Phase diagram of a binary mixture in a closed cavity.

Normally, the phase diagram is reported as a property of the binary mixture. We show that the phase diagram (that is, the zones of thermodynamic stability of the states of the binary mixture) is also affected by the size of the container. We investigate the thermodynamic stability of the binary mixture in a closed cavity, and identify the zone in parameters where the binary mixture is heterogeneous in equilibrium (the zone of spinodal decomposition), the zone where the mixture is always homogeneous in equilibrium, and the zone where the transition between these two states is possible (the metastable nucleation zone). In addition, we investigate the properties of the smallest single droplet that may be in equilibrium in the closed cavity (for the given average concentration, all smaller droplets would always dissolve). We show that the size of such droplets depends on the cavity's size, as ∼L^{1/2}.