Reaction hysteresis of the CO + O --> CO2 reaction on palladium(111)

Rate measurements of the reaction CO + O --> CO(2) on palladium(111) single crystal surfaces have been performed by means of mass spectroscopy under ultrahigh vacuum conditions. The total flux Phi of the impinging reactants CO and O(2) was held constant at 1 ML s(-1), whereas its CO fraction Y was varied between 0 (pure O(2)) and 1 (pure CO). The measurements have been performed for surface temperatures between 370 and 510 K and with a wide range of sampling times, evaluating the system parameter range for bistable behavior. Long-time measurements lasting several days proved the bistable behavior to result from two stable states rather than from slow processes not visible on usual experimental time scales. Pulselike modulations of the feed gas composition revealed the mechanisms confining the experimentally observed bistable range: the high CO fraction border of the bistability is given by the equistability condition of both states, whereas the other border is found to be associated with a saddle-node bifurcation in the corresponding system of reaction diffusion equations.