Activation Energies of the Addition of O(3P) Atoms to Olefins

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Abstract
Modulated generation of the ground electronic state oxygen atoms, O(3P), and phase-shift measurements have been used to determine the rates of O(3P) addition to ethylene, propylene, 1-butene, and isobutene in the temperature interval 25–200°C. Absolute values of the Arrhenius activation energies and pre-exponential factors have been determined and compared with the corresponding previous relative data from this laboratory and with other absolute measurements reported in the literature. Most of the experimental results are now seen to be mutually consistent. The apparently different previous conclusions regarding the activation energies of the O(3P) reactions with olefins based, respectively, on the relative and the absolute rate measurements can be reconciled in a simple manner. The rate constants and the Arrhenius parameters for the reaction of O(3P) atoms with NO have also been determined.