Temperature-jump studies of the complex formation of nickel(II) L-glutamate in aqueous solutions.
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概要
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Temperature-jump relaxation studies have been carried out on aqueous nickel(II)–L-glutamic acid solutions. The observed relaxation phenomenon is ascribed to the successive complex formation reactions:<BR>Ni<SUP>2+</SUP>+L<SUP>2−</SUP> \overset<I>k</I><SUB>1</SUB>\underset<I>k</I><SUB>-1</SUB>\rightleftharpoons NiL,<BR>NiL+L<SUP>2−</SUP> \overset<I>k</I><SUB>2</SUB>\underset<I>k</I><SUB>-2</SUB>\rightleftharpoons NiL<SUB>2</SUB><SUP>2−</SUP>,<BR>NiL<SUB>2</SUB><SUP>2−</SUP>+L<SUP>2−</SUP> \overset<I>k</I><SUB>3</SUB>\underset<I>k</I><SUB>-3</SUB>\rightleftharpoons NiL<SUB>3</SUB><SUP>4−</SUP>,<BR>where L<SUP>2−</SUP> denotes a glutamate ion. The rate constants are: 2.0×10<SUP>4</SUP>, 1.1×10<SUP>4</SUP>, and 9.2×10<SUP>3</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP> (1 M=1 mol dm<SUP>−3</SUP>) for <I>k</I><SUB>1</SUB>, <I>k</I><SUB>2</SUB>, and <I>k</I><SUB>3</SUB>, and 0.048, 0.69, and 27 s<SUP>−1</SUP> for <I>k</I><SUB>−1</SUB>, <I>k</I><SUB>−2</SUB>, and <I>k</I><SUB>−3</SUB>, respectively, at 25 °C and <I>I</I>=0.1. The rate-determining step of the complex formation reactions, which follows the initial formation of ion-pairs, is the dissociation of a water molecule from the inner hydration sphere of the nickel; the glutamate ion acts as a bidentate ligand forming a five-membered chelate ring in the complexes.
- 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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Funaki Yoshinori
Department of Chemistry, Faculty of Science, Hiroshima University
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