Voltammetry of Irreversible Surface Inactivation in Processes of Electrochemical Metal Alloys Dissolution

This work considers a theoretical analysis of voltammetric behavior in electrochemical systems where metal alloy dissolution is accompanied by irreversible surface inactivation of a given metal present in analyzed metallic alloy. The study mainly focuses on the influence of kinetic and chemical rate parameters that govern the interplay between active dissolution and the progressive loss of reactive surface sites. Mathematical modeling within the framework of square-wave voltammetry was developed to describe the transient current responses under conditions of surface passivation and alloy component selectivity. The analysis demonstrates how the rate of surface inactivation, relative to electron-transfer kinetics affects peak currents, potential shifts, and hysteresis in voltammetric profiles. The proposed theoretical approach provides a mechanistic interpretation of experimentally observed phenomena in alloy corrosion and electrochemical dissolution, offering insights into processes where the active surface area decreases irreversibly during anodic or cathodic polarization. The model serves as a foundation for understanding surface deactivation effects in complex metal systems and contributes to more accurate diagnostics of corrosion and dissolution mechanisms in many alloys.