The thermal decomposition of diazomethane (DM) into singlet methylene radicals and nitrogen has been studied from 225° to 450° in 10:1 olefin–diazomethane mixtures. At 2.5 cm pressure, k = 1.2 × 1012 exp (−34,000/RT) sec−1. The methylene radicals have similar reactivity to methylene generated from photolytic decomposition of DM, as judged by the follow-up reactions with ethylene and cis-butene-2. The structural isomerization reactions of energized cyclopropane and the structural and geometric isomerization of 1,2-dimethyl-cyclopropane (DMC), formed from the addition of the thermally generated methylene to the olefins, were measured from 250° to 450° over a wide range of pressures. For comparison, cyclopropane formed from photolysis at 4358 Å and 25° of DM and ethylene was studied. As judged from comparison of the experimental isomerization rate constants, the energy of the cyclopropanes formed at 350° in the thermal DM system is about the same as for cyclopropanes formed by photolysis at 4358 Å of DM at 25°. The experimental rate constants obtained on the assumption of strong collisions are compared with calculated rate constants which are based on quantum statistical models for kE which fit literature data on conventional thermal isomerization of cyclopropane and DMC. From this comparison, the average energies of the formed molecules in the thermal systems are estimated to be between 107 and 115 kcal/mole, depending upon the temperature. Photolysis at 25° of the ketene–ethylene system (3200 Å) and of DM–ethylene system (4358 Å) give cyclopropane characterized as being at 103 and 111 kcal/mole respectively. These energies deduced from kinetic data are compared with available thermochemical quantities; the existing value of ΔHf0(CH2N2) is questioned. Further support for fast intramolecular relaxation of vibrational energy in DMC, relative to the relaxation process for reaction, is noted. Comparison of data in the literature on the ketene and DM photolytic systems strongly suggests that a larger fraction of the excess light energy resides with methylene from ketene (0.65–0.8) than with methylene from DM (0.3–0.5). Various approximations for the calculation of kE are examined and are compared with accurate quantum statistical evaluation.
Time scale considerations on the relaxation of electronic and vibrational energy distributions in a nitrogen afterglow
