![]() | ||
Parameters a > 0 {displaystyle a>0} Support x ∈ ( 0 ; ∞ ) {displaystyle xin (0;infty )} PDF 2 π x 2 e − x 2 / ( 2 a 2 ) a 3 {displaystyle {sqrt {rac {2}{pi }}}{rac {x^{2}e^{-x^{2}/left(2a^{2}ight)}}{a^{3}}}} CDF erf ( x 2 a ) − 2 π x e − x 2 / ( 2 a 2 ) a {displaystyle operatorname {erf} left({rac {x}{{sqrt {2}}a}}ight)-{sqrt {rac {2}{pi }}}{rac {xe^{-x^{2}/left(2a^{2}ight)}}{a}}} where erf is the error function Mean μ = 2 a 2 π {displaystyle mu =2a{sqrt {rac {2}{pi }}}} Mode 2 a {displaystyle {sqrt {2}}a} |
In statistics the Maxwell–Boltzmann distribution is a particular probability distribution named after James Clerk Maxwell and Ludwig Boltzmann. It was first defined and used in physics (in particular in statistical mechanics) for describing particle speeds in idealized gases where the particles move freely inside a stationary container without interacting with one another, except for very brief collisions in which they exchange energy and momentum with each other or with their thermal environment. Particle in this context refers to gaseous particles (atoms or molecules), and the system of particles is assumed to have reached thermodynamic equilibrium. While the distribution was first derived by Maxwell in 1860 on heuristic grounds, Boltzmann later carried out significant investigations into the physical origins of this distribution.
Contents
- Distribution function
- Typical speeds
- Derivation and related distributions
- Distribution for the momentum vector
- Distribution for the energy
- Distribution for the velocity vector
- References
A particle speed probability distribution indicates which speeds are more likely: a particle will have a speed selected randomly from the distribution, and is more likely to be within one range of speeds than another. The distribution depends on the temperature of the system and the mass of the particle. The Maxwell–Boltzmann distribution applies to the classical ideal gas, which is an idealization of real gases. In real gases, there are various effects (e.g., van der Waals interactions, vortical flow, relativistic speed limits, and quantum exchange interactions) that can make their speed distribution different from the Maxwell–Boltzmann form. However, rarefied gases at ordinary temperatures behave very nearly like an ideal gas and the Maxwell speed distribution is an excellent approximation for such gases. Thus, it forms the basis of the Kinetic theory of gases, which provides a simplified explanation of many fundamental gaseous properties, including pressure and diffusion.
Distribution function
The Maxwell–Boltzmann distribution is the function
where
This probability density function gives the probability, per unit speed, of finding the particle with a speed near
The simplest ordinary differential equation satisfied by the distribution is:
or in unitless presentation:
Note that a distribution (function) is not the same as the probability. The distribution (function) stands for an average number, as in all three kinds of statistics (Maxwell–Boltzmann, Bose–Einstein, Fermi–Dirac). With the Darwin–Fowler method of mean values the Maxwell–Boltzmann distribution is obtained as an exact result.
Typical speeds
The mean speed, most probable speed (mode), and root-mean-square can be obtained from properties of the Maxwell distribution.
The typical speeds are related as follows:
Derivation and related distributions
The original derivation in 1860 by James Clerk Maxwell was an argument based on demanding certain symmetries in the speed distribution function. After Maxwell, Ludwig Boltzmann in 1872 derived the distribution on more mechanical grounds by using the assumptions of his Kinetic theory of gases, and showed that gases should over time tend toward this distribution, due to collisions (see H-theorem). He later (1877) derived the distribution again under the framework of statistical thermodynamics. The derivations in this section are along the lines of Boltzmann's 1877 derivation, starting with result known as Maxwell–Boltzmann statistics (from statistical thermodynamics). Maxwell–Boltzmann statistics gives the average number of particles found in a given single-particle microstate, under certain assumptions:
where:
The assumptions of this equation are that the particles do not interact, and that they are classical; this means that each particle's state can be considered independently from the other particles' states. Additionally, the particles are assumed to be in thermal equilibrium. The denominator in Equation (1) is simply a normalizing factor so that the Ni/N add up to 1 — in other words it is a kind of partition function (for the single-particle system, not the usual partition function of the entire system).
Because velocity and speed are related to energy, Equation (1) can be used to derive relationships between temperature and the speeds of gas particles. All that is needed is to discover the density of microstates in energy, which is determined by dividing up momentum space into equal sized regions.
Distribution for the momentum vector
The potential energy is taken to be zero, so that all energy is in the form of kinetic energy. The relationship between kinetic energy and momentum for massive non-relativistic particles is
where p2 is the square of the momentum vector p = [px, py, pz]. We may therefore rewrite Equation (1) as:
where Z is the partition function, corresponding to the denominator in Equation (1). Here m is the molecular mass of the gas, T is the thermodynamic temperature and k is the Boltzmann constant. This distribution of Ni/N is proportional to the probability density function fp for finding a molecule with these values of momentum components, so:
The normalizing constant c, can be determined by recognizing that the probability of a molecule having some momentum must be 1. Therefore the integral of equation (4) over all px, py, and pz must be 1.
It can be shown that:
Substituting Equation (5) into Equation (4) gives:
The distribution is seen to be the product of three independent normally distributed variables
Distribution for the energy
The energy distribution is found imposing
where
Using then (8) in (7), and expressing everything in terms of the energy
and finally
Since the energy is proportional to the sum of the squares of the three normally distributed momentum components, this distribution is a gamma distribution; in particular, it is a chi-squared distribution with three degrees of freedom.
By the equipartition theorem, this energy is evenly distributed among all three degrees of freedom, so that the energy per degree of freedom is distributed as a chi-squared distribution with one degree of freedom:
where
The Maxwell–Boltzmann distribution can also be obtained by considering the gas to be a type of quantum gas for which the approximation ε >> k T may be made.
Distribution for the velocity vector
Recognizing that the velocity probability density fv is proportional to the momentum probability density function by
and using p = mv we get
which is the Maxwell–Boltzmann velocity distribution. The probability of finding a particle with velocity in the infinitesimal element [dvx, dvy, dvz] about velocity v = [vx, vy, vz] is
Like the momentum, this distribution is seen to be the product of three independent normally distributed variables
where the distribution for a single direction is
Each component of the velocity vector has a normal distribution with mean
The Maxwell–Boltzmann distribution for the speed follows immediately from the distribution of the velocity vector, above. Note that the speed is
and the volume element in spherical coordinates
where