BenedictWebbRubin Equation of state
The BenedictWebbRubin equation of state (EOS) is an early fluid model used for describing real gas behavior^{1} developed by M. Benedict, G.B. Webb and L.C. Rubin in 1940. The original BWR EOS has been modified to more accurately predict real gas behavior by, among others, Starling^{2}, Jacobsen et al.^{3} and was also modified to describe multiphase fluid systems by Starling in 1966^{4}. Unlike the cubic EOS models like the PengRobinson (PR) and SoaveRedlichKwong (SRK) EOS models, the BWR models do not solve a polynomial representation of the Zfactor to describe the phase behavior of the fluid. The various BWR EOS models are socalled Virial EOS models.
Original BWR EOS
The original BWR EOS model can be described by
where the parameters \(a\), \(b\), \(c\), \(A\), \(B\), \(C\), \(\alpha\), \(\gamma\) are all empirical coefficients. The model parameters behave similar to those in a cubic EOS model and have their own mixing rules. These mixing rules are given in the mixing rules section below.
Modified BWR EOS
The modified BWR model by Starling in 1970 introduced three new parameters (\(D_0\), \(E_0\) and \(d\)) and is given by
where
Standing provides the parameter values for several light hydrocarbon (normal paraffins) and also gives a correlation for estimating the parameters for light hydrocarbons using the acentric factor.
McCarty Modification of BWR EOS
In 1974 McCarty expanded the BWR EOS model by introducing even more coefficients to the general structure of the model^{5}. The McCarty modified BWR EOS is given by
where \(a_n\) are functions of temperature (similar to \(p_1\) to \(p_3\)) and \(\gamma\) is an empirical constant.
The list of \(a_n\) can be found in McCarty's paper or in Pedersen's book Phase Behavior of Petroleum Reservoir Fluids^{6}.
Mixing Rules
The mixing rules for the parameters in the original and modified BWR EOS are given by
Soave's Modified BWR EOS
In 1996 Soave published a modification to the BWR (SBWR) EOS model^{7} shown by
In 1999 Soave^{8} further simplified the Eq. \eqref{eq:sbwr_96}, by removing the \(C\cdot \rho^2\) term resulting in
Even though Eq. \eqref{eq:sbwr_99} has one less term, Soave shows that the updated EOS is a more accurate model. Soave also gives all the relevant equations needed to calculate the fugacity, using the SBWR EOS model.
One advantageous feature of the SBWR that is that the EOS coefficients (B, D, E and F) are calculated using a composition (\(u_i\)) and mixing rules for the component properties, namely the critical pressure (\(p_c\)), critical temperature (\(T_c\)), critical Zfactor (\(Z_c\)), and acentric factor (\(\omega\)). The advantage of this approach is that it does not need any additional measured component specific properties.
The mixing rules for the component properties are given by
where
and
With the mixture properties calculated using Eq. \eqref{eq:mixing_rule_a} to \eqref{eq:mixing_rule_d}, the EOS properties can be calculated by
where
and
Finally, the equations for \(b_c\), \(d_c\), \(e_c\), and \(f_c=f\) are calculated from

M. Benedict, G. B. Webb, and L. C. Rubin. An empirical equation for thermodynamic properties of light hydrocarbons and their mixtures i. methane, ethane, propane and nbutane. The Journal of Chemical Physics, 8:334–345, 1940. doi:https://doi.org/10.1063/1.1750658. ↩

K. E. Starling and J. E. Powers. Enthalpy of mixtures by modified bwr equation. Industrial & Engineering Chemistry Fundamentals, 9:531–537, 1970. ↩

R. T. Jacobsen and R. B. Stewart. Thermodynamic properties of nitrogen including liquid and vapor phases from 63k to 2000k with pressures to 10,000 bar. Journal of Physical and Chemical Reference Data, 2:757–922, 1973. doi:https://doi.org/10.1063/1.3253132. ↩

K.E. Starling. A new approach for determining equationofstate parameters using phase equilibria data. Society of Petroleum Engineers Journal, 6:paper SPE–1481–PA, 1966. doi:https://doi.org/10.2118/1481PA. ↩

R. D. McCarty. A modified benedictwebbrubin equation of state for methane using recent experimental data. Cryogenics, 14:276–280, 1974. doi:https://doi.org/10.1016/00112275902288. ↩

K. S. Pedersen, P. L. Christensen, and J. A. Shaikh. Phase behavior of petroleum reservoir fluids. CRC press, 2014. ↩

G. S. Soave. A noncubic equation of state for the treatment of hydrocarbon fluids at reservoir conditions. Industrial & engineering chemistry research, 34:3981–3994, 1995. ↩

G. S. Soave. An effective modification of the benedict–webb–rubin equation of state. Fluid Phase Equilibria, 164:157–172, 1999. ↩