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

J Phys Chem A. 2012 Dec 13;116(49):12096-103. doi: 10.1021/jp307718m. Epub 2012 Nov 29.

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.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Bicyclic Monoterpenes
  • Bridged Bicyclo Compounds / chemistry*
  • Hydroxyl Radical / chemistry*
  • Kinetics
  • Mass Spectrometry
  • Molecular Conformation
  • Monoterpenes / chemistry*
  • Pressure
  • Temperature*

Substances

  • Bicyclic Monoterpenes
  • Bridged Bicyclo Compounds
  • Monoterpenes
  • Hydroxyl Radical
  • beta-pinene
  • alpha-pinene