Journal of Physical Chemistry A, Vol.118, No.45, 10688-10698, 2014
Reaction of Iodine Atoms with Submicrometer Squalane and Squalene Droplets: Mechanistic Insights into Heterogeneous Reactions
The gas-phase reaction of iodine atoms with hydrocarbon molecules is energetically unfavorable, and there is no direct evidence for iodinated product formation by either H abstraction or I addiction reactions at ambient termperature. Here we consider the possible heterogeneous reaction of I atoms with submicrometer droplets composed of a saturated alkane, squalane (Sq), and an unsaturated alkene, squalene (Sqe). The investigations are performed in an atmospheric pressure photochemical flow tube reactor in conjunction with a vacuum ultraviolet photoionization aerosol mass spectrometer and a scanning mobility particle sizer. Squalane, a branched alkane, is unreactive toward I atoms within the signal-to-noise, and an upper limit of the effective reactive uptake coefficient is estimated to be g(I)(Sq) = 8.58 x 10(-7). In contrast, the reaction of I atoms with unsaturated submicrometer squalene droplets results in observable iodinated squalene products. The effective reactive uptake coefficient of I atom with squalene particles is determined to be g(I)(Sqe) = (1.20 +/- 0.52) x 10(-4) at an average I concentration of 1.5 x 10(14) molecules cm(-3).