Thermodynamic properties of isoprene and monoterpene derived organosulfates estimated with COSMO<i>therm</i>

Organosulfates make significant contributions to atmospheric secondary organic aerosol (SOA), but little is still known about the thermodynamic properties of atmospherically relevant organosulfates. We have used the COSMOtherm program to calculate both gas- and condensed-phase properties of previously identified atmospherically relevant monoterpene and isoprene derived organosulfates. Properties include solubilities, activities and saturation vapor pressures, which are critical to the aerosol phase stability and atmospheric impact of organosulfate SOA. Based on the estimated saturation vapor pressures, the organosulfates of this study can all be categorized as semi- or low-volatile, with saturation vapor pressures 4 to 8 orders of magnitude lower than that of sulfuric acid. The estimated pKa values of all the organosulfates indicate a high degree of dissociation in water, leading in turn to high dissociation corrected solubilities. In aqueous mixtures with inorganic sulfate, COSMOtherm predicts a salting out of both the organosulfates and their sodium salts from inorganic co-solutes. The salting-out effect of ammonium sulfate (less acidic) is stronger than of ammonium bisulfate (more acidic). Finally, COSMOtherm predicts liquid-liquid phase separation in systems containing water and monoterpene derived organosulfates. The COSMOtherm estimated properties support the observed stability of organosulfates as SOA constituents and their long range transport in the atmosphere, but also show significant variation between specific compounds and ambient conditions.