Studies on the Reaction Kinetics and Mechanism of Iron(II) Reduction of the cis-Halogeno(cetylamine)bis(ethylenediamine)cobalt(III) Complex Ion in Aqueous Perchlorate Medium

Abstract

The electron-transfer kinetics of the ionic surfactant complex cis-chloro/bromo(cetylamine)bis(ethylenediamine)cobalt(III) by iron(II) in aqueous perchlorate medium at μ=1.0 mol⋅dm−3 ionic strength have been studied at 303, 308 and 313 K by spectrophotometry under pseudo-first-order conditions using an excess of the reductant. The effects of [H+], ionic strength and [Fe2+] on the rate were determined. The reaction was found to be second order and showed to be independence of the acid concentration in the range [H+]=0.05–0.25 mol⋅dm−3. The second order rate constant increased with surfactant–cobalt(III) concentration and the occurrence of aggregation of the complex itself altered the reaction rate. Activation and thermodynamic parameters have been computed. It is suggested that the reaction of Fe2+(aq) with the cobal (III) complex proceeds by an inner-sphere mechanism. The critical micelle concentration (CMC) values of these surfactant–metal complexes were obtained in aqueous solution from conductance measurements. Specific conductivity data (at 303, 308 and 313 K) served for the evaluation of the temperature-dependence of the critical micelle concentration (CMC) and the thermodynamics of micellization (ΔGmo,ΔHmo and ΔSmo).