ie504118r_si_001.pdf (1.85 MB)
Development of an Accurate Quintic Equation of State: The Necessity of the Irreducible Quadratic Polynomial in the Attractive Term
journal contribution
posted on 2015-03-11, 00:00 authored by Ju Ho Lee, Sang-Chae Jeon, Jae-Won Lee, Young-Hwan Kim, Guen-Il Park, Jeong-Won KangIn conventional van der Waals type
equation of state (EOS) modeling,
the denominator of the attractive contribution is regarded as being
a necessarily factorable quadratic polynomial for the closed-form
expression of the corresponding Helmholtz free energy. This study
evaluates the effect of the opposite case, an irreducible quadratic
polynomial, on the description of the volumetric behavior of real
fluid through a comparison with the critical isotherm data, coexistence
curve, and PVT isotherm data. In a generalized cubic EOS, an irreducible
quadratic polynomial was found to yield an improved description of
the flattened region around the critical density while a nonclosed
form of the Helmholtz free energy results. For an improved volumetric
description using an irreducible quadratic polynomial and a derivation
of the closed form of the Helmholtz free energy, we developed a quintic
EOS containing seven parameters, two of which are determined by correlating
the critical isotherm data and others, by regressing the sub- and
supercritical properties. In the description of the critical isotherms
of nine pure compounds, a comparison of the present model with the
Benedict–Webb–Robinson–Soave (BWRS) EOS showed
that the present model exhibits slightly larger deviations than those
with BWRS EOS; however, a good agreement was obtained with the reference
model of REFPROP 8.0 in the description of the saturated vapor pressure,
saturated density, and PVT isotherm data over a wide range of temperatures.