To understand the basic reaction kinetics and mechanisms of reactions on surfaces we perform in-situ XPS experiments that allow us to monitor the reaction and reaction intermediates.
See e.g. R. Streber et al. Angew. Chem. Int. Ed. 48 (2009) 9743,
or our review: C. Papp et al. Surf. Sci. Rep. 68 (2013) 446.
These are nice results from Streber et al.
The oxidation of sulfur on flat and stepped platinum surfaces.
That's how the reaction of sulfur with oxygen looks like
in a TP-XPS experiment and its analysis
and in isothermal experiments:
The results show us the reaction enthalpy of the rate determining step, show the role of steps in this reaction.
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