ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

 Solvent Effect on the Kinetics of Oxidation of [Co(en)₂SCH₂COO]⁺ by Periodate in Water-Methanol and Water—tert-Butanol Mixture

O. Vollárová and J. Benko

Department of Physical Chemistry, Faculty of Natural Sciences, Comenius University, CS-842 15 Bratislava

Abstract: Solvent effect on the oxidation of [Co(en)₂SCH₂COO]⁺ by IO₄^- in aqueous mixtures of methanol and tert-butanol was studied. The transfer Gibbs energy of activation Δ G_t^≠ increased monotonously with increasing cosolvent content, however the changes of Δ H_t^≠ and TΔS_t^≠ showed almost the mirror course. The changes in solvation on going from initial to the transition state were discussed on the basis of the transfer functions of Δ G_t^o, ΔH_t^o, and TΔS_t^o . The transfer enthalpies of reactants were evaluated from calorimetric measurements. The values of ΔH_t^o  and TΔS_t^o corresponding to the initial and transition states exhibited an extreme at x₂ approximate to x₂* cosolvent mole fraction.

Full paper in Portable Document Format: 474a207.pdf

Chemical Papers 47 (4) 207–209 (1993)