Condensed-phase versus gas-phase ozonolysis of catechol: A combined experimental and theoretical study

Anthropogenic emissions of volatile aromatic compounds contribute to the formation of secondary organic aerosols (SOA), especially in urban environments. Aromatic SOA precursors typically require oxidation by hydroxyl radicals, although recent work suggests that ozonolysis of 1,2-benzenediols produces SOA in high yields. We employed attenuated total reflectance and transmission infrared spectroscopy to investigate the heterogeneous ozonolysis of catechol thin films. Formation of the dominant condensed-phase product muconic acid was highly dependent on relative humidity (RH) with few products detected below 40% RH and a maximum reactive uptake coefficient of γ = (5.6 ± 0.5) × 10−5 measured at 81.2% RH. We also performed quantum chemical calculations mapping out several reaction pathways for the homogeneous ozonolysis of gaseous catechol. 1,3-cycloaddition transition states were rate limiting with the most favorable activation energies at 45.4 and 47.1 kJ mol−1 [CCSD(T)/6-311++G(d,p)] corresponding to addition across and adjacent to the diol CC, respectively. Gas-phase rate constants, calculated using transition state theory, were six orders of magnitude slower than experimental values. In contrast, a calculated activation energy was lower for the ozonolysis of a catechol•H2O complex, which serves as a first-approximation for modeling the ozonolysis of condensed-phase catechol. These combined results suggests that homogeneous ozonolysis of catechol may not be important for the formation of secondary organic aerosols but that ozonolysis of surface-adsorbed catechol may contribute to SOA growth.

► ATR-FTIR identified muconic acid as main product from catechol thin film ozonolysis. ► Thin film catechol + O3 reactive uptake coefficient increased with humidity. ► 1,3-Cycloaddition transition states were rate limiting for gaseous catechol ozonolysis. ► Theoretical rate constant for catechol ozonolysis 106 times slower than experiment. ► Theoretical activation energies for O3 + catechol•H2O much lower than catechol.