André de Freitas Gonçalves, Rodolfo José Amancio, Marcelo Castier, Luís Fernando Mercier Franco
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Classical Density Functional Theory Consistent with the SAFT-VR Mie Equation of State: Development of Functionals and Application to Confined Fluids
Classical density functional theory has provided a robust and consistent framework to thermodynamically describe systems with local density variations. The development of functionals that are consistent with homogeneous equations of state allows us to investigate inhomogeneous systems applying the same models used for homogeneous ones. Particularly for adsorption, this is extremely desirable since one ought to apply a consistent modeling for both bulk and adsorbed phases. In this work, new functionals for the Helmholtz energy are proposed by combining the Statistical Associating Fluid Theory for potentials of variable range of Mie type (SAFT-VR Mie) with the weighted density approximation (WDA) formalism of classical density functional theory. As a result, the SAFT-VR Mie equation of state is extended to inhomogeneous fluids and is applied in the prediction of density profiles of linear alkanes adsorbed in carbon slit pores. The density profiles of the adsorbed phases are compared to the results of molecular simulations performed with the Monte Carlo method in the grand-canonical ensemble. An example involving capillary condensation and hysteresis is also investigated. Despite the intrinsic differences between molecular simulation and the analytical model with regard to the representation of the molecular structure, a qualitative agreement and, to some extent, quantitative agreement are obtained.
期刊介绍:
The Journal of Chemical & Engineering Data is a monthly journal devoted to the publication of data obtained from both experiment and computation, which are viewed as complementary. It is the only American Chemical Society journal primarily concerned with articles containing data on the phase behavior and the physical, thermodynamic, and transport properties of well-defined materials, including complex mixtures of known compositions. While environmental and biological samples are of interest, their compositions must be known and reproducible. As a result, adsorption on natural product materials does not generally fit within the scope of Journal of Chemical & Engineering Data.