Reaction of iodine atoms with submicrometer squalane and squalene droplets: mechanistic insights into heterogeneous reactions

J Phys Chem A. 2014 Nov 13;118(45):10688-98. doi: 10.1021/jp5085247. Epub 2014 Nov 4.

Abstract

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 addition reactions at ambient temperature. 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 γI(Sq) ≤ 8.58 × 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 γI(Sqe) = (1.20 ± 0.52) × 10(–4) at an average I concentration of 1.5 × 10(14) molecules·cm(–3).

Publication types

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

MeSH terms

  • Aerosols / chemistry
  • Iodine / chemistry*
  • Kinetics
  • Mass Spectrometry
  • Molecular Structure
  • Photolysis
  • Squalene / analogs & derivatives*
  • Squalene / chemistry*
  • Ultraviolet Rays

Substances

  • Aerosols
  • Squalene
  • Iodine
  • squalane