Glass Transition Temperatures of Organic Mixtures from Isoprene Epoxydiol-Derived Secondary Organic Aerosol

Abstract

The phase states and glass transition temperatures (T g ) of secondary organic aerosol (SOA) particles are important to resolve for understanding the formation, growth, and fate of SOA as well as their cloud formation properties. Currently, there is a limited understanding of how T g changes with the composition of organic and inorganic components of atmospheric aerosol. Using broadband dielectric spectroscopy, we measured the T g of organic mixtures containing isoprene epoxydiol (IEPOX)-derived SOA components, including 2-methyltetrols (2-MT), 2-methyltetrolsulfate (2-MTS), and 3-methyltetrol-sulfate (3-MTS). The results demonstrate that the T g of mixtures depends on their composition. The Kwei equation, a modified Gordon−Taylor equation with an added quadratic term and a fitting parameter representing strong intermolecular interactions, provides a good fit for the T g -composition relationship of complex mixtures. By combining Raman spectroscopy with geometry optimization simulations obtained using density functional theory, we demonstrate that the non-linear deviation of T g as a function of composition may be caused by changes in the extent of hydrogen bonding in the mixture.