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DOI: 10.1039/A805440A (Paper) Reference Section for: J. Chem. Soc., Faraday Trans., 1998, 94, 3289-3292

Investigation of the heterogeneous NO2 conversion on perchloric acid surfaces

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J. Kleffmann, K. H. Becker and P. Wiesen

Abstract

The heterogeneous conversion of NO2 on perchloric acid surfaces into HONO, HNO3 and N2O was investigated in a bubbler system under simulated atmospheric conditions. NO2, HONO and N2O were monitored time resolved by long-path tunable infrared diode laser absorption spectrometry using single vibrational rotational lines. The experimental results show that NO2 is heterogeneously converted on acid surfaces into HONO and consecutively into N2O. HONO formation in the reaction system occurs by the heterogeneous reaction of NO2 with water. The solubility of HONO in perchloric acid was determined at 298 K as a function of the acid concentration. The effective Henry's law constant (KHeff) is well described by:

The experimental findings indicate that the nitrosyl ion (NO+) plays an important role in converting HONO into N2O and HNO3. A reaction scheme is proposed which is in excellent agreement with the experimental observations. For the global source strength of N2O by heterogeneous conversion processes on acidic aerosols an upper limit of ca. 300 kt N2O year-1 was estimated which indicates that these reactions are probably of minor importance for the global N2O budget.

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