The results of a study of chemically activated isobutane and neopentane produced by excited singlet-state methylene radical insertion into the secondary and tertiary C-H bonds of propane and isobutane, respectively, are reported. The methylene radicals were produced at two energies by the 4358- and 3660-Å photolyses of diazomethane. The measured decomposition rates for the energized isobutane are 1.9×107 and 3.6×10 7 sec-1 in the 4358- and 3660-Å photolysis systems, respectively, and for the energized neopentane are 4.4×106 and 6.8×106 sec-1 in the 4358- and 3660-Å photolysis systems, respectively. These rates correlate well via RRKM theoretical calculations with thermal A factors in the range of 10 16.3-1016.9 sec-1 for isobutane and 10 16.5-1016.9 sec-1 for neopentane.
|Number of pages||9|
|Journal||The Journal of Chemical Physics|
|State||Published - 1970|