Properties of Real

Gases

Properties of Real Gases

COMPARISON BETWEEN IDEAL AND

A real gas is one in which
An ideal gas is the one REAL GASES
which
1. The molecules act like
point masses.
2. There are no
intermolecular forces of
attraction.
3. The volume occupied by
the molecules is
negligible compared to
the total volume
occupied by the gas.
4. The gas does not exhibit
properties like viscosity,
surface tension etc.
5. Its equation of state is
given by pV=mRT
6. The gas obeys laws
such as Charles and

1. The molecules do not

behave as point
masses.
2. There are
intermolecular forces of
attraction.
3. Volume occupied by
the molecules is not
negligible compared to
the total volume
occupied by the gas
4. The gas does exhibit
properties like
viscosity, surface
tension etc.
5. The equation of state is
given by pV=mRT is
not accurate

Properties of Real Gases

COMPARISON BETWEEN IDEAL AND

REAL GASES

At very low pressures, real gases tend to

behave like ideal gases.

This is because at very low pressures, the

density of the gas is very low and hence
molecules are very widely spaced as a result
of which ,the intermolecular forces of
attraction are negligible and the volume
occupied by the molecules becomes
negligible in comparison with the total
volume occupied by the gas.
But as the pressure increases the molecules
are brought closer to one another and hence
the real gas behavior deviates from that of

Properties of Real Gases

VAN DER WAALS EQUATION OF

STATE

To account for the deviation of real gas behavior from that of an

ideal gas Van Der Waal proposed two correction terms.
1. To account for the reduction in pressure exerted due to the
cohesive forces of attraction, a constant a was introduced
as follows:-

where
is the reduction in pressure due to the cohesive
forces explained
as being proportional to the square of the
density of the gas.
2. ToThus
account for the reduction in volume due to the finite
volume occupied by the molecules, a constant b was
introduced as follows:-

Properties of Real Gases

VAN DER WAALS EQUATION OF

STATE

We have the ideal gas equation of state:Substituting for pideal and videal we have

This is the Van Der Waals Equation of State for real gases

Properties of Real Gases

REDUCED COORDINATES
The p-V charts when plotted for different gases indicate that
they are qualitatively similar but quantitatively different as
shown.

Properties of Real Gases

REDUCED COORDINATES
This qualitative similarity is used to define certain
dimensionless parameters or co-ordinates called reduced coordinates
parameters.
REDUCEDor
PRESSURE
(Pr) is defined as the ratio of pressure of
the gas at any particular state to its critical pressure Pr =
(P/Pc)
REDUCED VOLUME (Vr) is defined as the ratio of volume of the
gas at any particular state to its critical volume Vr = (V/Vc)
REDUCED TEMPERATURE (Tr) is defined as the ratio of
temperature of the gas at any particular state to its critical
temperature Tr = (T/Tc)

Properties of Real Gases

COMPRESSIBILITY FACTOR (Z)
Due to its simplicity, the ideal gas equation of state can be used even
for real gases at. At low pressure the equation of state gives
sufficiently accurate values even if real gases.
But over what range of pressures does the ideal gas equation of state
hold good and to what extent a real gas deviates from an ideal gas is
determined by defining a term called compressibility factor with a
symbol Z.

From the above expression, we cam deduce that

1. Z=1 for ideal gases.
2. The value of z provides the extent of deviation for any particular
gas at a particular state, from ideal gas behavior.
3. The value of Z also provides a measure of the accuracy of ideal gas
equation of state.

Properties of Real Gases

Compressibility
Chart
The following points can
be observed in the
compressibility chart for
Nitrogen:
1. For
all
isotherms
drawn ranging from
130K to 300K as
pressure
tends
towards
zero,
Z
tends towards 1.
2. At temperatures of
300K and above, Z is
near unity, up to a
pressure of almost
10MPa. From this we
conclude that for this
temperature
and
pressure range, the
ideal gas equation of

Compressibility Chart is a plot of

compressibility
factor
Z
versus
pressure for different values of
temperature.

Properties of Real Gases

At a pressure of around 3 - 4 MPa, somewhere near the critical point

it can be observed that if the temperature is decreased for a
constant pressure, Z falls very sharply. This means that the actual
density of gas deviates from the ideal gas equation of state. This is
because in this range, the molecules are in close proximity and the
intermolecular forces of attraction being greater due to the proximity
results in an increase in the density of the molecules. Reduction in
temperature brings the molecules closer to one another resulting in
increased molecular attraction which results in the real gas behavior
deviating sharply from the ideal gas behavior and this is reflected in

Properties of Real Gases

At very high pressures of 30 MPa and above, Z values are greater

than one. This is because at very high pressure the molecules
become packed too close to one another resulting in repulsive force
which obviously results in a increased number of collisions with the
contact surface resulting in the Z value going above one. This also
means that the density of the gas in actual is lower than the
predicted by the ideal gas equation of state.

Properties of Real Gases

COMPRESSIBILITY CHART FOR HYDROGEN

Properties of Real Gases

GENERALIZED COMPRESSIBILITY CHART
This is a plot of
Z on the y-axis
verses reduced
pressure Pr on
the x-axis for
different values
of
reduced
temperature.
This chart can
be used with
reasonable
degree
of
accuracy
for
most
of
the
gases.

Properties of Real Gases

GENERALIZED COMPRESSIBILITY CHART

One can notice for the
generalized
compressibility chart that
at values of reduced
pressures in the range
between 1 and 3 there is
a sharp fall in the value of
Z with reduced Tr
All the isotherms tend
toward a Z value of 1 for
values of Pr tending
towards zero.
The
generalized
compressibility chart is a
very useful tool and this
can be used to define the
state of most of the gases
if the data is available
regarding
the
critical

Properties of Real Gases

ETERMINATION OF VAN DER WAALS CONSTANT

Properties of Real Gases

ETERMINATION OF VAN DER WAALS CONSTANT

From these two equation, by rearranging and dividing we get

Properties of Real Gases

ER WAALS EQUATION IN TERMS OF REDUCED COORDIN

Substituting for a, b and R in terms of critical parameters in the
Van Der Waals equation and rearranging equation we get

The above equation reduces the properties of all gases to one

formula. This can be used as an equation of state with reasonable
accuracy.

Properties of Real Gases

LAW OF CORRESPONDING STATES

STATEMENT: Two different gases are said to be in
corresponding states if their pressures, volumes and
temperatures are of same fraction or multiples of their
critical pressures, volumes and temperatures.
In terms of reduced co-ordinates we have the Van Der
Waals equation of state:

The above expression can be taken as the expression

governing law of corresponding states