Effects of Temperature and Physical State on Heterogeneous Oxidation of Oleic Acid Droplets with Ozone

The heterogeneous reactions of pure micrometer-sized oleic acid droplets with ozone were studied as a function of temperature and physical state. Oxidation reactions were monitored using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FT-IR) and UV-vis spectrometry. Variations in droplet morphology due to the extent of oxidation were monitored using an optical microscope. Oleic acid droplets were maintained in either solid or liquid state at 9.0 °C. The physical state of the aerosol was determined from the IR absorbance spectra. Oxidation of solid state oleic acid with ozone at 9.0 °C was rapidly converted to the liquid state, which was most likely due to the presence of oxidation products on the surface of the droplets. The fast melting process that resulted from exposure of solid-phase droplets to ozone produced an oxidation rate similar to that for liquid-phase droplets exposed to ozone at the same temperature. Analysis of the carboxylic IR absorbance ratio for esters vs carboxylic acids indicates that the larger ester C═O-to-carboxylic acid C═O ratios at higher temperature appeared to correspond to the production of α-acyloxyalkyl hydroperoxide oligomers and polymers. The wide variation in product yields will result in vastly different physical properties of aerosol particles under different ambient environmental conditions.