A SEARCH FOR HOT RADICAL REACTIONS IN FLASH PHOTOLYSIS.

Flash photolysis of diethyl ketone produced carbon monoxide, butane, ethylene, ethane, propane, propionaldehyde, hydrogen and methyl ethyl ketone as products of decreasing importance. The observation of diethyl ketone-d sub 5 among the flash photolysis products of a mixture of diethyl ketone and diethyl ketone-d sub 10 confirmed the importance of the propionyl radical at 24 C and its temperature dependence. While most of the products were explainable in terms of the low intensity photolysis mechanism, it was necessary to postulate reactions of vibrationally hot species to explain the production of hydrogen, propane, methyl ethyl ketone and the large relative yield of ethylene. Observed products from flash photolysis of diethyl mercury at room temperature were butane, ethylene, ethane, propane and hydrogen in decreasing importance. The reaction products from the ethyl mercury radical were not observed. Because of the relatively high yield of ethylene, it was necessary to invoke mechanisms involving reactions of hot ethyl radicals including unimolecular decomposition and disproportionation reactions. Author