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Kinetics of the solvolysis oftrans-dichlorotetra-(4-t-butylpyridine)-cobalt(III) ions in water +t-butyl alcohol mixtures

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Abstract

Rates of solvolysis of the complex cation [Co(4tBupy)4Cl2]+ have been determined in mixtures of water with the hydrophobic solvent, t-butyl alcohol. The solvent composition at which the extremum is found in the variation of the enthalpy ΔH* and the entropy ΔS* of activation correlates well with the extremum in the variation of the relative partial molar volume of t-butyl alcohol in the mixture and the straight line found for the variation of ΔH* with ΔS* is coincident with the same plot for water + 2-propanol mixtures. A free energy cycle is applied to the process initial state (Cn+) going to the transition state [M(n+1)+...Cl] in water and in the mixture using free energies of transfer of the individual ionic species, ΔG t o (i), from water into the mixture. Values for ΔG t o (i) are derived from the solvent sorting method and from the TATB/TPTB method: using data from either method, changes in solvent structure on going from water into the mixture are found to stabilize the cation in the transition state, M(n+1)+, more than in the initial state, Cn+. This is compared with the application of the free energy cycle to the solvolysis of complexes [Co(Rpy)4Cl2]+ and [Coen2LCl]+ in mixtures of water with methanol, 2-propanol or t-butyl alcohol: the above conclusion regarding the relative stabilization of the cations holds for all these complexes in their solvolyses in water+alcohol mixtures using values of ΔG t o (Cl) from either source.

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Correspondence to Cecil F. Wells.

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Halawani, K.H.M., Wells, C.F. Kinetics of the solvolysis oftrans-dichlorotetra-(4-t-butylpyridine)-cobalt(III) ions in water +t-butyl alcohol mixtures. J Solution Chem 19, 1073–1084 (1990). https://doi.org/10.1007/BF00649452

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Key words

  • Solvolysis
  • kinetics
  • mixtures of water+cosolvent