Permeation of mixtures of organic liquids through polymeric membranes: Role of liquid–liquid interactions

The permeation of pure organic liquids and mixtures of organic liquids through commercial butyl, neoprene, and nitrile membranes was studied using dynamic material deformation (swelling) and permeation techniques. The derived parameters, the breakthrough time (t_BT), steady‐state permeation rate (SSPR), and initial swelling rate (SR), show deviations from additivity for the mixtures, based on the parameters of the pure liquids on a mol fraction basis. In the majority of cases for the three membranes examined, the deviations are independent of the nature of the membranes, and the signs of the deviations for t_BT are opposite to those for SSPR or SR, provided that the membranes are not degraded by one of the solvents. An approach that considers only solvent–solvent interactions based on the enthalpy of mixing was used to predict deviations for mixtures. For mixtures where the enthalpy of mixing is large and exothermic, the permeation of the mixture is less than expected, while for systems where the enthalpy of mixing is large and endothermic, the permeation is larger than expected. A simple semiempirical model predicts the sign and magnitude of the permeation of 73% of the system–permeation property combinations investigated, which show significant deviations from ideality. It is interesting to note that the wrong predictions are for systems where the predictions are positive, that is, for SSPR and SR rates with endothermic systems and for t_BT with exothermic systems. The exceptions also seem to be for systems that correspond to materials having a high resistance to one of the solvents and a very low resistance to the other solvent. Examples of ternary–mixture permeation data are also given and show that, even if two of the pure components do not permeate through a membrane, the membrane will offer little protection if the third component shows a high affinity for the membrane and if the enthalpies of mixing of this component with the other liquids are endothermic. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 195–215, 2002