Partial crystallization and deliquescence of particles containing ammonium sulfate and dicarboxylic acids

The partial crystallization and deliquescence of ammonium sulfate (AS) particles internally mixed with malonic acid (MA), glutaric acid (GA), and succinic acid (SA) were studied. Hygroscopic properties, elastic light scattering, and Raman spectra were measured during water uptake and evaporation of single particles suspended in an electrodynamic balance. AS/MA particles remained partially crystallized at RHs as low as 16%, while AS/GA and AS/SA particles became completely dry at about 30-36% RH and below. Partial deliquescence was observed at intermediate RHs of 90% for the AS/MA, AS/GA, and AS/SA particles, respectively. Solid inclusions in various amounts were in equilibrium with the aqueous solutions. The Raman spectra show solid inclusions of both AS and MA in AS/MA particles, suggesting the heterogeneous crystallization of MA on solid AS. AS was found to deliquesce first at 76% RH in the AS/GA system, followed by GA at 78% RH. In the SA/AS system, AS was observed to dissolve at 80% RH, while SA remained as solid for RH as high as 90%. Comparisons to the thermodynamic model E-AIM demonstrated the necessity to correctly predict the solid phase during partial deliquescence for accurate water content estimation. The Raman spectra also revealed the formation of metastable forms of organic acids upon crystallization from supersaturated droplets of AS/GA and AS/SA. Transformation of metastable solids to stable forms was observed before water uptake in the AS/GA particles, while the SA in AS/SA particles transformed in the presence of water. Copyright 2008 by the American Geophysical Union.