Participation of aluminum hydride in the anodic dissolution of aluminum in alkaline solutions

The mechanism of anodic alkaline dissolution of aluminum was investigated through the analysis of cyclic voltammetry (CV) and potential step experiments. Attention was focused on the role of aluminum hydride (AlH3) as a reaction intermediate, as suggested by the recent detection of AlH3 formation during open-circuit dissolution. Potential step experiments at pH 11.75 revealed that the potential at the metal-surface film interface was close to the Nernst potential of AlH3 oxidation. This finding suggested a reaction mechanism in which an interfacial AlH3 layer is formed continuously by reaction of cathodically formed H with Al, and is then oxidized to the dissolution product, aluminate [Al(OH)(4)(-)] ions. However, potential step experiments at pH 11 did not indicate the presence of interfacial AlH3; instead, the metal-film interface was close to the equilibrium potential of Al oxidation. Analysis of the CV indicated an abrupt transition in dissolution behavior between the two pH values, from a relatively rapid dissolution controlled by diffusion and film conduction in highly alkaline solutions, to a slow dissolution at a lower pH controlled by a highly resistive surface film. The formation of interfacial AlH3 occurs readily at the higher pH, but is suppressed as the pH approaches neutrality. (c) 2008 The Electrochemical Society.