Rate Constants for the Gas-Phase β-Myrcene + OH and Isoprene + OH Reactions as a Function of Temperature

摘要

Rate constants for the gas-phase reactions of the hydroxyl radical with the biogenic hydrocarbons, β-myrcene and isoprene, were measured using the relative rate technique over the temperature range 313-413 K and at ~1 atm total pressure. OH was produced by the photolysis of H2O2, and helium was the diluent gas. The reactants were detected by online mass spectrometry, which resulted in high time resolution allowing for large amounts of data to be collected and used in the determination of the Arrhenius parameters. Many experiments were performed over the temperature range of interest, leading to more accurate parameters than previous investigations. The following Arrhenius expression has been determined for these reactions (in units of cm~3 molecule~(-1) s~(-1)): for isoprene k = (3.14_(-0.19)~(+0.20)) X 10~(-11) exp[(338± 19)/T] and for β-myrcene k = (9.19_(-1.89)~(+2.38)) X 10~(-12) exp[(1071 ± 82)/T ].'The Arrhenius plot for the isoprene + OH reaction indicates curvature in this relationship and is given by k = (3.47 ± 0.14) X 10~(-17) T~2 exp((1036± 14)/T]. Our measured rate constant for the β-myrcene + OH reaction at 298 K is higher, but not significantly, than current literature values. This is the first report of β-myrcene's rate constant with OH as a function of temperature.