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Purpose Two corrosion inhibitors for closed cooling water systems, nitrite-based and mixture of nitrite and molybdate corrosion inhibitor, are often compared to each other. This study aims to optimize these two inhibitors in terms of concentration and pH for carbon steel protection, with insights into the double layer structure on surface and its impact on corrosion inhibition. Design/methodology/approach Electrochemical analysis including electrochemical impedance spectroscopy and potentiodynamic test are carried out for quick assessment of corrosion inhibition efficiency and optimization, which is confirmed by immersion test and microscopic analysis. The electronic properties of the surface film are analyzed through Mott–Schottky method which provides new insights into the inhibition mechanism and the role of each component in mixture inhibitor. Findings Mixture of nitrite and molybdate is shown to present higher inhibition efficiency, owning to the double layer structure. Nitrite alone can form a protective surface film, whereas molybdate leads to an n-type semiconductive film with lower donor density, hence giving rise to a better inhibition effect. Research limitations/implications Surface after inhibitor treatment has been carefully characterized to the microscopic scale, implying the effect of micro-structure, chemical composition and electronic properties on the corrosion resistance. Inorganic corrosion inhibitors can be tuned to provide higher efficiency by careful design of surface film structure and composition. Originality/value Almost every study on corrosion inhibitor applies such method for quick assessment of corrosion inhibition effect. Mott–Schottky test is one of electrochemical methods that reveals the electronic properties of the surface film. Previous works have studied the surface layer mainly through X-ray photoelectron spectroscopy. This study provides another insight into the surface film treated by nitrite and molybdate through Mott–Schottky analysis, and relates this structure to the corrosion inhibition effect based on multiple analysis including electrochemistry, microscopic characterization, thermodynamics and interface chemistry.