The corrosion of pure iron in carbon dioxide saturated solutions at low temperatures has been investigated in this study. Both dc polarisation and ac impedance techniques were used in conjunction with a rotating disc electrode to investigate the reaction sequence leading to hydrogen evolution at 30 degrees C. The results indicate that protons from the low pH solution, the bicarbonate ion and the undissociated carbonic acid molecule contribute to the reaction sequence leading to eventual hydrogen evolution. The corrosion mechanism involves both activation and diffusion processes. A rotating disc electrode in combination with ac techniques and the enzyme carbonic anhydrate II, EC 4.2.1.1, were used to characterise the diffusion effects. A chemical-electrochemical cathodic reaction mechanism is proposed.