Action of chelators on solid iron in phosphate-containing aqueous solutions

To study the effect of strong iron-ligands on steel corrosion, mild steel electrodes were immersed in solutions containing 20 mM phosphate buffer (pH=7.2) and between 0.01 mM and 1 M of either the iron(II)-chelators 2,2^′-bipyridine or FerroZine, or the iron(III)-chelators citrate or acetylacetonate. Resulting surface reactions were investigated by quantifying the electrochemical potential (E), the electrochemical polarization resistance (R_p), the corrosion current (I_corr) and the release of iron into solution. The surface was further analyzed by scanning electron microscopy (SEM/SEM-EDAX) and atomic force microscopy. Concentrations of 0.1 mM of any of the chelators led to slight, temporary changes in E, I_corr and R_p. Concentrations of 10 mM resulted in characteristic changes of E, which were the same for all chelators and in the precipitation of FePO₄ in the case of citrate and acetylacetonate, or vivianite Fe₃(PO₄)₂ · 8H₂O] in the case of bipyridine and FerroZine. Concentrations of 1 mM of both iron(III)-chelators led to a temporary drop of E similar to that found with 0.1 mM chelator. With iron(II)-chelators, E dropped to about −500 mV before oscillating for several days. The amplitudes of the oscillations were up to 200 mV with periods of 30 and 20-25 min for bipyridine and FerroZine, respectively.