Reaction of Chlorine Molecules with Unsaturated Submicron Organic Particles

Abstract

The reaction of closed shell Cl

Experimental evidence that halogen bonding catalyzes the heterogeneous chlorination of alkenes in submicron liquid droplets

“…The kinetic evolution of each product generation, n (SqeCl n ), shown in Fig. 1A appears statistical and is consistent with a sequential reaction model analysis 46 conducted by Popolan et al 33 as well as other systems exhibiting multi-generational kinetics. 43–45 The sequential reaction model applies to particles that are well-mixed on the timescale of the reaction, where the population of reactive species in the aerosol ( i.e.…”

“…1A shows the normalized decay of Sqe as a function of Cl 2 exposure, which when fit to an exponential function yields γ Sqe eff = 3.5 × 10 −5 using eqn (1) . This value is slightly smaller than previously reported value by Popolan et al 33 ( i.e. 6.6 × 10 −5 ).…”

“…1C), aer accounting for -(HCl) n elimination produced by dissociative photoionization as shown previously. 33,44 For example, the rst-generation neutral product SqeCl 2 (C 30 H 50 Cl 2 ) appears at a m/z corresponding to either SqeCl (C 30 H 49 Cl) or Sqe-2 (C 30 H 48 ) aer one or two -HCl eliminations, respectively. This pattern is also consistent with -(HI) n elimination observed during dissociative photoionization of iodohydrocarbons.…”

“…Here we examine the heterogeneous reaction of Cl 2 with squalene (Sqe) – a branched hydrocarbon with six C C bonds. This reaction has been previously well-characterized by Popolan et al 33 These prior results are leveraged to examine how the heterogeneous reaction rate depends upon temperature and the presence of small spectator molecules in the gas, which are unreactive towards Cl 2 (water, ethanol, acetone, and acetic acid). We also examine how doping a fatty acid, an ester, alcohol, or an alkane together with squalene in the aerosol phase alters its reactivity towards Cl 2 .…”

The atmospheric chemistry of indoor environments

“…For liquid squalene, the reaction is slower than that of HOCl. 229,230 Together, HOCl and Cl 2 react in the dark with terpenes such as limonene, probably via a surface reaction. 107 Although used at very high mixing ratios in hospitals as a disinfecting agent, there are no studies of H 2 O 2 heterogeneous reactions motivated by potential indoor chemistry.…”