Abstract
The heterogeneous hydrolysis of NO{sub 2} at surfaces in the atmosphere is believed to be a significant source of HONO, a key OH precursor in urban areas. However, the mechanism of this reaction is not known. The uptake of 2.9 Torr of NO{sub 2} in N{sub 2} at a total pressure of 508 Torr on a porous glass surface with varying amounts of surface-adsorbed water was studied using FTIR at 294 K. The ratio of N{sub 2}O{sub 4} to NO{sub 2} was enhanced on the glass surface relative to the gas phase. On a relatively dry surface, the formation of surface-adsorbed HNO{sub 3} was observed over a period of {approximately}20 h, likely due to the reaction with small amounts of water on the surface. Gas-phase NO and N{sub 2}O were also generated. When larger amounts of water were initially present on the surface, surface-adsorbed HNO{sub 3} was formed immediately, as well as gas-phase NO, N{sub 2}O, and HONO. Although the NO{sub 2} concentrations used in the present studies are much larger than those found in the atmosphere, this work suggests that N{sub 2}O{sub 4} should be considered as a key intermediate in the heterogeneous hydrolysis of NO{sub 2} to formmore » HONO.« less
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