Kinetics Study of Reactions of α-Pinene and β-Pinene with Hydroxyl Radical at 1–8 Torr and 240–340 K Using the Relative Rate/Discharge Flow/Mass Spectrometry Method

Abstract

The kinetics of reactions of α-pinene and β-pinene with hydroxyl radicals (OH) has been investigated at 1-8 Torr and 240-340 K using the relative rate/discharge flow/mass spectrometry (RR/DF/MS) technique. Our kinetic results indicate that at 298 K the rate constant of the reactions of α-pinene and β-pinene with hydroxyl radicals has little pressure dependence over the 1-8 Torr pressure range, suggesting that the high pressure limit of these reactions has been reached at 1 Torr. The rate constant of these reactions was found to negatively depend on the temperature at 240-340 K, which is consistent with previous investigations using different techniques. The Arrhenius equation for α-pinene and β-pinene with hydroxyl radical was determined to be k(α-pinene) = (1.21 ± 0.20) × 10(-11)exp[(441 ± 46)/T] cm(3) molecule(-1) s(-1) and k(β-pinene) = (1.65 ± 0.10) × 10(-11)exp[(470 ± 17)/T] cm(3) molecule(-1) s(-1), respectively. Using the rate constant determined at 277 K in this work and the average global hydroxyl radical concentration, the atmospheric lifetime of α-pinene and β-pinene was estimated to be 5.8 and 3.8 h, respectively.