Insights into the Reactions of Hydroxyl Radical with Diolefins from Atmospheric to Combustion Environments

Hydroxyl radicals and olefins are quite important from a combustion and an atmospheric chemistry standpoint. Large amounts of olefinic compounds are emitted into the earth’s atmosphere from both biogenic and anthropogenic sources. Olefins make a significant share in transportation fuels (e.g., up to 20% by volume in gasoline), and they appear as important intermediates during hydrocarbon oxidation. As olefins inhibit low-temperature heat release, they have caught some attention for their applicability in future advanced combustion engine technology. Despite their importance, the literature data for the reactions of olefins are quite scarce. In this work, we have measured the rate coefficients for the reaction of hydroxyl radicals (OH) with several diolefins, namely 1,3-butadiene, cis-1,3-pentadiene, trans-1,3-pentadiene, and 1,4-pentadiene, over a wide range of experimental conditions (T = 294–468 K and p ∼ 53 mbar; T = 881–1348 K and p ∼ 1–2.5 bar). We obtained the low-T data in a flow reactor using lase...