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The effect of nitrate ions on the electrochemical behaviour of iron (ferrite) and two carbon steels (martensite and pearlite) in sulphate solutions of different pH values was investigated by cyclic voltammetry, polarization and electrochemical impedance spectroscopy The pitting inhibiting effect of nitrate ions on ferrite in sulphate media is pH dependent. Nitrate ions were unable to inhibit the pitting on ferrite in neutral sulphate solutions, but did effectively protect passivated ferrite from pitting in acidic sulphate solutions. No pitting occurred on the surface of the martensite and pearlite specimens in sulphate solutions, regardless of the pH of the solutions. At the open-circuit corrosion potentials, the three materials underwent general corrosion. The impedance spectra for die three materials measured in neutral sulphate solutions containing nitnates and chlorides at the corrosion potentials all showed a capacitive loop, while in acidic sulphate solutions their impedance spectra were greatly reduced in size and displayed at least a low frequency impedance loop (inductive or capacitive loop) besides the well-known high frequency capacitive loop. The variation of the impedance behaviour with pH is explained.