Quantification of hydroxycarbonyls from OH-isoprene reactions.
Hydroxycarbonyls arising from OH-initiated reactions of isoprene have been quantified by the technique of a flow reactor coupled to proton-transfer reaction mass spectrometry (PTR-MS) detection. The yields of C5- and C4-hydroxycarbonyls are (19.3 +/- 6.1)% and (3.3 +/- 1.6)%, respectively, measured at a flow tube pressure of about 100 Torr and at a temperature of 298 +/- 2 K. A yield of (8.4 +/- 2.4)% is obtained for the unsaturated carbonyl C5H8O, confirming that internal OH addition represents the minor channel in the initial OH-isoprene reaction. The results show that those carbonyl compounds account for the most previously unquantified carbon, enabling the isoprene carbon closure. The study also reveals novel aspects of the delta-hydroxyalkoxy radical degradation mechanism, which is essential for modeling tropospheric O3 formation. In addition, this work demonstrates the application of PTR-MS for quantification of products of hydrocarbon reactions, which should have profound impacts on elucidation of the chemistry of atmospheric anthropogenic and biogenic hydrocarbons.
Zhao
Jun
J
Department of Atmospheric Sciences, Texas A&M University, College Station, Texas 77843, USA. zhang@ariel.met.tamu.edu
Zhang
Renyi
R
Fortner
Edward C
EC
North
Simon W
SW