Structure of the vapor–liquid interface near the critical point

Abstract

We measured the thicknesses of the vapor–liquid interfaces near the critical points of carbon dioxide (CO2), sulfur hexafluoride (SF6), and trifluoromethane (CHF3) using ellipsometry. The data (when scaled by the refractive index difference Δn and the correlation length ξ) are in agreement with other ellipticity data for binary and pseudobinary mixtures at low pressures. Fully constrained theories of the interface correctly predict the temperature dependence and scaling of the thickness but systematically overestimate the thickness itself by 15%–20%. The theory can be brought into agreement with experiment when an intrinsic interfacial stiffness is added to the theory. A novel feature of the present measurements is that the effects from pressure-induced window strain were measured and mitigated by using a cylindrically-symmetric pressure cell with floating seals.