Chapter 8

Real Gases

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Equations of State

The Ideal gas law is inadequate to explain the behaviour of real gases.

At low molar volumes or high pressures, the molecules come very close to each other and
molecular interactions cannot be neglected.

Many equations of state have been proposed to explain the actual behaviour of gases; These
include but are not limited to:

Van Der Waals equation

Redlich-Kwong Equation
Virial Equation

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 Van Der Waals Equation

Van der Waals proposed the following equation to explain the P-V-T behaviour of real
gases:
 a 
 P  V  b   RT
2
 V 

Where a and b are van der Waals constants which can be evaluated by:

27 R 2Tc2 RTc
a ; b
64 Pc 8Pc

Where Tc is the critical temperature and Pc is the critical pressure.

R is the gas constant.

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Example 8.1

One kilo mole CO2 occupies a volume of 0.381 m3 at 313 K. Calculate the pressure
using:
(a) Ideal gas equation;
(b) Van der Waals equation
Take the van der Waals constants to be a = 0.365 Nm4/mol2 and b = 4.28x10-5 m3/mol.

Example 8.2

Calculate the volume occupied by one mole of oxygen at 300 K and 100 bar using:
(a) Ideal gas law;
(b) The van der Waals equation
Take a = 0.1378 Nm4/mol2 and b = 3.18x10-5 m3/mol.

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 The Virial Equation

The ratio PV/RT is called the compressibility factor (Z).

It is the ratio of the volume of a real gas (V) to the volume if the gas behaved ideally at
stated temperature and pressure (RT/P).

Virial equations express the compressibility factor of a gas or vapour as a power series
expansion in P or 1/V.

PV
Z  1  BP  C P 2  DP3    
RT

PV B C D
Z  1    
RT V V 2 V 3

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The above equations are known as virial equations and constants B, C, D and B', C',
D' are known as virial coefficients.

B and B' are called second virial coefficients; C and C' are called third virial
coefficients, and so on.

For a given gas, these coefficients are functions of temperature only.

The two sets of coefficients are related as:

B C  B2
B  C 
RT RT 2

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 𝑃𝑉 𝐵𝑃
𝑍= =1+
𝑅𝑇 𝑅𝑇
This equation expresses a direct proportionality between Z and P, and is often applied
to vapours at subcritical temperatures up to their saturation pressures

𝑃𝑉 𝐵
𝑍= =1+
𝑅𝑇 𝑉

The equation below allows you to solve for volume using the virial equation

𝑃𝑉 𝐵 𝐶
𝑍= =1+ + 2
𝑅𝑇 𝑉 𝑉

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Example 8.3
Reported values for the virial coefficients of isopropanol vapour at 200 deg cel are:
B = -388 cm3/mol
C = -26000 cm6/mol2
Calculate V and Z for isopropanol vapour at 200 deg cel and 10 bar by
(a) The ideal gas law
𝑃𝑉 𝐵𝑃
(b) 𝑍 = =1+
𝑅𝑇 𝑅𝑇
𝑃𝑉 𝐵 𝐶
(c) 𝑍 = =1+ + 2
𝑅𝑇 𝑉 𝑉

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 Redlich-Kwong Equation

A two-parameter equation of state widely used in engineering calculations.

RT a
P 
V  b T 0.5V V  b

The constants a and b are evaluated as:

0.4278R 2Tc2.5 0.0867 RTc

a ; b
Pc Pc

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Example 8.4
Calculate the compressibility factor and molar volume for methanol vapour at 500 K
and 10 bar by using the following equations.
(a) Truncated form of virial equation
(b) Redlich-Kwong equation

Experimental values of virial coefficients are, B = -2.19x10-4 m3/mol;

C = -1.73x10-8 m6/mol2. The critical temperature and pressure of methanol are 512.6 K
and 81 bar.

Chemical Engineering Thermodynamics - 2019