The photon driven chemistry of adsorbates on Ag(111) will be illustrated using results from sulfur dioxide, trifluoromethyl iodide and, in greater detail, methyl nitrite. The focus of the presentation will be a discussion of the angular and velocity distributions of nitric oxide moieties ejected from irradiated methyl nitrite. The dependence of these properties on photon energy (3 to 6 eV) and coverage (submonolayer to thick multilayer) is interpreted in terms of direct excitation of methyl nitrite with negligible contributions from substrate mediated processes. Comparisons with gas phase photochemistry of methyl nitrite will be made.