Oxidation of aqueous sulfide solutions by dioxygen - Part II: Catalysis by soluble and immobilized cobalt(II) phthalocyanines

The oxidation of sulfide in oxygen-saturated aqueous solutions is accelerated by dissolved or silica-bonded cobalt phthalocyanines. On the basis of thermodynamical considerations it is postulated that the catalyst enhances the formation of disulfide as the initial elementary reaction step. The following reaction steps are largely unaffected by the catalyst, as indicated by a product ratio sulfate/thiosulfate = 0.86, comparable to that of the uncatalyzed autoxidation. A Langmuir-Hinshelwood formalism is developed for the catalytic reaction step and is demonstrated to fit best with the kinetics. In addition, from the kinetic data free enthalpies for the adsorption of HS- (i) at the dissolved phthalocyanine (Delta G=-17.6 kJ/mole) and (ii) at the immobilized complex (Delta G=-20.0 kJ/mole) are calculated.