Water content and phase transitions in particles of inorganic and organic species and their mixtures using micro-Raman spectroscopy

Hygroscopicity and phase transitions were measured with deposited particles of ammonium sulfate (AS), ammonium nitrate (AN), malonic acid (MA), glutaric acid (GA), glyoxylic acid (GlyA), as well as two mixed particle systems AS-MA and AS-GA using micro-Raman spectroscopy. Hygroscopicity was presented in terms of water-to-solute mass ratios, which were obtained from the integrated area ratios of the Raman water band to a distinct solute peak. Deliquescence and crystallization were confirmed by abrupt changes in the Raman peak positions and the full-width-half-heights of distinct solute peaks. The results for AS, AN, MA, and GA agreed well with literature reports and model predictions. For GlyA, we detected the Raman water band at near 0% RH, indicating that the spectral technique is sensitive for hygroscopic measurements at very low RH. Additional spectral feature at 0% RH was also observed. In the case of more complicated AS-dicarboxylic acid mixed systems, the partial phase transitions of the organic components were identified using the intensity ratios of aqueous to solid C = O peaks. AS-MA particles did not completely crystallize and gradual water uptake with increasing RH from 3% was observed. Moreover, it was found that AS-GA particles showed step-wise crystallization in which the AS fraction crystallized prior to the GA fraction. The measured water content and complete DRH of both mixed systems were consistent with the published values. The results show the utility of micro-Raman spectroscopic analysis in studying hygroscopicity and phase characterizations of the chemical species in mixed particles.