Helmholtz energy, extended corresponding states and local composition model for fluid mixtures

Abstract

We present a model for the calculation of mixture properties. This model is based on the mixture residual Helmholtz energy given by the sum of two terms: one is the residual Helmholtz energy calculated by an extended corresponding states (ECS) model while the other is a correction term. The ECS model is based on methane as the reference fluid and shape factors that carry out the scaling of properties between the fluid of interest and the reference fluid. These shape factors are given by correlations in terms of reduced temperature and density. The application to mixtures is carried out with the one-fluid van der Waals mixture model. The correction term is temperature- and density-dependent as is given by a local composition mixing rule. Local compositions were calculated from a coordination number model based on lattice gas theory. With respect to binary-mixture properties, densities were calculated with an average absolute deviation (AAD) of 0.12%; speeds of sound were calculated with an AAD of 0.16% and bubble pressures were calculated with an AAD of 1.77%. Also, natural gas densities were calculated with AAD of 0.03% and natural gas speeds of sound were calculated with AAD of 0.049%. All these results are very satisfactory when compared with those obtained by modern mixture models.