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Selection of a thermodynamic model
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General advice
The weakest link in simulating chemical engineering operations is uncertainty in the
physical properties, particularly phase equilibria required for modeling distillation,
stripping, absorption and extraction. See, for example, the excellent paper: Uncovering
the realities of simulation, part 1 Part 2

Experimental data
When possible one should either use experimental data to check the predictions of
simulators, or to use these data to fit suitable thermodynamic models.
An excellent source of binary and ternary phase equilibria data as of 1975 is Band 3,
Gruppe IV of the Neue Serie of the Landolt-Brnstein Zahlenwerte und Functionen aus
Naturwissenschaften und Technik, Springer-Verlag (1975) Ref R541/9 U58nt.
A newer comprehensive source is DETHERMA from DECHEMA. Search and then pay
for data found. (Professor Taylor has most volumes in his laboratory.)
Recent original publications with data often can be found by searching the Engineering
Village.
Search also Fluid Phase Equilibria , the Journal of Chemical & Engineering Data, and the
Journal of Chemical Thermodynamics

Expert systems and decision trees (flow charts)
Decision tree and property models from Aspen Plus help
Aspen Plus models with decision tree
Decision tree from a thermodynamics text
AIChE student tool Selecting Thermodynamic Models for Process Simulation of Organic
VLE and LLE Systems (also at Suppes advice).
Aspen advice
Figure 8.4 on p 471 of Towler & Sinnott
Dont Gamble with Physical Properties for Simulations, by E.C. Carlson, Chem. Eng.
Prog. (October 1996) pp 35-46. Includes a decision tree, which is one of two found in the
Encyclopedia on the CD accompanying the text Product and Process Design Principles:
Synthesis, Analysis, and Evaluation, 2
nd
ed., by W.D. Seider, J.D. Seader, D.R. Lewin
(Wiley, NY, 2004), with a needed revision at
http://www.seas.upenn.edu/~dlewin/Upgrade_2004.htm .

Henrys Law
Henrys Law states that the solubility of a gas is proportional to its partial pressure, with the
constant of proportionality called Henrys Law Constant.
Unfortunately, Henrys Law Constant varies, particularly with temperature. How to
correct for the variation.
Environmental engineering implications.
Henrys Law should not be used when there is dissociation or reaction in either phase. A
common example is the dissociation of diatomic molecules (hydrogen, oxygen, nitrogen)
when they dissolve in a liquid or solid metal. When this occurs, the solubility is
proportional to the square root of the partial pressure, a dependence known at Sieverts
Law. One consequence of Sieverts Law is that the driving force for mass transfer of a
diatomic gas across a metal is proportional to the difference in square roots of the partial
pressures in the contacting gas.
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Aspen Plus
Below are four methods to select thermodynamic models in Aspen Plus. Note that Aspen
Plus includes several varieties of the NRTL, UNIQUAC and Wilson activity coefficient
models. With these names alone, an activity coefficient model is used for the liquid phase
while the vapor phase is taken to be ideal. The following varieties account for non-idealities
in the vapor phase due to high pressure and association: NRTL-HOC, NRTL-NTH, NRTL-
RK, UNIQ-HOC, UNIQ-NTH, UNIQ-RK, WILS-HOC, WILS-NTH, WILS-RK, WILS-HF,
WILS-LR and WILS-GLR. Tools/Property Method Selection Assistant
Listing of Thermodynamic Property Models. Excellent! From Aspens Help. The
methods are organized by type, with links to pages clearly explaining each. However,
the links in this pdf copy do not function. To access the original, with functioning
links, do the following while in Aspen Plus. Help, Contents, Accessing Other Help,
click on the Aspen Physical Properties System Help link, in the Contents select Aspen
Physical Property System Reference, Physical Property Methods and Models
Reference Manual, Chapter 3 Property Model Description, Thermodynamic
Property Models, Overview.
Help, Contents, Using Aspen Plus, Entering Data for Simulation, Physical Property
Methods, Available Property Methods, Overview. For activity coefficient models it
specifies what method is used for vapor fugacity coefficients. For more information
about any method, use the Help Search.
Help, Contents, Using Aspen Plus, Entering Data for Simulation, Physical Property
Methods, Choosing a Property Method, Overview.
Aspen Plus models with decision tree
Calculation of binary and ternary phase diagrams, azeotropes and residue curves
Tutorial

HYSY and UniSim
First read the material in Help under Property Package Descriptions and property
package. Also see the SimulationBasis.pdf provided with the documentation for Aspen
HYSYS and UniSim Design.
The expert system developed by Hyprotech (does not work with UniSim)
If you have data for vapor-liquid or liquid-liquid equilibria, select the thermodynamic
model that agrees best with those data using the predictions of HYSYS or UniSim.

Activity coefficient models
Activity coefficient models are needed for non-ideal liquid mixtures. The following is from a
HYSYS web seminar on 2 August 2005, as well as SimulationBasis.pdf. The binary
interaction parameters (BIPs) provided by the simulator for activity coefficient models were
found by regression of binary vapor-liquid data assuming equilibrium with an ideal gas.
These BIPs are not expected to be valid for very high pressures. For low to moderate
pressures, use an activity coefficient model for the liquid, and take the gas as ideal. When
the pressure exceeds 5 atm , use an EOS model such as PR, SRK or RK for the vapor phase.
If there are strong vapor-phase interactions between the molecules a vapor-phase model
must be used that accounts for these interactions. For example, HYSYS recommends you
use the Virial option for organic acid components (like formic acid, acetic acid, propionic
acid, butyric acid, and heptonic acid. For operations involving only gases, e.g.
compression, it may be desirable to use an equation of state model just for that one unit.

Advanced equation of state models introduces the Twu models, which are included in
HYSYS and UniSim but not in the expert systems or decision trees mentioned above.

Missing BIPs
It is common for some BIPs to be missing for a multicomponent mixture. If, on the Binary
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Coeffs page, a coefficient estimation method is given, return to the Setup page and change
the temperature to a value suitable for your process, return to the Binary Coeffs page, then
click on VLE (vapor-liquid equilibria) or LLE (for a liquid-liquid extraction column) and
then Unknowns Only. If you change your mind, hit Reset Params.

Multiple thermodynamic models.
The following is taken from the Aspen support site. "Beginning with HYSYS 3.0, you no
longer need to use Sub-Flowsheets when creating model with multiple Fluid Packages. Each
Unit Operation and Stream can have its own associated Fluid Package. A Stream Cutter
Operation is automatically inserted into the flowsheet at the point where a transition from
one Fluid Package to another occurs. The Stream Cutter defines the Component mapping
and Transition Basis for the transfer. Among other things, this capability allows the use of
separate Fluid Packages for the Shell and Tube sides of a Heat Exchanger." For a vapor-
liquid separation such as distillation, you may want to select a model specifically for the light
and heavy keys, e.g. with the most number of BIPs. Heres more information from Aspen.
Following are the steps to follow:
1. Add the new equipment to your pfd, but do not connect it to the streams
2. In the Basis Environment, define the desired new Fluid Package.
3. On the Fluid Pkgs page indicate the package to be used for each piece of equipment.
4. If, while returning to the Simulation Environment, you encounter a warning, then select
a more suitable transfer basis.
5. Connect the streams to the equipment. Run the simulation.
6. While, in principle, manual insertion of stream cutters is not required, in practice that
sometimes doesnt work and an error message persists, probably that the transfer basis
isnt known. When this happens, delete the equipment and insert stream cutters in both
inlet and outlet streams. Then reinsert and connect the equipment to the streams. If the
transfer basis error recurs, go to the Flowsheet Setup page of the equipment and select a
reasonable transfer basis for all streams. At some point, HYSYS may offer to delete the
stream cutters. Decline this invitation.


Last modified August 9, 2011. Please submit all questions, comments and suggestions to W.R.
Wilcox

Disclaimer: The material on these pages is intended for instructional purposes by Clarkson
University students only. Neither Clarkson University nor Professor Wilcox is responsible for
problems caused by using this information.

Wilcox home ChE design home Profession General Properties Equipment Separation HYSYS & UniSim
Costs Safety Case studies Excel MATLAB Data Analysis
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