The catalytic oxidation of carbon monoxide on Fe catalyst was studied at 300-500degreesC and atmospheric total pressure. The reaction was studied under both open- and closed-circuit operation in an yttria-stabilized zirconia solid electrolyte cell. The technique of Solid Electrolyte Potentiometry (SEP) was used to monitor the thermodynamic activity of oxygen adsorbed on the Fe electrode under open circuit. Kinetic and potentiometric measurements were combined in order to elucidate the reaction mechanism. The results are in agreement with a Langmuir-Hinselwood type of adsorption-reaction with two different adsorption sites for carbon monoxide and oxygen. Under closed circuit, the effect of electrochemical oxygen "pumping" to the catalyst was examined. The operation of the cell was almost Faradaic as the rate enhancement factor (A) values measured were close to unity.