Multidentate ligand kinetics. III. The ligand-substitution reaction between the ethylenediaminetetraacetatocuprate(II) ion and the tetraethylenepentaminezinc(II) ion.
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概要
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The kinetics and mechanism of the ligand-substitution reaction between the ethylenediaminetraacetatocuprate(II) ion (Cu(II)-edta) and the tetraethylenepentaminezinc(II) ion (Zn(II)-tetren) were studied spectrophotometrically over the pH range from 7.0 to 9.0 at <I>I</I>=0.2 M (1 M= mol dm<SUP>−3</SUP>) and 25.0 °C. The substitution reaction was shown to proceed by means of a chain-reaction mechanism where the chain-propagating steps are the reaction of Cu(II)-edta with tetren and the reaction of Zn(II)-tetren with edta. Each chain-propagating step was investigated. The ligand-substitution reaction of Zn(II)-tetren with edta was studied by the use of the chain reaction. The rate law is expressed as<BR>−\frac<I>d</I>[Zn(II)-tetren]<I>dt</I>=<I>k</I><SUB>L</SUB>[Zn(tetren)<SUP>2+</SUP>][edta<SUP>4−</SUP>]+<I>k</I><SUB>HL</SUB>[Zn(tetren)<SUP>2+</SUP>][Hedta<SUP>3−</SUP>]+<I>k</I>′<SUB>HL</SUB>[Zn(Htetren)<SUP>3+</SUP>][Hedta<SUP>3−</SUP>].<BR>The rate constants, <I>k</I><SUB>L</SUB>,<I>k</I><SUB>HL</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>≈3×10<SUP>2</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP>, <I>k</I><SUB>HL</SUB>=(4.1±0.7)×10<SUP>2</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP>, and <I>k</I>′<SUB>HL</SUB>=(1.7±0.2)×10<SUP>5</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP>.
- 公益社団法人 日本化学会の論文
著者
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Katsuyama Tetsuo
Department Of Chemistry And Chemical Engineering Faculty Of Engineering Yamagata University
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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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