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 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 Gt increased monotonously with increasing cosolvent content, however the changes of Δ Ht and TΔSt 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 Gto, ΔHto, and TΔSto . The transfer enthalpies of reactants were evaluated from calorimetric measurements. The values of ΔHto  and TΔSto 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)

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