Effect of chemical structure on secondary organic aerosol formation from C_(12) alkanes

The secondary organic aerosol (SOA) formation from four C_(12) alkanes (n-dodecane, 2-methylundecane, hexylcyclohexane, and cyclododecane) is studied in the Caltech Environmental Chamber under low-NO_x conditions, in which the principal fate of the peroxy radical formed in the initial OH reaction is reaction with HO_2. Simultaneous gas- and particle-phase measurements elucidate the effect of alkane structure on the chemical mechanisms underlying SOA growth. Reaction of branched structures leads to fragmentation and more volatile products, while cyclic structures are subject to faster oxidation and lead to less volatile products. Product identifications reveal that particle-phase reactions involving peroxyhemiacetal formation from several multifunctional hydroperoxide species are key components of initial SOA growth in all four systems. The continued chemical evolution of the particle-phase is structure-dependent, with 2-methylundecane SOA formation exhibiting the least extent of chemical processing and cyclododecane SOA achieving sustained growth with the greatest variety of chemical pathways. The extent of chemical development is not necessarily reflected in the oxygen to carbon (O : C) ratio of the aerosol as cyclododecane achieves the lowest O : C, just above 0.2, by the end of the experiment and hexylcyclohexane the highest, approaching 0.35.