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The Maxwell–Boltzmann distribution applies to ideal gases close to thermodynamic
equilibrium, negligible quantum effects, and non-relativistic speeds. It forms the basis of
the kinetic theory of gases, which explains many fundamental gas properties, including
pressure and diffusion. The Maxwell–Boltzmann distribution is usually thought of as the
distribution for molecular speeds, but it can also refer to the distribution for velocities,
momenta, and magnitude of the momenta of the molecules, each of which will have a
different probability distribution function, all of which are related.
In the classical picture of an ideal gas, molecules bounce around at a variety of different
velocities, never interacting with each other. Though this qualitative picture is obviously
flawed (since molecules always do interact), it is a useful model for situations where the
particle density is very low; in a more quantitative sense, this means that the particles
themselves are very small when compared to the volume between them.
Accordingly, we will want to know exactly how many of these molecules are moving
around at a given speed. The Maxwell speed distribution (MSD), named after James
Clerk Maxwell, is a probability distribution describing the "spread" of these molecular
speeds; it is derived, and therefore only valid, assuming that we're dealing with an ideal
gas. Again, no gas is truly ideal, but our own atmosphere at STP behaves enough like the
ideal situation that the MSD can be used.
Note that speed is a scalar quantity, describing how fast the particles are moving,
regardless of direction; velocity also describes the direction that the particles are moving.
It is elementary using statistical mechanics to find that the MSD must be proportional to
the probability that a particle is moving at a given speed. Another important element is
the fact that space is three dimensional, which implies that for any given speed, there are
many possible velocity vectors.
The probability of a molecule having a given speed can be found by using Boltzmann
factor; considering the energy to be dependent only on the kinetic energy, we find that:
Here, m is the mass of the molecule, k is Boltzmann's constant, and T is the temperature.
In 3-dimensional velocity space, the velocity vectors corresponding to a given speed v
live on the surface of a sphere with radius v. The larger v is, the bigger the sphere, and the
more possible velocity vectors there are. So the number of possible velocity vectors for a
given speed goes like the surface area of a sphere of radius v.
Multiplying these two functions together gives us the distribution, and normalising this
gives us the MSD in its entirety.
Derivation
The original derivation by Maxwell assumed all three directions would behave in the
same fashion, but a later derivation by Boltzmann dropped this assumption using kinetic
theory. The Maxwell–Boltzmann distribution can now most readily be derived from the
Boltzmann distribution for energies (see also the Maxwell–Boltzmann statistics of
statistical mechanics):
For the case of an "ideal gas" consisting of non-interacting atoms in the ground state, all
energy is in the form of kinetic energy. The relationship between kinetic energy and
momentum for massive particles is
where p2 is the square of the momentum vector p = [px, py, pz]. We may therefore rewrite
Equation 1 as:
Since the energy is proportional to the sum of the squares of the three normally
distributed momentum components, this distribution is a chi-square distribution with
three degrees of freedom:
where
The Maxwell–Boltzmann distribution
can also be obtained by
considering the gas to be a
Distribution for the velocity vector
Recognizing that the velocity probability density fv is proportional to the momentum
probability density function by
Like the momentum, this distribution is seen to be the product of three independent
normally distributed variables vx, vy, and vz, but with variance . It can also be seen that
the Maxwell–Boltzmann velocity distribution for the vector velocity [vx, vy, vz] is the
product of the distributions for each of the three directions:
where the distribution for a single direction is
This distribution has the form of a normal distribution, with variance . As expected
for a gas at rest, the average velocity in any particular direction is zero.
The speed probability density functions of the speeds of a few noble gases at a
temperature of 298.15 K (25 °C). The y-axis is in s/m so that the area under any section
of the curve (which represents the probability of the speed being in that range) is
dimensionless.
Usually, we are more interested in the speeds of molecules rather than their component
velocities. The Maxwell-Boltzmann distribution for the speed is written as
Note that the units of f(v) in equation are probability per speed, or just reciprocal speed as
in the graph at the right.
Since the speed is the square root of the sum of squares of the three independent,
normally distributed velocity components, this distribution is a Maxwell–Boltzmann
distribution, with .
We are often more interested in quantities such as the average speed of the particles
rather than the actual distribution. The mean speed, most probable speed (mode), and
root-mean-square can be obtained from properties of the Maxwell–Boltzmann
distribution.