Nucleation and Boiling Near the Gas–Liquid Critical Point

Abstract

Nucleation near the gas–liquid critical point depends sensitively on whether the pressure or the volume is fixed. We consider near-critical fluids close to the coexistence curve. (i) Upon decompression to a constant pressure with a fixed boundary temperature, bulk nucleation can well be induced from a gas state, whereas from a liquid state boiling is easily triggered in the thermal diffusion layer near the boundary. In this case, bulk nucleation in a metastable gas is described by the classical Lifshitz–Slyozov theory. (ii) Upon cooling of the boundary temperature under the fixed-volume condition, bulk nucleation can be realized in a liquid and a modified Lifshitz–Slyozov theory follows. However, if a gas is cooled from the boundary at a fixed volume, liquid droplets readily appear in the thermal diffusion layer, apparently suggesting no metastability in a gas in agreement with previous experiments. (iii) On the other hand, if a liquid is heated at the boundary wall, boiling readily occurs both at a fixed volume and at a fixed pressure.