Photolysis of 2,5- and 2,4-Dimethylpyrrole Vapors at Room Temperature

Both 2,5- and 2,4-dimethylpyrrole vapors at pressures from 0.05 to 0.70 Torr were irradiated at 2139 and 2288 Å at room temperature. The products were H2, CH4, C2H6, and polymer. No ring cleavage products were found. Φ{H2} and Φ{CH4} were remarkably insensitive to which pyrrole was used, its pressure,Ia, or the wavelength of the incident radiation. They were ~0.10–0.15 and ~0.01–0.02, respectively. Φ{C2H6} was comparable to Φ{CH4} and was also invariant to which substrate was used or the incident wavelength. However Φ{C2H6} did increase at low pressure or as Ia was reduced.The effect of scavengers showed that the products were produced mainly from free radical precursors. The main primary steps are:[Formula: see text]where DMP* is an electronically excited state of the dimethylpyrrole and Fa and Fb are radical fragments. Experiments with quenching gases showed that DMP* could be quenched, but that this reaction was less important than the first-order steps below 1 Torr.