Thin film composite membranes consist of an ultra thin active layer of polymer that governs the membrane's salt rejection and water permeation properties. However, the fragility of the ultrathin layer makes it challenging to select a technique capable of differentiating between the properties of this layer from the supporting layer. In this study, we isolated enough active layer material to characterise the water vapour sorption and free volume cavity size as functions of water activity. The sorption data were modelled using the Guggenheim-Anderson-De Boer (G.A.B.) isotherm and from this the number of sorption sites for water was calculated to be 189 x 10(19) per gram for the active layer from a commercial Dow Filmtec SW30 membrane and 188 x 10(19) per gram for an aromatic polyamide material prepared in house. The activation energy for diffusion of water through the active layer of SW30 was also evaluated and found to be 6.95 kcal/mol, lower than the heat of liquefaction of water. This suggests that water does not permeate as individual molecules in the vapour state, but rather as clusters of water molecules. The free volume cavity size in the active layer as a function of moisture uptake was also investigated and the results were explained using a pore filling and pore swelling mechanism. This study sheds light on the mechanisms of water entry into the active layer, water transport through the active layer, and the corresponding response of the polymer chains, thereby giving critical insight for the development of more novel systems. (C) 2012 Elsevier B.V. All rights reserved.