A Nuclear Magnetic Resonance Study on Ligand Exchange Reaction in U(VI) Nitrato Complex with n-Octyl(phenyl)-N, N-Diisobutylcarbamoylmethylphosphine Oxide in Acetone Containing Oxalic Acid

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In order to examine the effect of oxalic acid(H<SUB>2</SUB>ox) on the exchange reaction of n-octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (oφcmpo) in U(VI) nitrato complex with oφcmpo, structural and kinetic studies have been carried out for the solutions prepared by dissolving UO<SUB>2</SUB>(NO<SUB>3</SUB>)<SUB>2</SUB>(oφcmpo), oφcmpo, and H<SUB>2</SUB>ox in CD<SUB>3</SUB>COCD<SUB>3</SUB> using <SUP>31</SUP>P and <SUP>13</SUP>C NMR method. The number of coordinated oφcmpo was determined to be 2 by the area integration of <SUP>31</SUP>P NMR signals of free and coordinated oφcmpo. From the area integration of <SUP>13</SUP>C signals of free H<SUB>2</SUB>ox and coordinated oxalate(Cox), the number of Cox was estimated to be 1. Hence, the complex with composition ratio of UO<SUP>2+</SUP><SUB>2</SUB>:oφcmpo: Cox=1:2:1 was supposed to be formed in the present solution system. The exchange rate of oφcmpo in this complex was found to show a first-order dependence on the free oφcmpo concentrations and to decrease with increasing free H<SUB>2</SUB>ox concentrations. From these results, it is proposed that the exchange reaction of oφcmpo proceeds through the interchange(I) mechanism and that the retardation effect of free H<SUB>2</SUB>ox is due to the formation of outer-sphere complex.

収録刊行物

  • Journal of nuclear science and technology

    Journal of nuclear science and technology 34(12), 1133-1139, 1997-12-25

    Atomic Energy Society of Japan

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各種コード

  • NII論文ID(NAID)
    10002078549
  • NII書誌ID(NCID)
    AA00703720
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    00223131
  • NDL 記事登録ID
    4371577
  • NDL 雑誌分類
    ZM35(科学技術--物理学)
  • NDL 請求記号
    Z53-A460
  • データ提供元
    CJP書誌  NDL  J-STAGE 
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