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124) on Ir( 110). 29. Thermal desorption spectra for oxygen adsorption on Pt(ll0) for various initial coverages (125). tion energy, respectively. A double logarithmic plot of the desorption rate vs. the initial coverage at points of constant temperature should give a line whose slope is the desorption order provided that v and E are not strongly coverage dependent. 2. Values of n > 2 result from a decrease in Ed(8)with increasing coverage and are not physically meaningful. However, the first-order dependence on 8 at low coverages indicates that in this range the rate-determining step is the transfer of the incorporated oxygen from the oxide to the chemisorbed layer rather than the desorption of the 0, molecule that limits the desorption rate at higher coverages.

1 Torr the stationary CO coverage will be For T >, 500 K and pco 5 small. If, however, po2 > pco, under steady-state conditions the oxygen coverage increases (since 0, desorption is negligible) and r becomes independent of po,. This effect of r switching over from first- to zero-order kinetics with respect to po, can again be seen in curve a of Fig. 37. 08 r is even independent of the oxygen coverage (176). 25 and CO, formation proceeds along the domain boundaries. Since the metal-oxygen bond is about twice as strong as that for CO, the latter molecule will diffuse much faster over the surface and the reaction may be considered to approximately take place between highly mobile CO and a quasi-fixed matrix of O,, (see also Section 11,D).

24. It is thus predicted that the peak at -6 eV in the UP spectra consists of a doublet. The spectra from Pt and Ir in Fig. 5 eV, respectively, which is ascribed to this effect. An alternate interpretation would be that this is due to emission from states with different orbital symmetry as was discussed for the system O/Ni(l00) (144). 24. (a) Enhancement factor R(E)as a function of the energy relative to the Fermi level for field emission from oxygen covered iridium (100) and (1 10) surfaces. (b) Schematic representation of the oxygen derived levels at the surface (51).

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