THERMAL-DECOMPOSITION OF DIMETHYLDIOXIRANE

The thermal decomposition of dimethyldiaxirane (DMDO) was followed by uv/vis spectroscopy at 340 nm. At high concentration of DMDO (approximately 0.1M) the decomposition was found to to have an induction period followed by rapid decay. The rapid decay was shown to be caused by presence of reaction products. At low concentration of DMDO (approximately 0.02M) the decomposition was found to be first order with an Ea of 24.9 kcal/mol. Based on this result it is estimated that the dioxybiradical produced by cleavage of the O-O bond shows an activation energy of about 10 kcal/m for reclosure back to the DMDO.