Dissociation constants of relevant secondary organic aerosol components in the atmosphere.

The presented studies focus on measuring the determination of the acidity constant (pKa) of relevant secondary organic aerosol components. For our research, we selected important oxidation products (mainly carboxylic acids) of the most abundant terpene compounds, such as α-pinene, β-pinene, β-caryophyllene, and δ-3-carene. The research covered the synthesis and determination of the acidity constant of selected compounds. We used three methods to measure the acidity constant, i.e., 1H NMR titration, pH-metric titration, Bates-Schwarzenbach spectrophotometric method. Moreover, the pKa values were calculated with Marvin 21.17.0 software to compare the experimentally derived values with those calculated from the chemical structure. pKa values measured with 1H NMR titration ranged from 3.51 ± 0.01 for terebic acid to 5.18 ± 0.06 for β-norcaryophyllonic acid. Moreover, the data determined by the 1H NMR method revealed a good correlation with the data obtained with the commonly used potentiometric and UV-spectroscopic methods (R2 = 0.92). In contrast, the comparison with in silico results exhibits a relatively low correlation (R2Marvin = 0.66). We found that most of the values calculated with the Marvin Program are lower than experimental values obtained with pH-metric titration with an average difference of 0.44 pKa units. For di- and tricarboxylic acids, we obtained two and three pKa values, respectively. A good correlation with the literature values was observed, for example, Howell and Fisher (1958) used pH-metric titration and measured pKa1 and pKa2 to be 4.48 and 5.48, while our results are 4.24 ± 0.10 and 5.40 ± 0.02, respectively.