Connecting the Phase State and Volatility of Dicarboxylic Acids at Elevated Temperatures

The partitioning of semivolatile organic molecules between condensed phases and the vapor phase has broad application across a range of scientific disciplines, with significant impacts in atmospheric chemistry for regulating the evolving composition of aerosol particles. Vapor partitioning depends on the molecular interactions and phase state of the condensed material and shows a well-established dependence on temperature. The phase state of solid organic material is not always well-defined, and many examples can be found for the formation of amorphous subcooled liquid states rather than crystalline solids. This can lead to significant changes to vapor equilibrium processes by modifying the thermodynamics and kinetics of evaporation. Here, we explore the influence of phase state on the evaporation dynamics of a series of straight-chain dicarboxylic acids across a range of above-ambient temperatures. These molecules show an odd/even alteration in some of their properties based on the number of carbon atoms that may be connected to their phase state under dry conditions. Using a newly developed linear-quadrupole electrodynamic balance, we levitate single particles containing the sample and expose them to dry conditions across a range of temperatures (ambient to ∼350 K). Using the rate of evaporation measured from the change in the size or relative mass, we derive the vapor pressure and enthalpy of vaporization. Light scattering data allows for unambiguous identification of the phase of the particles (crystal vs amorphous) allowing the vapor equilibrium properties to be attributed to a particular state. This work highlights a new experimental method for characterizing vapor pressures of low volatility substances and extends the temperature range of available data for the vapor pressure of terminal dicarboxylic acids. These measurements show that crystalline and subcooled liquid states persist at elevated temperatures and provide a direct comparison between subcooled and crystal phases under the same experimental conditions.