Critical point shifts in binary fluid mixtures

Abstract

An empirical observation is made of an apparent universal shift in the consolute point (Xc=critical composition, Tc=critical temperature) of binary fluid mixtures when the system identity is perturbed. The shift in a ‘‘pure’’ system’s critical point (Xco, Tco) when perturbed becomes (Xc,Tc) which seems to obey (Tc−Tco)/Tco= (Xc−Xco)/Xco. This relation has been observed to hold in a wide range of systems including closed-loop coexistence curves (guaiacol–glycerol–water, or tertiary butyl alcohol in secondary butyl alcohol and water), deuterated systems (methanol–cyclohexane, or isobutyric acid–water), impurities added to methanol–cyclohexane, the molecular weight dependence in polystyrene–methylcyclohexane, and the pressure dependence of methanol–cyclohexane.