Outer-sphere association of ions in DMSO solutions of nickel(II) salts

The visible absorption spectra and the molar conductance curves of solutions of NiI 2, NiBr 2, Ni(BF 4) 2, Ni(ClO 4) 2 and Ni(CF 3COO) 2 DMSO at 25°C have been determined. The results indicate a weak association which is only of the outer-sphere type, in each case involving the Ni(DMSO) 2 + 6 comple...

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Bibliographic Details
Published in:Electrochimica acta 1984-01, Vol.29 (10), p.1453-1458
Main Authors: Puchalska, D., Libus, W., Pethybridge, A.D.
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Solubility
Solution properties
Solutions
Solvation. Solvent properties
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Summary:The visible absorption spectra and the molar conductance curves of solutions of NiI 2, NiBr 2, Ni(BF 4) 2, Ni(ClO 4) 2 and Ni(CF 3COO) 2 DMSO at 25°C have been determined. The results indicate a weak association which is only of the outer-sphere type, in each case involving the Ni(DMSO) 2 + 6 complex. The conductance data are analysed using the Lee-Wheaton conductance equation for unsymmetrical electrolytes. The first-step association constants ( K 1) and the limiting ionic conductances, λ 0, for the Ni(DMSO) 2 + 6 cation as well as for the BF − 4 and CF 3COO − anions are obtained. A linear relation between log K 1 and the reciprocal of the anionic radius is observed. On the basis of this relation, the relative contribution of the outer-sphere association for solutions of NiCl 2 in DMSO is estimated.
ISSN:0013-4686
1873-3859
DOI:10.1016/0013-4686(84)87027-9