Abstract
Rates of solvolysis of [Co(CN) 5 Cl]3− have been determined in a range of water-rich water + 2-propanol mixtures over a range of temperatures and they show no simple correlation with dielectric constant. The variation of the enthalpy and entropy of activation with solvent composition show broad extrema and these are discussed in relation to the physical properties of the media. The application of a free energy cycle to the dissociative loss of the chloride ion in the transition state shows that the effect of changes in solvent structure as the alcohol content increases is to stabilize the emergent pentacyanocobaltate(III) ion Co(CN) 2− 5 relative to the chloropentacyanocobaltate(III) anion in the initial state.
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El-Subruiti, G.M.A., Wells, C.F. & Sidahmed, I.M. Kinetics of the solvolysis of chloropentacyanocobaltate(III) ions in water + 2-propanol mixtures. J Solution Chem 21, 93–103 (1992). https://doi.org/10.1007/BF00648982
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DOI: https://doi.org/10.1007/BF00648982