Thin aqueous equilibrium film studies and surface tension measurements on a mixed surfactant system consisting of polyethylene oxide (a model frother) and potassium ethyl xanthate (a model collector) enable the interaction between the two surfactants at the air/solution interface to be elucidated. For the film containing the non-ionic frother, the interface was charged and addition of low concentrations of xanthate acted as a common electrolyte and reduced the thickness of the film inducing rupture. However, at high xanthate collector concentrations, the negative charge xanthate was found to interact with the non-ionic and caused a buildup of negative charge at the air/solution. Higher frother concentrations were necessary to produce non-rupturing thin films upon increasing the xanthate concentration.