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Statistical Molecular Thermodynamics: Christopher J. Cramer

1) The document discusses a partition function Q that can derive an equation of state for a gas based on constants r and s. 2) Taking the natural log of Q and differentiating with respect to volume V yields an expression for pressure P in terms of temperature T, number of moles N, volume V, and constants r and s. 3) The resulting equation has the same form as the van der Waals equation of state, relating pressure P, volume V, amount of substance N, and constants a and b.

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43 views5 pages

Statistical Molecular Thermodynamics: Christopher J. Cramer

1) The document discusses a partition function Q that can derive an equation of state for a gas based on constants r and s. 2) Taking the natural log of Q and differentiating with respect to volume V yields an expression for pressure P in terms of temperature T, number of moles N, volume V, and constants r and s. 3) The resulting equation has the same form as the van der Waals equation of state, relating pressure P, volume V, amount of substance N, and constants a and b.

Uploaded by

Alvaro
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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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 &

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