Heterogeneous conversion of NO2 on carbonaceous surfaces

Abstract

In the present study the heterogeneous conversion of NO2 on commercial soot, freshly prepared flame soot and commercial soot treated with sulfuric acid has been investigated. The experimental results indicate a complex reaction mechanism in which the soot has to be treated as a reactant leading to deactivation of active sites on the surface with increasing NO2 consumption. Mean uptake coefficients γ for the first few minutes of the reaction of ∽10-6 have been determined for a consumption of ∽1013 NO2 cm-2. The γ-values decrease to <10-8 for a consumption of ∽1015 NO2 cm-2, indicating that the influence of soot on the partitioning of NOx in the atmosphere is negligible. Nitrous acid (HONO) and nitric oxide (NO) were found to be the major gas phase products. HONO yields up to 80% are observed, clearly showing that the nature of the reaction is non-catalytic. The humidity dependence of the reaction system was studied and indicates that water is necessary for HONO formation. In the reaction of pure HONO on soot surfaces, high yields of NO were observed, indicating a consecutive process: NO2→HONO→NO. When soot was coated with sulfuric acid the yield of HONO decreased while that of NO increased. This behaviour is caused by an increasing reactivity of the intermediate HONO on the modified surface. The experimental results indicate that without any recycling mechanism HONO formation on soot surfaces is not of major importance in the atmosphere.