Four series of reinforced concrete specimens have been studied over 3 years exposure in a 100% relative humidity atmosphere. Addition of CaCl2,NaNO2, and a mixture of CaCl2 and NaNO2 changed the cement chemistry with respect to an ordinary portland cement series of samples used as reference series. The study, based on low-scan rate cyclic voltammetry and electrochemical impedance spectroscopy, confirms previous results obtained in alkaline medium, i.e. the redox activity in the rebar's oxides layer greatly influences the electrochemical behaviour of rebars in the passivity potential domain. Different redox processes also influence the active and cathodic protection domains that make corrosion rate estimations very difficult. The possibilities of estimating corrosion rate are discussed in terms of cement chemistry and corrosion potential of the system.