By John B. Butt
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Additional resources for Activation, Deactivation, and Poisoning of Catalysts
We consider single and multiple main reactions, each on homogeneous and heterogeneous surfaces. In a later section, we consider empirical or semi27 28 2. Mathematical Description of Deactivating Systems empirical forms of deactivation functions and, where possible, relate them to the more fundamental forms developed in the earlier sections. I. DEACTIVATION OF SYSTEMS HAVING A SINGLE MAIN REACTION Our first task is to define a quantity that we shall call the activity, a, and to establish how this factor appears in the rate expression for the main reaction.
Let us consider reactions on two homogeneous ensembles, each having different sites. The simplest consecutive reaction network is A _^B^Uc (2-49) For convenience, assume that the reaction A->B occurs on a group of identical sites called X sites and correspondingly the reaction B -»C occurs on identical Y sites. We adopt an LHHW model for each of these reactions similar to that in Section I,A represented by the elementary steps fcl 2 k 3, k A + S, « = * [A · S,] — + [B · SJ * = ± B + S, (2-50) I Φ k4 Ψ I k_4 and k[ k'2 B + S2^=±[B-S2] hi >[C-S 2 ]<==±C + S2 (2-51) I Φ k-4 K ψ I w2 Making assumptions similar to those used to derive Eqs.
Indeed, in certain cases, only sites in a selected narrow range of heats of formation for the particular adsorbent can act to adsorb, react, and desorb products at a significant overall rate. That is, if the heat of adsorption for the reaction is too small, the activation barrier for adsorption will be high and the rate of adsorption will be rate-limiting. Similarly, if the heat of formation is too high, the activation barrier for the decomposition of the intermediate will be large and the corresponding rate will become limiting.