Power generation by reverse electrudialysis (RED) depends on ionic mass transfer through alternately at cation- and anion-exchange membranes. Chronopotentiometric measurements were carried out in an EDR-Z Mini stack (MEGA as.), equipped with Ralex heterogeneous membranes, separated by either sheet flow spacers or mesh-free gaskets. Various concentrations of model NaCI solutions were used to study the ohmic and non-ohmic resistances in the stack under different hydrodynamic conditions. In order to eliminate the uncertainties associated with a non-uniform distribution of the applied current over the membrane surface, the relaxation zone of the obtained chronopotentiograms was used to estimate the diffusion boundary layer thickness. It was found that this approach provide more accurate data under RED operating conditions, which are strongly influenced by entrance effects on mass transfer, especially for a spacer-free channel configuration. For shorter flow channels, since the salt concentration profile across the diffusion boundary layer is not yet fully developed, more power can be obtained than in the case of longer channels. The presence of spacers was found to reduce the boundary layer thickness, but also increased the ohmic resistance, due to their shadow effect over the membrane surface. The description of the impact of flow entrance effects on mass transfer, and therefore on diffusion boundary layer thickness, can be useful for characterization and further design and/or optimization of RED stacks performance. (C) 2014 Elsevier B.V. All rights reserved,