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KMID : 1059519890330060588
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Journal of the Korean Chemical Society
1989 Volume.33 No. 6 p.588 ~ p.595
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Studies on the Complexes of Lanthanide ion with Multidentate Ligand (I). Determination of Thermodynamic Parameters with Solution Calorimetric Method in Nonaqueous Solvents
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Kang Sam-Woo
Koo Won-Fae
Lee Soo-Min
Chang Choo-Hwan
Suh Moo-Yul
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Abstract
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Log K, △H and △S for the complexation of La3+, Ce3+ and Eu3+ with various multidentate ligand containing crown ether, diaza crown ether and diamine ether have been determined in methanol and acetonitril solutions at 25℃ by solution calorimetric titration method. The greater stability constant of La3+-15C5 than those of 18C6 diaza [2.2] in methanol are discussed in terms of the size of metal ion and the ligand cavity and of metal ion solvation. The stabilities of Ce3+ and La3+ ion complexes with a various multidentate ligand in acetonitril are in the order of (diamine ether) < 18C6 < 15C5 < diaza [2. 1] < diaza [2.2]. This result are discussed in terms of the covalent bonding of -NH group in diaza ligand in addition to the ion-dipole interaction and of the optimum size concept and of the macrocyclic effect. The stability constants of Ce3+, La3+ and Eu3+-diaza [2.2] complexes in acetonitril are increased with the following order: Eu3+ < La3+ < Ce3+, that is increasing order of the optimum size and of the charge density of metal ion.
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