Van der Waals equation of state

Adrian Down
November 30, 2005
1 Van der Waals equation of state
1.1 Review
Last lecture, we introduced the two corrections in the Van der Waals approx-
imation.
1.1.1 Volume
The eective volume available to the molecules is reduced by the eective
volume of each molecule, denoted by b.
V

= V Nb
n

=
N
V Nb
1.1.2 Pressure
We also found that there is a correction to the Helmholtz free energy,
F =
N
2
a
V
1.2 Van der Waals equation
For the ideal gas, the free energy is given by
F = N
_
log
_
n
Q
n
_
+ 1
_
1
Introducing the two corrections discussed above,
F
VDW
= N
_
log
_
n
Q
(V Nb)
N
_
+ 1
_

N
2
a
V
The pressure is found from the derivative,
p =
_
F
VDW
V
_
,N
= N

n
Q
(V Nb)

n
Q
N

N
2
a
V
2
=
N
V Nb

N
2
a
V
2
Some algebraic manipulation gives the Van der Waals equation for a gas.
_
p +
N
2
a
V
2
_
(V Nb) = N
1.3 Notes
The VDW equation is the same form as the ideal gas equation, pV =
N
The correction to the pressure increases the eective pressure. The
attraction in the Van der Waals gas reduces the eective pressure on
any container containing a gas, since the molecules are drawn towards
the center of the gas. This leads to an alternative derivation of the
pressure correction which is more qualitative.
The mean separation r between the molecules is proportional to
1
n
1
3
.
The Van der Waals force is proportional to
1
r
6
n
2
.
Hence the additional pressure is proportional to an
2
= a
N
2
V
2
The corrections are carried through the derivation and turn out to be
independent of each other in the nal result.
a and b are usually found by experiment.
This result allows us to predict the location of critical points and phase
transitions in a gas, as demonstrated in the next section.
2
2 Critical behavior
2.1 PV diagram
Recall the PV diagram for a substance. The coexistence curve slopes down-
wards, plateaus, and then decreases further for increasing V . The height of
this plateau increases with temperature. The width of this plateau corre-
sponds to the intersection of the coexistence curve with a concave-downward
parabola.
There is a particular value of for which the coexistence curve inter-
cepts the parabola at exactly one point. The point of intersection along this
isotherm is the critical point.
Dene the values of the thermodynamic parameters at this point to be
p
c
, V
c
, and
c
. Since the critical point is a point of inection on the PV
diagram, at this point, the following conditions are satised.
_
p
V
_

= 0
_

2
p
V
2
_

= 0
These conditions, along with the VDW equation, allow to nd conditions
for the critical point.
2.2 VDW equation
2.2.1 Take derivatives
Our goal is to express all quantities in the VDW equation of state in terms
of N and a and b.
Taking derivatives of the VDM equation,
p =
N
V Nb

N
2
a
V
2
_
p
V
_

=
N
(V Nb)
2
+
2N
2
a
V
3
= 0
This gives the relation
2Na
V
3
=

(V Nb)
2
(1)
3
The second derivative must also be equal to 0.
_

2
p
V
2
_

=
2N
(V Nb)
3

6bN
2
a
V
4
= 0
This yields a second relation,
3Na
V
4
=

(V Nb)
3
(2)
2.2.2 Solve for V
c
The most obvious course of action is to divide (1) by (2), which yields
2V
c
3
= V
c
Nb
Hence measuring V
c
gives b,
V
c
= 3Nb (3)
2.2.3 Solve for
c
Now, substitute (3) into (1). Rearranging to solve for
c
,

c
=
2Na
27N
3
b
3

_
2Nb
2
_
Simplifying, the critical temperature is given by

c
=
8
27
a
b
(4)
2.2.4 Solve for p
c
Insert (3) and (4) into the original expression for p.
p
c
=
8
27
N
a
b
2Nb

N
2
a
9N
2
b
2
=
4
27
a
b
2

3
27
a
b
2
The critical pressure is then
p
c
=
a
27b
2
(5)
4
2.2.5 Dimensionless equation of state
We can now insert the three critical parameters into the VDW equation to
recast the equation in a surprising way. Our goal is to eliminate a, b, and N
from the Van der Waals equation of state. There is no direct motivation for
the following algebraic manipulations, other than the nal result.
_
_
_
_
_
p +
_
V
c
3b
_
2
. .
(3)
_
27b
2
p
c
V
2
_
. .
(5)
_
_
_
_
_
_
_
_
_
V
V
c
3
..
(3)
_
_
_
_
=
V
c
3b
..
(3)
(6)
To eliminate b, consider (5) divided by (4), which gives
p
c

c
=
a
27b
2

27b
8a
=
1
8b
(7)
With this substitution,
(6) =
8
3
V
c
p
c

c
. .
(7)
Divide (6) by p
c
v
c
, which gives
_
p
p
c
+
3V
2
c
V
2
__
V
V
c

1
3
_
=
8
3

c
This unexpected formulation of the VDW equation involves only the re-
duced parameters,
p =
p
p
c

V =
V
V
c
=

c
With these substitutions,
_
p +
3

V
2
__

V
1
3
_
=
8
3

Note. This is a universal result that applies to any gas to the extent
that it obeys the VDW equation of state. In essence, this result says
that all gasses behave the same way.
If two (or more) gasses share the same values of p,

V , or , the gasses
are said to be in corresponding states.
5
2.3 Plateaus on the PV diagram
The location of the plateaus on the PV diagram can also be determined from
the above result. Multiply the equation by

V
2
to obtain
_
p

V
2
+ 3
_
_

V
1
3
_
=
8
3


V
2
For a given value of , this is a cubic equation in

V . In general, these
will give s-shaped curves with two turning points. Connecting the two
turning points for a given value of gives a straight lines which correspond
to the plateau of the isotherm on the PV diagram. These s-shaped curves
only occur for <
c
. The parts of these curves in the region of the plateau
give rise to metastable states.
6