In this work, transient and SSITKA experiments with isotopic 1802 were conducted to study the nature of oxygen species participating in the reaction of ethane oxidative dehydrogenation to ethylene and obtain insight in the mechanistic aspects of the ODH reaction over Ni-based catalysts. The study was performed on NiO, a typical total oxidation catalyst, and a bulk Ni-Nb-O mixed-oxide catalyst (Ni0.85Nb0.15) developed previously [E. Heracleous, A.A. Lemonidou, J. Catal., in press], a very efficient ethane ODH material (46% ethene yield at 400 degrees C. The results revealed that over both materials, the reaction proceeds via a Mars-van Krevelen-type mechanism, with participation of lattice oxygen anions. However, the O-18(2) exchange measurements showed a different distribution of isotopic oxygen species on the two materials. The prevalent formation of cross-labelled oxygen species on NiO indicates that dissociation of oxygen is the fast step of the exchange process, leading to large concentration of intermediate electrophilic oxygen species on the surface, active for the total oxidation of ethane. Larger amounts of doubly exchanged species were observed on the Ni-Nb-O catalyst, indicating that doping with Nb makes diffusion the fast step of the process and suppresses formation of the oxidizing species. Kinetic modeling of ethane ODH over the Ni0.85Nb0.15 catalyst by combined genetic algorithm and nonlinear regression techniques confirmed the above, since the superior model is based on a redox parallel-consecutive reaction network with the participation of two types of active sites: type I, responsible for the ethane ODH and ethene overoxidation reaction, and type II, active for the direct oxidation of ethane to CO2. The kinetic model was able to successfully predict the catalytic performance of the Ni0.85Nb0.15 catalyst in considerably different experimental conditions than the kinetic experiments (high temperature and conversion levels). (c) 2005 Elsevier Inc. All rights reserved.