The kinetics of oxygen reduction were studied on passivated iron in bo
rate buffered and unbuffered solutions of pH ranging from 7.4 to 13.8.
A rotating disk electrode was employed. The 02 reduction on iron unde
r these conditions was found to occur on the oxidized surfaces. The re
action orders with respect to 02 and OH- are 1 and -1, respectively, i
n solutions of pH > 11 and 1 and 0 in solutions of pH < 11. The OH - r
eaction order was explained as being due to the acid-base properties o
f the passive film. The Tafel slope value is about -85 mV. In solution
s of pH < 11 there are two Tafel regions, whereas at higher pH values
Tafelian behavior is observed only in the high current density region.
Two reaction mechanisms are proposed having the same rate determining
step which is the adsorption of 02 molecules on Fe(II)ox surface site
s which act as the active centers.