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Gas-phase reaction of NO3 radicals with isoprene: a kinetic and mechanistic study

✍ Scribed by Torsten Berndt; Olaf Böge

Publisher
John Wiley and Sons
Year
1997
Tongue
English
Weight
233 KB
Volume
29
Category
Article
ISSN
0538-8066

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✦ Synopsis

The gas-phase reaction of NO 3 radicals with isoprene was investigated under flow conditions at 298 K in the pressure range 6.8 Ͻ P(mbar) Ͻ 100 using GC-MS/FID, direct MS, and long-path FT-IR spectroscopy as detection techniques. By means of a relative rate method, the rate constant for the primary attack of NO 3 radicals toward isoprene was determined to be (6.86 Ϯ 2.60) ϫ 10 Ϫ13 cm 3 molecule Ϫ1 s Ϫ1 .

The formation of the possible oxiranes, 2-methyl-2-vinyl-oxirane and 2-(1-methyl-vinyl)oxirane, was observed in dependence on total pressure.

In the presence of O 2 in the carrier gas, the product distribution was found to be strongly dependent on the reaction pathways of formed peroxy radicals. If the peroxy radicals mainly reacted in a self-reaction, the formation of organic nitrates was detected and 4-nitroxy-3methyl-but-2-enal was identified as a main product. On the other hand, when NO was added to the gas mixture and the peroxy radicals were converted via RO 2 ϩ NO : RO ϩ NO 2 , the formation of methyl vinyl ketone as the main product as well as 3-methylfuran and methacrolein was observed.

From the ratio of the product yields if NO was added to the gas mixture it was concluded that the attack of NO 3 radicals predominantly takes place in the 1-position.

A reaction mechanism is proposed and the application of these results to the troposphere are discussed.

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