The Hygroscopic Properties of Dicarboxylic and Multifunctional Acids: Measurements and UNIFAC Predictions

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Abstract
The role of water-soluble organic compounds on the hygroscopic properties of atmospheric aerosols has recently been the subject of many studies. In particular, low molecular weight dicarboxylic acids and some multifunctional organic acids have been found or are expected to exist in atmospheric aerosols in urban, semiurban, rural, and remote sites. Unlike for their inorganic counterparts, the hygroscopic properties of organic acids have not been well characterized. In this study, the hygroscopic properties of selected water-soluble dicarboxylic acids (oxalic acid, malonic acid, succinic acid, and glutaric acid) and multifunctional acids (citric acid, dl-malic acid, and l-(+)-tartaric acid) were studied using single droplets levitated in an electrodynamic balance at 25 °C. The water activities of bulk samples of dilute solutions were also measured. Solute evaporation was observed in the dicarboxylic acids but not in the multifunctional acids. Oxalic acid, succinic acid, and glutaric acid droplets crystallize upon evaporation of water, but, except for glutaric acid droplets, do not deliquesce even at 90% relative humidity (RH). Mass transfer limitation of the deliquescence process was observed in glutaric acid. Neither crystallization nor deliquescence was observed in malonic acid, citric acid, dl-malic acid, or l-(+)-tartaric acid. Malonic acid and these three hydroxy-carboxylic acids absorb water even at RH much lower than their respective deliquescence RH. The growth factor (Gf), defined as the ratio of the particle diameter at RH = 10% to that at RH = 90%, of oxalic acid and succinic acid was close to unity, indicating no hygroscopicity in this range. The remaining acids (malonic acid, glutaric acid, citric acid, malic acid, and tartaric acid) showed roughly similar hygroscopicity of a Gf of 1.30−1.53, which is similar to that of “more hygroscopic” aerosols in field measurements reported in the literature. A generalized equation for these four acids, Gf = (1−aw)-0.163, was developed to represent the hygroscopicity of these acids. Water activity predictions from calculations using the UNIFAC model were found to agree with the measured water activity data to within 40% for most of the acids but the deviations were as large as about 100% for malic acid and tartaric acid. We modified the functional group interaction parameters of the COOH−H2O, OH−H2O, and OH−COOH pairs by fitting the UNIFAC model with the measured data. The modified UNIFAC model improves the agreement of predictions and measurements to within 38% for all the acids studied.