The efficiency of benzotriazole as inhibiting agent for the corrosion of cobalt was probed at pH ranging from 8.3 to 10.2 in a sodium bicarbonate solution, chosen to simulate mild natural environments. From electrochemical, Raman spectroscopy, atomic force microscopy and ellipsometry experiments, we have demonstrated that benzotriazole markedly affects the electrodissolution reactions, which become modeled by the formation of a [Co(II)(BTA)2·H2O]n film according to two different mechanisms. Surface-enhanced Raman spectroscopy has shown that the polarization of a cobalt electrode at cathodic potentials with respect to its potential of zero charge allows a mechanism of specific adsorption of the neutral form of benzotriazole to take place through a suspected metal-to-molecule electron transfer and which follows Frumkin's adsorption isotherms. At the onset of the anodic dissolution, some experimental evidence suggests that these adsorbed neutral benzotriazole molecules deprotonate to yield a very thin [Co(II)(BTA)2·H2O]n polymer-like and water-insoluble protective film, responsible for the inhibition of active dissolution processes occurring at slightly more anodic potentials. In the anodic dissolution region, deprotonated benzotriazole species present in the bulk solution favors the formation of a multilayered [Co(II)(BTA)2·H2O]n film, which also contributes to the inhibition of any further cobalt dissolution usually observed at higher electrode potentials.

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In H2CO3/HCO3-/CO32- solutions, the anodic dissolution and the active–passive transition of cobalt lead to complex electrochemical phenomena. In order to identify each individual process, a numerical method has been developed and used to resolve into single processes the electrochemical behaviour. Indeed, by using a deconvolution method, we have been able to establish the sequence of processes and the involvement of each chemical species at the rotating cobalt electrode surface during potentiodynamic scans in H2CO3/HCO3-/CO32- solutions at pH ranging from 7.65 to 8.30. Moreover, using different convective conditions, we identified the types of controls that govern the dissolution processes. The results presented in this paper improve and confirm theories reported in literature.

The electrochemical behaviour of a cobalt rotating electrode in H2CO3/HCO3–/CO32– aqueous solutions was investigated in the pH region from 7 to 9. The effects of H2CO3/HCO3–/CO32– concentration, pH, and the presence of phosphates as inhibitors was explored using a rotating disc electrode at 1000 rpm. Some potentiodynamic experiments indicate that for pH 8.5 and higher, carbonate and bicarbonate species play a key role on the rate of electrooxidation of cobalt. For pH lower than 8.5, the electrochemical behaviour of cobalt changes drastically and very aggressive corrosion is observed. The involvement of carbonic acid must be considered in the corrosion process of cobalt in this pH region. The study of passive film potential decay under open circuit potential and galvanostatic reduction was performed on preanodized cobalt electrodes in solutions of various compositions. These experiments indicated the phenomena occurring at the electrode–solution interface during the corrosion process. A mechanism involving competitive adsorption of different species is suggested on the basis of the experimental evidence.Key words: cobalt, bicarbonate, phosphate, carbonic acid, corrosion.

The electrochemical behaviour of a cobalt rotating electrode in H2CO3/HCO3 /CO32- aqueous solutions was investigated in the pH region from 7 to 9. The effects of H2CO3/HCO3 /CO32- concentration, pH, and the presence of phosphates as inhibitors was explored using a rotating disc electrode at 1000 rpm. Some potentiodynamic experiments indicate that for pH 8.5 and higher, carbonate and bicarbonate species play a key role on the rate of electrooxidation of cobalt. For pH lower than 8.5, the electrochemical behaviour of cobalt changes drastically and very aggressive corrosion is observed. The involvement of carbonic acid must be considered in the corrosion process of cobalt in this pH region. The study of passive film potential decay under open circuit potential and galvanostatic reduction was performed on preanodized cobalt electrodes in solutions of various compositions. These experiments indicated the phenomena occurring at the electrode-solution interface during the corrosion process. A mechanism involving competitive adsorption of different species is suggested on the basis of the experimental evidence.