Abstract
Propionaldehyde at partial pressures of from 0.0006 to 0.04 mm was photooxidized at 3 100 Å in the presence of 150 mm of oxygen. The major products were ethyl hydroperoxide and carbon monoxide. Acetaldehyde was formed at intermediate concentrations and formaldehyde, ethanol, methanol, hydrogen peroxide, and ethane were minor products. No ozone, peroxy acids, or diacyl peroxides could be detected.The results can be explained on the basis of a free-radical mechanism. Certain radical disproportionation reactions which are often postulated are unimportant because of the low partial pressures of propionaldehyde. An alternative mechanism involving direct chemical reaction of an oxygen molecule with the triplet state of the propionaldehyde may be of some significance, but cannot account for all of the products obtained. The present results indicate the importance of alkyl hydroperoxides as products in photooxidations at low partial pressures of aldehyde in the presence of large excesses of oxygen.
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