Heterogeneous chemistry of octanal and 2, 4‐hexadienal with sulfuric acid
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Recent experimental studies using the environmental chamber have suggested that acid-catalyzed particle-phase reactions of organic carbonyls lead to multifold increases in secondary organic aerosol (SOA) mass, but the kinetics and mechanism of the heterogeneous chemistry of carbonyls with sulfuric acid remain largely uncertain. We report the first measurements of heterogeneous uptake of octanal and 2, 4-hexadienal on liquid H2SO4 in the acid range of 60 to 85 wt % and between 250 and 298 K. Octanal was physically absorbed by sulfuric acid without undergoing irreversible reaction. From the time-dependent uptake the effective Henry's law solubility constant (H*) was determined. Irreversible reactive uptake was observed for 2, 4-hexadienal, and the uptake coefficient decreased with decreasing acid concentrations. The uptake of octanal and 2, 4-hexadienal on liquid H2SO4 is explained by aldol condensation, dependent on acidity. The results suggest that aldol condensation of the aldehydes can be important in the upper troposphere, but may not significantly contribute to secondary organic aerosol formation in the lower troposphere. Copyright 2005 by the American Geophysical Union.
author list (cited authors)
Zhao, J., Levitt, N. P., & Zhang, R.