The interaction of flotation collectors with sulfide minerals takes place at the solid - solution interface. The electrochemistry of the processes which affect this interface are discussed. The interaction of xanthates with sulfides is an electrochemical process, xanthates being electro-oxidised 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 oxidised xanthate species. The action of reagents which can activate or depress the flotation of sulfides is discussed briefly.