The coupling boundary condition to be imposed at the evaporative surface of a porous medium is studied from pore network simulations considering the capillary regime. This paper highlights the formation of a thin edge effect region of smaller saturation along the evaporative surface. It is shown that this thin region forms in the breakthrough period at the very beginning of the drying process. The size of this region is studied and shown to be not network size dependent. This region is shown to be the locus of a nonlocal equilibrium effect. The features lead to the consideration of a coupling boundary condition involving an interfacial mass transfer resistance and an external mass transfer resistance. Contrary to previous considerations, it is shown that both resistances depend on the variation of the saturation, i.e., the fluid topology, and the size of the external mass transfer layer, i.e., the mass transfer rate. This is explained by the evolution of the vapor partial pressure distribution at the surface which becomes increasingly heterogeneous during evaporation and depends on both the evolving fluid distribution in the interfacial region and the mass transfer rate. However, the geometric effects due to the configuration of the fluids can be separated from rate effects that arise due to the nonequilibrium mass transport.