0000000000451431
AUTHOR
Joan Gregori
Growth of passive layers on nickel during their voltammetric anodic dissolution in a weakly acid medium
Abstract Quartz crystal microbalance in combination with voltammetry has been used for studying the electrochemical oxidation behaviour of a nickel deposit in a weakly acid medium. The instantaneous mass/charge ratio (Fdm/dQ) analysis allows to obtain the fraction of charge consumed in the passivation process, and, that way, the experimental kinetic equation of the passive layer growth. This experimental law has been fitted to the theoretical equation derived from the point defect model theory under voltammetric conditions.
Effect of Anions and Oxygen on the Kinetics of the Anodic Dissolution of Nickel
An electrochemical impedance spectroscopy study on electrochemical dissolution and active/passive transition of polycrystalline nickel in acid media has been performed in sulfate and nitrate aqueous solutions. Oxygen favors the nickel electrodissolution in a nitrate aqueous acid medium, but the dissolution decreases in the sulfate medium due to nickel passivation. The anion and oxygen effect is analyzed from a model where Ni(I) species are stabilized on the Ni metal surface and all anions present in the solution compete in the neutralization of Ni(I) and Ni(II) and in the solubilization of Ni(II).
A kinetic interpretation of a negative time constant in impedance equivalent circuits for the dissolution/passive transition
Abstract A theoretical impedance function is proposed for the active/passive transition of nickel in an acid sulphate medium. It is considered that passivating species progressively covers the electrode surface. This approximated model predicts the appearance of negative time constants in the impedance spectra when coverage coefficient θ values for passive species are greater than 0.5.
Usefulness of the Instantaneous Mass-charge Ratio for Elucidating the Ions Role in the Stabilization and Dissolution Processes in Prussian Blue Films
The conversion process of 'insoluble' Prussian Blue films into the 'soluble' structure has been followed by the simultaneous measurement of current and mass changes during voltammetric experiments and focusing on the possibilities of the use of the instantaneous mass/electrical charge ratio at each potential. A similar procedure was used for the analysis of the mechanism of reduction of Prussian Blue films to the Everitt's Salt form and to follow the partial dissolution of iron species during the oxidation to the Pussian Yellow form. The possibility of covering Prussian Blue films by Nafion membranes which make difficult the transport of anions through it allows to discern the role of anion…
Simultaneous Anodic Dissolution and Passivation of Nickel in Moderate Acid Medium
The EQCM results show that nickel electrodissolution and nickel passivation occur simultaneously in a sulphate acid media of pH = 3.5. Mass balances have been done from the instantaneous F(dm/dQ) function. The fitting of the experimental i = f(E) and -dm/dt = g(E) curves to the theoretical equations allow to obtain information about the kinetic parameters and the molecular mass of the species involved in the electrochemical processes.