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This study explores the flotation behavior of chalcopyrite in the presence of different concentrations of sodium sulfide (Na2S·9H2O) at pH 12 under controlled potential conditions. It was observed that the flotation of chalcopyrite is not depressed completely when the pulp potential is low, even at high concentrations of sodium sulfide, i.e., 10-1-10-2 mol/L. However, a partial and controlled oxida-tion of pulp does enhance the effectiveness of sodium sulfide on the depression of chalcopyrite. Characterization of the chalcopyrite particle surface by X-ray photoelectron spectroscopy allowed the identification of hydrophilic and hydrophobic surface species, which are responsi-ble for the depression and flotation of chalcopyrite. Changes in pulp potential were found to be an effective float controlling parameter, by which Na2S can be used to initiate or depress the flotation behavior of chalcopyrite.