The University of Jordan

School of Engineering
Department of Chemical Engineering
Advanced Thermodynamics (0945721)

A Summary of “The State of the Cubic Equations of State ”

Prepared by : Sojoud Al-Yousef (8220063) Instructor: Dr. Ali Al-Matar

Outlines

• Introduction
• Development of cubic EoS
• Applications to Mixtures
• Classical Mixing Rules
• Nonquadratic Mixing Rules
• EoS + Gibbs free Energy models
• Volumes dependent Mixing rules
• Applications of Cubic EoS
 Introduction

❖ Equations of state represent the cornerstone of thermodynamic models.

❖ Thermodynamic models are required in:

• A wide range of industries.
• Processes and Products Design.
• Applications in which diverse properties:
❑ Various types of phase equilibrium
❑ thermal
❑ transport properties, should be used.
 Introduction

❖ Many EoS have been proposed through the years and several theories have been devised to
better represent PVT properties and vapor-liquid equilibrium.
Development of cubic EoS

The end of 18th century

• Bernoulli:
suggested including the volume of the molecules into the repulsive term (Ignored)

• Hirn and Dupre revived the idea. Dupre named it "covolume“ .

• none was able to answer the many questions related to fluid behavior.

1873
• Van der Waal:
➢ Consolidated a majority of the experimental understanding of fluid properties into
one equation. that: repulsive
➢ explains deviations from the behavior of an ideal gas
➢ predicts the existence of a critical point.
➢ considers both the liquid and vapor phases.
➢ considers phase equilibrium below the critical point. attractive
➢ considers the separation of phases above it
Development of cubic EoS

1880
• Clausius:
• molecules at low temperature do not move freely but form clusters of molecules in
which stronger attractions occur.
• modified the volume dependency of the attractive term.
• The attractive term in the equation of state should be temperature-dependent

• gave the rise to “three parameter equations”.

• Zc is not constant.

1873 - 1949

• More than 200 EoS appeared:

• Otto: list of 56 equations (1929)
• Vulakovich and Novikov: a list of 150 EoS (1944)
• Walas: gives a list of about 60 equations
Development of cubic EoS

1949
• Redlich- Kwong (RK):
• How to improve upon VdW.
• Their equation gives a good results for many gaseous systems.
• During the period of 1960-1980, the RK equation was extensively modified and can
be considered the most modified EoS ever.(150 RK-type equations)
• Total of 400 cubic EoS proposed to date in the literature.

1960s- 1972
• Wilson:
• Introduced acentric factor (𝜔) into the attractive term. (Ignored)

• Soave:
• Redefined 𝛼(𝑇𝑅 , 𝜔).
• The most popular EoS in the H-C industry.
• SRK used in:
❑ Computer simulation
❑ Optimization
Development of cubic EoS

1976
• Peng- Robinson (PR)
• Recalculation of 𝛼(𝑇𝑅 , 𝜔).
• Modifying the V dependency in the attractive term.
• Better results of liquid volume.
• Better VLE representation.

More accurate prediction

Modification of 𝛼(𝑇𝑅 ).
of (𝑃𝑣𝑎𝑝 ) and VLE

Cubic EoS after Modification of V- dependency Volume translation

Soave and PR of 𝑃𝑎𝑡𝑡𝑟𝑎𝑐𝑡𝑖𝑣𝑒 term concept

use of 3rd substance-

three- parameter models
dependent parameter
Modification of 𝛼(𝑇𝑅 )

1949

• m,n p,q and Γ

Component dependent
Most Popular

parameters.
• available for about 500
substances.

2001
 Volume- translated Equations

❖ Modifying the Volume by adding “ Component dependent molar volume” correction factor.

❖ Peneloux (1982):
• proposed a volume correction in the SRK equation of state, which improves volume predictions without
changing the VLE conditions.
• highly recommended for calculating phase and volumetric behavior of hydrocarbon mixtures and reservoir
fluids.
❖ Tsai and Chen (1998):
• Volume- translated Peng- Robinson (VTPR).
• it yields good predictions of molar volumes of liquid mixtures.
 Three- Parameter EoS

EoS Zc
VdW 0.375
RK and SRK 0.333
PR 0.307

❖ The fixed value of (Zc) should be replaced by a substance-dependent adjustable critical parameter.
❖ Clausius’ equation allows for the use of an additional empirical parameter, because the critical compressibility
factor is no longer constant.
❖ The idea did not gain popularity because of the success of other simpler equations.
 Application to Mixtures

❖ Representation of mixed-fluid properties is the main

purpose of using cubic and generalized van der Waals
equations of state.
❖ Solórzano et al. concluded that the most accurate
assessment of the efficacy of mixing rules can be
obtained by applying them to multicomponent mixtures.

Volume –
Nonquadratic
Dependent

EoS + 𝐺 𝐸𝑥
Classical
models
Mixing
Rules
 Classical Mixing Rules

✓ Most widely used.

✓ Simple.

If we take 3 parameter EoS: Arithmetic mean

Geometric mean

✓ a, b, and c are Quadratic Concentration dependent.

✓ 𝑎𝑖𝑗 , 𝑏𝑖𝑗 , and 𝑐𝑖𝑗 Concentration independent.
✓ 𝑘𝑖𝑗 , 𝛽𝑖𝑗 , and 𝛿𝑖𝑗 Interaction parameters (Calculated by regression analysis).
 Classical Mixing Rules

❖ Some authors have attempted to obtain binary interaction parameters from pure-component
property data.
❖ As an example for a translated and modified PR EoS:

CO /hydrocarbons:
2

CO /methane:
2

❑ not always suitable for extrapolation and, in many cases, are only applicable to
particular mixtures

❑ limited to non-polar and slightly polar mixtures.

 Volumes dependent Mixing rules

❖ The functional form of composition-dependent Mixing rules may have some inaccuracies.
❖ better results could be obtained if the constants of a selected equation of state were allowed to depend not only on
composition and, sometimes, temperature, but also on density.

The attractive parameter can be written as :

❖ The density-dependent mixing rules do not improve the results of phase-equilibrium computations over the, composition-
dependent combining rules.
❖ The loss of accuracy for ternary and multicomponent systems is also shared by the density-dependent mixing rules.
❖ At the same time, the density-dependent mixing rules eliminate the third-order density dependence of cubic equations of
state and impose a higher-order dependence.
Nonquadratic Mixing Rules

Panagiotopoulos -Reid (PR)

• Introduced a second interaction parameter.

• Concentration dependent interaction parameter.

General nonquadratic mixing rule

• Two parameters.
• successfully applied to binary mixtures containing a supercritical
component
 EoS + Gibbs free Energy models

❖ Seem to be the most appropriate for modeling mixtures with highly asymmetric components.
❖ These models have been extensively used and applied to:
➢ low- and high pressure vapor-liquid mixtures
➢ liquid-liquid equilibria
➢ gas-solid equilibria.

Wong – Sandler (WS)

• derived considering the excess Helmholtz energy at infinite

pressure. (𝐴∞ )
• Almost independent of pressure and almost equal to (𝐺 𝐸𝑥 ) at low
pressure.
• for strongly polar-nonpolar mixtures, the combination WS +
NRTL gives the best results
• for strongly polar + strongly polar mixtures, the combination WS
+ UNIQUAC gives the best results.
EoS + Gibbs free Energy models
 Applications of Cubic EoS
Reservoir Fluids
▪ Cubic – EoS have shown good
capabilities for correlating VLE and
volumetric properties of complex
reservoir fluids.
▪ PTV and modified RK are the best.
▪ For liquid density: SRK and PR
improved by Volume translation.
▪ Unsatisfactory phase volumes.
▪ reasonable phase concentrations.
Applications
Supercritical Components
▪ The first efforts to model the phase
behavior were made using the virial
EoS (not successful).
▪ SRK and PR obtained the best results.
▪ the use of Gibbs free energy models in
the EoS parameters and nonquadratic
mixing rules with interaction
parameters in the volume constants of
the EoS give the best results.
Polymer Solutions
▪ Some contradictory statements can be
found in the literature:
➢ “Cubic equations can be extended to
accurately correlate and predict VLE
in polymer mixtures”.
➢ “The complexity of polymer mixtures
requires more advanced approaches
that go beyond the simplicity of cubic
EoS”.
Conclusion

Advantages Disadvantages

The volume is cubic and calculations are relatively easy to

Actual PVT data tends to follow a fourth-degree equation.
perform.

The known inaccuracies of both terms cancel each other

Both the attractive and repulsive terms of equations of state
out when EoS are used to calculate fluid properties,
(EoS) are inaccurate.
particularly VLE.

For most applications, cubic EoS can be adjusted to give

Cannot represent all properties of a fluid within all ranges
accurate values for any volumetric or thermodynamic
of pressure and temperature.
property.

since interactions between unlike molecules are unknown,

It is relatively easy to extend equations to mixtures using
most of these rules are empirical and require interaction
mixing and combining rules of any complexity.
parameters.

suitable for the application of modern mixing rules, which In applications to complex mixtures, several interaction
include Gibbs free energy models or concentration- parameters might be required, even with the use of modern
dependent parameters. mixing rules.
 References

❖ Sengers, J. V., Kayser, R. F., Peters, C. J., White, H. J., Jr., Eds. Equations of State for Fluids and Fluid Mixtures;
International Union of Pure and Applied Chemistry (IUPAC): Research Triangle Park, NC, 2000.
❖ Solórzano-Zavala, M., Barragán-Aroche, F., & Bazúa, E. R. (1996). Comparative study of mixing rules for cubic
equations of state in the prediction of multicomponent vapor-liquid equilibria. Fluid Phase Equilibria, 122(1-2), 99-
116.
❖ Valderrama, J. O. (2003). The state of the cubic equations of state. Industrial & engineering chemistry research,
42(8), 1603-1618.
❖ Kontogeorgis, G. M., Liang, X., Arya, A., & Tsivintzelis, I. (2020). Equations of state in three centuries. Are we
closer to arriving to a single model for all applications?. Chemical Engineering Science: X, 7, 100060.