Statistical rate theory insight into evaporation and condensation in multicomponent systems.

Current approaches to mathematically modeling liquid-vapor mass transport (e.g., film theory, penetration theory, boundary layer theory) treat bulk phase transport accurately with diffusion models, but leave the transport across the interface to be described by empirically determined mass transfer coefficients. In multicomponent systems, this requires empirical mixing rules for the single-component mass transfer coefficients. Such approaches can only give estimates of net rates at the interface but cannot examine the movement of individual components. Here we use statistical rate theory to provide new physical insight into evaporation and condensation at interfaces in systems containing multiple volatile components. In contrast to the traditional multicomponent mass transfer approach, we show ranges where one component evaporates while the other condenses even when the net transport is unidirectional.