A kinetic study of poly(acrylic acid)-copper(II) interactions in aqueous solutions.
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概要
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Concentration-jump kinetic studies of the aqueous poly(acrylic acid)–copper(II) system reveal the presence of a relaxation phenomenon in the time range of 10<SUP>2</SUP> ms. Kinetic data under various pH's and compositions, together with the potentiometric results, indicate that this relaxation effect is due to the following complex-formation reaction:<BR>CuL<SUB>2</SUB>+L<SUB>2</SUB><SUP>2−</SUP>\overset<I>k</I><SUB>2</SUB>\underset<I>k</I><SUB>−2</SUB>\rightleftharpoonsCu(L<SUB>2</SUB>)<SUB>2</SUB><SUP>2−</SUP>,<BR>where L<SUB>2</SUB><SUP>2−</SUP> is a coordination unit consisting of two adjacent carboxylato side groups on the polymer chain. The specific features of the pH dependence of the τ<SUP>−1</SUP> value are discussed in relation to the degree of dissociation of the carboxyl groups. The rate and stability constants of the reaction are determined to be: <I>k</I><SUB>2</SUB>=5.6×10<SUP>3</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP> (1 M=1 mol dm<SUP>−3</SUP>), <I>k</I><SUB>−2</SUB>=0.7 s<SUP>−1</SUP>, and <I>K</I><SUB>2</SUB> (=<I>k</I><SUB>2</SUB>⁄<I>k</I><SUB>−2</SUB>)=7.9×10<SUP>3</SUP>, at pH 7.0, <I>I</I>≈0, and 25 °C. The overall complex-formation mechanism, involving the very rapid formation of CuL<SUB>2</SUB>, is discussed.
- 公益社団法人 日本化学会の論文
著者
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Harada Shoji
Department Mechanical Engineering Kyushu Institute Of Technology
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Tamura Kiyoshi
Department Of Cardiovascular Surgery Musashino Red Cross Hospital
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Yasunaga Tatsuya
Department of Chemistry, Faculty of Science, Hiroshima University
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Yamada Ryuichi
Department of Chemistry, National Defense Academy
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