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Extraction studies of lanthanide(III) ions with ${it N,N'}$-dimethyl-${it N,N'}$-diphenylpyridine-2,6-dicarboxyamide(DMDPhPDA) from nitric acid solutions

${it N,N'}$-dimethyl-${it N,N'}$-diphenylpyridine-2,6-dicarboxyamide(DMDPhPDA)による硝酸溶液からのランタノイド(III)イオン抽出に関する研究

島田 亜佐子; 矢板 毅; 成田 弘一; 館盛 勝一; 奥野 健二*

Shimada, Asako; Yaita, Tsuyoshi; Narita, Hirokazu; Tachimori, Shoichi; Okuno, Kenji*

${it N,N'}$-dimethyl-${it N,N'}$-diphenylpyridine-2,6-dicarboxyamide(DMDPhPDA)を用いて1-5Mの硝酸溶液からランタノイドを抽出したときの分配比を求め、抽出剤及び酸濃度依存性によるスロープアナリシス及びイオン半径に対する分配比の変化から抽出機構を議論した。ランタノイド抽出は2つの機構によって説明されることを明らかにした。(1)3M以下の硝酸濃度において、2つのDMDPhPDAと軽ランタノイドによる内圏錯体が生成する,(2)軽ランタノイドに対しては3M以上の硝酸濃度、重ランタノイドでは1-5Mの硝酸濃度において、内圏錯体に加え第3のDMDPhPDAが外圏に配位した錯体を生成することによりランタノイドイオンは抽出される。また、硝酸は外圏錯体の生成において重要な役割を果たすことを見いだした。

The distribution ratios of lanthanides with ${it N,N'}$-dimethyl-${it N,N'}$-diphenylpyridine-2,6-dicarboxyamide(DMDPhPDA) from 1-5M nitric acid solutions were determined and the extraction mechanism was discussed on the basis of the slope analyses of acid and ligand concentration dependencies and lanthanide patterns (variation of the distribution ratio as a function of ionic radius). The lanthanide extractions were explained through two mechanisms from the standpoint of the formation of the extracted complex as follows: (1) the formation of inner-sphere complex with two DMDPhPDA molecules for light lanthanides in the extraction from HNO$$_{3}$$ less than 3M, and (2) the formation of outer-sphere complex with the third DMDPhPDA molecules in addition to the inner-sphere complex in the extraction of light lanthanides from HNO$$_{3}$$ more than 3M, and those of heavy lanthanides from 1-5M HNO$$_{3}$$ solutions. Nitric acid concentration is more influential than the ligand concentration in the formation of outer-sphere complex.

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パーセンタイル:80.68

分野:Chemistry, Multidisciplinary

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