Rate coefficients at 298 K and 1 atm for the tropospheric degradation of a series of C6, C7 and C8 biogenic unsaturated alcohols initiated by Cl atoms

• Published in: Atmospheric environment (1994) 2014-09, Vol.94, p.564-572
• Main Authors: Gibilisco, Rodrigo G., Bejan, Iustinian, Barnes, Ian, Wiesen, Peter, Teruel, Mariano A.
• Format: Article
• Language: English
• Subjects: (E)-2-hexen-1-ol; (E)-3-hexen-1-ol; (Z)-3-hepten-1-ol; (Z)-3-hexen-1-ol; (Z)-3-octen-1-ol; Alcohols; Applied sciences; Atmospheric pollution; Atmospherics; Chambers; Chemical composition and interactions. Ionic interactions and processes; Chlorine atoms; Correlation; Degradation; Earth, ocean, space; Exact sciences and technology; External geophysics; Meteorology; Nuclear power generation; Pollutants physicochemistry study: properties, effects, reactions, transport and distribution; Pollution; Reaction kinetics; Unsaturated
• ISSN: 1352-2310; 1873-2844
• DOI: 10.1016/j.atmosenv.2014.05.050

Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated biogenic alcohols at 298 ± 3 K and 1 atm have been measured by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained using 1-butene and isobutene as reference compounds were (in units of 10−10 cm3 molecule−1 s−1): k1((E)-2-hexen-1-ol) = (3.49 ± 0.82), k2((E)-3-hexen-1-ol) = (3.42 ± 0.79), k3 ((Z)-3-hexen-1-ol) = (2.94 ± 0.72), k4((Z)-3-hepten-1-ol) = (3.80 ± 0.86) and k5((Z)-3-octen-1-ol) = (4.13 ± 0.68). This work constitutes the first kinetic study of the reactions cited above. The rate coefficients are compared with those for other unsaturated alcohols and a correlation between the reactivity of unsaturated alcohols toward Cl atoms and the energy of the HOMO of the unsaturated alcohols is presented. Based on the obtained results, the atmospheric lifetimes of the unsaturated alcohols have been estimated and possible atmospheric implications assessed. [Display omitted] •First kinetic study of Cl + C6, C7, C8 unsaturated alcohols.•Relative rate coefficients by in situ FTIR detection at 298 K and 1 atm.•Small increase of the rate coefficient with the chain length.•Rate coefficients correlated with the HOMO of the unsaturated alcohol.•Atmospheric lifetimes of hours indicate local impact over on air pollution.