The instantaneous kinetics of oxide formation and growth, in competition with passive film dissolution and breakdown, were investigated for Ni-22 Cr and Ni-22 Cr-6 Mo (wt%) during single step passivation at +0.2 V-SCE. Experiments were conducted in selected acidic and alkaline chloride-containing environments using simultaneous AC and DC electrochemistry; including on-line Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). In parallel experiments, in-situ neutron reflectometry (NR) and ex-situ X-ray photoelectron spectroscopy (XPS) were utilized to characterize the formation of surface oxide films as a function of time. The specific roles of pH and Mo during passivation and breakdown kinetics are highlighted, providing an insight into the fate of the elements which comprise the alloys, and their effects on passivation behavior. It was observed that early oxidation of both Ni and Cr-species occurred in acidic electrolyte. Preferential dissolution of Ni2+ at later times enabled gradual Cr3+ enrichment within the surface film. However, greater relative stability of NiO and Ni(OH)(2) was observed in the alkaline condition. Upon alloying Ni-Cr with Mo, Cr3+ became increasingly enriched in the surface film during anodic polarization. Oxides were interpreted to consist of non-stoichiometric solid solutions formed via solute capture. (C) The Author(s) 2019. Published by ECS.