Comparison of

Thermodynamic Models in
prediction of n-Hexane – CO2
VLE Behavior
Ameen Siddiqui
Muhammad Umar Jamil
Introduction
The binary system carbon dioxide
(1)/hexane (2) has several industrial
applications either as raw material,
intermediate products, or final products in
many chemical processes
• Supercritical extraction of hexane using
liquid carbon dioxide. Eg: soybean oil
• Most important applications for this
binary system are in the oil and gas
industry due to is a common practice the
injection of carbon dioxide to crude oil
wells used as a technique of enhanced oil
recovery.
Objective
To study the phase equilibria using various thermodynamic models for given binary mixture.
To simulate the phase concentration and corresponding pressure of binary mixture at various
temperature using ASPEN software.
To compare the results of simulation with experimental data
To determine accuracy of various thermodynamic models
To recommend best available thermodynamic model for C02-nhexane system based on this
study.
Selection of thermodynamic model
Among the equations used in thermodynamic analysis there are Equations of State (EOS)
and activity coefficient models.
The equations of state are commonly used to describe the behavior of mixtures at high
pressure
Activity coefficient models are equations used to describe the phase equilibrium of
mixtures at low pressures in which exist significant differences of size, shape and polarity of
the molecules which conform the liquid phase.
Two rules of thumb in the selection of the thermodynamic model are the pressure of the
system and the behavior of the liquid phase.
High Pressure - Equations of state
Low Pressure with variation in shape, size & polarity – Activity coefficient model
Low Pressure with no variation in shape, size & polarity – Raoult’s law
Selection of thermodynamic models
Component MW Tc (bar) Pc (bar) ω Vliq (cm3/mol) μ (debye)

CO2 44.01 304.12 73.74 0.225 - 0.00

C6H14 86.177 507.6 30.25 0.300 131.59 0.00

• According to the values of the parameters showed in table 1, we can see that there
are small differences between the shape of the molecules, no differences in polarity
finally regarding size of the molecules we can’t state nothing, the reason is that the
liquid molar volume of carbon dioxide is unknown.
• Apparently, due to differences in size, shape, and polarity are low it would be expect
that Raoult’s law is applicable,
• However, the vapor-liquid equilibrium of the system carbon dioxide (1)/n-hexane (2)
takes place at high pressures hence is expected that EOS will give the better
approximations describing the behavior of this system.
Simulation Method &
Analysis
SRK EOS
PR EOS
PR-BM EOS
Simulation Method & Analysis
Sample Calculations
Temperature: 40 ºC (SRK)
Exp Pressure Exp Mole fraction Exp Mole fraction Sim Sim Mole fraction
(psia) CO2 (l) CO2 (v) Pressure CO2 (v)
113 0.080 0.949 65.650 0.915

240 0.17 0.972 137.314 0.957

354 0.252 0.977 206.564 0.970

480 0.356 0.982 300.715 0.978

600 0.450 0.982 393.030 0.982

733 0.574 0.984 527.885 0.985

844 0.687 0.985 667.655 0.987

973 0.829 0.984 876.473 0.989

1039 0.882 0.982 968.375 0.990

1085 0.915 0.981 1031.250 0.990

Total 26.873 0.881

*Vapor-Liquid Phase Equilibrium for Carbon Dioxide-n-Hexane at 40, 80, and 120 °C - Ying-Hsiao LI et. Al 1981
Experimental Values

*Vapor-Liquid Phase Equilibrium for Carbon Dioxide-n-Hexane at 40, 80, and 120 °C - Ying-Hsiao LI et. Al 1981
SRK EOS

*G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 - 1203.
*A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich-Kwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 7–23.
SRK EOS 120.00

100.00

P-x SRK (T=40°C)

80.00 P-y SRK (T=40°C)
P-x SRK (T=80°C)
P-y SRK (T=80°C)
P(bar)

P-x SRK (T=120°C)

60.00
P-y SRK (T=120°C)
P-x Exp. (T=40°C)
P-y Exp. (T=40°C)

40.00 P-x Exp. (T=80°C)

P-y Exp. (T=80°C)
P-x Exp. (T=120°C)
P-x Exp. (T=120°C)
20.00

0.00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Modifications to SRK
PR EOS

*D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind. Eng. Chem. Fundam., Vol. 15, (1976), pp. 59–64.
PR EOS 120

100

P-x Exp. (T=40°C)

80 P-y Exp. (T=40°C)
P-x Exp. (T=80°C)
P-y Exp. (T=80°C)
P (bar)

P-x Exp. (T=120°C)

60
P-y Exp. (T=120°C)
P-x Peng-Rob. (T=40°C)
P-y Peng-Rob. (T=40°C)

40 P-x Peng-Rob. (T=80°C)

P-y Peng-Rob. (T=80°C)
P-x Peng-Rob. (T=120°C)
P-y Peng-Rob. (T=120°C)
20

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
PR-BM EOS

*D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind. Eng. Chem. Fundam., Vol. 15, (1976), pp. 59–64.
*P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules for multicomponent mixtures: the problem of invariance," Fluid Phase Equilibria, Vol 67, (1991), pp. 31-44.
*H. Knapp, R. Döring, L. Oellrich, U. Plöcker, and J. M. Prausnitz. "Vapor-Liquid Equilibria for Mixtures of Low Boiling Substances." Dechema Chemistry Data Series, Vol. VI.
PR-BM EOS 120

100

P-x Exp. (T=40°C)

80 P-y Exp. (T=40°C)
P-x Exp. (T=80°C)
P-y Exp. (T=80°C)
P (bar)

P-x Exp. (T=120°C)

60
P-y Exp. (T=120°C)
P-x PR-BM. (T=40°C)
P-y PR-BM. (T=40°C)

40 P-x PR-BM. (T=80°C)

P-y PR-BM. (T=80°C)
P-x PR-BM. (T=120°C)
P-y PR-BM. (T=120°C)
20

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Quantitative Analysis
SRK PR PR-BM

AAD% AAD% AAD% AAD% AAD% AAD%

T (ºC)
(P) (y) (P) (y) (P) (y)

40 26.87 0.88 3.96 0.32 3.88 0.31

80 25.93 2.91 4.42 0.80 3.85 0.77

120 22.44 5.17 4.67 1.94 3.10 1.48

 T 255.98–408.15 K
P 0.1–16.48 MPa
Quantitative Analysis PR
PR-BM
2.24–5.74%
0.75–3.36%
Mixture T (K) P(MPa) AAD% (PR) AAD%(PR-BM)

CO2-butane 255.98-393.07 0.10-8.08 2.24 0.75

CO2-pentane 343.4-408.15 0.621-9.10 3.98 2.63

CO2-isopentane 310.89-408.07 0.37-8.89 5.74 1.77

CO2-hexane 273.15-392.97 0.90-11.60 2.82 3.36

CO2-benzene 273.15-393.20 0.11-13.30 4.87 1.94

CO2-heptane 293.15-403.15 2.30-13.40 3.18 2.8

CO2-octane 313.20-372.53 1.15-13.77 4.19 2.79

CO2-decane 310.95-377.60 0.89-16.48 3.89 1.46

Conclusion
PR-BM predicts more accurately for n-alkanes – CO2 mixtures
than SRK & PR
Thank you!
Any questions?