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Reinforcement corrosion might lead to cracking and spalling of the concrete cover owing to the volume expansion associated with the deposition of some of the possible corrosion products. This is not only aesthetically unpleasing, it might also accelerate deterioration processes or become a safety issue for passing traffic. The present paper discusses first the mechanisms of carbonation‐ and chloride‐induced reinforcement corrosion and considers the chemistry of aqueous iron in order to identify the type of corrosion products as well as their location of formation. Furthermore, practical examples are summarised in order to compare the documented behaviour of a number of real structures with the theoretical considerations made. It is shown that for the case of purely chloride‐induced (pitting) corrosion, precipitation of corrosion products is strongly delayed or may even not occur. Implications are discussed with …