On the study of the vapor-liquid interface of associating fluids with classical density functional theory

Abstract

Classical density functional theory (DFT) is applied to study the vapor-liquid interface of associating fluids. Our classical DFT implementation uses a Helmholtz free energy functional that reduces to the perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state in the bulk limit. We apply a new association functional, presented in one of our previous works, based on the weighted density approximation to calculate the interfacial tension of associating fluids and compare them with two of the most used association functionals from literature. It is found that classical DFT with the three association functionals and the current molecular parameters of PC-SAFT is not able to predict satisfactorily the interfacial tension of alkanols. Therefore, the experimental interfacial tension of alkanols and some associating fluids is included in the determination of the pure molecular parameters of PC-SAFT. With this approach the determination of interfacial tension of pure associating fluids can be greatly improved with the new parameters, but at the expense of slightly higher deviations in the vapor pressure. The new parameters are tested for the determination of vapor-liquid equilibria (VLE) and the prediction of interfacial tension of binary mixtures containing at least one associating compound. Good agreement is found between experimental data of VLE and interfacial tension of the binary mixtures and the three association functionals. Furthermore, we discuss about the limitations and capabilities of the current classical DFT implementation in the study of the vapor-liquid interface of associating fluids.