Average kinetic energy of escaping molecule from a container

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I run into a question which haunts me for a while. Can anyone help me out?

The problem is:

0

Consider the effusion of molecules through an opening of diameter d in the

walls of a container with volume V. Show that, while the average kinetic
energy of the molecules in the container is 3/2kT, the average kinetic
energy of the effusing molecules is 2kT, where T is the quasi-static
temperature of the gas in the container.

I understand how people get 3/2kT by using Maxwell-Boltzmann distribution; I

don't know how the 2kT appear by using Maxwell-Boltzmann distribution. Can't do
the integral right.

kinetic-theory

Share Cite edited May 30, 2018 at 16:44 asked Sep 19, 2017 at 23:43
Improve this question sammy gerbil Lonitch
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Related: Effusion of Ideal Gas. From comments: check Landau and lifshitz statistical
mechanics section 39. – stafusa Sep 19, 2017 at 23:53

It seems like one would probably integrate with the Maxwell-Boltzmann velocity vector but
only over the half of velocity space corresponding to vz > 0. This should be doable in
∞ 2 3 −−−−−
spherical coordinates as 2π ∫0 v2 dv αv2 e−βv = 4
α√π 3 /β 5 or so, with the 2π coming
from the solid angle and the angular integral being standard. One might also need to
multiply by 2 to normalize the probability distribution. – CR Drost Sep 20, 2017 at 0:03

1 @CRDrost, with the equation above, we can only get 3kT/2m, which leads to the average
kinetic energy= 3kTT/4m. – Lonitch Sep 20, 2017 at 0:13
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Picking up where @CR Drost leaves off (thank you Dorst getting this started. For
completeness sake, I'll complete the question and address the normalization
2 constant you mentioned), we have the volume element of velocity space that is
exiting the container.

vz f(v)θ(vz )dvdθdϕ

We can integrate over velocity space to determine the total number of particles that
are exiting.

⟨N⟩ = ∫ d 3 v nvz f(v)θ(vz )

Note: (1) θ(vz ) is the step function because (as Drost notes) only positive
velocity will travel through the hole. (2) d 3 v = dvdθdϕ and n is the
multiplicity factor for number flux. (3) The number flux will also now
serve as our normalization constant (just like in x̄ = ∑ x i pi = N1 ∑ x i ni )

So to calculate the expectation value of an exiting particle's kinetic energy we

compute compute the average kinetic energy over all the escaping particles (with
appropriate normalization):

mv2 mv2
⟨ ⟩ = ∫ d3v ( ) nvz f(v)θ(vz )/
2 2

∫ d 3 vnvz f(v)θ(vz )

For a classical gas we have the Boltzman distribution f(v) = exp(−βmv2 /2) ,
βm
where β = 1/T , the inverse temp. So simplifying with a = 2
and d 3 v = 4πv2 dv
then we arrive at,
∞5 −av 2
mv2 m ∫0 dv v e
⟨ ⟩=
2 2 ∫ ∞ dv v3 e−av2
0

for which we can evaluate the integral (https://www.wolframalpha.com/input/?

i=Integral%5Bx%5EnExp%5B-ax%5E2%5D%2C%7Bx%2C0%2Cinfinity%7D%5D)
to arrive at
:
 mv2 m −1 Γ(3)
⟨ ⟩= a = 2T
2 2 Γ(2)

Note: Factors of Kb are dropped throughout entire derivation

Share Cite Improve this answer Follow answered Oct 20, 2019 at 20:51
ThomasTuna
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Reading Landau and Lifschitz I think this is the issue:

Imagine that we fix a hemisphere at distance r from the hole. In some time dt some
0
particles with speed v from this hemisphere have passed through the hole, and we
want to get a grip on the velocity distribution of the particles that pass through. I
will use spherical coordinates with z^ pointing normal to the surface into the gas,
where the hemisphere is 0 < θ < π/2 and 0 < ϕ < 2π .

At some point (r, θ, ϕ) on the hemisphere there is a small volume

v dt r 2 sin θ dθ dϕ of particles. Now get into the psychology of one of these
particles: their direction is uniformly distributed about the spherical "sky" around
them as they see it; and the area A of the hole only takes up a proportion
A cos θ/(4π r 2 ) of this sphere because it's seen partly in profile depending on θ.
Combining these we can see that the flux of particles with velocities in (v, v + dv)
which make it to the hole must look like

f(v) dv ⋅ v sin θ cos θ dθ dϕ.

There is a normalization constant on this and it's something like NA/(4πV ), but
there is probably a better way to work it out explicitly by demanding that the
resulting probability distribution sum to 1. Adding the v cos θ term can be
interpreted as adding a vz term and normalizing basically means that we construct
the expectation value ⟨U⟩walls for any dynamical variable U is the expectation
⟨U vz ⟩/⟨vz ⟩ in terms of the Maxwell-Boltzmann distribution. This would also
presumably apply to the kinetic energy 12 mv2 .

Share Cite edited Sep 20, 2017 at 5:19 answered Sep 20, 2017 at 5:10
Improve this answer CR Drost
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