The pH and potential dependencies of the steady‐state iron dissolution and hydrogen evolution reactions were determined for zone‐refined iron in H2‐saturated acidic sulfate solutions. The mechanistic significance of the data is examined in detail. The results of this investigation serve to resolve the conflict concerning the mechanism of iron dissolution in noninhibiting media and to provide an experimental and mechanistic base for the interpretation of the electrochemical behavior of the active iron electrode in inhibiting media.