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

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著者

    • 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

抄録

The kinetics of the complexation reaction of zirconium(IV) and hafnium(IV) with Semixylenol Orange (H<sub>4</sub>L) have been studied spectrophotometrically by means of a stopped-flow technique. The rate of formation of the complex is expressed as d[MHL<sup>+</sup>]/d<i>t</i>=<i>k</i><sub>1</sub>[M<sup>4+</sup>][H<sub>5</sub>L<sup>+</sup>][H<sup>+</sup>]<sup>-2</sup>+<i>k</i><sub>2</sub>[M<sup>4+</sup>][H<sub>5</sub>L<sup>+</sup>][H<sup>+</sup>]<sup>-3</sup>-<i>k</i><sub>3</sub>[MHL<sup>+</sup>][H<sup>+</sup>]-<i>k</i><sub>4</sub>[MHL<sup>+</sup>][H<sup>+</sup>]<sup>2</sup> for both metal ions (M<sup>4+</sup>). With values of <i>k</i><sub>1</sub> and <i>k</i><sub>2</sub>, 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 MOH<sup>3+</sup> and M(OH)<sub>2</sub><sup>2+</sup> 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<sup>-</sup> 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 : the international journal of the Japan Society for Analytical Chemistry  

    Analytical sciences : the international journal of the Japan Society for Analytical Chemistry 11(6), 903-908, 1995-12-01 

    The Japan Society for Analytical Chemistry

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各種コード

  • NII論文ID(NAID)
    10002406876
  • NII書誌ID(NCID)
    AA10500785
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    09106340
  • データ提供元
    CJP書誌  IR  J-STAGE 
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