A Nuclear Magnetic Resonance Study on Ligand Exchange Reactions in U (VI) Nitrato Complexes with Ligands Containing Phosphoryl Group in Non-aqueous Solvents

この論文にアクセスする

この論文をさがす

著者

抄録

The exchange reactions of tributyl phosphate (TBP) and dihexyl-N, N-diethylcarbamoylmethylphosphonate (CMP) in U(VI) nitrato complexes with TBP or CMP (abbreviated as U(VI)-TBP or U(VI)-CMP) have been studied by means of <SUP>31</SUP>P NMR method in CD<SUB>3</SUB>COCD<SUB>3</SUB> or CD<SUB>2</SUB>Cl<SUB>2</SUB>. The number of TBP coordinated to uranyl nitrate was directly determined to be 1 in CD<SUB>3</SUB>COCD<SUB>3</SUB> and 2 in CD<SUB>2</SUB>Cl<SUB>2</SUB> by the area integrations of <SUP>31</SUP>P NMR signals of free and coordinated TBP. Similarly, the number of coordinated CMP was evaluated as 1 in CD<SUB>3</SUB>COCD<SUB>3</SUB>. The exchange rate constants of TBP and CMP in U(VI)-TBP and U(VI)-CMP complexes were calculated by the two-site exchange model. The exchange rate of TBP in U(VI)-TBP is independent of the free TBP concentrations ([TBP]<SUB>f</SUB> ), while that in U(VI)-CMP is dependent on [CMP]<SUB>f</SUB>. From these results, the dissociative (D) and interchange (I) mechanisms were proposed for the exchange reactions of TBP in U(VI)-TBP and CMP in U(VI)-CMP, respectively. Kinetic parameters are as follows: rate constant (25°C), ΔH<SUP>≠</SUP>(kJ-mol<SUP>-1</SUP>), ΔS<SUP>≠</SUP>(J•K<SUP>-1</SUP>•mol<SUP>-1</SUP>); 9.9×10<SUP>3</SUP>s<SUP>-1</SUP>, 33.7, -55.4 (U(VI)-TBP system), 2.3×10<SUP>4</SUP> m<SUP>-1</SUP>•s<SUP>-</SUP>1 (apparent second-order), 25.2, -75.9 (U(VI)-CMP system).

収録刊行物

  • Journal of nuclear science and technology

    Journal of nuclear science and technology 34(3), 298-303, 1997-03-25

    Atomic Energy Society of Japan

参考文献:  30件中 1-30件 を表示

  • <no title>

    SIDDALL T. H.

    J. Inorg. Nucl. Chem. 25, 883, 1963

    被引用文献2件

  • <no title>

    SCHULZ W. W.

    Transplutonium Elements, 1976

    被引用文献2件

  • <no title>

    SIDDALL T. H.

    J. Inorg. Nucl. Chem. 26, 1991, 1964

    被引用文献2件

  • <no title>

    STEWART W. E.

    J. Inorg. Nucl. Chem. 32, 3599, 1970

    被引用文献2件

  • <no title>

    PETRZILOVA H.

    J. Radioanal. Chem. 51, 107, 1979

    被引用文献2件

  • <no title>

    SHOUN R. R.

    ISEC 77 21, 101, 1977

    被引用文献2件

  • <no title>

    KALINA D. G.

    Sep. Sci. Technol. 16, 1127, 1981

    被引用文献5件

  • <no title>

    MARSH S. F.

    LA-11191, 1998

    被引用文献1件

  • <no title>

    HORWITZ E. P.

    Sep. Sci. Technol. 16, 403, 1981

    被引用文献2件

  • <no title>

    BOWEN S. M.

    Inorg. Chim. Acta 61, 155, 1982

    被引用文献1件

  • <no title>

    JESSUP J. S.

    lnorg. Chim. Acta 73, 261, 1983

    被引用文献1件

  • <no title>

    BOWEN S. M.

    Inorg. Chem 21, 261, 1982

    被引用文献1件

  • <no title>

    BOWEN S. M.

    Inorg. Chem. 24, 1191, 1985

    被引用文献1件

  • <no title>

    BOWEN S. M.

    Inorg. Chem. 22, 286, 1983

    被引用文献3件

  • <no title>

    KARTHIKEYAN S.

    Inorg. Chim. Acta 144, 135, 1988

    被引用文献2件

  • <no title>

    HATAKEYAMA K.

    J. Nucl. Sci. Technol. 32, 1146, 1995

    被引用文献5件

  • <no title>

    HORWITZ E. P.

    M85010251, 1985

    被引用文献1件

  • <no title>

    BINSCH G.

    Topics Stereochem. 3, 97, 1968

    被引用文献1件

  • <no title>

    IKEDA Y.

    Inorg. Chem. 23, 1356, 1984

    被引用文献4件

  • <no title>

    MARCUS Y.

    Ion Exchange and Solvent Extraction of Metal Complexes, 1969

    被引用文献4件

  • <no title>

    GUTMANN V.

    Coord. Chem. Rev. 12, 263, 1974

    被引用文献1件

  • <no title>

    LANGFORD C. H.

    Ligand Substitution Processes, 1974

    被引用文献3件

  • <no title>

    LO S. T. D.

    Inorg. Chem. 15, 1881, 1976

    被引用文献3件

  • <no title>

    IKEDA Y.

    Bull. Chem. Soc. Jpn. 56, 1060, 1983

    被引用文献4件

  • <no title>

    FUOSS R. M.

    J. Am. Chem. Soc. 89, 5059, 1958

    被引用文献3件

  • <no title>

    DOINE H.

    Bull. Chem. Soc. Jpn. 56, 1989, 1983

    被引用文献3件

  • <no title>

    CALDIN E. F.

    J. Solution Chem. 2, 217, 1973

    被引用文献3件

  • <no title>

    HORWITZ E. P.

    Solvent Extr. Ion Exch. 4, 449, 1986

    被引用文献8件

  • <no title>

    EGOZY Y.

    J. Inorg. Nucl. Chem. 33, 1451, 1971

    DOI 被引用文献1件

  • <no title>

    BENNETTO H. P.

    J. Chem. Soc. A, 2198, 1971

    DOI 被引用文献2件

各種コード

  • NII論文ID(NAID)
    10002076743
  • 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
    4176283
  • 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 
ページトップへ