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Hydrometallurgical thermodynamics—III. Solvent effects on the activities and distribution of Hal−, Hal2 and HaL−3, in acetonitrile and propionitrile—water mixtures and applications to zinc—halogen batteries

Singh, P., Clare, B.W., Kenna, C.C. and Muir, D.M. (1986) Hydrometallurgical thermodynamics—III. Solvent effects on the activities and distribution of Hal−, Hal2 and HaL−3, in acetonitrile and propionitrile—water mixtures and applications to zinc—halogen batteries. Electrochimica Acta, 31 (5). pp. 535-543.

Link to Published Version: http://dx.doi.org/10.1016/0013-4686(86)85029-0
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Abstract

The free energies of transfer of Hal−, Hal2 and Hal−3 from water to acetonitrile—water and propionitrile—water mixtures are reported. Relative changes in ΔGι are discussed in terms of the neutral and electrostatic contributions to the solvation energy of these species and are compared with values of other complex anions and neutral species in protic and aprotic solvents. It is shown that solvent activity effects dominate the solvation energy of Hal2, Br−3 and I−3, but hydrogen bonding effects dominate the solvation energy of Hal− and Cl−3 in aqueous acetonitrile. Nitrile-rich compositions strongly favour the formation of Br−3. The solubility and the solvation characteristics of Br−, Br2 and Br−3 in water-saturated propionitrile are particularly useful in the development and understanding of the zinc-bromine redox battery.

Publication Type: Journal Article
Murdoch Affiliation: School of Mathematical and Physical Sciences
Publisher: Elsevier
URI: http://researchrepository.murdoch.edu.au/id/eprint/20676
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