Decomposition reactions catalyzed by the solid product

Dehydration reactions. In early studies of dehydration reactions (e.g. of CuS04 5 H20 [400]), the surfaces of large crystals of reactant were activated through the incorporation of product into surfaces by abrasion with dehydrated material. An advantage of this pretreatment was the elimination of the problems of kinetic analysis of the then little understood relationship between a and time during the acceleratory process. Such surface modification resulted in the effective initiation of reaction at all boundary surfaces and rate studies were exclusively directed towards measurement of the rate of interface advance into the bulk. 

Decomposition of Ag20. Dubinin et al. [642] have shown that the induction period to Ag20 decomposition at 603 K is reduced and the initial reaction rate is increased by the deposition of a thin film of Ag (or of Ni) on the reactant surface. Close contact between reactant and additive must be established for the effective promotion of salt breakdown since no activating influence was detected during reactions of mechanical mixtures of Ag20 and Ag. 

It is seen from these examples that, in appropriate systems, it is possible to introduce product into the reactant in such a manner that an effective reaction interface is established before the reactant has been heated to the decomposition temperature. Accordingly, the induction period is removed and the acceleratory process may be less pronounced or eliminated altogether. Artificial nucleation results in changes in reaction geometry with consequent variation in the a—time curve shape and the maximum value of da/dt but does not enhance the rate of interface advance. We have found no studies in which increases in reaction rates were quantitatively correlated with the increased interfacial area and/or density of nucleation which resulted from the reactant pretreatment. 

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