An equation of state based upon a ratio of polynomials (rational) form for the residual Helmholtz energy: application to nitrogen, argon and methane¹

This work presents an equation of state that contains the residual Helmholtz free energy as a ratio of polynomials in density with temperature-dependent coefficients and demonstrates that it is a viable alternative for describing thermodynamic properties accurately. The specific form of the equation in this work has six density terms in the numerator, three density terms in the denominator, and five temperature parameters for each temperature-dependent coefficient. Nitrogen, argon, and methane serve as prototype fluids to demonstrate the capability of the form to describe p–ρ–T behaviour, vapour pressures, speeds of sound, and isochoric heat capacities up to 1000 MPa. Characteristic curves for several properties of nitrogen generated using the equation exhibit proper behaviour at high temperatures and pressures. Because the equation contains no exponential terms or non-integer exponents, the computational time associated with the new equation is more than a factor of 10 less than that required for similar equations with comparable accuracy.