Two supported liquid membranes (SLMs) containing two different carriers but formed by the same polymer support polyvinylidene difluoride (PVDF) and the same organic phase (xylene), were used to realize the facilitated transport of vanadium ions (VO2+) from the concentrated acid solutions. The SLM support was a micro porous PVDF polymer film of thickness 100 mu m with pore size 0.45 mu m which has been impregnated with a solution of xylene containing 0.01 M of one of the carriers, the Di-(2-ethylhexyl) phosphoric acid (D2EHPA) or the Trioctylphosphine oxide (TOPO). The permeabilities P and the initial fluxes J(0) for the transport of the VO2+ ions were calculated from the proposed kinetic model for the two SLMs used. These two macroscopic parameters depend on both the concentration of the carrier (T) and that of the substrate (S) to be transported. The proposed mechanism indicates the formation of a complex (1/1) carrier-substrate (TS), and the migration of this complex through the organic phase of the SLM, is the rate-determining step in the transport mechanism. The initial flux J(0) is related to the initial substrate concentration C-0 in the feed phase by a saturation law, which allowed the determination of the apparent diffusion coefficients D* and the association constants K-ass of the complexes (TS), formed in the organic phase of the two studied SLMs. These results clearly indicate that the values of these two microscopic parameters (D* and K-ass), depend certainly on the acidity of the medium and probably the concentration of co-ions NO3-. (C) 2010 Elsevier B.V. All rights reserved.