Confinement-Induced Supercriticality and Phase Equilibria of Hydrocarbons in Nanopores

For over a century, the phase behavior of bulk fluids has been described as PVT (pressure-volume-temperature) three-dimensional properties, but it has become increasingly clear that the liquid-vapor phase behavior in confined geometries is significantly altered from the bulk. Efforts have been devoted to accessing confined phase transitions using sorption, molecular simulations, and theoretical methods. However, a comprehensive picture of PVT relationships for confined hydrocarbons remains uncertain. Herein, we introduce d (confining pore diameter) as a fourth dimension, and we present PVT-d behavior of confined fluids in nanopores. For the first time, a T-d phase diagram is presented for n-hexane, n-octane, and n-decane under multiple confinement scales (37.9, 14.8, 9.8, 6.0, 4.1, 3.3, and 2.2 nm cylindrical pore diameter) using experimental differential scanning calorimetry and PVT-d equation of state theory at atmospheric pressure. As pore diameter decreases from 37.9 to 4.1 nm, the bubble point increases by as much as 15 K above bulk, until we observe behavior consistent with a supercritical state, pointing to confinement-induced supercriticality. Remarkably, experimental and theoretical findings overlap very well, showing that this approach effectively captures the phase boundaries between the liquid, vapor, and supercritical fluid regions. The model and completed EOS are additionally extended to calculation of isothermal capillary adsorption, and its validity is discussed.