Mata, Arrianne Jaye N. Dr.

Erison Roque
Thermodynamics 1 September 15, 2014

Analysis and Comparison of the Alpha Functions of SRK
Equation of State

By LUO Mingjian, HU Bing, JIANG Tao, XIA Shuqian and MA Peisheng

In 1972, Soave proposed an important modification to the RK EOS, a
modification to vdW EOS. Between the time of vdW EOS and Redlich-Kwongs, a new
concept for fluid characterization was being discussed.
The model applies to non-polar compounds and improves on the original Redlich
Kwong model by generalizing the attraction term to depend on the acentric factor, which
accounts for molecules being non-spherical, and accounting for a range of vapor
pressure data in the development of the temperature dependency of this parameter.
All modifications to the vdW EOS had focused on the temperature dependency of
the attractive parameter. Soave expanded this by proposing a two-variable dependency
for a:

It was the first time that a was expressed not only as a function of temperature,
but also as a function of the shape (sphericity) of the molecules (through w, Pitzers
acentric factor). Pitzers acentric factor is a measure of the configuration and sphericity
of the molecule. It can also be seen as a measure of the deformity of the molecule.
In this research paper, alpha functions of Soave-Redlich-Kwong (SRK) equation
of state were compared in modeling methane-alkanes equilibria with van der Waals
mixing rule and Modified Huron-Vidal (MHV1) mixing rule, respectively.

The prediction results of gas-liquid equilibrium of methane-alkanes were used for
verifying alpha functions when Tr>1 because there are abundant solubility data of
methane in alkanes, and recommended values are available, too. Furthermore, the
intermolecular force of methane and alkanes are similar, and it is reasonable to set the
interaction parameters in mixing rules as zero, thus it avoids the possibility of offsetting
the deficiency of alpha functions by interaction parameters.

Both prediction results of methane alkanes equilibrium and comparison results
with virial equation of state show that Luos alpha function is most suitable for SRK
equation of state when Tr>1. Results showed that with a linear decreasing alpha
function, the SRK equation of state provides more accurate gas-liquid equilibria
prediction at high temperatures, and it is more consistent with second virial equation of
state.

Other results also showed that Luos alpha function was a little more accurate than
Soaves, and Twus alpha function lacked accuracy in modeling methane- alkanes
equilibrium. SRK equation of state was expanded as virial form, and then the equivalent
terms were contrasted with terms of virial equation of state. Results showed that
Soaves and Luos alpha functions matched the tendency of virial coefficient better than
Twus, and Luos alpha function matched better than Soaves in wide temperature
range, which sustained the conclusions of phase equilibria calculation.