APPLICATION OF WILSON, UNIFAC AND NRTL MODELS

The better-known solution models include equations Margules, van Laar, Wilson, NRTL, and
UNIQUAC models. Of these, based on frequencies of best fits, the following choices are best
when only one liquid is anticipated:

 For aqueous organics, NRTL

 For alcohols, Wilson
 For alcohols and phenols, Wilson
 For alcohols, ketones, and ethers Wilson or Margules (Wilson is preferred due to its
improved ability to correct for changes in temperature)
 For C4-C18 hydrocarbons, Wilson for aromatics Wilson or Margules (Wilson is
preferred due to its improved ability to correct for changes in temperature)
 When in doubt for VLE calculations, use the Wilson equation. Apply this rule under
the assumption that binary interaction coefficients are available or can be estimated.

Table 1.0 Frequency with which each equation provided the best fit in DECHEMA
Vapor-Liquid Equilibrium Data Collection.
Mixture
Wilson NRTL Best Fit
Classification
Aqueous
0.240 0.403 NRTL
Organics
Alcohols 0.395 0.223 Wilson
Alcohols and
0.342 0.225 Wilson
phenols
Alcohols,
0.243 0.155 Wilson
ketone, ethers
C4-C6
0.365 0.232 Wilson
hydrocarbons
C7-C18
0.260 0.209 Wilson
hydrocarbons
Aromatics 0.225 0.160 Wilson
 Table 2.0 Thermodynamic Model Selection Recommended by Application
Chemicals
K-value method Application
Wilson  Highly non-ideal
 Homogeneous azeotrope
NRTL  Highly non-ideal &2 liquid phases
Heterogeneous azeotrope
UNIFAC  P (0-4atm) T(275-475K)
 Non-ideal &2 liquid phases
 Heterogeneous azeotrope
 Group Contribution Predictive

The UNIFAC method is most successful. It has been used in many areas, for example;

1. To calculate vapour-liquid equilibria (VLE)

2. For calculating liquid-liquid equilibria
3. For calculating solid-liquid equilibria
4. For determining activities in polymer solutions
5. For determining vapour pressures of pure components
6. For determining flash points of solvent mixtures
7. For determining solubility’s of gases
8. For estimation of excess enthalpies.

Table 3.0 Recommended Models and their Limitations

Low pressures – High pressures –
Type of mixtures recommended recommended Limitations
models models
 Systems with
Activity complex
EoS/GE models e.g
coefficients models chemicals.
General MHV2, LCVM,
(Wilson, NRTL and Water-HB
PSRK and WS
UNIFAC) compounds,
solids, liquids,
 polymers,
electrolytes
 LLE, VLLE
 Multicomponent,
multiphase
equilibria

 Systems and
Activity
Size / asymmetric gases for which
coefficients models, LCVM
systems parameters are
modified UNIFAC
not available
 Often good only
for preliminary
design
EoS/GE using
Predictions UNIFAC  Many UNIFAC
UNIFAC
parameter tables
for VLE, LLE,
water systems
REFERENCE

1. Galen J. Suppes, Selecting Thermodynamic Models for Process Simulation of

Organic VLE and LLE Systems, Department of Chemical Engineering The University
of Missouri-Columbia. Available at
https://pdfs.semanticscholar.org/d02d/3efaee030db68a249bad67c684a635e565e3.pdf.
[Accessed on 28th April 2019].

2. John E. Edwards, Process Modelling Selection of Thermodynamic Methods.

Available at
https://www.chemicalprocessing.com/assets/Media/MediaManager/thermo.pdf.
[Accessed on 28th April 2019].

3. Managobinda Behera, (2010), Vapour Liquid Equillibrium Modeling Using Unifac

Group Contribution Method and Its Application In Distillation Column Design And
Steady State Simulation, Department of Chemical Engineering National Institute of
Technology, Rourkela. Available at http://ethesis.nitrkl.ac.in/1975/1/unifac.pdf.
[Accessed on 28th April 2019].

4. Georgios M. Kontogeorgis, Georgios K. Folas, (2010), Thermodynamic Models for

Industrial Applications from Classical and Advanced Mixing Rules to Association
Theories, Technical University of Denmark, Lyngby, Denmark. Available at
https://books.google.com.my/books?id=kLFpSK_PmjIC&pg=PA188&lpg=PA188&d
q=application+of+wilson,+nrtl+and+unifac+thermodynamic+model&source=bl&ots=
bzIVKEps4d&sig=ACfU3U0PrBGS-
hjUjwldH3f6Pb1FJzpxvQ&hl=en&sa=X&ved=2ahUKEwjAgrO2_vPhAhUJuY8KHa
fyAfw4FBDoATADegQICRAB#v=onepage&q=application%20of%20wilson%2C%
20nrtl%20and%20unifac%20thermodynamic%20model&f=false [Accessed on 28th
April 2019]