CHAPTER 1

INTRODUCTION

An equation of a state is the mathematical relation connecting the thermodynamic

parameters pressure (P), volume (V) and temperature (T) of a substance. A perfect gas is
defined as a gaseous mass which obeys the following relation

PV = nRT

Where R is the universal gas constant whose value is given by 8.314 J/mol K and n is the
number of moles of the gas. The above equation is known as the ideal gas equation and the
gas obeying the above relation are said to be ideal gases. The ideal gas equation was put to
experimental test by scientists working with different gases and it was found that the gases
behaved differently than what it was predicted by the ideal gas equation. It was also found
that deviation occurred for all gases. From experiments it was found that the behaviour of real
gases usually agrees with the predictions of ideal gas equation within 5% at normal
temperatures and pressures. At low temperatures or high pressures, real gases deviate
significantly from ideal gas behaviour.

The ideal gas equation was established from the postulates of the kinetic theory of gases by
Maxwell with the following assumptions:

(1) There is little or no attraction between the molecules of the gas

(2) Volume occupied by the molecules is negligibly small compared to the volume of gas

Ideal gas equation of state is applicable to gas with very small pressure or very high
temperature. With increase in pressure the intermolecular force of attraction and repulsion
increases, and also the volume of the molecules becomes appreciable compared to the gas
volume. Under such condition the ideal gas equation fails and other equations of state (real)
gas equations are to be used.
 1. Deviation from perfect gas behaviour

The equation of state of a real gas implies that at a given temperature, the product PV will be
constant. That is if we plot PV as a function of P, the curve obtained is a straight line parallel
to the pressure axis. Similarly, if pressure variation is studied versus volume, the curve called
an isotherm will be a part of the rectangular hyperbola. For a set of temperatures, these
isotherms should be parallel. But experimental results reveal to the contrary.

That is "Ideal Gas Law" is "ideal" because it only works when you assume the conditions
are "ideal". And well, all gases behave ideally under conditions of high temperature and low
pressure. At low temperature, there are less gas molecules in a certain volume. And at high
temperatures, interactions between the gas molecules are minimized because the energy of
the molecules is relatively higher than the intermolecular forces (among the molecules).
Under low temperature and high pressure, intermolecular forces and molecular size become
important to be considered and are no longer negligible, so ideal gas law won't work.

2. Critical constants

The critical temperature, T C , is characteristic of every gas and may be defined as: “The
temperature below which the continuous increase of pressure on a gas ultimately brings about
liquefaction and above which no liquefaction can take place no matter what so ever pressure
be applied”.

The pressure required to liquefy the gas at critical temperature is called critical pressure and
the volume occupied by 1 mole of gas under these conditions is called the critical volume.

For the sake of discussion let us consider the Van der Waal’s equation.

Van der Waals equation may be written as:

a
( P+
V2)( V −b ) =RT ,

Where R is the universal gas constant having value 8.314 J/mol K.

Or
 a ab
PV + −Pb− 2 =RT
V V

Or

PV 3 + aV −Pb V 2−ab−RTV 2=0

Or

V 3− ( RTP +b) V + aVP − abP =0

2

This is the general gas equation of van der Waals. Since this equation is cubic hence it
should have three values of volume, V, for a given pressure. At critical temperature all the
three values of V become identical. This is due to the fact that at critical temperature and
pressure the distinction between liquid and vapour disappears. The identical volume, V is
called critical volume, V C .
CHAPTER TWO

EQUATIONS OF STATE

An Equation of State is the relation between functions of state, such as temperature (T), pressure
(P), volume (V), internal energy or specific heat. It characterizes the state of matter of a material
under a given set of physical conditions. Equations of states are used to describe gases, fluids,
fluid mixtures and solids. There are many equations of state describing real gases. These
equations take in consideration molecular volume and interactions. The most well-known such
equations are probably the Van der Waals equation. In this section we are interested in studying
other equations of state of real gases along with Van der Waal’s equation.

1. Van der Wall’s equation of state

The Van der Wall’s equation of state is given by

a
(P + ) (V-b) = RT
V2

Where P is the pressure, V is the volume, R is the universal gas constant whose value is given by 8.314
J/mol K and ‘a’ and ‘b’ are Van der Waal’s constant.

2. Clausius equation of state

According to Clausius, the equation of state is

'

( P+
a
T (V + c)
2 ) (V-b) = RT

a'
The constant a of the Van der Waal’s equation has been changed to in order to incorporate the
T
variation of a with temperature. This equation fits for some gases but fails in the case of other gases.

3. Berthelot equation of state

Berthelot proposed an equation of state of the form

 a'
( P+
TV
2 ) (V-b) = RT

This equation shows better agreement with experiment at moderate pressure.

4. Dieterici equation of state

According to Dieterici the equation of state is

RT
P=
V −b
exp ( RTV
−a
)
This equation agrees with experimental observation up to a pressure of 12 atmosphere but fails at high
pressures.

5. Saha and Bose equation

Saha and Bose derived an equation of state from thermodynamic consideration and theory of probability
which gives

RT
P=
(V −b)
exp ( RTV
−a
) ln ( V −2V b )

So far we have the above equations of state and we are interested in studying them in order to find out
that which equations gives the value of critical constants up to a good approximation in the case of
different gases.

The values of critical constants predicted by the above equations are found out theoretically and
compared with the experimental values for different gases. By studying this we will have an idea about
the deviation of the theoretical value of critical coefficient from the experimental value. Thus we may
find out which equation gives the best approximation of the critical coefficient for a particular gas.

The experimental values of the critical coefficients are given in the following table.

Substance T c in Pc in atm Specific Critical

Kelvin in cm 3 /Kg volume coefficient

RTC
PC VC

Helium 5.1 2.25 15.4 3.13

Hydrogen 33.1 12.8 32.2 3.28

Nitrogen 125.9 33.5 3.21 3.42

Oxygen 154.2 49.7 2.32 3.42

Carbon 304 72.8 2.17 3.48

dioxide
CHAPTER THREE

ESTIMATION OF CRITICAL CONSTANTS

Here we are interested in calculating the value of critical coefficients theoretically for different equations
of states.

1. Van der Waal’s equation of state

Pressure

Volume

Consider the critical isothermal ACB. At the critical point C, ( dVdP )=0 . At this point the tangent

also crosses the curve. Therefore the tangent at such appoint is said to be stationary and the point is called
‘point of inflexion’. At point of inflexion we have

d2 P
( )
dV
2 = 0.

dP
Here at critical point C, we have =0
dV

d2 P
And ( )dV 2
=0.

The Van der Waal’s equation is

a
(P + ) (V-b) = RT
V2
 dP −RT 2a
= 2 + 3 ......(2)
dV (V −b) V

d2 P 2 RT 6a
( )
dV 2
=
(V −b)3
-
V4

At critical point C we have

T = TC

P= PC

V= V C

dP
=0
dV

d2 P
( ) dV
2
=0 .

Substituting the above conditions in equations (1), (2) and (3), we have

RTC a
PC = −
(V C −b) V 2C

V C −b
¿
¿
¿2
¿
RTC
¿

2RTC 6a
3
= 4
(V C −b) VC

Dividing the above equations, we get,

V C −b V C
=
2 3

3 V C −3 b=2V C

V C =3 b

Thus Van der Waal’s equation predicts a critical volume of 3b and value of b is determined
experimentally.

Substituting the value of V C in the above equation,

 RTC 2a
2
= 3
(3 b−b) (3 b)

RTC 2a
2
= 3
4b 27 b

8a
TC =
27 bR

Substituting the values of V C and T C in above equation we get

8 aR a
PC = −
27 bR(3 b−b) (3 b)2

8a a
PC = 2
− 2
54 b b

¿
a 8
9 b2 6 [ ]
−1

a
∗1
9 b2
¿
3

a
PC =
27 b2

The critical coefficient CC is defined by

RTC
CC =
PC V C

Therefore in the case of Van der Waal’s equation, the critical coefficient is given by

8a
∗27 b
27 b
CC =
3a

8
CC =
3

That is, Van der Waal’s equation predicts that the critical coefficient is equal to 8/3 and same for all gases
irrespective of their nature. As seen, the Van der Waal’s equation predicts a lower value of the critical
coefficient.
 2. Clausius equation of state

The Clausius equation is

'

( P+
a
)
T ( V +c )
2
( V −b )=RT

a'
Where the Van der Waal’s constant ‘a’ has been modified to and an additional constant c has been
T
introduced.

Rearranging the above equation,

a' RT
P+ 2
=
T (V + c) (V −b)

RT a'
P= −
(V −b) T (V + c)2

Differentiating with respect to volume, the above relation becomes

dP −RT 2 a'
= +
dV (V −b)2 T (V + c)3

Again differentiating the above relation with respect to volume we have

 d2 P 6 a'
( )
dV
2
=
2 RT
3
−
(V −b) T (V +c)
4

At critical point we have,

T = TC

P= PC

V= V C

dP
=0
dV

( )
d P
dV 2
=0 .

dP
∧d2 P
Substituting the above in the relations of dV , we have,
2
dV

V
a'
(¿¿ C−b)−
T C (V C +c)2
RT
PC = ¿ C

RT C 2a
'

2
= 3
(V C −b) T C ( V c + c)

2RTC 6a
'

3
= 4
(V C −b) T C (V C + c)

RT C 3a
'

3
= 4
(V C −b) T C (V C + c)

Dividing the above two equations,

2
( V C−b )=(V C +c ) 3

(V − 23 V )= 23 c+ b
C C

V C =2 c +3 b

Now substituting the value of V C in above equation,

 RT C 2a
'

2
= 3
(V C −b) T C ( V C + c)

Becomes

RTC 2 a'
2
= 3
(2 c+ 2b) T C (3 c+3 b)

R T 2C 2 a'
=
4( b+c ) 27 (b+c )3
2

8a'
RT 2C =
27( b+c )

1
8a'
TC = ( 27 ( b+ c ) R ) 2

Now substituting the values of T C ∧V C in above equation,

V
a'
(¿¿ C−b)−
T C (V C +c)2
RT
PC = C
¿

Now multiplying by T C ,

V
a'
(¿¿ C−b)−
( V C + c)2
RT 2C
P C T C= ¿

Becomes,

R 8a' a'
PC T C = ( −
(2c +2 b) 27 R( b+c ) (3 b+ 3 c)2 )
4a' a'
PC T C = −
27( b+c ) 9(b+c )2
2

a' 4
PC T C =
9(b+c ) 3
2
−1 ( )
a' 1
PC T C =
9(b+c ) 3
2 ()
Now substituting the value of T C in the above expression, we get,

1
PC =
a'
2
9(b +c) 3
1
( )( 27 R(b+ c)
8 a' ) 2

1
R ( b+c )
PC =
a'
(b +c) 216 a '
2 ( ) 2

' 1
PC =
( aR
216 ( b+c )
3 ) 2

Therefore the critical coefficient CC is

RTC
CC =
PC V C

That is,

1 1
CC =R
8a'
(
27 R(b+ c) )(
2 b+c
2 c+ 3 b )( 216( b+c )
a' R ) 2

1 1
8 b+ c
¿ ( )(
27
2
2 c +3 b )
(216) 2

8 (b+c )
CC =
(2 c+ 3 b)

Now assuming c=3 b the critical constant becomes

32 b
CC =
9b

That is

32
CC = =3.56
9

Thus the value of critical constant given by the Clausius equation is CC =3.56.
3. Berthelot equation of state

The Berthelot equation is

a'
( P+
TV )
2
( V −b ) =RT

Rearranging

( P+ TVa' )= (VRT−b)
2
 RT a'
P= − 2
V −b TV

Differentiating the above relation with respect to volume

dP −RT 2a'
= + 3
dV (V −b) TV
2

Again differentiating the above relation with respect to volume

( )
d P
dV
2
=
2 RT
3
6a'
− 4
(V −b) TV

At critical point, we have,

T = TC

P= PC

V= V C

dP
=0
dV

( )
d P
dV
2
=0

Substituting these conditions in above relations,

RT C a'
PC = −
V C −b T C V 2C

RT C 2a'
2
=
(V C −b) T C V 3C

RT C 3a'
3
= 4
(V C −b) T CV C

Dividing the above two relations,

2
( V C−b )= 3 V C

3 V C −3 b=2V C

V C =3 b
Substituting the value of V C in the above equation,

RT 2C 2 a '
=
(2 b)2 27 b

Which give the value of T C as

1
8 a'
TC = ( 27 Rb ) 2

Substituting the values of T C ∧V C we have,

2
RT C a'
PC T C = − 2
V C −b V C

Becomes

R 8a' a'
PC T C = ( − 2
2 b 27 Rb 9 b )
a' 4 1
¿ ( −
9 b2 27 9 )
a'
PC T C = 2
27 b

Substituting the value of TC in above equation,

1
a ' 27 Rb
PC =
27 b2 8 a ' ( ) 2

1
1 Ra '
PC = (
b 216 b ) 2

The critical coefficient CC is given by

RTC
CC =
PC V C

That is,

1 1
1 8 Ra' 216 b
CC = (
3 27 b )(
2
Ra ' ) 2

1 1
¿( ) ( 216) ( 13 )
8
27
2 2
 8
CC =
3

The value of critical coefficient as predicted by the Berthelot equation is 8/3 which is the same as that of
Van der Waal’s equation.

4. Dieterici’s equation

The Dieterici equation of state is given by

RT
P=
V −b
exp ⁡ ( )
−a
RTV

Differentiating with respect to volume,

 dP RT −a
=
−RT
dV (V −b)2
exp
−a
+ ( )
RTV V −b RTV ( )( −a
RT )
exp (
RTV )
−a

dP
=
RT
dV V −b
exp
−a
RTV ( ) [ RTVa − V −b
2
1
]
Which gives

dP
dV
=P
a
[ −
1
RTV V −b
2 ]
Again differentiating the above relation with respect to volume,

d2 P
dV 2 [
=P'
a
2
−
1
RTV V −b
+
RT V][ ( )
a −2
3
+
1
( V −b )2
P
]
Where P’ is the first derivative of pressure with respect to volume.

At critical point,

T = TC

P= PC

V= V C

dP
=0
dV

( )
d P
dV
2
=0

Applying these conditions in above equations, we get

RT C
PC =
V C −b
exp
( −a
RT C V C )
1 a
=
V C −b RT C V 2C

And

1 2a
2
= 3
(V C −b) RT C V C

Dividing the above two equations,

 VC
( V C−b )=
2

Which gives

V C =2 b .

Substituting the value of V C in above equation we get,

1 a
=
b RT C 4 b2

From this we get the value of critical temperature T C as,

a
TC =
4 Rb

Substituting the values of V C ∧T C in above equations,

a −a
PC =
4 Rb2
exp
( 2bR ( 4 aRb ) )
a 2
PC =
4b 2
exp −a
a( ( ))
a
PC = 2 2
4b e

The critical coefficient CC is,

RTC
CC =
PC V C

Substituting all the values, we get CC as

a 2 be2
C c=
4b a( )
1 2
C c= e
2

CC =3.694

Therefore in the case of Dieterici’s equation of state, the value of critical coefficient CC is given by
CC =3.694 .
5. Saha and Bose equation of state

The Saha and Bose equation of state is given by

 V −2 b
P=
−RT
2b
exp
−a
RTV(ln
V ) (
…(1) )
Taking logarithm on both sides of the above equation,

lnP=ln ( −RT a
2b ) ( RTV )
−
{ V −2V b )}
+ ln ln (

Now differentiating the above equation with respect to volume,

1 dP a 1 V
=
P dV RTV 2
+
V −2b ( V −2b )( 2Vb ) 2
ln (V )

[ ]
dP a 2b 1
=P + …(2)
dV 2
RTV V (V −2b) ln V −2 b
V ( )
Now differentiating the above equation again with respect to volume,

[ ][ ]
d P a 2b 1 a 2b 1
2
=P' 2
+ +P 2
+
dV RTV V (V −2 b) ln V −2b RTV V (V −2b) ln V −2 b
V ( ) V ( )

[{ [ ]
V 2b
2 ( )
V −2b V )( 2

[ ]
d P a 2b 1 1 2 V −2b
V −2 b V ( V −2b ) )
(
−1
2
=P' + 2
+ P 2b − 2 2
dV RTV V (V −2 b) ln V −2b V (V −2 b) V −2 b
( V ) ln ( V ) ( V ) ln 2

[ ]{
2
d P a 2b 1 −2b 2b 1 2b (2V −2 b
2
=P' 2
+ +P − 2
dV RTV V (V −2 b) V −2b V (V −2 b) V (V −2b) 2 V −2b V −2 b V (V −2 b
ln( V ) ln
V
ln
V ( ) ( )
At critical point,

T = TC

P= PC

V= V C

dP
=0
dV

( )
d P
dV 2
=0
Therefore equation (1) becomes,

V −2 b
)( )
−RT C
PC =
2b
exp
−a
RT C V C (
ln C
Vc
…(4 )

Thus equation (2) becomes,

V
1 −a
(¿¿ C−2 b) = …(5)
V C −2b RT C V C
ln
VC ( )
2b
¿

Also equation (3) becomes,

−2 b 1 2b (2 V C −2 b) 2a
2
− − =0
V C −2 b V C ( V C −2 b ) RT C V 3C
2 2 2
V ( V C −2b ) V C −2 b
C
ln 2 ( VC ) ( ln
VC )

[ ]
2b 1 2b 2a
+2 V C −2 b + =0
V ( V C −2b )2
2
V −2 b V C −2 b RT C V 3C
C
ln C
VC( ) ( ln
VC )

[ ]
2b 1 2b −2 a
2
+ 2V C −2 b = … (6)
( V C−2 b ) V −2b V C −2 b RT CVC
(
ln C
VC ) ( ln
VC )
Dividing equation (6) by equation (5), we get

[( ]
1 2b
+2V C −2 b =2
(V C −2 b) V C −2 b
ln
VC )
2b
+2 V C −2 b=2V C −4 b
V C −2 b
ln
VC ( )
2b
=−2 b
V C −2 b
ln (VC )
V C −2b
ln ( VC
=−1)
Taking exponential on both sides of the above equation,
 V C −2 b 1
( VC
=
e)
2b 1
1− =
VC e

1 2b
1− =
e VC

V C =2 b ( e−1e )… (7)
Now from equation (5),

−a V C −2b V −2 b
TC =
RV C( 2b
ln C
VC )( )
Now

2 be
V C −2 b= −2b
e−1

¿2b ( e−1e −1)

2b
V C −2 b= …(7 b)
e−1

V C −2 b 2 b e−1 1
= = …(7 c )
VC e−1 2 be e

Substituting (7b) and (7c) in T C ,

−a (e−1) 2b 1 1
TC =
2 beR ( )
e−1 2b
ln
e ()
−a
TC = ( ln 1−lne )
2 beR

a
TC = …(8)
2 beR

Substituting (8) in (4),

a
−R
( ) −a
( 1e )
PC =
2 b 2 beR
exp
((R
a
2 beR
2 be
)( (e−1) ) ) ln
 PC =
a
2
4b e
exp
−a(e−1)
a ( )
a
PC = exp ( −(e−1) )
4 b2 e

a 1
PC = 2
4 b e exp ⁡( e−1)

a 1
¿ 2
4 b e exp ⁡( 1.718)

a
PC =0.1794
4 b2 e

The critical coefficient CC is

RTC
CC =
PC V C

In this case

a
RT C =R ( 2 beR )
a
¿
2 be

And

PC V C =0.1794
( 4 ba e )( e−1
2
2be
)
a
¿ 0.1794 ( 2 b(e−1) )
Therefore CC is given by

a 2b (e−1) 1
CC =
2 be a 0.1794

¿ ( e−1e )∗5.574
¿ ( 1.718
2.718 )
∗5.574
 CC =0.632∗5.574

CC =3.523

That is, the value of critical coefficient as predicted by the Saha and Bose equation is 3.523.

CHAPTER FOUR

A STUDY OF THE RESULTS

So far we have calculated the value of critical coefficients of the various equations of state theoretically.
Now we have to compare our theoretical value to the value obtained from experiments for different gases
and find out which equation of state gives the approximate value of critical coefficient for a particular gas.
So from now onwards we study the theoretical and experimental value of critical coefficient for different
gases.

 Helium

Equation of state Theoretical value of critical Experimental value of critical

coefficient coefficient

Van der Waal’s equation 2.67 3.13

Clausius equation 3.56 3.13

Berthelot equation 2.67 3.13

Dieterici’s equation 3.69 3.13

Saha and Bose equation 3.52 3.13

From the above table it is clear that in the case of helium, among the above five equations of state, the
value of critical coefficient predicted by Clausius equation is somewhat closer to the experimental value.

 Carbon dioxide
Equation of state Theoretical value of Experimental value of
critical coefficient critical coefficient

Van der Waal’s equation 2.67 3.48

Clausius equation 3.56 3.48

Berthelot equation 2.67 3.48

Dieterici’s equation 3.69 3.48

Saha and Bose equation 3.52 3.48

In the case of carbon dioxide the theoretical value predicted by the Clausius equation is in good
agreement with the experimental value. There is only a deviation of 2.24% from the experimental
value. Also the value predicted by Dieterici’s equation is also somewhat closer to the experimental
value. There is deviation of about 5.7% from the experimental value in the case of Dieterici’s
equation. But the equation which gives the most accurate value of critical coefficient in the case of
helium is the Saha and Bose equation. There is a deviation of only about 1.13% from the
experimental value. But the Van der Waal’s equation and Berthelot equation fails to give a
satisfactory value of the critical coefficient.

 Oxygen
Equation of state Theoretical value of Experimental value of
critical coefficient critical coefficient

Van der Waal’s equation 2.67 3.42

Clausius equation 3.56 3.42

Berthelot equation 2.67 3.42

Dieterici’s equation 3.69 3.42

Saha and Bose equation 3.52 3.42

In the case of oxygen, the Clausius equation gives a good approximation which shows a
deviation of 3.93% from the experimental value. Saha and Bose equation shows a deviation of
2.84% from the experimental value. Dieterici’s equation shows a deviation of 7.31% from the
experimental value of critical coefficient. Van der Waal’s and Berthelot equation fails to give a
good approximate value of critical coefficient in the case of oxygen.

 Nitrogen
Equation of state Theoretical value of critical Experimental value of
coefficient critical coefficient

Van der Waal’s equation 2.67 3.42

Clausius equation 3.56 3.42

Berthelot equation 2.67 3.42

Dieterici’s equation 3.69 3.42

Saha and Bose equation 3.52 3.42

Nitrogen has the same value of critical coefficient as of oxygen. In the case of Nitrogen, the
Clausius equation gives a good approximation which shows a deviation of 3.93% from the
experimental value. Saha and Bose equation shows a deviation of 2.84% from the experimental
value. Dieterici’s equation shows a deviation of 7.31% from the experimental value of critical
coefficient. Van der Waal’s and Berthelot equation fails to give a good approximate value of
critical coefficient in the case of Nitrogen.

 Hydrogen
 Equation of state Theoretical value of critical Experimental value of
coefficient critical coefficient

Van der Waal’s equation 2.67 3.28

Clausius equation 3.56 3.28

Berthelot equation 2.67 3.28

Dieterici’s equation 3.69 3.28

Saha and Bose equation 3.52 3.28

In the case of Hydrogen, any of the above equation fails to give a satisfactory value of critical
coefficient that matches with the experimentally measured value. The equation which comes close to the
experimentally measured value is the Saha and Bose equation which shows a deviation of 6.81%. Van
der Waal’s and Berthelot equation shows a deviation of 18.6% from the experimental value. Clausius
equation shows a deviation of 7.86% from the experimental value where as Dieterici’s equation shows a
deviation of 11.11% from the experimentally determined value.

CHAPTER FOUR

CONCLUSION
We started our discussion with the ideal gas equation or perfect gas equation and found out that these
equations were too ideal for the real physical world. So we wanted to study other equations of state for
real gases which give a good model of the real physical systems. So we started investigating other
equations of state which are Van der Waal’s equation, Berthelot equation, Dieterici’s equation, Clausius
equation and Saha-Bose equation of state. The above mentioned equation of state takes into account of
interaction of molecules or atoms of gases and are pretty good approximations of the non-hypothetical
real gases compared to the ideal gas equation. In each of these equations modifications are made to the
pressure and volume terms in order to match with the experimentally measured results. Thus we
proceeded to calculate the critical coefficients as predicted by each of these equations of state
theoretically and compared them with the experimentally measured results for different gases. At last it
was found that some equations of states predicted the behaviour of some gases correctly but failed in
other gases. That is, none of the equations we studied were able to explain the true behaviour of all the
gases we considered completely.

In Van der Waal’s equation of state the gas molecules were assumed to have finite size and were
regarded as point masses. Also it was assumed that molecules attract one another with a weak force which
depends only upon the distance between them which implies the gas molecules have both kinetic and
potential energies but considered the only interaction between the nearest neighbours into account. Also it
was assumed that the number of collisions with the walls of the container is exactly the same for point
and finite size molecules. But still the Van der Waal’s equation could not explain the experimental results
with accuracy. Therefore it is clear that some of the assumptions which were made in the Van der Waal’s
equation of the state has to be modified in order to correctly explain the experimental data. It is from this
point the other equations of state become important. Some of our above studied equations of state could
explain the experimental results for some gases with great accuracy. It means that the underlying
assumptions in the Van der Waal’s equation of state has been change or modified so that it could match
with the experimentally measured values. Thus in each of the equations of state, there were some
correction factors included in terms containing pressure and volume so it could explain the experimental
results.
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