Matrix effect on surface-catalyzed photolysis of nitric acid

Photolysis rate constant of HNO(3) on the surface (HNO(3(s))) has been found to be enhanced by 1–4 orders of magnitude from that of gaseous HNO(3), with HONO and NO(2) as the main products. Such Re-NOx-ification pathway extends the apparent lifetime of reactive nitrogen species and modifies the atmospheric oxidative capacity along its long-rang transport. Despite of its importance, the detailed kinetics and mechanisms of HNO(3(s)) photolysis are still not clear. Surface film of HNO(3) and organic compounds is ubiquitous in the environment and imposes matrix effect on HNO(3(s)) photolysis. Here we studied photolysis of HNO(3) on Pyrex glass in a photochemical flow reactor over a wide range of HNO(3) surface density (D(HNO3)) with or without the presence of model organic compounds. The photolysis rate constant of HNO(3(s)) varied with D(HNO3) and surface-catalysis mechanism was proposed. Organic compounds further enhance the photolysis rate constant by up to one order of magnitude via both photosensitization and H-donating reaction. The H-donating reaction enhances as well the secondary HONO yield from reaction between the primary product NO(2) and adjacent H-donor, and thus increases the HONO/NO(2) production ratio. Finally, detailed mechanisms involving surface-catalyisis, photosensitization and H-donating reactions was integrated.