
Journal of Physical Chemistry p. 4563 - 4569 (1982)
Update date:2022-08-10
Topics:
Atkinson, Roger
Aschmann, Sara M.
Carter, William P. L.
Winer, Arthur M.
Pitts, James N.
The yields of alkyl nitrates formed in the NOx-air photooxidations of the homologous series of n-alkanes from ethane through n-octane have been determined at 299 +/- 2 K and 735 torr total pressure for two different chemical systems.Alkyl peroxy radicals were generated by reaction of the n-alkanes with OH radicals (generated from the photolysis of methyl nitrite in air) or Cl atoms (from photolysis of Cl2 in air).The alkyl nitrate yields obtained from the two systems, corrected for secondary reactions, were in agreement within the experimental errors and increased monotonically with the carbon number of the n-alkane, from = 1percent for ethane to ca. 33percent for n-octane, with the yields apparently approachimg a limit of ca. 35percent for large n-alkanes.The relative yields of the various secondary alkyl nitrate isomers in the n-pentane through n-octane systems were in good agreement with those expected from OH radical or Cl atom reaction with the corresponding secondary C-H bonds.However, the relative yields of the primary alkyl nitrates in the propane and butane systems were a factor of ca. 2 lower than expected.The data are consistent with the alkyl nitrates being formed almost entirely from the reaction of peroxy radicals with NO, and the ratios of the corrected alkyl nitrate yields thus reflect the fraction of RO2 radicals which react with NO to form alkyl nitrates.These nitrate yields from the reaction of RO2 radicals with NO are important inputs into chemical computer models of the atmospheric NOx-air photooxidations of the large n-alkanes.
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