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The ratio of final products is dependent on the structure of the individual alkenes. 28 For the less alkyl substituted alkenes, there is a greater yield of HOx and bifunctional organic nitrate products but a lesser regeneration of NOx. Therefore, depending on the mix of hydrocarbons, NO3 chemistry can act to either recycle NOx, therefore inhibiting the formation of nitrate 43 Chemistry of the Atmosphere aerosol or HNO3 at night and potentially lead to the generation of a night-time source of HOx.

This situation often pertains in urban areas where NOx levels are high and other potential oxidants of NO to NO2 such as peroxy radicals are suppressed. 25) has to be modified as 27 Chemistry of the Atmosphere the NO/NO2 partitioning is shifted to favour NO2, viz ½NO2 Š ¼ ðk2:24 ½O3 Š þ k2:19 ½HO2 Š þ k2:21 ½RO2 ŠÞ=j2:2 ½NOŠ ð2:27Þ Though the radical concentrations are typically ca. 1000 times smaller than the [O3], the rate of the radical oxidation of NO to NO2 is ca. 500 times larger than the corresponding oxidation by reaction with O3.

The nitrate radical is highly reactive towards certain unsaturated hydrocarbons such as isoprene, a variety of butenes and monoterpenes, as well as reduced sulfur compounds such as dimethylsulfide (DMS). 58) are relatively slow, with the alkyl radical reacting with oxygen under atmospheric conditions to form a peroxy radical. In the case of RH being an aldehyde, acyl products will form acylperoxy radicals (R Á CO Á O2), potential sources of peroxyacylnitrates. 3 The reaction channel that produces the nitrated acetones also yields peroxy radicals, leading to the potential for a night-time source of OH, either by reaction (HO2 þ O3) or by the direct reaction of the peroxy radical with NO3.

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