Temperature dependent kinetic study of the gas phase reaction of ozone with 1-penten-3-ol, cis-2-penten-1-ol and trans-3-hexen-1-ol: Experimental and theoretical data

Carmen Kalalian (1) , G. El Dib (2) , H.J. Singh , P.K. Rao , Estelle Roth (1) , Abdelkhaleq Chakir (1)

1 GSMA - Groupe de spectrométrie moléculaire et atmosphérique
2 IPR - Institut de Physique de Rennes

C5 and C6 unsaturated alcohols are a family of biogenic volatile organic compounds (BVOC) emitted in the atmosphere from vegetation in response to their injuries. In this work, we report the first temperature dependent rate constants for the reaction of three unsaturated alcohols 1-penten-3-ol (1P3OL), cis-2-penten-1-ol (c-2P1OL) and tran-3-hexen-1-ol (t-3H1OL) with ozone in a pyrex reactor coupled to a FTIR spectrometer and to a GC/MS at four different temperatures (273, 298, 313 and 333 K), at atmospheric pressure, using a relative method. The Arrhenius expressions obtained are (cm3 molecule−1 s−1) The studied reactions were also explored theoretically using computational methods based on quantum chemical theory characterizing the intermediates, transition states and the subsequent formation of reaction products. The rate constants were calculated at room temperature employing a modified transition-state theory (MTST). Both results obtained experimentally and theoretically, were discussed in terms of structure-reactivity relationships and temperature dependence. Tropospheric lifetimes of the investigated species with respect to ozone are calculated. The obtained results showed that these species are not persistent towards ozonolysis process.

Mots clés: Rate constants; Tropospheric lifetimes; DFT method; Unsaturated alcohols; Biogenic volatile organic compounds (BVOC); Ozonolysis; Molecular physics

Domaines: Physique [physics]; Sciences de l'environnement

Carmen Kalalian, G. El Dib, H.J. Singh, P.K. Rao, Estelle Roth, et al.. Temperature dependent kinetic study of the gas phase reaction of ozone with 1-penten-3-ol, cis-2-penten-1-ol and trans-3-hexen-1-ol: Experimental and theoretical data. Atmospheric Environment, 2020, 223, pp.117306. ⟨10.1016/j.atmosenv.2020.117306⟩. ⟨hal-02472864⟩