Metal-Catalysed Reactions of Hydrocarbons / 01-Metals and Alloys

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predictions. One further factor has however emerged as being important. With the ordered superlattices Cu3Au, CuAu and CuAu3, gold segregation has been detected,113 although this is not what the sublimation energies would lead one to predict. The additional factor is the relative sizes of the atoms, those of gold being squeezed out of the bulk because they are the larger; the strain is thereby relieved.105 This also explains the unexpected sense of segregation (based on Gibbs theory) in the cases of platinum alloyed with iron, cobalt, nickel and rhodium. The simple application of ideal or regular solution theory cannot be expected to work perfectly when the sizes of the atoms are much different.

For the purposes of chemisorption and catalysis, we need to know the composition and structure of the surface. The average composition is now easily measured, and can be checked against relevant theory, but for structure we have to find the arrangement of the two kinds of atoms at the atomic level. Assuming an average composition and the equality of all interaction energies in the surface, it is a straightforward use of binomial theorem to calculate the population of groups of two, three etc. of atoms of one kind.114 Unfortunately this simple procedure does not apply where there are atoms of different CN or where there is a tendency to cluster formation.115 Other computational and experimental methods are required, and these will feature in the next chapter in the context of small metal particles. We shall also discover in due course how the presence of a chemisorbed layer can alter the surface composition of an alloy.

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