Criteria for diffusion control of a catalytic reaction

To assess whether a reaction is influenced by intraparticle diffusion effects, Weisz and Prater [11] developed a criterion for isothermal reactions based upon the observation that the effectiveness factor approaches unity when the generalised Thiele modulus is of the order of unity. It has been shown that the effectiveness factor for all catalyst geometries and reaction orders (except zero order) tends to unity when 

Petersen [12] points out that this criterion is invalid for more complex chemical reactions whose rate is retarded by products. In such cases, the observed kinetic rate expression should be substituted into the material balance equation for the particular geometry of particle concerned. An asymptotic solution to the material balance equation then gives the correct form of the effectiveness factor. The results indicate that the inequality (23) is applicable only at high partial pressures of product. For low partial pressures of product (often the condition in an experimental differential tubular reactor), the criterion will depend on the magnitude of the constants in the kinetic rate equation. 

The usual experimental criterion for diffusion control involves an evaluation of the rate of reaction as a function of particle size. At a sufficiently small particle size, the measured rate of reaction will become independent of particle size. The reaction rate can then be safely assumed to be independent of intraparticle mass transfer effects. At the other extreme, if the observed rate is inversely proportional to particle size, the reaction is strongly influenced by intraparticle diffusion. For a reaction whose rate is inhibited by the presence of products, there is an attendant danger of misinterpreting experimental results obtained for different particle sizes when a differential reactor is used, because, under these conditions, the effectiveness factor is sensitive to changes in the partial pressure of product. 

When reaction conditions within the particle are non-isothermal. Weisz and Hicks [8] showed that a suitable criterion defining conditions under which a reaction is not controlled by diffusion and heat transfer effects in the solid is 

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