Gas phase thermal and oxidative dehydrogenation of ethane and propane are explored experimentally and mikrokinetically. Kinetic data for the elementary reactions postulated were adopted from the literature. The results show that oxygen plays a dominating role in the primary activation of the alkanes by producing an HO2 center dot and a hydrocarbon radical. The kinetic sequences developed predict satisfactorily conversion and products yields for ethane and propane oxidative dehydrogenation. (c) 2005 Elsevier B.V. All rights reserved.