Examination of the Butler Equation for the Surface Tension of Liquid Mixtures

The classical Butler equation used to describe surface tension and the surface composition of liquid mixtures is revisited. A straightforward derivation is presented, separating basic chemical thermodynamics and assumptions proper to Butler's model. This model is shown to conceal an approximation not recognized by other researchers. The shortcoming identified consists of not allowing surface standard values to vary with surface tension by virtue of the changing composition. A more rigorous equation is derived and shown to yield the Butler equation in case of incompressible surface phases. It is concluded that the Butler equation slightly overestimates ideal surface tensions. Butler's surface-phase concentrations of the surface-active component are also slightly overestimated in the surface-active component dilute range, being just underestimated at higher concentrations. Despite this, Butler's model stands as a very good standard due to its versatility.