Kinetics of the Gas-Phase Reactions of OH and NO3 Radicals and O3 with the Monoterpene Reaction Products Pinonaldehyde, Caronaldehyde, and Sabinaketone

Abstract

Using a relative rate method, rate constants have been measured for the gas-phase reactions of OH and NO3 radicals with pinonaldehyde, caronaldehyde and sabinaketone at 296 ± 2 K. The OH radical reaction rate constants obtained are (in units of 10−12 cm3 molecule−1 s−1): pinonaldehyde, 48 ± 8; caronaldehyde, 48 ± 8; and sabinaketone, 5.1 ± 1.4, and the NO3 radical reaction rate constants are (in units of 10−14 cm3 molecule−1 s−1): pinonaldehyde, 2.0 ± 0.9; caronaldehyde, 2.5 ± 1.1; and sabinaketone, 0.036 ± 0.023, where the error limits include the estimated overall uncertainties in the rate constants for the reference compounds. Upper limits to the O3 reaction rate constants were also obtained, of <2 × 10−20 cm3 molecule−1 s−1 for pinonaldehyde and caronaldehyde, and <5 × 10−20 cm3 molecule−1 s−1 for sabinaketone. These reaction rate constants are combined with estimated ambient tropospheric concentrations of OH radicals, NO3 radicals and O3 to calculate tropospheric lifetimes and dominant transformation process(es) of these and other monoterpene reaction products.