Abstract
The stability constants, β1, of each monochloride complex of Ln(III) (Ln=Nd or Tm) have been determined in the mixed system of dimethyl sulfoxide (DMSO) and water with 1.0 mol·dm−3 ionic strength using a solvent extraction technique. The values of β1 of Ln(III) decrease to about 0.2 mole fraction of DMSO (X s) in the mixed solvent system and then increase withX s (>about 0.2). However, the variation mode of β1 of Nd(III) withX s somewhat differs from that of Tm(III). Calculation of Ln3+−Cl− distance using a Born-type equation of the Gibbs' free energy derived from the β1 evealed the followings: (1) For Tm3+ with coordination number 8, the estimated distance between Tm3+ and Cl− (d Tm-Cl) increases linearly withX s in 0.00≤X s≤0.17. This means an enlargement of the primary solvation sphere size of Tm3+ withX s. On the other hand, thed Tm-Cl shows a decrease withX s in 0.17<X s<0.28. (2) The estimatedd Nd-Cl increases linearly withX s in 0.00≤X s<0.06 and 0.06<X s≤0.17, but their slopes are different. The larger slope againstX s in 0.06<X s≤0.17 is attributable to a lowering of the β1 by a coordination of ClO4 − into the secondary solvation sphere of Nd3+ and/or by an increase in the solvation number of the primary solvation sphere of Nd3+.
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Suganuma, H., Nakamura, M., Satoh, I. et al. On the variation of the distances of Nd3+−Cl− and Tm3+−Cl− in mixed system of dimethyl sulfoxide and water. J Radioanal Nucl Chem 227, 55–60 (1998). https://doi.org/10.1007/BF02386431
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DOI: https://doi.org/10.1007/BF02386431