Deliquescence phase transition measurements by quartz crystal microbalance frequency shifts

Measurements of the hygroscopic properties of aerosols are needed to better understand the role of aerosols as cloud condensation nuclei. Several techniques have been used to measure deliquescence (solid to liquid) phase transitions in particular. In this study, we have measured the deliquescence relative humidity (DRH) of organic and inorganic salts, organic acids (glutaric and succinic acid), and mixtures of organic acids with ammonium sulfate using a quartz crystal microbalance (QCM). The QCM allows for measurement of the deliquescence phase transition due to inherent measurement differences between solids and liquids in the oscillation frequency of a quartz crystal. The relative humidity dependent frequency measurements can be used to identify compounds that adsorb monolayer amounts of water or form hydrates prior to deliquescence (e.g., lithium chloride, potassium and sodium acetate). Although the amount of water uptake by a deliquescing material cannot be quantified with this technique, deliquescence measurements of mixtures of hygroscopic and nonhygroscopic components (e.g., ammonium sulfate and succinic acid (DRH > 95%)) show that the mass fraction of the deliquescing portion of the sample can be quantitatively determined from the relative change in oscillation frequency at deliquescence. The results demonstrate the use of this technique as an alternative method for phase transition measurements and as a direct measurement of the mass fraction of a sample that undergoes deliquescence. Further, deliquescence measurements by the QCM may provide improved understanding of discrepancies in atmospheric particle mass measurements between filter samples and the tapered element oscillating microbalance given the similar measurement principle employed by the QCM.