Kinetics of the Ligand Substitution Reaction of the Cobalt(II)-(Ethylene glycol)bis(2-aminoethyl ether)-<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetraacetate Complex with 4-(2-Pyridylazo)resorcinol
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概要
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The kinetics of the ligand substitution reaction of the cobalt(II)-(ethylene glycol)bis(2-aminoethylether)-<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetraacetate complex (Co(II)-EGTA) with4-(2-pyridylazo)resorcinol (PAR) have been studied photometrically in the pH range 8–9.4 at an ionic strength of 0.1 and at 25°C. The reaction proceeds simultaneously through two different reaction paths. Thus the rate law can be written as<BR>\fracd[CoR_2^-]dt=k_1[CoY^2-][HR^-]+k_2[CoHY^-][HR^-] <BR>where Y<SUP>4−</SUP> and R<SUP>2−</SUP> refer to tetravalent EGTA and divalent PAR respectively. Rate constants, <I>k</I><SUB>1</SUB> and <I>k</I><SUB>2</SUB> are 3.2M<SUP>−1</SUP>sec<SUP>−1</SUP> and 2.1×10<SUP>4</SUP>M<SUP>−1</SUP>sec<SUP>−1</SUP>. Possible mechanism for the substitution is discussed. The stability constants for mercury(II)-EGTA complexes and cobalt(II)-EGTA complexes are determined by the mercury electrode method at μ=0.1 and 25°C in order to analyze the substitution reaction: <I>K</I><SUB>HgY</SUB>=10<SUP>23.86±0.10</SUP>, <I>k</I><SUB>HgHY</SUB><SUP>H</SUP>=10<SUP>3.06±0.10</SUP>, <I>K</I><SUB>CoY</SUB>=10<SUP>12.3±0.1</SUP>, <I>K</I><SUB>coHy</SUB><SUP>H</SUP>=10<SUP>4.9±0.1</SUP>, <I>K</I><SUB>CoH<SUB>2</SUB>Y</SUB><SUP>H</SUP>=10<SUP>3.3±0.3</SUP>.
- 公益社団法人 日本化学会の論文
著者
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Funahashi Shigenobu
Laboratory Of Analytical Chemistry Department Of Chemistry Faculty Of Science Nagoya University
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Tanaka Motoharu
Laboratory of Analytical Chemistry Faculty of Science Nagoya University
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