1999 Fiscal Year Annual Research Report

超臨界二酸化炭素中の状態分析・解析システムの開発

Research Project

Project/Area Number	11354009
Research Category	Grant-in-Aid for Scientific Research (A)
Research Institution	Nagoya University
Principal Investigator	舟橋重信名古屋大学, 大学院・理学研究科, 教授 (30022700)
Co-Investigator(Kenkyū-buntansha)	長村俊彦株式会社ユニソク, 科学機器開発研究所, 主任研究員稲田康宏名古屋大学, 物資科学国際研究センター, 助手 (60242814)
Keywords	超臨界二酸化炭素 / 状態分析 / 動態解析 / 可視紫外分光法 / 赤外吸収分光法 / NMR法 / ESR法 / 水 / 超臨界二酸化炭素二相分配
Research Abstract	本研究は、超臨界二酸化炭素中の金属錯体などの状態分析や動態解析の方法論の開発を行い、超臨界二酸化炭素中で進行する化学反応の平衡や速度を測定し、金属錯体などの溶存状態の分子論的解明を目的とした。まず、可視・紫外吸収および赤外吸収スペクトルが測定可能なセルユニットを設計・開発し、それらを接続して試料溶液を循環するための送液ポンプの開発に着手した。また、これらのセルユニットを用いて、種々のβ-ジケトナト配位子を有する各種金属錯体の吸収スペクトルや溶解度の測定を行った。さらに、2つの超臨界溶液を温度と圧力を保持したまま迅速に混合し、超臨界流体中で進行する化学反応を追跡することが可能なストップトフロー装置を世界で初めて開発し、それを用いて金属ポルフィリン錯体生成反応の速度論的研究を行った。また、超臨界二酸化炭素中に溶解した化学種のNMRおよびESRスペクトル測定が可能な、ジルコニアおよび石英製肉厚キャピラリー試料管の設計に着手した。さらに、水相および超臨界二酸化炭素相の両方を同時に観測することが可能な水/超臨界二酸化炭素二相分配セルを開発し、超臨界流体抽出のメカニズム解明に着手した。本研究で本年度に開発した各種超臨界二酸化炭素用観測セルは、従来の溶液がフローしているライン中に取り込むためのものではなく、いずれも単独で、もしくは、直列に接続して、閉じた流路内に配置するように設計している。これにより、従来の観測セルでは困難であった溶質の濃度を関数としたスペクトル変化の厳密な測定ができるようになり、化学種単位での状態分析や動態解析が可能になった。

Research Products
(15 results)

All Other

All Publications (15 results)

[Publications] Y.Inada,Y.Itoh,S.Funahashi: "Mechanistic Studies on Solvent Exchange of Tetrahedrally Solvated Cobalt(II) Ion in 1,1,3,3-Tetramethylurea as a Bulky Solvent"Inorganic Reaction Mechanism. (in press). (2000)
[Publications] Y.Inada,S.Funahashi: "Equilibrium and Structural Study of Complexation of Iron(III)Ion with Chloride in Acidic Aqueous Solution by Means of X-Ray Absorption Spectroscopy"Zeitschrift fuir Naturforschung B. (in press). (2000)
[Publications] M.Matsumoto,H.Kodama,S.Funahashi,and H.D.Takagi: "Reduction and Oxidation Reactions of Tetrakis(acetylacetonato)cerium(IV)and -(III)Complexes in Acetonitrile: Change in the Reaction Pathways with the Driving Force of the Reaction"Inorganic Reaction Mechanism. (in press). (2000)
[Publications] N.Koshino,Y.Kuchiyama,H.D.Takagi,and S.Funahashi: "Outer-Sphere Electron Transfer Reactions of Bis(2,9-dialkyl-1,10-phenanthroline)copper(II/I) in Acetonitrile: Alkyl=Methyl and Phenyl"Inorganic Reaction Mechanism. (in press). (2000)
[Publications] Y.Inada,H.Hayashi,K.Sugimoto,S.Funahashi: "Solvation Structures of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Ga(III) Ions in Methanol, Ethanol, Dimethyl Sulfoxide, and Trimethylphosphate"The Journal of Physical Chemistry. 103・10. 1401-1406 (1999)
[Publications] N.Koshino,Y.Kuchiyama,H.Ozaki,S.Funahashi,and H.D.Takagi: "An Interpretation of Gated Behavior: Kinetic Studies of the Oxidation and Reduction Reactions of Bis(2,9-dimethyl-1,10-phenanthroline)copper(I/II) in Acetonitrile"Inorganic Chemistry. 38・14. 3352-3360 (1999)
[Publications] M.Matsumoto,M.Itoh,S.Funahashi,and H.D.Takagi: "Electron Transfer Reactions of Bis(1,4,7-trithiacyclononane)palladium(III/II), -Platinum(III/II), and-gold(III/II) Complexes in Aqueous Solution and in Acetonitrile"Canadian Journal of Chemistry. 77. 1638-1647 (1999)
[Publications] N.Koshino,Y.Kuchiyama,S.Funahashi,and H.D.Takagi: "Electron Self-Exchange, Oxidation, and Reduction Reactions of Bis(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)copper(II/I) and Bis(6,6'-dimethyl-2,2'-bipyridine)copper(II/I) Couples in Acetonitrile"Canadian Journal of Chemistry. 77. 1498-1507 (1999)
[Publications] M.Matsumoto,S.Funahashi,and H.D.Takagi: "Electrochemical Electron Transfer reactions of M(ttcn)_2^<3+/2+> (M=Co,Pd,Pt,Au; ttcn =1,4,7-trithiacyclononane): the Relation of Reaction Volumes and Electron Transfer Rate Constants"Zeitschrift fuir Naturforschung B. 54. 1138-1146 (1999)
[Publications] Y.Tsutsui,H.Wasada,and S.Funahashi: "Reaction Mechanism of Water Exchange on Di-and Trivalent Cations of the First Transition Series and Structural Stability of Seven-Coordinate Species"Journal of Molecular Structure(Theoretical Chemistry). 461-462. 379-390 (1999)
[Publications] Y.Inada,Y.Tsutsui,H.Wasada,S.Funahashi: "Solvation Structure of Copper(I)Ion in Nonaqueous Solvents As Studied by EXAFS and ab Initio Molecular Orbital Methods"Zeitschrift fuir Naturforschung B. 54・2. 193-199 (1999)
[Publications] N.Koshino,Y.Kuchiyama,S.Funahashi,and H.D.Takagi: "Free Energy Barrier of Gated Electron Transfer Reactions: Reduction and Oxidation Reactions of Cu(6,6'-dimethyl-2,2'-bipyridine)_2^<2+/+> with Ru(hexafluoroacetylacetone)_3^<0/->"Chemical Physics Letters. 306. 291-296 (1999)
[Publications] H.D.Takagi,A.Takahashi,S.Iwatsuki、H.Hayashi,S.Funahashi,and K.Ogiyama: "An Investigation of the Photodegradation of Tetraphenyltin(IV)in THF"Phosphorus,Sulfur and Silicon. 150-151. 245-250 (1999)
[Publications] Y.Kanekiyo,S.Aizawa,N.Koshino,and S.Funahashi: "Complexation Equilibria of Oxy-acid-2-Amino-2-deoxy-D-gluconic acid-Metal Ion Ternary Systems in Aqueous Solution As Studied by Potentiometry. Binding Characteristics of Borate and Germanate"Inorganic Chimica Acta. 298/2. 154-164 (1999)
[Publications] 舟橋重信: "大学院錯体化学"講談社サイエンティフィク(印刷中). (2000)

1999 Fiscal Year Annual Research Report

超臨界二酸化炭素中の状態分析・解析システムの開発

Principal Investigator

舟橋 重信 名古屋大学, 大学院・理学研究科, 教授 (30022700)

Research Products

[Publications] Y.Inada,Y.Itoh,S.Funahashi: "Mechanistic Studies on Solvent Exchange of Tetrahedrally Solvated Cobalt(II) Ion in 1,1,3,3-Tetramethylurea as a Bulky Solvent"Inorganic Reaction Mechanism. (in press). (2000)

[Publications] Y.Inada,S.Funahashi: "Equilibrium and Structural Study of Complexation of Iron(III)Ion with Chloride in Acidic Aqueous Solution by Means of X-Ray Absorption Spectroscopy"Zeitschrift fuir Naturforschung B. (in press). (2000)

[Publications] M.Matsumoto,H.Kodama,S.Funahashi,and H.D.Takagi: "Reduction and Oxidation Reactions of Tetrakis(acetylacetonato)cerium(IV)and -(III)Complexes in Acetonitrile: Change in the Reaction Pathways with the Driving Force of the Reaction"Inorganic Reaction Mechanism. (in press). (2000)

[Publications] N.Koshino,Y.Kuchiyama,H.D.Takagi,and S.Funahashi: "Outer-Sphere Electron Transfer Reactions of Bis(2,9-dialkyl-1,10-phenanthroline)copper(II/I) in Acetonitrile: Alkyl=Methyl and Phenyl"Inorganic Reaction Mechanism. (in press). (2000)

[Publications] Y.Inada,H.Hayashi,K.Sugimoto,S.Funahashi: "Solvation Structures of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Ga(III) Ions in Methanol, Ethanol, Dimethyl Sulfoxide, and Trimethylphosphate"The Journal of Physical Chemistry. 103・10. 1401-1406 (1999)

[Publications] N.Koshino,Y.Kuchiyama,H.Ozaki,S.Funahashi,and H.D.Takagi: "An Interpretation of Gated Behavior: Kinetic Studies of the Oxidation and Reduction Reactions of Bis(2,9-dimethyl-1,10-phenanthroline)copper(I/II) in Acetonitrile"Inorganic Chemistry. 38・14. 3352-3360 (1999)

[Publications] M.Matsumoto,M.Itoh,S.Funahashi,and H.D.Takagi: "Electron Transfer Reactions of Bis(1,4,7-trithiacyclononane)palladium(III/II), -Platinum(III/II), and-gold(III/II) Complexes in Aqueous Solution and in Acetonitrile"Canadian Journal of Chemistry. 77. 1638-1647 (1999)

[Publications] M.Matsumoto,S.Funahashi,and H.D.Takagi: "Electrochemical Electron Transfer reactions of M(ttcn)_2^<3+/2+> (M=Co,Pd,Pt,Au; ttcn =1,4,7-trithiacyclononane): the Relation of Reaction Volumes and Electron Transfer Rate Constants"Zeitschrift fuir Naturforschung B. 54. 1138-1146 (1999)

[Publications] Y.Tsutsui,H.Wasada,and S.Funahashi: "Reaction Mechanism of Water Exchange on Di-and Trivalent Cations of the First Transition Series and Structural Stability of Seven-Coordinate Species"Journal of Molecular Structure(Theoretical Chemistry). 461-462. 379-390 (1999)

[Publications] Y.Inada,Y.Tsutsui,H.Wasada,S.Funahashi: "Solvation Structure of Copper(I)Ion in Nonaqueous Solvents As Studied by EXAFS and ab Initio Molecular Orbital Methods"Zeitschrift fuir Naturforschung B. 54・2. 193-199 (1999)

[Publications] N.Koshino,Y.Kuchiyama,S.Funahashi,and H.D.Takagi: "Free Energy Barrier of Gated Electron Transfer Reactions: Reduction and Oxidation Reactions of Cu(6,6'-dimethyl-2,2'-bipyridine)_2^<2+/+> with Ru(hexafluoroacetylacetone)_3^<0/->"Chemical Physics Letters. 306. 291-296 (1999)

[Publications] H.D.Takagi,A.Takahashi,S.Iwatsuki、H.Hayashi,S.Funahashi,and K.Ogiyama: "An Investigation of the Photodegradation of Tetraphenyltin(IV)in THF"Phosphorus,Sulfur and Silicon. 150-151. 245-250 (1999)

[Publications] Y.Kanekiyo,S.Aizawa,N.Koshino,and S.Funahashi: "Complexation Equilibria of Oxy-acid-2-Amino-2-deoxy-D-gluconic acid-Metal Ion Ternary Systems in Aqueous Solution As Studied by Potentiometry. Binding Characteristics of Borate and Germanate"Inorganic Chimica Acta. 298/2. 154-164 (1999)

[Publications] 舟橋重信: "大学院錯体化学"講談社サイエンティフィク(印刷中). (2000)

舟橋重信名古屋大学, 大学院・理学研究科, 教授 (30022700)