Formation of hydrogen peroxide by two-stage acid hydrolysis of trans(NO2,O2)-[.MU.-peroxo-bis{nitrtobis(ethylenediamine)-cobalt(III)}] and reaction kinetics.
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概要
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The aquation rate of <I>trans</I>(<I>NO</I><SUB>2</SUB>,<I>O</I><SUB>2</SUB>)-[(NO<SUB>2</SUB>)(en)<SUB>2</SUB>CoO<SUB>2</SUB>Co(en)<SUB>2</SUB>(NO<SUB>2</SUB>)]<SUP>2+</SUP> has been measured in acidic aqueous solution at [H<SUP>+</SUP>]=0.003–0.25 M and <I>I</I>=0.50 M (LiClO<SUB>4</SUB>), the final products being <I>trans</I>-[Co(NO<SUB>2</SUB>)(OH<SUB>2</SUB>)(en)<SUB>2</SUB>]<SUP>2+</SUP> and H<SUB>2</SUB>O<SUB>2</SUB> in marked contrast to the acid decomposition of [(NH<SUB>3</SUB>)<SUB>5</SUB>CoO<SUB>2</SUB>Co(NH<SUB>3</SUB>)<SUB>5</SUB>]<SUP>4+</SUP> where the final products are Co(II) and O<SUB>2</SUB>. The reaction consists of two stages, each of which has preequilibrium of protonation. The observed rate constants for the first and second stages are consistent with the formula, <I>k</I><SUB>1</SUB><SUP>obsd</SUP>=<I>k</I><SUB>1</SUB><I>K</I><SUB>1</SUB>[H<SUP>+</SUP>]⁄(1+<I>K</I><SUB>1</SUB>[H<SUP>+</SUP>]) (i=1, 2), indicating the existence of protonated reactive forms in both stages. The rate constants, activation parameters and equilibrium constants are <I>k</I><SUB>1</SUB>=7.46 s<SUP>−1</SUP> (25 °C), Δ<I>H</I><SUB>1</SUB><SUP>\neweq</SUP>=66.9±1.3 k J mol<SUP>−1</SUP>, Δ<I>S</I><SUB>1</SUB><SUP>\neweq</SUP>=−2.9±4.2 J K<SUP>−1</SUP>mol<SUP>−1</SUP>, and <I>K</I><SUB>1</SUB>=3.44 M<SUP>−1</SUP> (25 °C) for the first stage and <I>k</I><SUB>2</SUB>=0.400 s<SUP>−1</SUP> (25 °C), Δ<I>H</I><SUB>2</SUB><SUP>\neweq</SUP>=85.4±2.1 kJ mol<SUP>−1</SUP>, Δ<I>S</I><SUB>2</SUB><SUP>\neweq</SUP>=33.5±7.1 J K<SUP>−1</SUP> mol<SUP>−1</SUP>, and <I>K</I><SUB>2</SUB>=2.98 M<SUP>−1</SUP> (25 °C) for the second stage. The solution of the reaction intermediate [Co(NO<SUB>2</SUB>)(O<SUB>2</SUB>H)(en)<SUB>2</SUB>]<SUP>+</SUP> has been obtained by ion exchange technique and characterized by the UV and visible spectra. The factors which decide the reaction path are discussed.
- 公益社団法人 日本化学会の論文
著者
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SHIBAHARA Takashi
Department of Chemistry, Okayama University of Science
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Shibahara Takashi
Department Of Chemistry Faculty Of Science Okayama University Of Science
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Mori Masayasu
Department of Chemistry, Faculty of Science, Osaka City University
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Kuroya Hisao
Department of Chemistry, Okayama University of Science
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