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apj
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Homework Statement
I am trying to solve problem 1.4 from Statistical Mechanics by R.K. Pathria 2nd edition. This is the problem:
In a classical gas of hard spheres (of diameter [tex]\sigma[/tex]), the spatial distribution of the particles is no longer uncorrelated. Rougly speaking, the presence of [tex]n[/tex] particles in the system leaves only a volume [tex](V-nv_0)[/tex] available for the (n+1)th particle; clearly, [tex]v_0[/tex] would be proportional to [tex]\sigma^3[/tex]. Assuming that [tex]Nv_0 \ll V[/tex], determine the dependence of [tex]\Omega(N, V, E)[/tex] on V {For an ideal gas this would be [tex]\Omega \propto V^N[/tex]} and show that, as a result of this, V in the gas law (PV=nRT) gets replaced by (V-b), where b is four times the actual space occupied by the particles.
2. The attempt at a solution
I first tried:
[tex]\Omega(N, E, V) \propto (V-Nv_0)^N[/tex]
and then:
[tex]
\frac{P}{T} = \left( \frac{\partial S}{\partial V} \right)_{N,E} = \left( \frac{\partial}{\partial V} k_B \ln \Omega(N, E, V) \right)_{N,E} = k_B \frac{N}{(V-Nv_0)}
[/tex],
rearranging yields
[tex]
P(V-Nv_0) = k_B N T
[/tex]
which looks a lot like what I need to prove, however I did not prove the factor 4.
A second guess was more like a hand waving argument. Suppose two hard spheres of diameter [tex]\sigma[/tex] in close contact. Together they occupy a space twice the volume of a sphere of diameter [tex]\sigma[/tex]:
[tex]
\frac{4}{3} \pi \left( \frac{\sigma}{2} \right)^3 = \frac{1}{3} \pi \sigma^3
[/tex],
but they exclude a volume of a sphere of diameter [tex]2 \sigma[/tex]:
[tex]
\frac{4}{3} \pi \sigma^3
[/tex]
From here we find the factor 4
Third try:
Probably the best thing to do is to assume the following:
[tex]
\Omega \propto \prod_{i=0}^{N-1} (V-iv_0)
[/tex]
and then continue from thereon, but I don't know how to do this properly.
Any help would be appreciated greatly.