The oxidative dehydrogenation of ethane (ODE) was studied over Na2O/CaO, Sm2O3/CaO and Sm2O3 catalysts at 923 K using different oxygen partial pressures. The type of interaction of oxygen with these catalysts was derived from measurements of contact potential difference (CPD) between a gold electrode and the catalysts and pulse experiments in the Temporal Analysis of Product (TAP) reactor. Modelling of TAP oxygen responses in the temperature range from 673 to 873 K showed that a reversible dissociative adsorption via a molecular precursor provides a good description of the measured transient responses for all catalysts. Supplementary CPD results confirmed the transformation of adsorbed molecular oxygen species to atomic ones. Rate constants and activation energies of the elementary reaction steps of oxygen adsorption, desorption, dissociation and association were estimated from the TAP oxygen responses. The dependence of ethylene selectivity both on doping and oxygen partial pressure was explained by the ratio of Theta(O)/Theta(O2). This ratio is strongly affected by the constants of adsorption of oxygen and dissociation of molecular adsorbed oxygen.