Chemical reactions and transport of alkanes and their products in the troposphere

The product distributions have been calculated for more abundant alkanes contributing most of the carbon atoms in the alkane fraction of an ambient air hydrocarbon mixture reasonably representative of U.S. emissions. The effects of ambient temperatures on product yields has been calculated for a range of temperatures from 250 to 330 K. The sensitivity of product yields to uncertainties in alkoxy radical process rate constants has been examined with emphasis on uncertainties in decomposition reactions. Chemical lifetimes are estimated at 300 K under summertime conditions for hydrocarbons and for products of alkane photooxidation in the atmosphere. The atmospheric distribution of alkanes and products is evaluated in terms of the extent to which reaction processes are likely to occur in the planetary boundary layer compared to the free troposphere.The calculations predict a substantial effect of temperature on product yields. A large decrease in alkyl nitrate yields and a smaller decrease in ketone yields occur with increasing temperature. The yields of the short-lived, more reactive aldehydes undergo substantial increases with increasing temperature. Lower yields of ketones and higher yields of aldehydes are associated with the use of higher compared to lower decomposition process rate constants. For the type of U.S. hydrocarbon mixture available from measurements, 16 oxygenated products account for more than 60% of the total alkane carbon atoms converted to products, with most of these carbon atoms accounted for by four products. The effects of increased temperature on product reactivity and radical production may also influence O₃ production.