Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition
Atmospheric Chemistry and Physics Discussions
Secondary organic aerosols (SOA) account for a large fraction of submicron particles in the atmosphere. SOA can occur in amorphous solid or semi-solid phase states depending on chemical composition, relative humidity (RH), and temperature. The phase transition between amorphous solid and semi-solid states occurs at the glass transition temperature (<i>T</i><sub>g</sub>). We have recently developed a method to estimate <i>T</i><sub>g</sub> of pure compounds containing carbon, hydrogen, and
... hydrogen, and oxygen atoms (CHO compounds) with molar mass less than 450&thinsp;g&thinsp;mol<sup>&minus;1</sup> based on their molar mass and atomic O&thinsp;:&thinsp;C ratio. In this study, we refine and extend this method for CH and CHO compounds with molar mass up to ~&thinsp;1100&thinsp;g&thinsp;mol<sup>&minus;1</sup> using the number of carbon, hydrogen, and oxygen atoms. We predict viscosity from the <i>T</i><sub>g</sub>-scaled Arrhenius plot of fragility (viscosity vs. <i>T</i><sub>g</sub>&thinsp;/&thinsp;<i>T</i>) as a function of the fragility parameter <i>D</i>. We compiled <i>D</i> values of organic compounds from literature, and found that <i>D</i> approaches a lower limit of ~&thinsp;10 (&plusmn;1.7) as the molar mass increases. We estimated viscosity of α-pinene and isoprene SOA as a function of RH by accounting for hygroscopic growth of SOA and applying the Gordon-Taylor mixing rule, reproducing previously published experimental measurements very well. Sensitivity studies were conducted to evaluate impacts of <i>T</i><sub>g</sub>, <i>D</i>, hygroscopicity parameter (κ), and the Gordon-Taylor constant on viscosity predictions. Viscosity of toluene SOA was predicted using the elemental composition obtained by high-resolution mass spectrometry (HRMS), resulting in a good agreement with the measured viscosity. We also estimated viscosity of biomass burning particles using the chemical composition measured by HRMS with two different ionization techniques: electrospray ionization (ESI) and atmospheric pressure photoionization (APPI). Due to differences in detected organic compounds and signal intensity, predicted viscosities at low RH based on ESI and APPI measurements differ by 2&ndash;5 orders of magnitude. Complementary measurements of viscosity and chemical composition are desired to further constrain RH-dependent viscosity in future studies.