In this study, itaconic acid (IA) was grafted onto poly(vinyl alcohol) (PVA) with cerium(IV) ammonium nitrate as an initiator at 45degreesC. The grafted PVA was characterized with Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. IA-grafted PVA membranes were prepared with a casting method, and the permeation and separation characteristics of acetic acid/water mixtures were investigated with pervaporation (PV), evapomeation (EV) and temperature-difference evapomeation (TDEV) methods. The effects of the feed composition, operating temperature, and temperature of the membrane surroundings on the permeation rate and separation factor for the acetic acid/water mixtures were studied. The permeation rates in EV were lower than those in PV, whereas the separation factors were higher. With the TDEV method, the permeation rates decreased and the separation factors increased as the temperature of the membrane surroundings decreased. The prepared membranes were also tested in PV, EV, and TDEV to separate the various compositions of the acetic acid/water mixtures (20-90 wt % acetic acid) at 40degreesC. The highest separation factor, 686, was obtained in TDEV with a 90 wt % acetic acid concentration in the feed. The activation energies of permeation in PV and EV were calculated to be 8.5 and 10.2 kcal/mol, respectively, for a 20 wt % acetic acid solution. (C) 2004 Wiley Periodicals, Inc.