Under What Conditions Can Equilibrium Gas–Particle Partitioning Be Expected to Hold in the Atmosphere?

Abstract

The prevailing treatment of secondary organic aerosol formation in atmospheric models is based on the assumption of instantaneous gas–particle equilibrium for the condensing species, yet compelling experimental evidence indicates that organic aerosols can exhibit the properties of highly viscous, semisolid particles, for which gas–particle equilibrium may be achieved slowly. The approach to gas–particle equilibrium partitioning is controlled by gas-phase diffusion, interfacial transport, and particle-phase diffusion. Here we evaluate the controlling processes and the time scale to achieve gas–particle equilibrium as a function of the volatility of the condensing species, its surface accommodation coefficient, and its particle-phase diffusivity. For particles in the size range of typical atmospheric organic aerosols (∼50–500 nm), the time scale to establish gas–particle equilibrium is generally governed either by interfacial accommodation or particle-phase diffusion. The rate of approach to equilibrium varies, depending on whether the bulk vapor concentration is constant, typical of an open system, or decreasing as a result of condensation into the particles, typical of a closed system.