Current non-equilibrium distillation models do not explicitly include the coupling between thermal and mass fluxes. We present a calculation model for the coupled transfer of mass and thermal energy in the vapour-liquid region of a binary mixture. The region is modelled as a vapour-liquid interface in between two homogeneous films. The entropy production in the vapour-liquid region can be calculated using both irreversible thermodynamics and the entropy balance. The film thickness ratio is found by requiring the entropy production calculated with the two methods to be equal, while keeping the vapour film thickness fixed. Using a nitrogen-oxygen mixture as example, we show that neglecting the coupling between thermal and mass fluxes can have a large impact on the magnitude and direction of the theoretical (net) fluxes. The size of the impact depends on the vapour film thickness, but it is significant for all thicknesses. By increasing the number of control volumes that is used to represent the liquid and vapour films, we also show that the fluxes depend highly on the resistivity profiles in the films. They depend slightly on the interface resistance. A sensitivity analysis of the transport properties shows that accurate values of the Maxwell-Stefan diffusion coefficients in both homogeneous phases and of the liquid phase heat of transfer are most important. Especially the measurable heat flux at the liquid boundary of the system is sensitive to neglect of coupling, to neglect of the interface resistance and to uncertainties in the transfer properties. (C) 2009 Elsevier Ltd. All rights reserved.