Theory of phase equilibria for model mixtures of n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock surfactants

Abstract

An extension of the SAFT-VR equation of state, the so-called hetero-SAFT approach [Y. Peng, H. Zhao, and C. McCabe, Molec. Phys. 104, 571 (2006)], is used to examine the phase equilibria exhibited by a number of model binary mixtures of n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock surfactants. Despite the increasing recent interest in semifluori- nated alkanes (or perfluoroalkylalkane diblock molecules), the phase behaviour of mixtures involving these molecules with n-alkanes or perfluoroalkanes is practically unknown from the experimental point of view. In this work, we use simple molecular models for n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock molecules to predict, from a molecular perspective, the phase behaviour of selected model mixtures of perfluoroalkylalkanes with n-alkanes and perfluoroalkanes. In particular, we focus our interest on the understanding of the microscopic conditions that control the liquid–liquid separation and the stabilization of these mixtures. n-Alkanes and perfluoroalkanes are modelled as tangentially bonded monomer segments with molecular parameters taken from the literature. The perfluoroalkylalkane diblock molecules are modelled as heterosegmented diblock chains, with parameters for the alkyl and perfluoroalkyl segments developed in earlier work. This simple approach, which was proposed in previous work [P. Morgado, H. Zhao, F. J. Blas, C. McCabe, L. P. N. Rebelo, and E. J. M. Filipe, J. Phys. Chem. B, 111, 2856], is now extended to describe model n-alkane (or perfluoroalkane) þ perfluroalkylalkane binary mixtures. We have obtained the phase behaviour of different mixtures and studied the effect of the molecular weight of n-alkanes and perfluoroalkanes on the type of phase behaviour observed in these mixtures. We have also analysed the effect of the number of alkyl and perfluoroalkyl chemical groups in the surfactant molecule on the phase behaviour. In addition to the usual vapour–liquid phase separation, liquid–liquid, positive azeotropes, and Bancroft points are found for different mixtures. This rich phase behaviour is a consequence of a delicate balance between the alkyl–alkyl, perfluoroalkyl–perfluoroalkyl, and alkyl–perfluoroalkyl interactions in different molecules. We used the SAFT-VR microscopic description of chain-like systems to analyse the conditions that n-alkane (or perfluoroalkane) þ perfluoroalkyalkane mixtures should posses in order to exhibit complete liquid miscibility. Although the model proposed here is chosen to reproduce most of the quantitative features of the phase equilibria of some pure perfluoroalkylalkane diblock surfactants and their mixtures with n-alkanes, this is the first time the SAFT approach has been used to predict the phase behaviour of the mixtures considered here. The lack of experimental data for these systems does not allow us to test the accuracy of our theoretical predictions directly. However, since SAFT has proven to be an excellent approach for the prediction of the phase behaviour of complex mixtures, we expect that the theory will reproduce the most important qualitative trends exhibited by real mixtures.