Bound-Ligand Effect in the Complexation Kinetics of Hydroxozirconium(IV) and Hydroxohafnium(IV) Complexes.

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  • YAMADA Shinkichi
    Laboratory of Analytical Chemistry, Faculty of Engineering, Shizuoka University
  • YAMAUCHI Ichirou
    Laboratory of Analytical Chemistry, Faculty of Engineering, Shizuoka University
  • MURATA Akira
    Laboratory of Analytical Chemistry, Faculty of Engineering, Shizuoka University

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The kinetics of the complexation reaction of zirconium(IV) and hafnium(IV) with Semixylenol Orange (H4L) have been studied spectrophotometrically by means of a stopped-flow technique. The rate of formation of the complex is expressed as d[MHL+]/dt=k1[M4+][H5L+][H+]-2+k2[M4+][H5L+][H+]-3-k3[MHL+][H+]-k4[MHL+][H+]2 for both metal ions (M4+). With values of k1 and k2, assuming a dissociative interchange mechanism for the first two reaction paths in this rate equation, the rate constants of the loss of coordinated water molecules at MOH3+ and M(OH)22+ were estimated. With these rate constants, the γ parameters for both metal ions, which describe the acceleration effect of the bound ligand A (A=OH- in this study) on the water exchange rate at MA, were also estimated. With the same parameter, some possibilities to design a new kinetic-catalytic method of analysis based on ligand-substitution reactions involving zirconium(IV) were proposed.

収録刊行物

  • Analytical Sciences

    Analytical Sciences 11 (6), 903-908, 1995

    社団法人 日本分析化学会

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