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Thermodynamic study on the complexation of U(IV) with isosaccharinic acid

ウラン(IV)のイソサッカリン酸との錯生成に関する熱力学的研究

小林 大志*; 佐々木 隆之*; 北村 暁  

Kobayashi, Taishi*; Sasaki, Takayuki*; Kitamura, Akira

イソサッカリン酸(ISA)共存下におけるウラン(IV)水酸化物(U(OH)$$_{4}$$(am))の溶解度を、水素イオン濃度指数(pHc = -log [H$$^{+}$$])およびISA濃度の関数として調査した。中性付近では溶解度がpHcに依存しなかった一方で、アルカリ性水溶液中では溶解度がわずかにpHcの増加とともに高くなった。溶解度のISA依存性が両対数グラフで傾き約2の直線となったことと併せて、支配的な溶存化学種はジルコニウム-ISA系で報告されているものと同じ化学形であるU(OH)$$_{4}$$(ISA)$$_{2}$$$$^{2-}$$とU(OH)$$_{5}$$(ISA)$$_{2}$$$$^{3-}$$である可能性が示唆された。これらの化学種の錯生成定数を実験値の最小二乗適合により求めた結果、適合結果が実験値をよく説明できることがわかった。

The solubility of U(OH)$$_{4}$$(am) was investigated in the presence of isosaccharinic acid (ISA) as a function of hydrogen ion concentration (pHc) and ISA concentration. The solubility in neutral pH region was independent of pHc, while those in alkaline pH region slightly increased with increasing pHc. The solubility was investigated as a function of ISA concentration and found to increase with a slope of approximately 2 with increasing ISA concentration. It was therefore suggested that U(OH)$$_{4}$$(ISA)$$_{2}$$$$^{2-}$$ and U(OH)$$_{5}$$(ISA)$$_{2}$$$$^{3-}$$ were the dominant U(IV)-ISA complexes, which were similar to those observed in Zr(IV)-ISA system. Complex formation constants were determined by the least square fitting analysis of the solubility data and the calculated solubility curve well reproduced the experimental data.

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