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Zinc(II)-chloride complexes in acetonitrile-water mixtures
Journal article   Peer reviewed

Zinc(II)-chloride complexes in acetonitrile-water mixtures

B.W. Clare, G. Hefter and P. Singh
Australian Journal of Chemistry, Vol.43(2), pp.257-261
1990
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Abstract

Equilibrium constants for the formation of ZnCln2-n complexes have been measured in some acetonitrile ( MeCN )-water mixtures ranging from 0 to 100% MeCN at 25°C and I = 0.1 M (Et4NClO4), by potentiometric titration. The equilibria shift strongly in favour of the formation of the higher-order complexes (n = 3, 4) at high MeCN concentrations. This is shown to be due to differences in the magnitude of unfavourable solvation of the Zn2+, Cl - and ZnCln2-n ions in MeCN-H2O solutions. The Gibbs free energies of transfer of all of these ions from water to MeCN-H2O mixtures are strongly positive, but the net change in the transfer function for the formation of the higher-order complexes is favourable. Thus the formation of these complexes is predominant in MeCN -rich aqueous solutions. Approximate measurements in propiononitrile indicate that the ZnCln2-n complexes are even stronger than in acetonitrile.

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Citation topics
2 Chemistry
2.89 Ionic, Molecular & Complex Liquids
2.89.462 Excess Molar Volumes
Web Of Science research areas
Chemistry, Multidisciplinary
ESI research areas
Chemistry
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