The ion exchange of anionic polyelectrolytes (APEs) on the PVC membrane containing tridodecylmethyl-ammonium bromide as a carrier was analyzed by monitoring elution of the bromide from and penetration of APEs into the membrane. The equilibration time for exchange by APEs was around three times longer than that by a common anion of perchlorate. Heparin at 10(-4) mol L(-1) and poly(vinyl sulfate) (PVS) at 10(-2) mol L(-1) could completely replace the bromide in the membrane, while polyacrylate (PA) at 10(-2) Mol L(-1) could not. The chemical amount of the penetrated PVS was comparable to that of the eluted bromide, while that of PA was much larger than that of the eluted bromide and even the total amount of the carrier. PA penetrated into the organic phase within the membrane by coextraction with proton as well as by ion exchange, so as to avoid geometric restriction on multiple ion-pair formation. (C) 2010 Elsevier B.V. All rights reserved.