Multidentate ligand kinetics. II. The ligand substitution reactions of the triethylenetetraminecadmium(II) ion and the tetraethylenepentaminecadmium(II) ion with the ethylenediaminetetraacetatocuprate(II) ion.
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概要
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The kinetics and mechanism of the ligand-substitution reactions of triethylenetetraminecadmium(II) ion (Cd(II)-trien) and tetraethylenepentaminecadmium(II) ion (Cd(II)-tetren) with ethylenediaminetetraacetatocuprate(II) ion (Cu(II)-edta) were studied spectrophotometrically at <I>I</I>=0.2 M (1 M=1 mol dm<SUP>−3</SUP>) and at 25.0 °C. The ligand-substitution reactions were catalyzed by traces of either edta or the polyamine (triethylenetetramine and tetraethylenepentamine). The substitution reactions were shown to proceed by means of a chain reaction mechanism where the chain-propagating steps are the reactions of the metal complexes with the free ligands. Each chain-propagating step was investigated. The ligand-substitution reactions of Cd(II)-trien and Cd(II)-tetren with edta were studied by the use of the chain reactions in the pH range of 8.8–10.2. The rate law is expressed as: −d[CdR<SUP>2+</SUP>]/d<I>t</I>=<I>k</I><SUB>L</SUB>[CdR<SUP>2+</SUP>][edta<SUP>4−</SUP>]+<I>k</I><SUB>HL</SUB>[CdR<SUP>2+</SUP>][Hedta<SUP>3−</SUP>], where R refers to trien or tetren. The rate constants, <I>k</I><SUB>L</SUB> and <I>k</I><SUB>HL</SUB>, were determined at 25.0 °C and <I>I</I>=0.2 M as: <I>k</I><SUB>L</SUB>=(1.3±0.2)×10<SUP>6</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP> and <I>k</I><SUB>HL</SUB>=(6.5±1.5)×10<SUP>4</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP> for Cd(II)-trien, and <I>k</I><SUB>L</SUB>=(3.6±0.4)×10<SUP>5</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP> and <I>k</I><SUB>HL</SUB>=(1.0±0.2)×10<SUP>4</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP> for Cd(II)-tetren.
- 公益社団法人 日本化学会の論文
著者
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Kumai Toshihiko
Department of Basic Technology, Faculty of Engineering, Yamagata University
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Katsuyama Tetsuo
Department of Basic Technology, Faculty of Engineering, Yamagata University
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