VANDERWALLS EQUATION

Basing on two wrong assumption in KTG(Kinetic theory of Gases), Vanderwaals corrected

the ideal gas equation. The two wrong assumptions are
1. Actual volume of the gas molecules is negligible as compared to the total volume of
the gas
2. Intermolecular for of attractions between molecules negligible
According to Vanderwaals above assumptions, do not valid at high Pressure and low
temperature
Therefore, correction he made for ideal gas equation.
Pressure correction: If the molecule is present at middle of the container or vessel it is
attracted uniformly by the surrounding molecules, so the net force of attraction is zero.
But if the molecule is present at exterior 0r nearby walls of the container or vessel uniform
attractions do not exist ( only less no of molecules are surrounding). Hence, the molecule
strikes the wall with less velocity and will exert low pressure.
Reduction in pressure Concentration of molecules at centre x Conc at exterior part of the
contain

n
n
X
V
V
2
n
Reduction in pressure 2
a= constant (measure of strangeness of attraction force or
V
2
attraction force constant)
an
Reduction in pressure =
Correction factor ideal gas pressure = Real gas pressure or
2
V
Reduction in pressure

observed pressure + Correction factor

PI =PR +

a n2
Correction factor
V2

Kilopascals. L2.mol-2

or

Nm4

Units of a

P.V 2 ( K .Pa ) xL2 Units of a =

n2
mol 2 .mol-2
or atm. L2.mol-2

Volume correction: For ideal gas Volume of the container is the volume of the Gas.
However, for real gases it is not
Volume available for moving = Volume of the container - Volume unavailable for moving

Or
Free space for moving = Volume of the container 4V
Free space for moving = Volume of the container b (excluded volume or Co-volume)
or
Compressible Volume = Volume of the container - Incompressible Volume
When two molecules approaches together then volume unavailable is

4
3
2r
3

= 8x

4 3 This volume is unavailable for two molecules

r
For one molecule, the volume unavailable is 4 times its volume
3

b=4VN

for one

4 3
r x N per one molecule ( N Avogadro ' s number )
3

b 4

mole
b=4V
for single molecule
Excluded volume or Co-volume (b) 4 times greater than the original volume of the molecule
Units of b: V nb
b=V/n
b= l.mol -1
(modification of Ideal gas Equation)

PREAL

PREAL

= nRT

an
VContainer or ideal volume nb nRT
V 2
2

nRT

V nb

an 2

V 2

Limitations:
1. At critical temperature a and b do
not remains constant over entire range

of Pressure and Temperature.

2. Critical Volume (VC) = 3 b, but it vary from 2b to 4b

3.
of

RTC
2.67 for all gases, but it is ranging from 3 to 5 4.b values should be independent
PCVC
the Temperature and pressure, but it is not so.

Modifications:
1. At Low Pressure :
-Ve deviation. b is neglected in comparison to Volume
PV = RT a / V
or
Z = 1- a / Vm RT
2. At High pressure :
+Ve deviation. a/V is neglected in comparison to Pressure
PV = RT + Pb
or
Z = 1+ Pb / RT
3. At Ordinery Pressure: a / V and Pb are nearly Equal,
hence PV = RT
If u have any doubt about Z see below compressibility information

Various modification of Ideal gas Equations are given below: very good and
important

Compressibility factor (Z)

a. For Hydrogen and Helium : Z > 1 at all pressures due to strong repulsive forces, ( not
easily liquefied)
b. For N2, CO2, CH4, O2 :

Z<1 at low pressure hence more compressible (easily

liquefied). However at high pressure Z>1.

c. At very low pressure, Z is nearly one for all gases

Equation of state for real (non-ideal) gas or Virial equation:

Silent features:
1. At moderate pressures = squared and higher terms are neglected therefore
Z = 1 +B1 .P is approximation = linear (Z Vs P)
2. At high Pressure for Real Gas : Z Vs P , Slope = B1
If the relation between B and B1 are known we can calculate 2nd Virial quotient
can be calculated
3. P = 0, Close to Ideal gas behavior, but not exact
4. P = increases, then B contributes, linear relation between Z Vs P
5. P = High, then C and Higher terms contributes hence deviation from linearity can
take place