A comparative study on the free volume theories for diffusivity through polymeric membrane in pervaporation process

In this work, free volume theories are coupled with a thermodynamic model and generalized Fick's law to develop a mass transfer model based on solution‐diffusion mechanism for pervaporation process with a hydrophobic polymeric membrane. The Wesselingh, Fujita and Vrentas‐Duda's theories are used to calculate concentration‐dependent diffusion coefficient of permeants inside polydimethylsiloxane membrane. The sorption and pervaporation experiments on aqueous ethanol solutions are performed to validate the sorption and pervaporation models. The results reveal that the proposed models are able to predict influences of feed concentration and temperature as well as permeate‐side pressure on partial fluxes through the membrane. The comparative investigation indicated that Wesselingh's free volume theory underestimated the diffusion coefficients inside the membrane and the accuracy of the model used this theory is very low for prediction of the permeation flux. Generally, Fujita and Vrentas‐Duda's theories are found to be much more accurate especially for dilute aqueous feed solutions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40581.