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A kinetic and mechanistic study of the formation of alkyl nitrates in the photo-oxidation of n-heptane studied under atmospheric conditions

✍ Scribed by Stephen J. Harris; J. Alistair Kerr

Publisher: John Wiley and Sons
Year: 1989
Tongue: English
Weight: 542 KB
Volume: 21
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550210306

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✦ Synopsis

The photo-oxidation of n-heptane in synthetic air containing methyl nitrite and nitric oxide has been ivestigated in an atmospheric flow reactor. By measuring the total yields of heptyl nitrate products, relative to the depletion of the n-heptane, the rate constant ratio, k36/k30 has been determined for the reactions:

Over the temperature range 253-325 K and a t a total pressure of 730 Torr, the following relative Arrhenius equation has been obtained from the present study together with literature data:

These results confirm that the formation of alkyl nitrates from the photo-oxidation of n-alkanes arise from a primary reaction between the alkylperoxy radicals and nitric oxide. Furthermore the present experiments show that the lifetime of the intermediate in this type of reaction, presumed to be an alkyl peroxynitrite, ROONO, must be less than a few seconds.

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