EOS - Equations of state 

Fundamentals 

What is an Equation of state?

In general, they are thermodynamic relationships between three properties of a pure

substance or mixture:
- absolute Pressure
- absolute Temperature
- specific or molar volume

Can reproduce low-pressure gas PVT data with good accuracy. As pressure increase, we
require more complex EOS to match experimental data and adjust the equation with terms
that may not have theoretical basis.

Van der Waals equation

When Van der Waals is valid?

At low temperatures and high pressures.

What are the corrections for this equation?

- Formula for ideal gases: PV=nRT (funciona bien para líquidos y gases)
- Correction for volume: Because atoms and molecules take up space.
- Correction for pressure: Because of the intermolecular forces

- Corrected formula: (P + n2 a
V
2 ) (V − nb) = nRT
- Where a and b are constants for the particular gas.
- “b” is four times the “volume” of the molecule
- “a” reflects the intermolecular attractions
- The term V-nb corresponds to the free volume available for unimpeded
molecular motion after the effective volume occupied by the molecules has
been deducted.

Compressibility Factor
● The compressibility factor is a way to measure the deviation from an ideal behavior to
a real gas behaviour. Different gases deviate from ideal behaviour in different ways, it
can be positive (z>1) or negative (z<1). For an ideal gas z=1
● The equation goes as follows: z = PRTV
 ● Fugacity should replace pressure for real gases in the application of laws or
theoretical f ormulations as they are defined for ideal gases.
● The compressibility factor helps us to measure the behaviour of a real gas to obtain
the fugacity of a pure gas.
p
● Therefore: lnֆ = 1
RT ∫ (V m − RT
P )dP
0
PV m
z= RT
p P
(z−1)
lnֆ = 1
RT ∫ ( PRTV m
− P1 )dP = ∫ P dP
0 0
Virial Equation
The Virial equation comes from the latin word “​force” this equation is for the gaseous phase
of a substance and it differentiates from the ideal gas equation because it can only be
applied when there is a low and moderate densities.
It contains a large database for the coefficients that are necessary for the calculation. This
equation is useful to express a wide range of thermodynamic properties of pure gases and
mixtures. A close relationship exists between the coefficients and intermolecular forces, they
depend on the gas’s nature and are a function of temperature.
PV m 1+β α θ
z= RT = Vm Vm 2 Vm 2

The second coefficient depends only in the intermolecular interactions and said interactions
depend on the intermolecular potential.
The third virial coefficient depends on three body interactions.

The equation is important due to the fact that it describes intermolecular forces and provides
a route to know the interactions of molecules in pairs, triplets, etc. The virial equation is the
only equation of state for which rigorous mixing is viable.

Lee Kesler Correlation

Using the principle of corresponding states:
Reduced temperature and reduced pressure have identical compressibility factor and
deviation from ideal state.

This correlation is based on:

Lee Kesler EOS
z = z 0 + ωz 1
z 0 -> stands for simple molecules
ω -> is the accentric factor
z 1 -> stands for non spheric molecules.

Example:
Calculate ​f &​ φ of ethane @ 50 bar & 25°C:
T c = 305.5 K T r = 298.15
305.5 = 0.9759
50
P c = 4.48 M P a Pr = 44.8 = 1.116
ω Ethane = 0.099
Using the Lee-Kesler Correlation:

logφ = logφ0 + ω logφ1

logφ0 = − 0.2
logφ1 =− 0.06
logφ =− 0.2059
φ = 0.62
f = 31.1 bar

Figure 2:​Koretsky, M.(2013), Engineering and Chemical Thermodynamics John Wiley & Sons, chapter 4 page
401.

Virial Equation and compressibility factor correlation:

BP
Z = 1 + RT
p
f
ln( p ) = ∫ B
RT dp
pi

References:
Koretsky, M.(2013),​ Engineering and Chemical Thermodynamics John Wiley & Sons

Zhou, Li (2001) ​Determination of compressibility factor & fugacity coefficient of Hydrogen in

Studies of adsorptive storage. International journal of Hydrogen.