Statistical Molecular

Thermodynamics
Christopher J. Cramer
Video 3.5
van der Waals Equation of State Redux

A Trial Partition Function

q(V,")]
[
Q(N,V,") =

$ 2#m ' 2
q(V,") = & 2 ) V
% h "(

N!

Weve established that the above partition functions are

consistent with the ideal gas equation of state (by solving
!
! for the pressure as a function
of the partition function Q)

Lets now consider a different partition function Q

1 $ 2#m '
Q(N,V,") = & 2 )
N! % h " (

3N

(V * Nr) e

s"N 2 /V

where r and s are positive constants

The Associated Equation of State

1 $ 2#m '
Q(N,V,") = & 2 )
N! % h " (

3N

(V * Nr) e

s"N 2 /V

# "lnQ &
P = kBT%
(
$ "V ' N ,)

First, we expand lnQ,

!
2
3
s$N
lnQ = N (ln2"m # ln h 2 # ln$) + N ln(V # Nr) +
# ln N!
2
V

The Associated Equation of State

2
3
s$N
lnQ = N (ln2"m # ln h 2 # ln$) + N ln(V # Nr) +
# ln N!
2
V

Now, we differentiate with respect to V

# "lnQ &
N
s)N 2
*
%
( =
$ "V ' N ,) V * Nr
V2
With this in hand, we can finish solving for pressure

The Associated Equation of State

# "lnQ &
P = kBT%
(
$ "V ' N ,)
Continuing,

!
For N = NA,
and a and b
expressed in
! units

molar

# "lnQ &
N
s)N 2
*
%
( =
2
$ "V ' N ,) V * Nr
V

Nk BT sN 2
P=
" 2
V " Nr V
!
"
sN 2 %
$ P + 2 '(V ( Nr) = Nk BT
V &
#

"
a%
The van der Waals
$ P + 2 '(V ( b) = RT Equation of State
#
V &