With the aim to open a new window into corrosion processes this paper presents respirometric methods for real-time in situ monitoring of corrosion rates under immersion conditions. With these techniques, sensitive, non-destructive corrosion rate measurements are possible on basically all metals and alloys. Different methods are presented that enable to monitor HER, ORR or both reactions simultaneously based on the amount of evolved H2 or the amount of consumed O2 by volumetric, manometric and sensor-based approaches. Various research examples are presented, demonstrating the benefits and limitations of the different approaches. For Mg alloys, besides HER, ORR plays a role in the cathodic reactions and a good correlation of the total cathodic charge with mass loss was obtained. H2 dissolution into the electrolyte was identified as an important factor. The results obtained for Zn immersion corrosion in intermittent-flow and flow-through respirometric experiments suggest that the ORR mechanism leads to the generation of stable H2O2 under these conditions. As a result, the effective number of exchanged electrons for one O2 molecule was found to be in between two and four. The here introduced respirometric techniques allow new insights into corrosion mechanisms, in addition to enabling real-time monitoring of corrosion.
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