Reinvestigation of Some Absolute Rate Measurements of O-Atom Reactions with Olefins

Abstract

The rate constants, activation energies, and pre‐exponential factors for the primary reactions of atomic oxygen with ethylene, butene‐1, iso‐butene, and cis‐butene‐2 have been determined. The measurements were carried out in a fast‐flow system in which O atoms were produced by electrical discharge. Possible sources of error such as the presence of O₂ and the effect of surface reactions are shown to be unimportant. The results show a systematic deviation from those of previous studies in which a photolysis technique was used to obtain relative rate data. The possibility of secondary attack on the olefins is discussed and considered an unlikely cause for the observed discrepancies.