How Does Particle Size Affect Gas Laws in Hard Sphere Models?

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SUMMARY

The discussion focuses on the impact of particle size on gas laws within hard sphere models, specifically addressing how the volume available for particles decreases as more particles are added. It establishes that the spatial distribution of particles is correlated, leading to a modification of the ideal gas law. The volume V in the ideal gas law is effectively replaced by (V - b), where b is four times the volume occupied by the particles. The derivation involves the expression Ω(N,V,E) ∝ (V - nv₀)ⁿ, emphasizing the need to account for the decreasing available volume as particles are added sequentially.

PREREQUISITES
  • Understanding of classical gas laws and the ideal gas law (PV = nRT).
  • Familiarity with statistical mechanics concepts, particularly the partition function Ω(N,V,E).
  • Knowledge of hard sphere models and their implications in gas behavior.
  • Basic proficiency in calculus, particularly in manipulating logarithmic and polynomial expressions.
NEXT STEPS
  • Study the derivation of the ideal gas law and its assumptions in detail.
  • Explore the implications of hard sphere models on real gas behavior.
  • Learn about the statistical mechanics of particle distributions in confined volumes.
  • Investigate the use of logarithmic transformations in statistical mechanics calculations.
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Students and researchers in physics, particularly those studying thermodynamics and statistical mechanics, as well as anyone interested in the behavior of gases under varying conditions of particle size and density.

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Homework Statement


In a classical gas of hard spheres (of diameter D), the spatial distribution of the particles is no
longer uncorrelated. Roughly speaking, the presence of n particles in the system leaves only a volume (V − nv_0 ) available for the (n + 1)th particle; clearly, v_0 would be proportional to D^3. Assuming that Nv_0 \ll V, determine the dependence of \Omega(N,V,E) on V (compare to equation (1.4.1)) and show that, as a result of this, V in the ideal-gas law (1.4.3) gets replaced by (V − b), where b is four times the actual volume occupied by the particles.


Homework Equations


(1.4.1) \Omega (N,V,E) \propto V^N
(1.4.3) PV=NkT=nRT


The Attempt at a Solution


Well I took
<br /> (V-Nv_0)^N \approx V^N - N^2 v_0 V^{N-1}+...<br />
Then I tried to do something similar as to the construction of the ideal gas law by trying
<br /> \frac{P}{T}=k\frac{\partial \ln (\Omega)}{\partial V}\frac{\partial \Omega}{\partial V} <br />
assuming \Omega \propto V^N - N^2 v_0 V^{N-1} similar to the original derivation.
But to no success. So I'm stumped now. Please help.

Thanks,
 
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You got to \Omega \propto (V-Nv_0)^N, but when you think about it, this doesn't properly represent the situation - this actually represents putting a single particle into the remaining volume of the jar N times.

What you have to do is put one particle in, and then progressively add particles, one by one, with each successive particle having less and less space to occupy. Thus, the expression you need to begin with is \Omega \propto \prod_{n=0}^{N-1} (V-nv_0)

You can then use a logarithm to turn the product into a sum, make any needed simplifying assumptions, do all necessary manipulations to express the sum algebraically, which then let's you get a simple expression for \Omega.
 

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