Chemical Engineering Department

Auburn University
CHEN 4460
Mario Richard Eden & Ahmed Abdelhady

PHYSICAL PROPERTIES
AND SELECTION OF THERMODYNAMIC MODELS
A property method is a collection of equations used to calculate all physical properties. Each property
method contains a specific equation to calculate a given property, such as enthalpy, density, etc.
ASPEN Plus contains several property methods. How do you choose an appropriate method? This is
the focus of this tutorial.

The key thermodynamic property calculations performed in a simulation is phase equilibrium. The
basic relationship for every component i in the vapor and liquid phases of a system at equilibrium is
that fugacity in the liquid phase = fugacity in the vapor phase. What is fugacity??? (Here we go, past
courses coming back to haunt you ☺). Fugacity is a measure of the tendency of a component of a
liquid mixture to escape, or vaporize, from the mixture. The composition of the vapor form of the
mixture, above the liquid, is not the same as that of the liquid mixture; it is richer in the molecules of
that component that has a greater tendency to escape from the liquid phase. The fugacity of a pure
component fi 0 is related to the pressure that it exerts in the vapor phase through a fugacity coefficient
( φio ):

f i = φio P
0

In an ideal gas, φio = 1 and the fugacity is equal to the pressure. When we have mixtures, fugacity of
component I in the mixture is related to the pure-component fugacity by:

v
f i = yi f i ,v for the vapor and,
0

L
f i = xi f i , L for the liquid (where y and x represent mole fractions in the vapor and liquid phases).
0

v L
Hence, f i = φi , v yi P and f i = φi , L xi P . At equilibrium, both fugacities should be equal.

Fugacities can be calculated using two main methods: equations o f s tate, ac tivity c oefficient m odels,
ideal systems, and special models. Let us review all of them.

EQUATIONS OF STATE

Classical thermodynamics provides a means for properties such as enthalpies and densities from P-V-T
relations which are referred to as the Equations of State (EOS). Some of the common EOS include
cubic equations of state and the virial equations of state. Steam tables are an example of another type of

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equation of state. The simplest equation of state is the ideal gas law (PV = nRT). The ideal gas law
assumes that molecules have no size and that there are no intermolecular interactions. This can be
called absolute ideality, in contrast to ideality defined relative to pure component behavior, as used in
the activity coefficient approach. Examples of EOS Models for predicting properties include:

• Redlich-Kwong-Soave
• Redlich-Kwong
• Peng Robinson
• Sanchez-Lacombe (for polymers)

With an equation-of-state method, all properties can be derived from the

equation of state, for both phases.

ACTIVITY COEFFICIENT MODELS

At a given temperature, the ratio of a fugacity of a component in the mixture to its fugacity in some
standard state (e.g., fugacity of pure component) is termed activity, a. Hence,

fi
ai =
fi o

The activity is related to mole fractions via the activity coefficient γ as follows:

ai , v = γ i , v yi and ai , L = γ i , L xi

For ideal solutions: γ i , v = γ i , L = 1.0

In non-ideal solutions, the activity coefficient is estimated through a variety of models. Examples of
activity coefficient models include:

• Wilson
• Van Laar
• UNIFAC
• UNIQUAC
• Flory Huggins
• NRTL
• Electrolyte NRTL
• Scatchard Hildebrand

The activity coefficient represents the deviation of the mixture from ideality (as defined by the ideal
solution). The greater the deviation from unity, the more non-ideal the mixture is. In the majority of
mixtures, the activity coefficient is greater than unity. The result is a higher fugacity than ideal. As
mentioned earlier, the fugacity can be interpreted as the tendency to vaporize. If compounds vaporize
more than in an ideal solution, then they increase their average distance. So activity coefficients greater
than unity indicate repulsion between unlike molecules. If the repulsion is strong, liquid-liquid
separation occurs. This is another mechanism that decreases close contact between unlike molecules. It

Physical Properties and Thermodynamic Models 2 of 5

is less common that the activity coefficient is smaller than unity. Using the same reasoning, this can be
interpreted as strong attraction between unlike molecules. In this case, liquid-liquid separation does not
occur. Instead formation of complexes is possible.

Using an activity coeffici ent method, the vapor phas e properties are derived
from an equation of state, exactly as in the equation-of- state method. However
the liquid properties are determined from summation of the pure component
properties to which a mixing term or an excess term is added.

IDEAL MODELS

An ideal system is one that follows the ideal gas law (PV=nRT) in the vapor phase and Raoult's law in
the liquid phase. Ideal gas law is typically acceptable at low pressures. The ideal solution assumes that
all molecules in the liquid solution are identical in size and are randomly distributed. This assumption
is valid for mixtures containing molecules of similar size and character. Ideality can also exist between
polar molecules, if the interactions cancel out.

In general, you can expect non-ideality in mixtures of unlike molecules or when you have polar
components. An example of a strong polar compound is water. The following is a list of relative
polarities of functional groups starting with the most polar and ending with least polar:

1. Water
2. Organic acids
3. Amines
4. Alcohols
5. Esters
6. Ketones
7. Aldehydes
8. Ethers
9. Aromatics
10. Olefins
11. Paraffins

Either the size and shape or the intermolecular interactions between components may be dissimilar. For
short these are called size and energy asymmetry. Energy asymmetry occurs between polar and non-
polar molecules and also between different polar molecules. An example is a mixture of alcohol and
water.

The IDEAL property method accommodates both Raoult's law and Henry's law. This method employs
the following relationships and correlations:

• Ideal activity coefficient model for the liquid phase (activity coefficient = 1)
• Ideal gas equation of state for the vapor phase (PV = nRT)
• Ideal mixing in liquid

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SPECIAL MODELS

For specific systems, there are special models that can be used to predict properties. Examples of such
special models include:

• Steam Tables
• API Sour-Water Method
• Kent-Eisenberg

USE OF HENRY'S LAW

Henry's law is only used with ideal and activity-coefficient models. It is used to determine the amount
of a supercritical component or a light (non-condensable) gas (e.g., CO2, N2, etc.) in the liquid phase.
To use Henry's law for non-condensable components, you must designate these components as Henry's
components on the Components Henry-Comps form. Henry's constant model parameters (HENRY)
must be available for the solute with at least one solvent. Use the Properties Parameters Binary
Interaction form (HENRY-1) to enter Henry's constants or to review built-in parameters. ASPEN Plus
contains an extensive collection of Henry's constants for many solutes in solvents. Solvents are water
and other organic components. ASPEN Plus uses these parameters automatically when you specify the
IDEAL property method.

If you are doubtful about the ideality of a system, you can develop Y-X or T-Y-X plot to examine the
behavior of the mixture.

ROADMAP FOR CHOOSING A PROPERTY METHOD

In most cases, the comparison will be between the use of wither EOS models or activity coefficient
models. The following table describes some of the key features for each.

TABLE 1. Comparison Between EOS and Activity Coefficient Models

EOS Models Activity Coefficient Models

Limited in ability to represent non-ideal liquids Can represent highly non-ideal liquids

Consistent in critical region Inconsistent in critical region

Can represent the liquid phase only.

Can represent both the vapor and liquid phases Therefore, the gas phase must still be
described by an EOS model
Binary parameters are highly dependent on
Parameters extrapolate well with temperature
temperature

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If you don't have an exact model for your system, you may use the following tree search to select the
thermodynamic model.

Do you have any POLAR

components in your system?
NO YES

Are the operating conditions

Use EOS Model YES near the CRITICAL region of the
mixture?

NO

Do you have LIGHT gases or

SUPERCRITICAL components
in your system?
NO YES

Use Activity Coefficient Use Activity Coefficient

Model Model with Henry’s law

Fig. 1. Tree Search for Selection of Thermodynamic Model

TABLE 2. Recommended Models for Sample Systems

System Ideality Issues Recommended Model

Water-Benzene Water is polar Activity coefficient model

Propane-Ethane-Butane No polarity Equation of state (EOS)

Benzene-Toluene No polarity, but similar sizes Equation of state (EOS)

Water-Ethanol Water is polar Activity coefficient model

Activity coefficient model with

Acetone-Water-Carbon Dioxide Presence of light gases CO2 designated as Henry’s
compound

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 EQUILIBRIO LÍQUIDO VAPOR

Tabla 1. Modelos para el cálculo de coeficientes de actividad.

Modelo Ecuaciones
ln(γ 1) = [A12 + 2( A21 − A12 ) x1 ]x 2 2 ln(γ 2) = [A21 + 2( A12 − A21 ) x 2 ]x1 2
MARGULES

2 2
⎛ A21 x 2 ⎞ ⎛ A12 x1 ⎞
ln(γ 1) = A12 ⎜⎜ ⎟⎟ ln(γ 2) = A21 ⎜⎜ ⎟⎟
VAN LAAR ⎝ 12 1 + A21 x 2
A x ⎠ ⎝ 12 1 + A21 x 2
A x ⎠

2
⎛ Λ 12 Λ 21 ⎞
ln(γ 1) = − ln( x1 + Λ 12 x 2 ) + x 2 ⎜⎜ − ⎟⎟
⎝ 1
x + Λ x
12 2 x 2 + Λ 21 1 ⎠
x
2
⎛ Λ 12 Λ 21 ⎞
ln(γ 2) = − ln( x 2 + Λ 21 x1 ) − x1 ⎜⎜ − ⎟⎟
WILSON + Λ + Λ
⎝ 1
x x
12 2 x 2 21 1 ⎠
x
υ 2L ⎛ λ − λ11 ⎞ υL ⎛ λ − λ 22 ⎞
Λ12 = exp⎜⎜ − 12 ⎟⎟ ; Λ 21 = 1 exp⎜⎜ − 21 ⎟⎟
υ1L ⎝ RT ⎠ υ2
L
⎝ RT ⎠
υ iL Volumen molar del componente i en fase líquida

Tabla 2. Constantes para los modelos de Margules, Van Laar y Wilson de algunos sistemas LV

Tabla 3. Constantes para ecuación de Antoine. log Pi ( ) = A − B (T + C ) T en ºC ; P en torr

Sat

FUENTE: [Perry]