October 16, 2001

Reading: Chapter VIII

Homework: 8.1, 8.3, 8.5, 8.6, 8.7
Real Gases: Van der Waals Model:

The pressure exerted on the container wall is reduced (compared to the ideal gas)
in the real gas due to the interaction between gas molecules. Suppose the number density
of the gas is n=N/V, where N= total number of molecules and V=volume. The number of
molecules per unit area next to the wall is proportional to n=N/V. The probability that
there is a molecular just inside in the immediate vicinity of a molecular next to the wall is
also proportional to n=N/V. Thus, the inward force experienced by a molecule close to
the wall is proportional to n. Since the number of molecular close to the wall per unit area
n, then the net inward force per unit area n2. This is clearly negative internal)
pressure and we will write it as a/V2, where V is molar volume. (i.e., smaller the volume,
the stronger the interaction, the larger the negative pressure.) Now, let the pressure
exerted by the real gas is P. If it were an ideal gas, then the pressure exerted would have
been (P+a/V2), i.e., this is the pressure exerted by an equivalent ideal gas.
The volume of the real gas is V. However, each molecule occupies a finite volume
in space, around which some of the volumes are not accessible to other molecules.
Effectively, for every molecule, the accessible volume is (V-b), where b is related to the
molecular diameter, and b is known as the excluded volume. Thus, for an equivalent
ideal gas, the volume is (V-b). Therefore, the modified equation of state for the real gas,
written in terms of the ideal gas, is
a

P + 2 (V b ) = RT
V

This is referred to as Van der Waals equation of state, where P=actual pressure and
V=actual volume.
The above equation can be rearranged into
RT
a
P=
2
V b V

Or,
PV 3 (bP + RT )V 2 + aV ab = 0
This is a cubic equation. For given P and T, there are three roots for V. At a given T, over
a range of Ps, there can be either three real positive roots or one positive root (V must be
positive).

T1

Tc

T1>Tc>T2>T3

T2
T3

T
Tc is a critical temperature below which there are three real roots of V for a given
volume of P and T (cover some range of P). Also, below Tc, there are two values of V
P
at which
= 0 : one corresponding to a minimum, and the other corresponding to a
V T
2P
= 0 : an inflexion point. At
maximum. And there is one volume of V at which
2
V

T
the condition of criticality, all these three points merge into one. That is, at the critical
point,
2P
P
=0
= 0 ,

2
V Tcr
V Tcr

Now,
P=

RT
a
2
V b V

So,
RT
2a
P
=
+ 3 =0

2
V
(V b)
V T =Tcr

 2P
2 RT
6a

=
4 =0
2
3
V T =Tcr (V b) V
Thus,
Tcr =

3a (Vcr b) 3
RVcr4

P
Substitute into
=0
V Tcr

3a (Vcr b) 3 2a
R

+ 3 =0
RVcr4
Vcr
(Vcr b) 2

3(Vcr b)
+2=0
Vcr

Vcr = 3b
So,
Tcr =

3a (Vcr b) 3 3a (3b b) 3
8a
=
=
4
4
27bR
RVcr
R (3b)

Finally,
RTcr
8a
a
R
a
a
2 =

=
Pcr =
2
Vcr b Vcr (3b b) 27bR (3b)
27b 2

Thermal Expansion and Compressibility:

P=

RT
a
2
V b V

Lets examine partial derivation of P with respect to T at fixed P.

P=constant:
R
RT
2a V
P
V

=0=
+ 3

2
V b (V b) T P V T P
T

RT
2a V
R
3
=

2
V T P V b
(V b)
RTV 3 2a (V b) 2 V
R

=
2
3
(V b) V
T P V b

Thus,
RV 3 (V b)
V

=
3
2
T P RTV 2a (V b)
Then, the isobaric thermal expansion coefficient is
1 V
RV 2 (V b)
=
=
V T P RTV 3 2a (V b) 2
Note at critical point,
a
8a
Pcr =
, Vcr = 3b, Tcr =
2
27bR
27b
This gives

cr =

R (3b) 2 (3b b)
18b 3 R
=

8a
8ab 2 8ab 2
3
2
R
(3b) 2a (3b b)
27bR

So, the isobaric thermal expansion coefficient is infinite at the critical point.
Now,
P=

RT
a
2
V b V

RT
2a RTV 3 + 2a (V b) 2
P
=

+
=

(V b) 2 V 3
V 3 (V b) 2
V T
So,
V 3 (V b) 2
V

=
3
2
P T RTV + 2a (V b)
Then, isothermal compressibility, is
1 V
V 2 (V b) 2
=
=

V P T RTV 3 2a (V b) 2
At the critical point,
a
8a
Pcr =
, Vcr = 3b, Tcr =
2
27bR
27b

cr =

(3b) 2 (3b b) 2
R

8a
(3b) 3 2a (3b b) 2
27bR

36b 4

8ab 2 8ab 2

The isothermal compressibility also approaches infinity at the critical point. Note,
P
however,
remains finite, as shown below.
T V

P T V

= 1
T V V P P T
So,
1 V
V

V T P

P
T P
=
=

=
1 V

V
T V

V P T
P T
At critical point, and goes to infinite, but their ratio / remains finite.
RT
a
P=
2
V b V

R
P

=
T V (V b)
P
At the critical point, Vcr = 3b ,

T V

=
cr

R
R
=
3b b 2b

Isentropic (constant entropy) thermal expansion coefficient:

s =

1 V

V T s

Now,
V S T

= 1
T s V T S V

S
C

v
T

V
T
=

=
S

T s

V T V T

S
P
From Maxwells equation,
=

V T T V

So,

Cv
V
T = Cv / T = Cv / T

=
/
R /(V b)
T s P

T V
Thus,

s =

C /
C (V b)
1 V
= v

= v
V T s
TV
RTV

Adiabatic reversible (isentropic) compressibility:

s =

1 V

V P s

V P S

= 1
P s S V V P
S

V
P V

=
S
P s

V P
From Maxwells equation,
V S
S
P
=
,
=

P V
T s V P T s
So,

VS
V
T s
=

=
P
P s P

T s T s

P T S

= 1
T s S P P T
S

P
T P C p / T
=

=
S
S
T s


P T
P T

From Maxwells equation,

S
V
=

P T
T P

Cp /T
Cp
P
=
, ( = p )

=
T V
T s V

T P
So,
V 2T s
V s
V s
V
=
=

=
Cp
Cp
P s P

T s TV

s =

VT s VT C v C v
1 V
=

=
V P s
Cp
C p TV C p