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

The presented studies focus on measuring the determination of the acidity constant (pK) 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., H NMR titration, pH-metric titration, Bates-Schwarzenbach spectrophotometric method. Moreover, the pK values were calculated with Marvin 21.17.0 software to compare the experimentally derived values with those calculated from the chemical structure. pK values measured with H 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 H NMR method revealed a good correlation with the data obtained with the commonly used potentiometric and UV-spectroscopic methods (R = 0.92). In contrast, the comparison with in silico results exhibits a relatively low correlation (R = 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 pK values, respectively. A good correlation with the literature values was observed, for example, Howell and Fisher (1958) used pH-metric titration and measured pK and pK to be 4.48 and 5.48, while our results are 4.24 ± 0.10 and 5.40 ± 0.02, respectively.