Abstract
The shrinking-core equation for pore diffusion control has been extended to the case of a facile heterogeneous reaction coupled to a facile homogeneous reaction occurring within the pores of the product layer and in the bulk solution. The model considered is very general in that the simultaneous transport of all reacting species is included. The resulting equation is identical to the standard one for diffusional control by a single species except that the parabolic rate constant k d is considerably more complex and contains useful information concerning the system. Analysis of its dependence on the system parameters yields important criteria that determine the identity of the rate-controlling species and the direction of the heterogeneous reaction. Depending upon the relative values of the equilibrium constants of the two reactions, the dependence of k d on the bulk reactant concentration can vary significantly from the linearity expected from the standard model.
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