A semiempirical correlation between the optical band gap of binary oxides and the difference of electronegativity between the oxygen and metallic elements (Pauling's extraionic energy) is proposed. In the frame of the proposed correlation an estimate of the repulsive term in the total lattice energy of ionic oxides is obtained in very good agreement with the existing data. An extension of the correlation to the ternary oxides and hydroxides is proposed by using the concept of average cationic or anionic group electronegativity. The usefulness of the proposed correlation for the in situ characterization of passive films on metals and alloys by photocurrent spectroscopy is illustrated by reporting some preliminary experimental results on Sn and AlTi alloy.

A detailed photoelectrochemical study was c~rried out in order to identify the nature and the properties of the passive layers on chromium under different experimental conditions. Different compositions of the films, related to various hydration degrees of the Cr(III) oxides, have been inferred on the basis of the bandgap values measured at changing pH, electrode potential, and polarization time. By comparison with air-grown films, it has been concluded that anhydrous Cr203 is never formed in acidic solution. The water content in the passive film increases at decreasing potentials and for long polarization times. In some cases, especially at neutral pH values, passive films possess a duplex structure, consisting of two layers with different hydration degrees. The photoelectrochemical study suggests an insulating or a slightly p-type behavior of the passive layers.

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