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Effects of temperature and pressure on alkyl nitrate yields in the NO/sub x/ photooxidations of n-pentane and n-heptane

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100234a034· OSTI ID:6856492

The yields of alkyl nitrates formed in the NO/sub x/ photooxidations of n-pentane and n-heptane have been determined as a function of temperature (284-341 K) and pressure (56-740 torr). Alkyl peroxy radicals were produced by reaction of the n-alkanes with OH radicals generated from the photolysis of methyl nitrite in air or O/sub 2/. The alkyl nitrate yields were observed to be markedly temperature and pressure dependent, increasing with increasing pressure and decreasing temperature. These yields reflect the fraction of RO/sub 2/ radicals which react with NO to yield alkyl nitrates, and are thus important inputs into chemical computer models of the atmospheric NO/sub x/ photooxidations of the n-alkanes. The observed effects of pressure and temperature on the alkyl nitrate yields are discussed in terms of the mechanistic and thermochemical details of the RO/sub 2/ + NO reaction system, and a general empirical formula giving the alkyl nitrate yields for the C/sub 3/ through C/sub 8/ n-alkanes as a function of temperature and prssure is derived.

Research Organization:
Univ. of California, Riverside
OSTI ID:
6856492
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 87:11; ISSN JPCHA
Country of Publication:
United States
Language:
English