Hydrocarbon combustion on Pd(100) was studied using temperature-progra
mmed reaction spectroscopy (TPRS) at high oxygen coverages up to 1.1 o
xygen atom per palladium atom. The hydrocarbons studied included both
alkenes (propene, 1-butene, and 1,3-butadiene) and arenes (benzene, to
luene, and styrene). Alkanes (pentane and cyclohexane) were also studi
ed, but no reaction was detected. It was found that even at 1.1 O/Pd,
efficient combustion reactions occur at 350-650 K for all the alkenes
and arenes studied. It appears that higher chemisorption energies of h
ydrocarbon on the surface (butadiene > butene > propene; styrene > tol
uene > benzene) lead to lower activation energies and higher combustio
n yields. As the oxygen coverage increases from 0.25 O/Pd, the activat
ion energies for the combustion reactions increase, and the combustion
yields pass through a maximum, presumably due to a blocking effect of
O(a) on hydrocarbon adsorption.