Authors
Hannah K. Maben (CIRES), Paul J. Ziemann (CIRES)

Abstract

Organic aerosols decrease visibility, and negatively impact human and environmental health. Volatile organic compounds (VOCs) are emitted into the atmosphere, either biogenically or anthropogenically, can then be oxidized to form products that can partition into secondary organic aerosol (SOA). These products can undergo heterogeneous (surface) and multiphase (bulk) reactions, which impact the formation, composition, and chemical-physical properties of aerosol. Despite all of this, models/data describing the kinetics and equilibria of these reactions are lacking. To investigate these reactions a synthesized probe is used to determine the kinetics and equilibria for a single organic phase and an acid catalyzed reaction. The probe molecule with a carboxy substituent contains a nitrate group that absorbs in the UV so the reaction can be monitored using High-Performance Liquid Chromatography (HPLC) with UV-Vis detection. The probe is mixed with an alcohol (1-Octanol) and the reaction is monitored over 24 h to determine the rate and equilibrium constants. Sulfuric acid can be added as an acid catalyst. The carboxynitrate probe did not react with 1-Octanol in a single organic phase, but it did react when sulfuric acid was added. The catalyzed rate constants and equilibrium constant were found to be kf,c = 0.16 M-2 h-1, kr,c = 0.054 M-2 h-1 and 2.9 respectively.