Evaluation of the Kinetic Parameters of First-Order Reactions Following Charge Transfer by Applying a Long-Path-Length Spectroelectrochemical Technique

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抄録

A long-path-length spectroelectrochemical technique was developed for investigating the EC mechanism and evaluating the kinetic parameters under a semi-infinite condition. The chronoabsorbances were obtained by a digital simulation method. Simulated results showed that the shapes of A-t curves are markedly dependent upon the relative values of the molar absorptivities of spieces A, B and C. When εA=0, εB/ εC≥5 or εC=0, 0≤εA/εB<0.5, the system absorbance passes through a maximum (Amaxt) interestedly. While εB=0, 0.2≤εA/εC≤1, there appears a minimum (Amint). Either Amaxt or Amint is closely related to the chemical reactions following charge transfer. When there is Amaxt at moment tmax in the A-t curve, increasing the value of the first-order rate constant (k1) causes Amaxt and tmax to decrease; while increasing the diffusion coefficient (DB) for species B causes Amaxt to increase, but tmax to decrease. This opposite effect enables us evaluate k1 and DB both simultaneously and precisely. The elctrooxidation of p-aminophenol in an acid aqua solution was experimentally investigated by a long-path-length spectroelectrochemical technique. The pseudo first-order rate constant and the diffusion coefficient for the electrooxidized intermediate quinone imine were successfully evaluated by this method.

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 16(1), 87-91, 2000-01-10 

    社団法人 日本分析化学会

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各種コード

  • NII論文ID(NAID)
    10004704816
  • NII書誌ID(NCID)
    AA10500785
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    09106340
  • NDL 記事登録ID
    4966685
  • NDL 雑誌分類
    ZP4(科学技術--化学・化学工業--分析化学)
  • NDL 請求記号
    Z54-F482
  • データ提供元
    CJP書誌  NDL  J-STAGE 
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