The role of ion-molecule reactions in the conversion of N2O5 to HNO3 in the stratosphere

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Atmospheric Chemistry, Gas-Ion Interactions, Ionic Reactions, Molecular Interactions, Nitric Acid, Nitrogen Oxides, Reaction Kinetics, Stratosphere, Acetonitrile, Atmospheric Composition, Atmospheric Density, Catalysis, Ion Density (Concentration), Molecular Ions, Negative Ions, Polar Regions, Positive Ions

Scientific paper

The role of several ion-molecule reactions in the conversion of N2O5 to HNO3 was investigated. In the proposed conversion, an N2O5 molecule would react with an H2O molecule clustered to an inert ion to produce two HNO3 molecules. Subsequent clustering of an H2O molecule to the inert ion would make the reaction catalytic. If such an ion-catalyzed conversion of N2O5 to HNO3 occurs, it would probably play a role in the stratospheric chemistry at high latitudes in winter. Reaction rate constant measurements made in a flowing afterglow apparatus flor hydrated H3O(+), H(+)(CH3CN)m(m equals 1,2,3), and several negative ions reacting with N2O5 are presented. Slow rate constants were found for these ions for hydration levels that are predominant in the stratosphere. With the known stratospheric ion density, these slow rate constants preclude significant N2O5 conversion by ion-molecule reactions.

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