Graft copolymers of poly(vinyl alcohol) (PVA) with polyacrylamide were prepared and membranes were fabricated at 48 and 93% grafting of acrylamide onto PVA. These membranes were used in the pervaporation separation of water/acetic acid mixtures at 25, 35, and 45 degreesC. The permeation flux, separation selectivity, diffusion coefficient, and permeate concentration were determined. The highest separation selectivity of 23 for neat PVA at 25 degreesC and the lowest value of 2.2 for 93% acrylamide-grafted PVA membranes were observed. A permeation flux of 1.94 kg m(-2) h(-1) was found for the 93% grafted membrane at 90 mass % of water in the feed mixture. The diffusion coefficients in a water/acetic acid mixture had an effect on the membrane permselectivity. The Arrhenius equation was used to calculate the activation parameters for permeation as well as for the diffusion of water and of acetic acid. The activation energy values for the permeation flux varied from 97 to 28 kJ/mol.