The interaction of, flotation collectors with sulphide mmerals takes place at the solid-solution interface. The electrochemistry of the processes which affect this interface are discussed. The interaction of xanthates with sulphides is an electrochemical process, xanthates being electro-oxidized to chemisorbed xanthate and dixanthogen.The role of oxygen is to provide a cathodic process to allow the anodic oxidation to occur. The hydrophobic condition of the mineral surface is brought about by the presence of the oxidized xanthate species. The action of reagents which can activate or depress the flotation of sulphides is discussed briefly.