thermodynamics - How to explain the Maxwell Boltzmann distribution graph (physically)? - Physics Stack Exchange 12.04.

20, 21:03

How to explain the Maxwell Boltzmann distribution

graph (physically)?
Asked 1 month ago Active 26 days ago Viewed 393 times

While studying the kinetic theory of gases, I came to the section: "The Distribution of
Molecular Speed" of a book. The book first (without any explanation) proposes the
Maxwell's speed distribution law as
7
3/2
𝑃 (𝑣) = 4𝜋( )
𝑀 2
𝑣2 𝑒−𝑀 𝑣 /2𝑅𝑇
2𝜋𝑅𝑇

5
and then shows the distributional graphs for various gasses at different temperatures as
shown in the figure below.

One thing that bothered me was that it didn't provide any physical explanation for the
shape of the curve. Therefore, I would like to know how and why, via molecular collisions,
we achieve the same (exact) curve at a given temperature even if we start with a random
distribution of molecular speed (but given that 𝐾¯ = 3 𝑘𝑏 𝑇 )?
2

I would prefer an intuitive explanation rather than a mathematical one.

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Note that you needn't to comment on this portion of the question if you wish.

I searched for this over the internet and on Physics.SE but couldn't find any (do tell if you
know of any). I also discussed this with my friend came with an ad-hoc explanation but that
too raises many questions. If you are interested, the explanation is given below but as I
mentioned, it is not a good one and has many loopholes.

We considered a distribution in which the temperature is 𝑇 and every molecule

possesses the same speed (though in random direction) and hence the kinetic energy of
each molecule is 32 𝑘𝑏 𝑇 . When we continue further we see that the molecules collide
with one another and (most of the time) the collisions are between glancing and head-
on collision. It turns out that some molecules collide with other molecules in such a
way that in due time they gain kinetic energy, some other molecules collide in such a
way that there is a net loss of their kinetic energy and hence this distribution is
achieved.

But as I said earlier there are many questions to be asked and one them is given below.

Why are some type of collisions favoured more over the others?

thermodynamics statistical-mechanics collision speed kinetic-theory

edited Mar 17 at 0:19 asked Mar 11 at 17:04

kb314 Johan Liebert
802 2 23 3,200 1 13 48

1 why, via molecular collisions, we achieve the same (exact) curve at a given temperature
Because given temperature implies average molecule speed, and average molecule speed implies
Gaussian distribution of frequency density. You do not start with a uniform distribution of
molecular speed, but with Gaussian instead, that's a big difference. – Agnius Vasiliauskas Mar
12 at 13:00

5 Answers Active Oldest Votes

Semoi's answer is good. But since you say

9 I would prefer an intuitive explanation rather than a mathematical one

to express it more simply, and without formulae, the Maxwell distribution is the chi
distribution with three degrees of freedom (the components of velocity in Euclidean space).
The chi distribution is the distribution of the positive square root of the sum of squares of a
+150
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+150
set of independent random variables each following a standard normal distribution. The
normal distribution is the result of the central limit theorem, which basically says that
when you have loads of identical random variables added together, the result tends to a
normal distribution.

So, Maxwell assumed that the underlying distribution of velocities should be random, and
it should result from very large numbers of collisions, and consequently it should be
normally distributed in each direction. The Maxwell distribution graph follows from that,
using standard calculations.

Note on second part: I do not understand why you ask why some collisions are more
favoured. All collisions just have the effect of randomising the velocity distribution both in
magnitude and direction. They cannot change overall energy, which determines the mean
of the normal distribution in each direction.

edited Mar 17 at 8:55 answered Mar 15 at 20:00

Charles Francis
3,585 1 4 22

The phase space argument put forward by Shaswata is correct. From a thermodynamical
perspective this is is merely the result of the of the three dimensional ideal gas relation
8
= exp(−
𝑘𝐵 𝑇 )
𝑛𝑣 1 𝐸𝑣
𝑃𝑣 =
𝑁𝑡𝑜𝑡𝑎𝑙 𝑍
where 𝐸𝑣 = 𝑚 2
𝑣2 is the energy, 𝑛𝑣 is the number of particles with velocity 𝑣 = |𝑣|⃗ ,
𝑁𝑡𝑜𝑡𝑎𝑙 = ∑𝑣 𝑛𝑣 is the total number of particles, and 𝑍= ∑𝑣 exp(− 𝑘 𝑣𝑇 ) is the partition
𝐸
𝐵
function. You will find proper derivatives in many thermodynamics books. However, for me
this is not an intuitive or conceptional argument. Thus, here is how I like to obtain the
Maxwell-Boltzmann distribution.

1. Each component of the velocity vector, {𝑣𝑥 , 𝑣𝑦 , 𝑣𝑧 } , is normally distributed:

This follows from the fact that we obtain a normal distribution (= Gaussian), if we have
"many" independent random processes which contribute "equally" to the observable
variable. For justification check out the Poisson theorem and how the Poissonian
approached the normal distribution. Or check out the so called Central limit theorem.
2. The square of the velocity, 𝑣2 = ∑𝑖=𝑥,𝑦,𝑧 𝑣2𝑖 , is distributed as 𝜒32 (omitting the
normalisation constant): This simply is the definition of the 𝜒 2 distribution. Most
𝑘
often the definition reads: If 𝑍𝑖 ∼ 𝑁(0, 1) then 𝑌 = ∑𝑖=1 𝑍𝑖2 ∼ 𝜒𝑘2 . Note that the
tilde "∼ " should be read as "is distributed as …" and that the probability density
function is given by 𝑓𝑌 ∝ √𝑌 ‾‾ exp(−𝑌 /2) , for 𝑘 = 3 .
2
3. However, we are not interested in distribution of 𝑌 = 𝑣⃗ /𝜎𝑣2 , but we'd like to know the
distribution of 𝑣 = |𝑣|⃗ = 𝜎𝑣 √𝑌
‾‾ . Hence, we have to transform the 𝜒32 distribution.
However, this is straight forward. Using the transformation law (for continuous
random variables)

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∣ 𝑑𝑌 ∣
𝑓𝑣 𝑑𝑣 = 𝑓𝑦 ⋅ ∣ ∣ 𝑑𝑣
∣ 𝑑𝑣 ∣

( 2𝜎𝑣2 )
2𝑣 𝑣2
= 𝑓𝑦 ⋅ 𝑑𝑣 ∝ 𝑣2 exp − 𝑑𝑣
𝜎𝑣2
where 𝑓𝑣 is the so called probability density function for the random variable 𝑣 , we
obtain the Maxwell Boltzmann distribution.

In conclusion, the Maxwell Boltzmann distribution of |𝑣|⃗ is a direct consequence of the fact
that each velocity component, e.g. 𝑣𝑥 , is normally distributed.

edited Mar 17 at 18:52 answered Mar 15 at 19:25

Semoi
3,463 1 7 20

All the collisions are equally likely. The maxwell distribution can be derived from the
Boltzmann probabilities- namely the probability of a molecule having energy 𝐸 is 𝑒−𝛽𝐸 .
Once you can show this it is not so hard to derive the maxwell relation since for any velocity
6 1 2
𝑣 the number of states is proportional to 𝑒−𝛽 2 𝑚𝑣 . It is also proportional to 4𝜋𝑣2 since in
the 3D space 𝑣𝑥 , 𝑣𝑦 , 𝑣𝑧 can take any value given that 𝑣2𝑥 + 𝑣2𝑦 + 𝑣2𝑧 = 𝑣2 which is basically
proportional to the number of points on the surface of a sphere of radius 𝑣 .

So the real question is how the particles achieve through constant molecular collisions the
1 2
Boltzmann distribution. Why the probability of a molecule having energy 12 𝑚𝑣2 is 𝑒−𝛽 2 𝑚𝑣 .

Say in equilibrium the number of particles having velocity 𝑣𝑖 is 𝑛𝑖 . We are restricted to a

system where the ∑ 𝑛𝑖 = 𝑁 and the total energy ∑ 𝑛𝑖 12 𝑚𝑣2𝑖 = 𝐸 . The state having the
maximum multiciplity is,

𝑁! 1
𝑛𝑖 𝑚𝑣2𝑖 = 𝐸
∑ ∑ 2
arg max𝑛1 ,𝑛2 ,…𝑛𝑘 𝑛𝑖 = 𝑁,
𝑛1 !𝑛2 ! … 𝑛𝑘 !
We know that for the maximum multiplicity without the energy constraint is when all the
𝑛𝑖 are equal i.e. 𝑛𝑖 = 𝑁/𝑘 ∀𝑖 .
Hence it makes sense that when we have a very large energy (𝑣𝑗 > 𝑣 ) for one of the states
the corresponding 𝑛𝑗 will be small. Otherwise, the other 𝑛𝑖 will be too small due to the
energy constraint. And when we have one of the 𝑛𝑖 to be too large and the others are too
small we have a small multiplicity.

Similarly, a low energy will correspond to a high number of molecules in that state.

Hence when you let all kinds of collisions to take place the state that is most likely ends up
being the one in which most of the particles have low energy. This can be seen from if you
consider the collision of molecules as well. Say the two molecules have final velocities
𝑣1, 𝑣2 and initial velocities as 𝑢1 , 𝑢2 .

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From the conservation of energy,

𝑣21 + 𝑣22 = 𝑢21 + 𝑢22 = 𝑉 2

Basically, the solution space is the positive quarter of a circle of radius 𝑉 . Now it is not hard
to see that for 𝑣2 > 𝑉 /2 the number of cases is proportional to 1/3 (subtending an angle of
𝜋/6 ). On the other hand for 𝑣2 < 𝑉 /2 we have 2 times more cases (subtending an angle of
𝜋/3 ). In other words 𝑣21 and 𝑣22 counterbalance each other. What happens as a result is that
𝑣1 , 𝑣2 has a greater chance of reducing than of increasing.

answered Mar 11 at 19:15

shaswata
181 4

Some of the answers provided above are pretty good. Let me try to provide an answer from
a slightly different formulation for completeness. The approach I am going to take is to
start from the general non-equilibrium description of the gas in question, and motivate
4
what being in "equilibrium" means. The full non-equilibrium dynamics is governed by the
Boltzmann equation.

Physical Kinetics, the 10th book in the Landau-Lifshitz series is an excellent reference.
𝑝2
We start with a gas composed of particles obeying the dispersion relation 𝜖 = 2𝑚 (the gas
is isotropic) . In general, when the gas is not in equilibrium, it's physical state is described
by the "Boltzmann distribution function" 𝑓(𝑥, 𝑝, 𝑡) . Note that ∫ 𝑑𝑑 𝑝𝑓(𝑥, 𝑝, 𝑡) = 𝑛(𝑥, 𝑡) , the
number density at (x,t), d = number of spatial dimensions. We can see that this allows us to
describe non-equilibrium situations through its dependence on 𝑥 and 𝑡 .

The distribution function described above is governed by the Boltzmann equation. Let
me first write it down, and then I'll describe what it means:

[∂𝑡 + 𝑣. ∇ 𝑥 + 𝐹 . ∇ 𝑝 ]𝑓(𝑥, 𝑝, 𝑡) = .
𝑑 𝑑 𝑑 𝑑
∭ 𝑑 𝑝1 𝑑 𝑝2 𝑑 𝑝3 𝛿 (𝑝 + 𝑝1 − 𝑝2 − 𝑝3 )𝛿(𝜖(𝑝) + 𝜖(𝑝1 ) − 𝜖(𝑝2 ) − 𝜖(𝑝3 ))𝑤(𝑝, 𝑝1 → 𝑝2 , 𝑝3 )[𝑓(𝑝2 , 𝑥, 𝑡)𝑓(𝑝3 , 𝑥, 𝑡)
− 𝑓(𝑝, 𝑥, 𝑡)𝑓(𝑝1 , 𝑥, 𝑡)]

First, the LHS. 𝑣 = ∇𝑝 (𝜖) is the "velocity" of a particle with momentum 𝑝 , whereas 𝐹 is the
force experienced by it. The LHS is the net change in the number of particles in a given
phase space volume due explicit variation on time (first term) , or, phase space flows out of
the phase space volume (next two terms). The last two terms are usually called the
"streaming terms".

Now, the "collison term": The RHS is the rate at which collisions contribute to changing 𝑓 .
There must be some collisions that result in a final state that lies in the given phase space
volume. These contribute positively (+) to the collision term. In the reverse direction, there
are collisions that involve a particle in the given phase space volume. These contribute
negatively (-). We can motivate that the rate of any type of collision 𝑞𝐴 + 𝑞𝐵 → 𝑞𝐶 + 𝑞𝐷
must depend on the number of particles available to participate in this collision, ie,

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𝑓(𝑞𝐴)𝑓(𝑞𝐵 ) . These observations explain the term inside the square bracket.
A few more comments are in order. First, the delta functions. These come from the
assumption that the dynamics of the gas is symmetric under space-time translations. This
implies that total energy and total momentum are conserved quantities, which can only be
possible if we only allow, at the microscopic level, collisions that conserve energy and
momentum. This explains the deltas.

Finally, the collision rate 𝑤 . A natural question to ask is: why do we not have different
collision rates for the forward and backward reactions? ie, why is
𝑤(𝑝, 𝑝1 → 𝑝2 , 𝑝3 ) = 𝑤(𝑝2 , 𝑝3 → 𝑝, 𝑝1 ) ? The answer is that at the microscopic level, we
assume that the dynamics is invariant under time reversal, hence, in particular, forward
and backward reactions rates must be same. This is called the "principle of detailed
balancing".

So, bringing the streaming terms on the RHS, we can see what the Boltzmann equation tells
us; that the change in number of particles in a given phase space volume is totally
accounted for by the rate at which particles are "streaming" in (or out), and the rate at
which the particles are being "collided" into or out of, the given phase space volume.

Now, we are in a position to motivate what we mean by "equilibrium". Equilibrium is the

situation when each of the above terms is explicitly zero. For the first term, this implies
∂𝑡 𝑓 = 0. For the streaming terms, this implies ∇𝑥 𝑓 = 0 and 𝐹 = 0 . For the collision term,
we see that this implies that [𝑓(𝑝2 )𝑓(𝑝3 ) − 𝑓(𝑝)𝑓(𝑝1 )] = 0. The 𝑥, 𝑡 dependence can be
dropped, as now we are describing a gas in equilibrium.

We must remember the constraints imposed on the momenta due to the delta functions in
the collision term. In general, if I want to impose the above condition, given the constraint
𝑔(𝑝) + 𝑔(𝑝1 ) = 𝑔(𝑝2 ) + 𝑔(𝑝3 ) , for some function 𝑔 , then one solution to the above equation
(it can easily be checked) is 𝑓(𝑝) = 𝑒−𝛾𝑔(𝑝) , where 𝛾 is some constant. Here, we have two
things to conserve, energy and momentum, hence, the general equilibrium distribution is
described by 𝑓𝑒𝑞 (𝑝) = 𝑒−𝛽(𝜖(𝑝)−𝑝.𝑉 ) , where 𝛽 and 𝑉 are constants. Note that the case of non
zero 𝑉 signifies a gas in uniform motion (a gas in uniform motion is also in
"thermodynamic equilibrium") with velocity 𝑉 . We will assume that we are in the rest
frame of the gas at equilibrium, ie, 𝑉 = 0 . Hence, we obtain 𝑓𝑒𝑞 = 𝑒−𝛽𝜖(𝑝) . We identify
𝑇 = 1𝛽 as the "Temperature" (Boltzmann constant 𝑘𝐵 has been set to 1)

To compute the equilibrium speed distribution, we must integrate over a shell of

momentum magnitude |𝑝| . The (d-1) dimensional area of said shell ~ |𝑝|𝑑−1 . Identifying
𝑝2
|𝑝| as 𝑚𝑣 , where 𝑚 is the mass of a single particle, we finally obtain 𝑓𝑀𝑎𝑥𝑤𝑒𝑙𝑙(𝑣) ~ 𝑣2 𝑒−𝛽 2𝑚
𝑚𝑣2
~ 𝑣2 𝑒− 2𝑇 , which is what we set out to show.

edited Mar 15 at 22:38 answered Mar 15 at 22:20

insomniac
650 3 9

Spherical coordinates give R^2 sin

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Spherical coordinates give R^2 sin

0 The difference between

𝑑𝑁/𝑁 ∝ exp(−𝑣2𝑥 /𝑠2 )𝑑𝑣𝑥

and

𝑑𝑁/𝑁 ∝ 𝑣2 exp(−𝑣2 /𝑐2 )𝑑𝑣

lies in the detail about correctly moving from 𝑑𝑣𝑥 to 𝑑𝑣. Consider the infinitesimal volume
in cartesian and spherical coordinates

𝑑𝑣𝑥 𝑑𝑣𝑦 𝑑𝑣𝑧 ∝ 𝑣2 sin 𝜃 𝑑𝜙 𝑑𝜃 𝑑𝑣

This is how 𝑣2 appears before exponent (plus to confirming 𝑣2𝑥 + 𝑣2𝑦 + 𝑣2𝑧 = 𝑣2 inside it).

answered Mar 15 at 20:04

sanaris
642 3 8

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