Equation of state of a hard sphere gas

Click For Summary
SUMMARY

The discussion focuses on solving problem 1.4 from "Statistical Mechanics" by R.K. Pathria, which involves determining the dependence of the phase space volume function, Ω(N, V, E), on the volume V for a classical gas of hard spheres. The key conclusion is that the volume in the gas law (PV=nRT) is modified to (V-b), where b represents the volume occupied by the particles, specifically calculated as four times the actual space occupied. The participants explore various approaches to derive this factor, including the relationship between particle interactions and volume exclusion.

PREREQUISITES
  • Understanding of statistical mechanics principles, particularly phase space volume.
  • Familiarity with the ideal gas law and its modifications.
  • Knowledge of hard sphere models and their implications in gas behavior.
  • Basic calculus, specifically partial derivatives and logarithmic functions.
NEXT STEPS
  • Study the derivation of the excluded volume in hard sphere gases.
  • Learn about the implications of the Van der Waals equation on real gas behavior.
  • Explore the concept of phase space in statistical mechanics.
  • Investigate the mathematical techniques for handling products in phase space calculations.
USEFUL FOR

Students of statistical mechanics, physicists working on gas models, and researchers interested in the thermodynamic properties of hard sphere systems will benefit from this discussion.

apj
Messages
1
Reaction score
0

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.
 
Physics news on Phys.org
Hey can you please explain more elaborately how you got the factor of 4.
 

Similar threads

Replies
19
Views
3K
Replies
4
Views
1K
  • · Replies 1 ·
Replies
1
Views
3K
  • · Replies 2 ·
Replies
2
Views
2K
Replies
4
Views
5K
  • · Replies 4 ·
Replies
4
Views
2K
Replies
4
Views
2K
  • · Replies 6 ·
Replies
6
Views
2K
Replies
6
Views
3K
Replies
1
Views
2K