スズ化合物(OTC^+,トリブチルスズなど)のイオン対抽出過程をNaCl存在下で検討したところ,MC^-はCl^-よりも疎水的であるが油/水界面に吸着するため,OTC^+はCl^-と抽出された後、油滴中のCl^-と界面吸着したMC^-がゆっくりと交換されることが明らかとなった。本手法を用いて種々のイオン対抽出過程の速度論的議論が可能となった。
油/水界面電子移動過程のガルバニ電位差・自由エネルギー変化(ΔG)依存性を単一微小水滴/油系で行った。電位差決定イオンとして,テトラアルキルアンモニウムイオンを用いることで赤血塩とデカメチルフェロセン,ジメチルフェロセンの組合せでΔGを0〜-40kJ/mol変化させ解析したところ,液液界面電子移動に対するマーカス理論のみでは説明できないことがわかった。ΔG<-10kJ/molでは油相中におけるフェロセン誘導体の拡散が律速となり,スモルコフスキー式を液液界面系に応用したモデルで解析できた。単一水滴系では,同一のレドックス種の組合せで界面電子移動過程を解析できるので,溶媒の再配向パラメータ等の詳細な議論が可能になると考えられる。

Report

(3 results)
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] T.Negishi, K.Nakatani: "A Mechanistic Study on Ion Pair Extraction using Single Microdroplet Injection and Microelectrochemical Techniques"Phys.Chem.Chem.Phys.. 5(3). 594-598 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Chikama, T.Negishi, K.Nakatani: "Transfer Mechanism of Dodecyl Sulfate with Methylene Blue Across an Oil/Water Interface Studied by Single Droplet Injection and Microabsorption Methods"Bull.Chem.Soc.Jpn.. 76(2). 295-299 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Nakatani, J.Yamashita, T.Sekine, M.Toriumi, T.Itani: "A Nonaqueous Potentiometric Titration Study of the Dissociation of t-Butyl Methacrylate-Methacrylic Acid Copolymers"Anal.Sci.. 19. 775-777 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Nakatani, H.Kakizaki: "Analysis of Sorption into Single ODS-Silica Gel Microparticles in Acetonitrile-Water"Anal.Sci.. 19. 1211-1213 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Nakatani, T.Negishi: "Mass Transfer and Reaction Rate in the Nano-Region of Microdroplet/Solution Interfaces"Interfacial Nanochemistry, Kluwer Academic. (印刷中). chapter9 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Nakatani, T.Noguchi, T.Negishi: "Single Microdroplet/Water Extraction and In Situ Microanalysis by Microcapillary Injection and Differential Pulse Voltammetry"Anal.Sci.. 18. 533-536 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Negishi, K.Nakatani: "A Mechanistic Study on Ion Pair Extraction using Single Microdroplet Injection and Microelectrochemical Techniques"Phys.Chem.Chem.Phys.. 5. 594-598 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Chikama, T.Negishi, K.Nakatani: "Transfer Mechanism of Dodecyl Sulfate with Methylene Blue Across an Oil/Water Interface Studied by Single Drolet Injection and Microabsorption Methods"Bull.Chem.Soc.Jpn.. 76. 295-299 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Nakatani, T.Sekine, T.Negishi: "Microanalysis of Mass Transfer Processes on a Single Particle"Encyclopedia of Surface and Colloid Science, Marcel Dekker. 3. 3391-3401 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Hotta, N.Akagi, T.Sugihara, S.Ichikawa, T.Osakai: "Electron-Conductor Separating Oil-Water (ECSOW) System : a New Strategy for Characterizing Electron Transfer Processes at the Oil/Water Interface"Electrochem.Commun.. 4. 472-477 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Sawada, M.Taguma, T.Kimoto, H.Hotta, T.Osakai: "Complete Electrolysis Using a Microflow Cell with an Oil/Water Interface"Anal.Chem.. 74. 1177-1181 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Nakatani, T.Negishi: "Kinetic Analysis of Fast Mass Transfer across Oil/Water Interface using Single Microdroplet Injection and Potential Sten Electrolysis"Anal. Sci.. 17. 1109-1111 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 中谷 清治, 根岸 貴幸: "単一液滴の電気化学計測による油/水界面物質移動過程の解析"Rev. Polarogr.. 47. 88-97 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Nakatani, H.Nagatani, D.J.Fermin, H.H.Girault: "Transfer and Adsorption of 1-Pyrene Sulfonate across the Water/1,2-Dichloroethane Interface Studied by Potential Modulated Fluorescence Spectroscopy"J. Electroanal. Chem.. 518. 1-5 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Sekine, K.Nakatani: "Intraparticle Diffusion and Adsorption Isotherm for Sorption in Silica Gel Studied by Singl Microparticle Injection and Microabsorption Methods"Langmuir. 18. 694-697 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Nakatani, T.Sekine, T.Negishi: "Microanalysis of Mass Transfer Processes on a Single Particle"Encyclopedia of Surface and Colloid Science. (印刷中). (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2018-03-28  

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