Revisiting Kelvin equation and Peng–Robinson equation of state for accurate modeling of hydrocarbon phase behavior in nano capillaries

The thermodynamics of fluids in confined (capillary) media is different from the bulk conditions due to the effects of the surface tension, wettability, and pore radius as described by the classical Kelvin equation. This study provides experimental data showing the deviation of propane vapour pressures in capillary media from the bulk conditions. Comparisons were also made with the vapour pressures calculated by the Peng–Robinson equation-of-state (PR-EOS). While the propane vapour pressures measured using synthetic capillary medium models (Hele–Shaw cells and microfluidic chips) were comparable with those measured at bulk conditions, the measured vapour pressures in the rock samples (sandstone, limestone, tight sandstone, and shale) were 15% (on average) less than those modelled by PR-EOS.

Simple Universal Kelvin Equation Valid in Critical Point Vicinity, External-Internal State Correction, and their Application in Understanding of Oxygen Capillary Evaporation and Condensation in Mesoporous Silica MCM-41

A new simple universal form of the Kelvin equation, which can be used near the gas-liquid phase transition critical point, and the correction of the pressure and density for gas phase fluid outside the porous medium are taken into account for the oxygen meniscus effective curvature radius calculation at the phase equilibrium in mesoporous silica MCM-41, on the basis of the capillary evaporation and condensation experimental data.