The Dual Role Of Xanthate In The Induction Of Hydrophobicity Of Chalcocite

An infrared external reflection spectroscopy (ERS) technique has been developed to study the structure of the adsorbed layer of ethyl xanthate formed on copper and natural chalcocite (Cu2S) electrodes. The infrared technique provides information concerning the identity and the orientation of the adsorbed species at monolayer and submonolayer coverages. X-ray photoelectron spectroscopy (XPS) studies have also been conducted to monitor changes at the surface. The results show that the first oxidation peak on the voltammograms for copper and the first and second oxidation peaks on the voltammograms for chalcocite electrodes are not characteristic of a chemisorbed xanthate species, which is contrary to what has been reported by other investigators previously. As evidenced by the XPS spectra, there was an increase in sulfur relative to copper on the copper and chalcocite surfaces over the potential region where these oxidation processes occur. The spectroscopic results (ERS, XPS) indicate that the second and third (on copper) and the third and fourth (on chalcocite) oxidation processes recorded on the voltammograms are due to cuprous ethyl xanthate adsorption. The orientation of the adsorbed molecules of xanthate was observed to change with increasing surface coverage. Therefore, it has been concluded that xanthate can modify the copper and chalcocite surface in two different ways. At lower potentials, xanthate is a source of sulfur for the formation of a sulfur-rich surface. At higher potentials, an adsorption layer of cuprous ethyl xanthate is formed. Contact angle measurements show that both of these processes of xanthate surface modification lead to an increase in the hydrophobicity of the substrates.