The Oxidation of Formyl Radicals

Abstract

Steady state concentrations of formyl radicals were measured with a photoionization mass spectrometer. The reaction of ethylene with oxygen atoms in a system free of O2 was used to form CHO and CH3. Preliminary experiments showed that the reaction of methyl radicals did not interfere with the CHO measurements. By using low concentrations of O and short reaction times, it was possible to observe the initial growth of the CHO concentration. From the rate of approach of CHO to its steady state concentration, the absolute rate constant for the reaction O + CHO was determined to be (2.1+0.4)×10-10 cm3 molecule-1 sec-1. Addition of molecular oxygen to this system caused a decrease in the steady state CHO concentration, due to the reaction, CHO+O2→HO2+C0 as was suggested by Groth and coworkers in 1938. The rate constant for this reaction was calculated to be (5.7±1.2)×10-12 cm3 molecule-1 sec-1. The importance of these rate constants for combustion and atmospheric reactions are discussed briefly.