REAL GASES

DEVIATIONS OF REAL GASES FROM IDEAL BEHAVIOUR:

Positive
deviations

Negative deviation

Fig: 1

For an ideal gas, pV=nRT. But, experimental findings show that real gases do
not follow this ideal condition in most cases. The real gases always show
deviations from ideal behaviour. In the figure pV against p plots for a number
of real gases are shown. From the figure it is clear that the pV vs p plots for
real gases deviates from the ideal plot. We have observed here two types of
deviation. When pressure is low pV values for real gases is less than the ideal
pV value. This type of deviation is called negative deviation. At higher
pressure pV values for real gases are higher than the ideal pV values. This
type of deviation is called positive deviation. Thus a real gas shows negative
deviations at low pressure and positive deviations at high pressure.

If (i) (pV)observed = (pV)ideal a real gas shows ideal behaviour

(ii) (pV)observed > (pV)ideal a real gas shows positive deviation

(iii) (pV)observed < (pV)ideal a real gas shows negative deviation

COMPRESSIBILITY FACTOR, Z
The ratio between the observed pV value of a real gas to that of the pV value
of an ideal gas is known as compressibility factor denoted by Z.
(𝒑𝑽)𝒐𝒃𝒔 𝒑𝑽
Thus, Compressibility factor, Z = = 𝒏𝑹𝑻
(𝒑𝑽)𝒊𝒅𝒆𝒂𝒍

(since, (pV)ideal = nRT. Here, pV represents the observed pV value)

If compressibility factor, Z is plotted against temperature for a real gas (N 2) at

different temperatures we get the figure 2(i) and for different gases at
constant temperature we get the figure 2(ii) as shown below.

Fig: 2 (i) Fig: 2(ii)

Therefore, when Z = 1, the gas shows ideal behaviour

when Z > 1, the gas shows positive deviation

when Z < 1, the gas shows negative deviation

Compressibility factor, Z gives the extent of deviation caused by a real gas

from its ideal behaviour. eg. if two gases A and B have Z= 1.4 and 1.6 at a
particular temperature and pressure respectively then gas B will show more
positive deviation than A. Similarly, if two gases C and D have Z= 0.4 and 0.6
respectively then gas C will show more negative deviation than gas D at a
particular temperature and pressure.

BOYLE’S TEMPERATURE: TB

For every gas there is a temperature at which the real gas shows ideal
behaviour for a wide range of pressure (p→0). This temperature is known as
Boyle’s temperature denoted by TB.

CAUSES OF DEVIATION FROM IDEAL BEHAVIOUR:

A real gas do not obey ideal gas equation pV=nRT at all conditions of
temperature and pressure and shows deviations from ideal behaviour.
Therefore, ideal gas equation pV=nRT, the theoretical basis of which is the
Kinetic Theory of gases has some drawbacks due to which real gases deviates
from ideal behaviour. The Kinetic Theory was based on some postulates and
therefore some postulates may not valid at all temperatures and pressures of
the gas. Two postulates of Kinetic Theory are responsible for these deviations.

(1) The volume occupied by the gas molecule is negligible compared to the
total volume occupied by the gas.
(2) There is no any intermolecular forces of attraction exist among the gas
molecules.
 These two postulates are valid only when the total volume of the gas is very
large. We know that a gas occupies a large volume at very low pressure
and at very high temperature. Therefore, a real gas shows ideal behaviour
only under these conditions of temperature and pressure.

EQUATIONS OF STATE FOR REAL GASES:

Different equations of state for real gases were derived by different
scientists. Some of these are

• van der Waals equation

• Berthelot equation
• Dieterici equation
• Virial equation

Out of these van der Waals equation of state is widely used to describe
the equation of state for real gases.

VAN DER WAALS EQUATION:

van der Waals introduced two correction terms to the ideal gas
equation PV=nRT and obtained an equation of state for n mole of a
real gase as
𝒏𝟐 𝒂
(P + ) (V – nb) = nRT
𝑽𝟐

The first correction was made for the volume occupied by the gas
molecules and second correction was made for the force of
attraction between the gas molecules.
Correction due to volume occupied by the gas molecules:
When n moles of a gas are placed in a container of volume V, the space in
which the molecules are free to move is equal to V if the volume occupied by
the molecules themselves is negligible. Since the molecules have a finite size,
the actual volume available to them for their movement would not be V but
less than V. If b is the effective volume per mole of the gas then this volume
must be subtracted from the total volume in order to get the actual volume for
their movement. Therefore,

Videal = V- b

For n moles of the gas Videal = V- nb

b is also sometimes called the excluded volume and is usually treated as a

constant and characteristic of each gas. b can be calculated as follows:

Let us assume the bimolecular collisions between two similar impenetrable

spherical gas molecules as shown in the figure.

Suppose r is the radius and d (=2r) is the collision diameter of the gas
molecules. If we consider a sphere of radius d, equal to the collision diameter
indicated by the green sphere, then this space is not available to the pair of the
colliding molecules. This space is the excluded volume for a pair of molecules
𝟒
and is given by πd3 .
𝟑

𝟏 𝟒 𝟏 𝟒
Therefore, excluded volume per molecule = 𝟐 x πd3 = 𝟐 x π(2r)3
𝟑 𝟑

𝟒
=4x 𝟑
π r 3 = 4 vm
 𝟒
But, π r 3 = vm is the actual volume of one gas molecule.
𝟑

Thus, excluded volume per molecule= 4x actual volume of one gas molecule

The excluded volume per mole is represented by van der Waals constant b.

Correction due to intermolecular attraction:

Let us consider a molecule in the bulk of the gas. This molecule is

surrounded by similar molecules from all sides and the resultant force acting
on the molecule will be zero. But, if this molecule approaches near to the wall
of the container the molecule is not attracted equally from all sides. It will be
attracted more by bulk molecules and as a result it will collide with the wall
with a lesser velocity and hence with a lesser force as we expect for molecule
where there is no any intermolecular attraction. Thus, the pressure exerted by
the molecules on the wall will be lower than the molecules in ideal gases.
Therefore, ideal pressure will be always greater than the observed pressure
for a real gas.

Pideal = P + ∆p
This ∆p is called pressure defect. This pressure correction term ∆p can be
calculated as follows.

The net inward pull experienced by the molecules about to strike the wall of
the vessel is proportional to

(i) the number of molecules in the bulk of the gas which will depend on
the number density(number of molecules per unit volume) of the gas.
(ii) The number of molecules striking the wall per unit area at any
instant is also proportional to the number density of the gas.

Thus, ∆p α (Nʹ)2
𝒏
or, ∆p α ( 𝑽 )2
𝒂𝒏𝟐
or, ∆p = 𝑽𝟐
Where a is the constant of proportionality and is another van der
Waals constant.

𝒂𝒏𝟐
Thus, Pideal = P + 𝑽𝟐

Thus the ideal gas equation PV= nRT modified by van der Waals for a real
gas as

𝒂𝒏𝟐
(P + 𝟐 )
𝑽
+ (V – nb) = nRT

For one mole of a gas van der Waals equation becomes

𝒂
(P + ) + (V – b) = RT
𝑽𝟐

UNIT OF VAN DER WAALS CONSTANTS:

𝒂𝒏𝟐
Unit of a: Since, ∆p =
𝑽𝟐
 ∆𝒑𝑽𝟐
or, a = 𝒏𝟐

(𝒑𝒓𝒆𝒔𝒔𝒖𝒓𝒆)(𝒗𝒐𝒍𝒖𝒎𝒆)𝟐
or, a = 𝒎𝒐𝒍𝟐

(𝒂𝒕𝒎)(𝑳)𝟐
= 𝒎𝒐𝒍𝟐

= atm L2 mol-2
In S. I. Unit: Nm-2.(m3)2mol-2 = Nm4mol-2

Unit of b: van der Waals constant b is the excluded volume per mole. So, its
unit is the volume mol-1 ie. Lmol-1. In S.I. unit : m3mol-1

VAN DER WAALS EQUATION AT DIFFERENT TEMPERATURES AND

PRESSURES:

van der Waals equation for one mole of a gas is given by

𝒂
(P + ) + (V – b) = RT
𝑽𝟐

𝒂 𝒂𝒃
or, PV –Pb + 𝑽 - 𝑽𝟐 =RT
𝒂 𝒂𝒃
or, PV = RT +Pb - 𝑽 + ----(i)
𝑽𝟐

(i) At low pressures: When P is small, V is large. Thus both the terms
𝒂𝒃
Pb and 𝑽𝟐 in equation (i) may be neglected in comparison to
𝒂 𝒂
. Hence equation (i) becomes PV = RT - ie. PV< RT
𝑽 𝑽
and the gas show negative deviation.
(ii) At high pressures: At high pressures the volume of the gas is small
𝒂 𝒂𝒃
and the terms and are approximately equal. Since, they
𝑽 𝑽𝟐
are of opposite sign and cancel each other. In this condition
the equation (i) becomes PV = RT +Pb ie. PV > RT and the
gas show positive deviation.
 (iii) At very low pressures and at very high temperatures: Under these
𝒂
conditions the volume of the gas is very large and the terms and
𝑽
𝒂𝒃
will be very small and can be neglected. Under these
𝑽𝟐
conditions Pb is also negligible and the equation (i) becomes
PV = RT ie. the gas shows ideal behaviour.

Therefore a real gas behaves ideally only at very low pressures and at very
high temperatures.