The Mechanism Of The Adsorption Of Ethyl Xanthate Ion On Galena

It was first pointed out in 1934 by Gaudin (1) that the "oily" oxidation product of the alkyl xanthate ion-dialkyl dixanthogen, might be the "active flotation agent" on sulphide minerals and there have been a number of studies supporting this hypothesis (2,3,4). However, all of these studies have relied largely on electrochemical evidence. Galena, being a semiconductor, may be used as an electrode in aqueous solution and it was shown that ethyl xanthate ion does not adsorb with charge transfer in the absence of oxygen unless the potential of the galena surface is above -100 mv versus the hydrogen electrode (H2 E). At this potential the galena surface is slightly hydrophobic but does not become strongly hydrophobic unless the potential is raised to 210 mv (versus H2 E). It is suggested that, at potentials of 210 mv or above, ethyl xanthate ions are oxidised to diethyl dixanthogen and that chemisorption of oxygen raises the galena surface to this potential. On the other hand, examination of xanthated galena surfaces by chemical or physical methods (5,6,7) has failed to detect dixanthogen and it has been shown that dixanthogen may be reduced to lead xanthate at a lead sulphide surface. (5,8)*. It was suggested by Leja and Poling (5) that, as dixanthogen is a neutral molecule it would not be repelled by the negatively charged galena surface so that the adsorption was envisaged as taking place through homogeneous oxidation of the xanthate ion to dixanthogen, adsorption and reduction of the dixanthogen to a chemisorbed lead xanthate species. In paper I of this series (11) it was shown that the thiosulphate ion, which forms on galena surfaces in slurries at the pH normally used for flotation, will reduce dixanthogen. There is, therefore, the impasse that the electrochemical evidence requires that xanthate ion be oxidised to dixanthogen at the galena surface while the chemical evidence shows that the reverse reaction takes place.