Polarographic Studies of the Rates of the Dissociation Reactions of Cobalt(II)-Iminodiacetate, -Aspartate, and -2,2′-Ethylenedioxydi(ethylamine)-<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetraacetate Complexes
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The cobalt(II)-IDA, -Asp, and -GEDTA complexes produce kinetic wave due to their dissociation preceding the electron-transfer step at the electrode surface. From an experimental examination of the nature of these kinetic waves, the dissociation mechanisms were determined to be:<BR>i) IDA and Asp systems,<BR>CoX<SUB>2</SUB><SUP>2−</SUP>\rightleftarrowsCoX<SUP>0</SUP>+X<SUP>2−</SUP> rate-determining step<BR>CoX<SUP>0</SUP>+2e<SUP>−</SUP>+Hg\rightleftarrowsCo(Hg)+X<SUP>2−</SUP><BR>ii) GEDTA system,<BR>CoY<SUB>2</SUB><SUP>6−</SUP>\rightleftarrowsCoY<SUP>2−</SUP>+Y<SUP>4−</SUP> in a rapid equilibrium<BR>CoY<SUP>2−</SUP>\rightleftarrowsCoY<SUP>2−*</SUP> rate-determining step<BR>CoY<SUP>2−*</SUP>+2e<SUP>−</SUP>+Hg\rightleftarrowsCo(Hg)+Y<SUP>4−</SUP><BR>where CoY<SUP>2−*</SUP> is the electroactive cobalt(II)-GEDTA complex produced upon the partial dissociation of the normal cobalt(II)-GEDTA complex with a 1 : 1 composition. From the relative rate constants for these complexes, the detailed structures of the reaction intermediates in their dissociation were also obtained.
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