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The electrochemical corrosion rate of Magnesium (Mg) and Mg alloys depends on the stability of the formed surface layer. Based on the Mg substrate, the oxide structure comprises a dense MgO/Mg(OH)2 mixture underneath a porous plate-like Mg(OH)2 layer. While the kinetics of the anodic partial reaction has been mainly attributed to MgO, recent studies showed an effect of the Mg(OH)2 layer thickness on the cathodic partial reaction. A thinner Mg(OH)2 layer has been associated with a higher kinetics of the oxygen reduction rate. In the present study, the proposed mechanism has been further investigated via in situ respirometric measurements with Mg-Al-Ca solid solution in electrolytes with different pH values (pH = 8-13). The results indicate an additional effect based on the structure of the surface layer in the passive state of Mg corrosion. Furthermore, two different Al enriched interlayers at the Mg/MgO- and MgO/Mg(OH)2 interfaces were observed and discussed in terms of their thermodynamic stability under alkaline immersion conditions.