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

Kinetic Measurements of Cl Atom Reactions with C5–C8 Unsaturated Alcohols

“…Three hexenols among this series were also studied in the present work. The obtained rate constants are in good agreement with Gibilisco et al [39], with the relative differences between our determinations and Gibilisco et al's determinations [39] Atmosphere 2020, 11, 256 8 of 15 being of the order of 10% or less for all hexenols. For 1-octen-3-ol, no other measurements are available in the literature.…”

“…These very high local concentrations of Cl 2 may accelerate the reaction with the studied alcohol in the dark within the first few minutes after Cl 2 injection. Details concerning such dark reactions were already reported in previous studies for similar structurally unsaturated compounds [38,39,[48][49][50]. Nevertheless, these suspected side reactions are not expected to modify the kinetic measurements since (1) alcohol concentrations were stabilized a few minutes after the Cl 2 injection, and (2) studied kinetics between unsaturated alcohols and Cl atoms are very fast compared to the kinetics of these side reactions.…”

“…A series of reactions between Cl atoms and several unsaturated alcohols was investigated by Gibilisco et al [39] using Cl 2 as a source of Cl atoms. Three hexenols among this series were also studied in the present work.…”

“…In order to better understand the role of the OH group in the unsaturated alcohol chains, the rate constants for the reaction of five unsaturated alcohols with Cl atoms were compared to the rate Considering the series of 2-alken-1-ols (red) with 2-propen-1-ol [49], 2-buten-1-ol [50], (Z)-2-penten-1-ol ( [38] and this work), and (E)-2-hexen-1-ol ( [39] and this work), the increase in chain length seems to lead to higher rate constants. A similar trend is also observable for the reaction of Cl atoms with the series of 3-alken-1-ols (blue) with 3-buten-1-ol [62], (E)-3-hexen-1-ol, (Z)-3-hexen-1-ol ( [39] and this work), (Z)-3-hepten-1-ol, and (Z)-3-octen-1-ol [39]. The activation effect of the chain length on the rate constants was also observed in previous works for the reaction of Cl atoms with linear alcohols [63] and alkenes [22,[64][65][66].…”

“…The kinetics of (Z)-2-penten-1-ol with Cl atoms was solely determined in 2010 in a 400-L Teflon bag, using off-line gas chromatography with a flame ionization detector (GC-FID) and following a relative-rate kinetic approach [38]. For unsaturated hexenols, the rate constants for (E)-2-hexen-1-ol, (E)-3-hexen-1-ol, and (Z)-3-hexen-1-ol were determined only once also using the relative-rate kinetic approach in a 1080-L quartz glass simulation chamber with in situ Fourier-transform infrared (FTIR) spectroscopy [39]. No data are available regarding the rate constant of 1-octen-3-ol with chlorine atoms.…”