Dissolution of oxide films on iron in aqueous solutions containing complexing anions

The dissolution, in oxalic acid and oxalic acid plus ethylenediaminetetraacetate, of magnetite films grown at high temperature on iron has been studied under varying conditions of pH and temperature. For oxalate concentrations greater than about 2 x 10-3 mol dm-3, magnetite dissolves by direct chemical dissolution. The mechanism appears to involve adsorption of oxalate ions at ferric ion sites in the oxide lattice, followed by proton attack and desorption of cationic species. Once metal dissolution starts, β-ferrous oxalate dihydrate is precipitated on the electrode, leading to erratic fluctuations in the electrode potential and eventually to inhibition of metal dissolution. For oxalate concentrations < 2 x 10-3 mol dm-3, the predominant dissolution mechanism appears to involve reduction by the metal. Also, once solution penetration to the underlying metal has occurred, and the electrode has returned to the active state, autoreductive dissolution appears to predominate even at higher oxalate concentrations. This change in mechanism from predominantly chemical dissolution to predominantly autoreductive dissolution may be due, at least in part, to the desorption of oxalate ions at the more negative potentials achieved in the active state. (author)