Investigation of solid-phase ozonolysis reactions for use in a personal sampling method for ozone

Three ozonolysis reactions were tested in the solid phase for reproducibility and quantitative yield of an aldehyde reaction product. The three starting olefins were t-stilbene, 4,4'-dimethoxystilbene and 1,2-di-(4-pyridyl) ethylene which, when reacted with ozone, gave benzaldehyde, p-anisaldehyde and pyridine-4-aldehyde, respectively. The starting olefins were coated on a variety of solid substrates, exposed to known ozone concentrations and then analyzed for the corresponding aldehyde with a gas chromatograph equipped with a flame-ionization detector. The best combination found for all three reactions was with the starting olefin coated on 30/60 mesh Florisil. Consistent yield was obtained for the methoxystilbene reaction within one batch of sorbent; very reproducible results were obtained within four replicate samples for the pyridyl ethylene reaction. No consistency was obtained, however, with any of the reactions between batches of sorbents and between different sets of samples. Several problems were identified which led to the inconsistent results. The t-stilbene and pyridyl ethylene sorbents oxidized over time while stored to form high aldehyde blanks. All three aldehydes, once formed on the sorbent, were volatilized off the sorbent bed as a result of airflow through the bed. Several different solid sorbents were tried unsuccessfully as traps for the purged aldehydes. Finally, lower flow rates resulted in the finding that significant amounts of the aldehydes also were being formed by oxygen in the air sample. Since oxygen was a strong positive interferent, these reactions were considered unacceptable as indicators of ozone.