The photolysis of gaseous aldehydes. III. Formaldehyde and mixture of formaldehyde with acetaldehyde, acetone, and carbon dioxide

Abstract

The mechanism of formaldehyde photolysis proposed by Calvert and Steacie (1951) has been re-examined and a formyl chain step included as an essential part of the reaction. In addition, formyl radical decomposition has been considered as a bimolecular process with a higher energy of activation than that assumed by Calvert and Steacie, a result in agreement with the conclusions of the preceding paper of the present series. The experimental energy of activation for the overall photolysis was found to vary continuously with temperature even at 300 �C, where it was 14 kcal mole-1 ; this value cannot be assigned to a single stage in the reaction.