Accurate thermodynamics of simple fluids and chain fluids based on first-order perturbation theory and second virial coefficients: uv-theory.

Abstract

We develop a simplification of our recently proposed uf-theory for describing the thermodynamics of simple fluids and fluids comprising short chain molecules. In its original form, the uf-theory interpolates the Helmholtz energy between a first-order f-expansion and first-order u-expansion as (effective) lower and upper bounds. We here replace the f-bound by a new, tighter (effective) lower bound. The resulting equation of state interpolates between a first-order u-expansion at high densities and another first-order u-expansion that is modified to recover the exact second virial coefficient at low densities. The theory merely requires the Helmholtz energy of the reference fluid, the first-order u-perturbation term, and the total perturbation contribution to the second virial coefficient as input. The revised theory-referred to as uv-theory-is thus simpler than the uf-theory but leads to similar accuracy, as we show for fluids with intermolecular pair interactions governed by a Mie potential. The uv-theory is thereby easier to extend to fluid mixtures and provides more flexibility in extending the model to non-spherical or chain-like molecules. The usefulness of the uv-theory for developing equation-of-state models of non-spherical molecules is here exemplified by developing an equation of state for Lennard-Jones dimers.