Equilibrium and structural studies on the species formed in the extraction of divalent transition metal ions with 8-quinolinol.
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概要
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The equilibria were studied in the extraction of divalent transition metal ions (M<SUP>2+</SUP>: Co<SUP>2+</SUP>, Ni<SUP>2+</SUP>, Zn<SUP>2+</SUP>, Cd<SUP>2+</SUP>) with 8-quinolinol (Hq) from aqueous solutions containing various anions (X<SUP>−</SUP>) into some organic solvents. The effects of −log[H<SUP>+</SUP>] and total concentrations of 8-quiriolinol and metal ions on the distribution were examined in detail. Three species, M<SUB>2</SUB>q<SUB>3</SUB>(Hq)<SUB>3</SUB>X, Mq<SUB>2</SUB>(Hq), and M<SUB>2</SUB>q<SUB>4</SUB>(Hq)<SUB>2</SUB> are responsible for the extraction. The extraction of M<SUB>2</SUB>q<SUB>3</SUB>(Hq)<SUB>3</SUB>X is favorable when hydrophobic anions and polar solvents are used. On the other hand, the extraction constants of Mq<SUB>2</SUB>(Hq) are almost the same for each metal ion irrespective of anions and solvents. With increasing the metal ion concentration in the organic phase, Mq<SUB>2</SUB>(Hq) dimerizes to form M<SUB>2</SUB>q<SUB>4</SUB>(Hq)<SUB>2</SUB>. The decrease in the distribution ratio by prolonged shaking under certain conditions is reasonably ascribed to the slow precipitation of Mq<SUB>2</SUB>·2H<SUB>2</SUB>O which has been made supersaturated by the rapid establishment of all the equilibria except the precipitation reaction. An X-ray crystallographic study for Ni<SUB>2</SUB>q<SUB>4</SUB>(Hq)<SUB>2</SUB> showed that two nickel atoms are surrounded by three bidentate ligands with facial and meridional configurations about their oxygen atoms and these two isomers form a binuclear structure jointed by two strong hydrogen bonds.
- 公益社団法人 日本化学会の論文
著者
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Yuchi Akio
Department Of Applied Chemistry Graduate School Of Engineering Nagoya Institute Of Technology
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Wada Hiroko
Department Of Applied Chemistry Nagoya Insitute Of Technology
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Imai Kenji
Department Of Cardiology Nagoya University Graduate Of School Of Medicine
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Shiro Motoo
Shionogi Research Laboratry Shionogi & Co. Ltd.
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Nakagawa Genkichi
Department of Applied Chemistry, Nagoya Institute of Technology
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Imai Kenji
Department of Applied Chemistry, Nagoya Institute of Technology
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Imai Kenji
Department of Applied Chemistry, Faculty of Engineering, Kanagawa University
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