- #1
Clever-Name
- 380
- 1
Homework Statement
I have come across a rather interesting conundrum. Given the configurational potential energy partition function for a non-ideal gas:
[tex]
Z = Z_{internal}\frac{1}{N!}\left(\frac{2\pi m}{h^{2}\beta}\right)^{\frac{3N}{2}}(V^{N} - B_{2}(T)N^{2}V^{N-1})
[/tex]
where [itex] B_{2}(T) [/itex] is the second virial coefficient.
I'm supposed to solve for the pressure.
Homework Equations
[tex] p = \frac{1}{\beta Z}\frac{\partial Z}{\partial V} [/tex]
or
[tex] p = \frac{1}{\beta}\frac{\partial ln(Z)}{\partial V} [/tex]
The Attempt at a Solution
If we calculate it using the first expression for p we arrive at
[tex]
p = \frac{1}{\beta}\left(\frac{N}{V} - B_{2}(T)N^{2}(N-1)V^{-2} \right)
[/tex]
However if you do it using the second form for p you can arrive at two different answers depending on how you 'prepare' the 3rd term in Z
Ignoring terms that don't involve V, if you start with it as written and evaluate
[tex]
\frac{\partial}{\partial V} ln(V^{N} - B_{2}(T)N^{2}V^{N-1})
[/tex]
[tex]
= \frac{NV^{N-1} - B_{2}(T)N^{2}(N-1)V^{N-2}}{(V^{N} - B_{2}(T)N^{2}V^{N-1})}
[/tex]
in the denominator (for each case) we assume [itex] B_{2}(T) [/itex] is small, so we can write the denominator just as [itex] V^{N} [/itex]
So we arrive at
[tex]
\frac{N}{V} - B_{2}(T)N^{2}(N-1)V^{-2}
[/tex]
OK, great that's what it should be, but if you start out with:
[tex]
\frac{\partial}{\partial V}ln(V^{N}(1-B_{2}(T)N^{2}V^{-1}))
[/tex]
[tex]
= \frac{\partial}{\partial V}\left(ln(V^{N}) + ln(1-B_{2}(T)N^{2}V^{-1})\right)
[/tex]
[tex]
= \frac{N}{V}+ \frac{B_{2}(T)N^{2}V^{-2}}{(1-B_{2}(T)N^{2}V^{-1})}
[/tex]
Again, [itex] B_{2}(T)[/itex] is small, so:
[tex]
= \frac{N}{V} + B_{2}(T)N^{2}V^{-2}
[/tex]
Now we have a different answer...
Why is this happening??
In my prof's notes he uses the second derivation, where we get a different answer from every other calculation.
I suspect
[tex]
\frac{N}{V} - B_{2}(T)N^{2}(N-1)V^{-2}
[/tex]
is the correct form but I can't see what's wrong with the other way.