This expression has been taken from the link -

https://farside.ph.utexas.edu/teaching/sm1/Thermalhtml/node87.html

It is in the best form easier than it is given at other places with full
explanation. We will also discuss this in class.

Maxwell Velocity Distribution

Consider a molecule of mass in a gas that is sufficiently dilute for the intermolecular forces to
be negligible (i.e., an ideal gas). The energy of the molecule is written

(7.202)

where is its momentum vector, and is its internal (i.e., non-translational) energy. The
latter energy is due to molecular rotation, vibration, et cetera. Translational degrees of freedom
can be treated classically to an excellent approximation, whereas internal degrees of freedom
usually require a quantum-mechanical approach. Classically, the probability of finding the

molecule in a given internal state with a position vector in the range to , and a

momentum vector in the range to , is proportional to the number of cells (of

``volume'' ) contained in the corresponding region of phase-space, weighted by the

Boltzmann factor. In fact, because classical phase-space is divided up into uniform cells, the
number of cells is just proportional to the ``volume'' of the region under consideration. This

``volume'' is written . Thus, the probability of finding the molecule in a given internal
state is

(7.203)

where is a probability density defined in the usual manner. The probability

of finding the molecule in any internal state with position and momentum
vectors in the specified range is obtained by summing the previous expression over all possible
internal states. The sum over just contributes a constant of proportionality

(because the internal states do not depend on or ), so

(7.204)

Of course, we can multiply this probability by the total number of molecules, , in order to
obtain the mean number of molecules with position and momentum vectors in the specified
range.

Suppose that we now wish to determine : that is, the mean number of

molecules with positions between and , and velocities in the range and .

Because , it is easily seen that

(7.205)

where is a constant of proportionality. This constant can be determined by the condition

(7.206)

In other word, the sum over molecules with all possible positions and velocities gives the total
number of molecules, . The integral over the molecular position coordinates just gives the
volume, , of the gas, because the Boltzmann factor is independent of position. The integration
over the velocity coordinates can be reduced to the product of three identical integrals (one for

, one for , and one for ), so we have

 (7.207)

Now,

(7.208)

so . (See Exercise 2.) Thus, the properly normalized distribution

function for molecular velocities is written

(7.209)

Here, is the number density of the molecules. We have omitted the variable in the

argument of , because clearly does not depend on position. In other words, the distribution
of molecular velocities is uniform in space. This is hardly surprising, because there is nothing to
distinguish one region of space from another in our calculation. The previous distribution is
called the Maxwell velocity distribution, because it was discovered by James Clark Maxwell in
the middle of the nineteenth century. The average number of molecules per unit volume with

velocities in the range to is obviously .

Let us consider the distribution of a given component of velocity: the -component (say).

Suppose that is the average number of molecules per unit volume with the -

component of velocity in the range to , irrespective of the values of their other

velocity components. It is fairly obvious that this distribution is obtained from the Maxwell

distribution by summing (integrating actually) over all possible values of and , with in
the specified range. Thus,
 (7.210)

This gives

(7.211
)

or

(7.212)

Of course, this expression is properly normalized, so that

(7.213)

It is clear that each component (because there is nothing special about the -component) of the
velocity is distributed with a Gaussian probability distribution (see Section 2.9), centered on a
mean value

(7.214)
with variance

(7.215)

Equation (7.214) implies that each molecule is just as likely to be moving in the plus -direction
as in the minus -direction. Equation (7.215) can be rearranged to give

(7.216)
in accordance with the equipartition theorem.

Note that Equation (7.209) can be rewritten

(7.217)

where and are defined in an analogous way to . Thus, the probability that

the velocity lies in the range to is just equal to the product of the probabilities that
the velocity components lie in their respective ranges. In other words, the individual velocity
components act like statistically-independent variables.

Suppose that we now wish to calculate : that is, the average number of molecules per

unit volume with a speed in the range to . It is obvious that we can obtain
this quantity by summing over all molecules with speeds in this range, irrespective of the
direction of their velocities. Thus,

(7.218)

where the integral extends over all velocities satisfying

(7.219)

This inequality is satisfied by a spherical shell of radius and thickness in velocity space.

Because only depends on , so , the previous integral is just

multiplied by the volume of the spherical shell in velocity space. So,
(7.220)

which gives
 (7.221)

This is the famous Maxwell distribution of molecular speeds. Of course, it is properly

normalized, so that

(7.222)

Note that the Maxwell distribution exhibits a maximum at some non-zero value of . The reason
for this is quite simple. As increases, the Boltzmann factor decreases, but the volume of phase-
space available to the molecule (which is proportional to ) increases: the net result is a
distribution with a non-zero maximum.

Figure: The Maxwell velocity distribution as a function of molecular speed, in units of the most
probable speed ( ). The dashed, dash-dotted, and dotted lines indicates the most probable
speed, the mean speed, and the root-mean-square speed, respectively.

The mean molecular speed is given by

 (7.223)

Thus, we obtain

(7.224)

or

(7.225)

Now

(7.226)

(see Exercise 2), so

(7.227)

A similar calculation gives

(7.228)

(See Exercise 14.) However, this result can also be obtained from the equipartition theorem.
Because

(7.229)
then Equation (7.228) follows immediately. It is easily demonstrated that the most probable
molecular speed (i.e., the maximum of the Maxwell distribution function) is

(7.230)

The speed of sound in an ideal gas is given by

(7.231)

where is the ratio of specific heats. This can also be written

(7.232)

because and . It is clear that the various average speeds that we have just
calculated are all of order the sound speed (i.e., a few hundred meters per second at room

temperature). In ordinary air ( ) the sound speed is about 84% of the most probable
molecular speed, and about 74% of the mean molecular speed. Because sound waves ultimately
propagate via molecular motion, it makes sense that they travel at slightly less than the most
probable and mean molecular speeds.

Figure 7.7 shows the Maxwell velocity distribution as a function of molecular speed in units of
the most probable speed. Also shown are the mean speed and the root-mean-square speed.