(1) The van der Waals equation (or van der Waals equation of state; named after Johannes

Diderik van der Waals) is based on plausible reasons that real gases do not follow the ideal
gas law. The ideal gas law treats gas molecules as point particles that do not interact with
each other but only the walls. In other words, they do not take up any space, and are not
attracted or repelled by other gas molecules.[1] The Ideal Gas Law states that volume (V)
occupied by n moles of any gas has a pressure (P) at temperature (T) in Kelvin. The
relationship for these variables, P V = n R T, where R is known as the gas constant, is called
the ideal gas law or equation of state.(WIKIPEDIA)
(2) The van der Waals equation corrects for the volume of, and attractive forces between,
gas molecules:

(P + )(V - nb) = nRT

There are two corrective factors in van der Waals equation. The first, , alters the pressure
in the ideal gas equation. It accounts for the intermolecular attractive forces between gas
molecules. The magnitude of a is indicative of the strength of the intermolecular attractive

force. a has units of .

The factor - nb accounts for the volume occupied by the gas molecules. b has units of L/mol.
Since b corresponds to the total volume per mole occupied by gas molecules, it closely
corresponds to the volume per mole of the liquid state, whose molecules are closely layered.
b is generally much smaller in magnitude than a. The values of a and b generally increase
with the size and complexity of the molecule.
(http://www.sparknotes.com/chemistry/gases/real/section1/)

(3) Key Points

o The van der Waals equation is an equation of state that corrects for two
properties of real gases: the excluded volume of gas particles and attractive
forces between gas molecules.
o The van der Waals equation is frequently presented as: [latex](P +
\frac{an^2}{V^2})(V-nb) = nRT[/latex] .
o The constants a and b represent the magnitude of intermolecular attraction and
excluded volume respectively, and are specific to a particular gas.

Terms

 van der waals equationa relation between particles of a fluid that have a non-zero
volume and a pairwise attractive inter-particle force
 ideal gas lawan equation describing the properties of an ideal gas, generally presented
as PV = nRT
The Ideal Gas Law is based on the assumptions that
gases are composed of point masses that undergo perfectly elastic
collisions. However, real gases deviate
from those assumptions at low temperatures or high pressures. Imagine a container where the
pressure is
increased. As the pressure increases,
the volume of the container decreases. The
volume occupied by the gas particles is no longer negligible compared to the
volume of the container and the volume of the gas particles needs to be taken
into account. At low temperatures, the
gas particles have lower kinetic energy and do not move as fast. The gas particles are
affected by the
intermolecular forces acting on them, which leads to inelastic collisions between
them. This leads to fewer collisions
with the container and a lower pressure than what is expected from an ideal
gas.( https://courses.lumenlearning.com/introchem/chapter/van-der-waals-equation/)

(4) Van der waal’s equation

Thought the equation PV=RT was arrived at first experimentally and then theoretically,
yet it fails to explain the behaviour of real gases. van der Waals attributed the deviation
of real gases from gas equation to the following faulty assumptions of the kinetic theory:

(i) The actual volume of the gas molecules is negligible as compared with the total
volume of the gas.

(ii) The gas molecules do not exert any appreciable attraction on each other.

Both these assumptions are not true at high pressure and low temperature. At high
pressure the volume is reduced to a great extent and the actual volume of the molecules
cannot be supposed as negligible under such conditions. Moreover, the molecules come
closer and the attractive force between them should also be taken into consideration.

Van der Waals introduced the necessary corrections as follows:

(a) Volume correction: At higher pressure, the volume is much reduced and at this
state the volume of gas molecules no longer remains negligible in comparison with the
total volume V occupied by the gas. Thus the free space available for motion of
molecules is reduced. If v be the volume of the molecules at rest, effective volume when
they are in motion must be greater. It has been calculated to be approximately four times
the actual volume of the molecules.

I. e.

4v and is generally denoted by b. Therefore the actual volume available in which the
molecules are free to move will be

= Total volume — Effective volume.

(5) i.e., correct volume(V – b)

(b) Pressure correction:The pressure of a gas is due to the hits of the molecules on the
walls of the containing vessel. The attractive force between the molecules comes into
play when the molecules are brought close together by compressing the gas. A molecule
in the body of the gas is attracted in all the directions when forces acting in opposite
directions cancel out, but a molecule, the boundary of the gas is subjected to an inward
pull due to unbalanced molecular attraction.

In this way some of the energy of the molecule about to strike the wall of the vessel is
used up in overcoming this inward pull. Therefore, it will not strike the opposite wall
with the same force. The observed pressure consequently will be less than the ideal
pressure. Therefore the ideal pressure, Pi will be equal to observed pressure P plus a
pressure correction, Pa depending upon the attractive forces,

I.e. Pi = P + Pa

Now, force of attraction number of molecules in the interior which are attracting (i.e. ,
density)

Total force of attraction

Or, pressure due to force of attraction

i.e.,

(where V is the volume of the gas and ‘a’ is the coefficient of attraction)

Introducing, both these corrections, the equation becomes

It is known as van der Waals equation. This equation explains the behaviour of real gases
with great accuracy and also the deviations of gas laws from ideal behaviour.

The units of ‘a’ and ‘b’ are expressed in the units of pressure and volume as the unit of
‘a’ is atm that of ‘b’ is and

Significance of van der Waals Constants

(i) The value of ‘a’ is higher for easily liquefiable gases (as etc.)
while lower for permanent gases (as , He etc.). This is due to the fact that
 liquefiable gas has greater intermolecular forces of attraction, therefore the value of ‘a’ is
said to be a measure of the intermolecular forces of attraction. Order of liquification of
some gases:

(ii) Since the constant ‘b’ is the effective volume of the gas molecules hence it indicates that
the gas molecules are incompressible.( http://www.sciencehq.com/chemistry/van-der-waals-
equation.html)