Horiuti-Polanyi reaction scheme

The Horiuti-Polanyi reaction scheme shows that in the case of isobutane, the reaction scheme involves isobutyl and adsorbed olefin intermediates. Cremer et al. (49) identified 2-propyl, r-bonded propylene, and di-a-bonded propylene surface species on platinum during propylene hydrogenation. 

Kinetic Parameters for the Horiuti-Polanyi Reaction Scheme for Isobutane Dehydrogenation and Isobutylene Hydrogenation... 

Before we examine the hydrogenation of each type of unsaturation, let us first take a look at the basic mechanism assumed to be operating on metal catalytic surfaces. This mechanism is variously referred to as the classic mechanism, the Horiuti-Polanyi mechanism, or the half-hydrogenated state mechanism. It certainly fits the classic definition, since it was first proposed by Horiuti and Polanyi in 193412 and is still used today. Its important surface species is a half-hydrogenated state. This mechanism was shown in Chapter 1 (Scheme 1.2) as an example of how surface reactions are sometimes written. It is shown in slightly different form in Fig. 2.1. Basically, an unsaturated molecule is pictured as adsorbing with its Tt-bond parallel to the plane of the surface atoms of the catalyst. In the original Horiuti-Polanyi formulation, the 7t-bond ruptures... 

Fig. 39. Reaction scheme for the hydrogenation of 1,2-dimethylcyclohexene by a Horiuti—Polanyi mechanism as proposed by Siegel [221].

Accordingly, in order to understand the roles of active sites in catalysis, we should clarify not only the intermediates but also the functions of active sites in relation to elementary processes. For this reason, it may be an interesting question whether the two reactions taking place via the same kind of intermediates occur on the same or different active sites. One good example is the isomerization of olefins via alkyl intermediates and their subsequent hydrogenation. In the Horiuti and Polanyi mechanism, complete overlapping of the intermediates, as well as the reaction routes, was tacitly assumed as described in Eq. (1). In this reaction scheme, step (1) and step ( ) are the... 

The early use of deuterium in place of hydrogen in the study of catalytic hydrogenation led to the recognition that the process was not simply the addition of H2 to the double bond. Horiuti and Polanyi proposed that both H2 and alkene (1) are bound to the catalyst surface and transformed to products by a sequence of elementary steps, which they represented as shown in Scheme 1, where an asterisk ( ) represents a vacant site on the catalyst.The last step, (d), is virtually irreversible under the usual hydrogenation conditions, but can be observed in the exchange reactions of D2 with alkanes. The mechanism accounts for the isomerization of an alkene if the reversal of step (c), which involves the formation of the alkyl intermediate (3), involves the abstraction of a hydrogen atom other than the one first added, and is coupled with the desorption of the alkene, (2) - (1). At present, the bond between the alkene and the metal often is represented as a ir-complex (4), as in equation (7). ... 

In 1934 Horiuti and Polanyi proposed that both reaction components, hydrogen and alkene, are bound to the catalyst and transformed to the products by a sequence of steps shown in Scheme 1, where M represents a vacant site on the catalyst11. 

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