COMPUTATION OF THE COMPRESSION FACTOR AND

FUGACITY COEFFICIENT OF REAL GASES

I.

Introduction

The kinetic model of gases is an attempt to describe the behavior of gases. Atkins and de Paula
(2010) said that it operates on the assumptions that:
1. Gas is composed of molecules with a mass and moves in a unending random motion;
2. The size of gas molecules is insignificant compared to the average distant molecules travel
during collisions;
3. Molecules attract and repel each other by elastic collisions.
Elastic collisions are collisions where there is conservation of the total translational kinetic of the
molecules. The kinetic model of gases holds when the pressure approaches zero because the average
separation of the gas molecules are negligible, therefore, they exhibit properties akin to ideal gases
(Atkins and de Paula,2010). However, when conditions are far from ideality, corrections to the ideal gas
law can be made.
An equation of state is an equation that shows the relationship between T, V, P and n. Several
equations of state can be used to modify the ideal gas law to better represent real gas behavior.

Several of them are the following:

The constants a and b are the van der Waals coefficients. The first coefficient, a, is used to
represent the attraction between molecules and the latter, b, is used to represent the repulsion

between molecules. They vary for each gas and are independent of temperature (Atkins and de Paula,
2010).
Deviations from ideality can also be expressed in terms of compressibility factor, Z and fugacity
coefficient, .
The compressibility factor is a ratio of the actual molar volume, V (pagawa na lang ito na V bar),
and the ideal molar volume, Videal (pati ito pagawa ng Vbar tapos ideal sa ilalim), isothermally as a
function of pressure. When the gas is assumed to be ideal, Z is equal to unity and is independent of
pressure (Castellan, ____).
=

(Equation 2-7)

(lahat ng V dito pagawa na Vbar)

For a van der Waals gas, Z can be computed from the following equations:

Using power series expansion and expressing V from equation 2-9 as RT/P from the ideal gas law
yields:

At pressure approaching zero, equation 2-10 reduces to Z=1, which is a characteristic of an ideal
gas. In addition, the equations of state mentioned above reduce to the ideal gas law as the molar
volume of real gas approaches infinity.
Fugacity, f, is used to determine Gibbs free energy of a real gas as pressure measures Gibbs
free energy for an ideal gas; it also takes the unit of pressure (Castellan, ___; Atkins and de Paula,
2010). The fugacity coefficient, , is the ratio of fugacity and pressure.

When the fugacity coefficient is equal to one, the fugacity and pressure have the same values.
This illustrates an ideal gas behavior.
To represent the fugacity coefficient in terms of the compressibility factor, the molar Gibbs free
energy fundamental equation can be used:

Integration at constant temperature for an ideal gas yields equation 2-13 when * corresponds
to the reference pressure P*. Replacing the pressure coefficients, P and P* with their real gas
equivalents, f and f*, yields equation 2-14

Combining equations 2-12 and 2-14 at constant T gives:

Integrating 2-15 yields

Going back to 2-12 and integrating it at constant T then combining it with 2-13 yields

Adding 2-16 and 2-17 results to

Rearranging 2-18 and expressing f/P as the fugacity coefficient,

ln

Assuming that P* = f* and expressing the term inside the integral in terms of Z:

Equation 2-20 can be used in this exercise to compute for the fugacity coefficient of real gases.

Going back to 2-2, replacing the P for V/RT, and rearranging yields the succeeding equations:

Using Taylor series expansion for the first term and assuming that the three expansions are enough
results in the compressibility factor equation 2-23:

Using the ideal gas law, the molar volume will be expressed as RT/P and 2-23 becomes:

Moving 1 to the left side and recalling 2-20, and integrating the resulting equation (2-25):

An alternative method to solve 2-16 for the van der Waals equations is through integration by parts.

Vbar* is the molar volume at P*. Replacing the last term by expressing P as the van der Waals
equation and further rearranging:

Assuming at low pressures, P* approaches zero, Vbar* approaches infinity, and P* Vbar* approaches
RT yields

Going back to 2-4, the Redlich-Kwong equation, and again expressing P in terms of Z:

Again using Taylors series expansion, assuming a third degree expansion is enough, the equation
above becomes:

Replacing Vbar with RT/P, transferring 1 to the left hand side and incorporating the resulting
equation to 2-20:

Lastly, integrating 2-34 will yield 2-35.

As seen in equations 2-20, 2-26, 2-30, and 2-35, either f or can be computed by integration from
P* to P.

References:
Atkins, Peter and Julio de Paula. (2010). Atkins Physical Chemistry (9th edition). United States:
Oxford University Press
Castellan, Gilbert. (1983). Physical Chemistry (3rd edition). United States: Addison-Wesley Publishing
Company