Plant Design Lab

Table of Contents
1 Soave-Redlich-Kwong EOS (1972) ......................................................................................................... 1
2 Peng-Robinson EOS (1976) ................................................................................................................... 1
3 NRTL ...................................................................................................................................................... 2
4 Benedict–Webb–Rubin equation .......................................................................................................... 2
5 UNIQUAC ............................................................................................................................................... 2
6 Van Laar Equation ................................................................................................................................. 3
7 Selection of the fluid package ............................................................................................................... 3
 Plant Design Lab

FLUID PACKAGES
1 Soave-Redlich-Kwong EOS (1972)
In 1972, Soave proposed an important modification to the RK EOS — or shall we say, a
modification to vdW EOS. Between the time of vdW EOS and Redlich-Kwong’s, a new concept
for fluid characterization was being discussed. Pitzer had introduced the concept of acentric
factor in 1955.

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, Pitzer’s acentric factor). As we
recall, Pitzer’s 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.

The Soave-Redlich-Kwong EOS is given by the expression:

2 Peng-Robinson EOS (1976)

The Peng-Robinson EOS has become the most popular equation of state for natural gas systems
in the petroleum industry. During the decade of the 1970’s, D. Peng was a PhD student of Prof.
D.B. Robinson at the University of University of Alberta (Edmonton, Canada). The Canadian
Energy Board sponsored them to develop an EOS specifically focused on natural gas systems.
When you compare the performance of the PR EOS and the SRK EOS, they are pretty close to a
tie; they are “neck to neck,” except for a slightly better behavior by the PR EOS at the critical
point. A slightly better performance around critical conditions makes the PR EOS somewhat
better suited to gas/condensate systems.

Peng and Robinson introduced the following modified vdW EOS:

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or, explicitly in pressure

3 NRTL
The non-random two-liquid model (short NRTL equation) is an activity coefficient model that

x u
correlates the activity coefficients iof a compound i with its mole fractions ij in the liquid phase
concerned. It is frequently applied in the field of chemical engineering to calculate phase equilibria. The
concept of NRTL is based on the hypothesis of Wilson that the local concentration around a molecule is
different from the bulk concentration. This difference is due to a difference between the interaction
energy of the central molecule with the molecules of its own kind and that with the molecules of the other
kind . The energy difference also introduces a non-randomness at the local molecular level. The NRTL
model belongs to the so-called local-composition models

4 Benedict–Webb–Rubin equation

The Benedict–Webb–Rubin equation (BWR), named after Manson Benedict, G. B. Webb, and L. C.
Rubin, is an equation of state used in fluid dynamics. Working at the research laboratory of M. W.
Kellogg Limited, the three researchers rearranged the Beattie–Bridgeman equation of state and increased
the number of experimentally determined constants to eight

5 UNIQUAC
UNIQUAC (universal quasichemical) is an activity coefficient model used in description of
phase equilibria. The model is a so-called lattice model and has been derived from a first order
approximation of interacting molecule surfaces in statistical thermodynamics. The model is
however not fully thermodynamically consistent due to its two liquid mixture approach. In this
approach the local concentration around one central molecule is assumed to be independent from
the local composition around another type of molecule.

The UNIQUAC model can be considered a second generation activity coefficient because its
expression for the Excess Gibbs energy consists of an entropy term in addition to an enthalpy
term. Earlier activity coefficient models such as the Wilson equation and the Non-random two-
liquid model (NRTL model) only consist of enthalpy terms

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6 Van Laar Equation

The Van Laar equation is an activity model, which was developed by Johannes van Laar in
1910-1913, to describe phase equilibria of liquid mixtures. The equation was derived from the
Van der Waals equation. The original van der Waals parameters didn't give good description of
vapor-liquid equilibria of phases, which forced the user to fit the parameters to experimental
results. Because of this, the model lost the connection to molecular properties, and therefore it
has to be regarded as an empirical model to correlate experimental results

7 Selection of the fluid package

Non-polar gases at low pressures (< 10 atm)

Use the Raoult's Law Property Package. It assumes that both phases (gas and liquid) are ideal.

Non-polar gases at high pressures (> 10 atm)

Use one of the Equation of State models like Peng-Robinson, Soave-Redlich-Kwong and
PRSV2.

Polar gases at high pressures (> 10 atm)

Use the PRSV2 Property Package. Check if it has the required parameters for your system as
DWSIM lacks many parameters for this model. If it doesn't, fallback to an EOS model like PR or
SRK.

Systems with high Hydrogen content

You can use the Chao-Seader, Grayson-Streed or Lee-Kesler-Plöcker model. The LKP model is
very slow but can be more reliable depending on the system. The LKP model is very sensitive to
the interaction parameter values being used.

Air Separation / Refrigeration systems

Use the CoolProp or FPROPS Property Package.

Steam/Water simulations

Use the Steam Tables Property Package.

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Polar chemicals

Use one of the activity coefficient models like NRTL or UNIQUAC. If no interaction parameters
are available for your system, you can fallback to one of the UNIFAC-type models. Modified
UNIFAC (NIST) is recommended.

Salt/Water systems

Use the Seawater Property Package.

Aqueous Electrolytes

DWSIM has limited support for aqueous electrolytes due to the lack of model parameters. You
can try the Extended UNIQUAC model, but be ready for many convergence errors. It may or
may not work. If you don't need information about pH and/or don't care about precipitation of
solids, you can always use one of the available activity coefficient models instead.