High Intensity Photolysis of Azo Compounds at 3600 A

摘要

The objective of the work was to develop a technique for studying the relative rates of disproportionation and combination of unlike radicals and the first system studied was ethyl - propyl. To obtain this value it was necessary to reinvestigate the rates of disproportionation and combination of ethyl and propyl radicals under high intensity conditions. The ratios were found to be constant with pressure for azo ethane and azo propane photolysis. These ratios are 0.138 = 0.009 for ethyl and 0.142 = 0.015 for propyl radicals. The cross disproportionation to combination ratios were found to be 0.045 = 0.012 for ethylene + propane and 0.049 = 0.016 for ethane + propylene. In addition to the ratios of rate constants, the quantum yields of decomposition were studied as a function of pressure of the azo compounds. Based on the analytical results and the quantum yields, reaction mechanisms for the decomposition of the azo compounds under high intensity conditions were postulated. (Author)