| Project/Area Number |
62550587
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
工業物理化学
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| Research Institution | Kyoto University |
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Principal Investigator |
KATAGIRI Akira College of Liberal Arts, Kyoto University, 教養部, 助教授 (30026207)
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| Co-Investigator(Kenkyū-buntansha) |
MATSUBARA Takaharu College of Liberal Arts, Kyoto University, 教養部, 助手 (50026811)
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| Project Period (FY) |
1987 – 1988
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1988: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1987: ¥1,300,000 (Direct Cost: ¥1,300,000)
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| Keywords | binuclear copper complex / sulfite / dithionate / catalysis / 電解酸化 |
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| Research Abstract |
Copper ion is known as a catalyst in many chemical and electrochemical reactions. It is significant to elucidate the mechanism of such reactions because of the importance of their industrial applications. The present investigators have noticed a series of catalytic reactions which may involve binuclear copper complexes, and have particularly investigated the electro-oxidation of sulfite catalyzed by copper ion.
It was found that dithionate was formed almost selectively at the anode during electrolysis of a sulfite solution containing copper(I). UV-visible spectroelectrochemical measurements with an optically transparent electrode (OTE) and electrochemical measurements with a rotating ring-disk electrode revealed that a divalent copper species was formed as an intermediate. Steady-state current-potential relationship and the transient of absorbance at the OTE were consistent with the assumption that the decomposition of the copper(II) species is of the second order, suggesting the existence of a binuclear copper(II) complex in the reaction sequence. Potential step chronoamperometry gave the apparent formal potential of the Cu(II)/Cu(I) couple in sulfite solutions as well as the apparent rate constant of the decomposition of the intermediate copper(II)species, indicating that the binuclear copper(II) complex is hexasulfitodicuprate(II) ion with two bridging sulfite groups. binuclear complexes of this type may possibly be involved in similar reactions and some enzyme reactions. The technique employed in this work may also be applied to the investigation of other unstable metal complexes.
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