Perovskites, with exclusive selectivity for oxygen over nitrogen, offer significant promise as potential high temperature adsorbents for air separation. Results from fixed bed, breakthrough experiments at 500 C on two perovskite samples having compositions SrCo0.5Fe0.5O3-delta and La0.1Sr0.8Ag0.1Co0.5Fe0.5 O3-delta that were short-listed in our previous thermogravimetric study are presented here. The oxygen equilibrium capacities obtained from the breakthrough runs compared well with those from the thermogravimetric data. A numerical simulation model featuring axially dispersed plug flow with independently estimated axial dispersion coefficient, Langmuir isotherm fitted to the measured equilibrium data, and a linear driving force rate expression for mass transfer with a large rate constant was developed that effectively captured the essential features of the measured column dynamics.