TABLE 3: Calculated values of charge transfer energy decrease ( Ec) and activation energy (E) for the reaction of various peroxyl radicals and propene. Ec values are calculated using and values from table 2, while the activation energies are determined using equation 6.
a The error bound quoted is the standard error in the calculated activation energies. b Experimental values: CH3 C(O)O2,6 HO2.15 c For comparison, an activation energy for methylperoxyl was evaluated using the correlation between activation energy for epoxidation by methylperoxyl radicals and the alkene ionisation energy (figure 1).
Ec(kJ/mol) E (kJ/mol)
CH3C(O)O2 25.3 37.0±5.3a (32.5±3.8)b CH3O2 11.9 61.3±5.3 (57.1±5.2)c HO2 12.0 69.5±5.3 (62.3±5.0)b C2H3C(O)O2 26.1 35.5±5.3 HOC3H6O2 15.4 55.0±5.3 HOCH2O2 18.1 50.1±5.3 C3H5O2 14.1 57.4±5.3