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  • 1 Shizuoka University Radiochemistry Research Laboratory, Faculty of Science 836 Ogya 422 Shizuoka-shi Japan
  • | 2 Tohoku University Institute for Materials Research 2-1-1 Katahira, Aoba-ku 980 Sendai-shi Japan
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The stability constants, 1, of each monochloride complex of Nd(III) and Tm(III) have been determined in the mixed system of methanol and water with 1.0 mol·dm–1 ionic strength using a solvent extraction technique. The values of 1 of Nd(III) and Tm(III) increase as the mole fraction of methanol in the mixed solvent system (Xs) increases. However, the variation mode of 1 againstXs in the region of 0.00Xs0.40 differs from each other, a concave curve for the Nd(III) and a convex curve for the Tm(III). The LnCl2+ formed is present as a solvent-shared ion-pair. Since Cl is a structure breaking ion, it was assumed that the primary solvation sphere of Ln3+ directly contacted with Cl. Calculation of Ln3+–Cl distance using Bom-type equation revealed the followings: (1) for Tm3+ with coordination number 8, the estimated distance between Tm3+ and Cl increases linearly withXs in 0.00Xs0.40. The results mean an increase of the primary solvation sphere size of Tm3+ withXs. (2) For Nd3+, the distance between Nd3+ and Cl decreases linearly withXs in 0.00Xs<0.13, where both coordination numbers of 9 and 8 coexist, while it increases withXs in 0.13<Xs0.40. The results mean a decrease of the primary solvation-sphere size of Nd3+ withXs in 0.00Xs<0.13 and an increase of that withXs in 0.13<Xs0.40.

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Journal of Radionalytical and Nuclear Chemistry
Language English
Size A4
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Founder Akadémiai Kiadó
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Springer Nature Switzerland AG
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ISSN 0236-5731 (Print)
ISSN 1588-2780 (Online)