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While these reactions would be negligible for CH 3O 2 and aliphatic RO 2 at room temperature, this might not be the case for acyl-, and perhaps hydroxy-, allyl- and other substituted RO 2. Monitoring directly the radicals with chemical ionization mass spectrometry led to rate coefficients larger than expected from previous combustion studies but following similar trends in terms of alkenes, with (in molecule −1 cm 3 s −1) = 10 −18 to 10 −17 × 2/2 and = 10 −14 to 10 −13 × 5/5.

In this work, the reactions of methyl-, 1-pentyl- and acetylperoxy radicals (CH 3O 2, C 5H 11O 2, and CH 3C(O)O 2, respectively) with 2-methyl-2-butene, 2,3-dimethyl-2-butene and for the first time the atmospherically relevant isoprene, α-pinene, and limonene were studied at room temperature (298 ± 5 K). Until now the reactions of organic peroxy radicals (RO 2) with alkenes in the gas phase have been essentially studied at high temperature ( T ≥ 360 K) and in the context of combustion processes, while considered negligible in the Earth's atmosphere.