RESUMO
The presence or absence of liquid-liquid phase separation (LLPS) in aerosol particles containing oxidized organic species and inorganic salts affects particle morphology and influences uptake into, diffusion through, and reactivity within those particles. We report here an accessible method, similar to ice core analyses, using solutions that are relevant for both aerosol chemical systems and aqueous two-phase extraction systems and contain ammonium sulfate and one of eight alcohols (methanol, ethanol, 1-propanol, 2-propanol, 2-butaonol, 3-methyl-2-butanol, 1,2-propanediol, or 1,3-propanediol) frozen in articulated (bendable) straws to probe LLPS. For alcohols with negative octanol-water partitioning coefficient (K OW) values and O/C ratios ≥0.5, no LLPS occurs, while for alcohols with positive K OW values and O/C ratios ≤0.33, phase separation always occurs, both findings consistent with observations using different experimental techniques. When a third species, glyoxal, is added, the glyoxal stays in the aqueous phase, regardless of whether LLPS occurs. When phase separation occurs, the glyoxal forms a strong intermolecular interaction with the sulfate ion, red-shifting the ν3(SO4 2-) peak by 15 cm-1. These results provide evidence of chemical interactions within phase-separated systems that have implications for understanding chemical reactivity within those, and related, systems.
