Numerical heat and mass transfer analysis of a configuration where a cool liquid hydrocarbon is suddenly introduced to a hotter gas at supercritical pressure shows that a well-defined phase equilibrium can be established before substantial growth of typical hydrodynamic instabilities. The equilibrium values at the interface quickly reach near-steady values. Sufficiently thick diffusion layers form quickly around the liquid-gas interface (e.g., 3-10 mu m for the liquid phase and 10-30 mu m for the gas phase in 10-100 mu s), where density variations become increasingly important with pressure as mixing of species is enhanced. While the hydrocarbon vaporizes and the gas condenses for all analyzed pressures, the net mass flux across the interface reverses as pressure is increased, showing that a clear vaporization-driven problem at low pressures may present condensation at higher pressures. This is achieved while heat still conducts from gas to liquid. Analysis of fundamental thermodynamic laws on a fixed-mass element containing the diffusion layers proves the thermodynamic viability of the obtained results. (C) 2018 Elsevier Ltd. All rights reserved.