MaxwellBoltzmann distribution

Not to be confused with MaxwellBoltzmann statistics.

Probability density (s/m)

Maxwell-Boltzmann Molecular Speed Distribution for Noble Gases

In statistics the MaxwellBoltzmann distribution is

a particular probability distribution named after James
Clerk Maxwell and Ludwig Boltzmann. It was rst dened 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.[1]
While the distribution was rst derived by Maxwell in
1860 on heuristic grounds,[2] Boltzmann later carried out
signicant investigations into the physical origins of this
distribution.

4 He

20

Ne

40Ar

0.002

132

Xe

0.001

500

1000

1500

2000

2500

Speed (m/s)

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.

per unit speed, of nding the particle with a speed near v .

This equation is simply the Maxwell distribution
(given in
the infobox) with distribution parameter a = kT /m
. In probability theory the MaxwellBoltzmann distribution is a chi distribution
with three degrees of freedom
and scale parameter a = kT /m .
The simplest ordinary dierential equation satised by
the distribution is:
(
)
kT vf (v) + f (v) mv 2 2kT = 0,

2 m ( m )3/2
f (1) =
e 2kT

kT
or in unitless presentation:
)
(
a2 xf (x) + x2 2a2 f (x) = 0,

2 2a12
e
.
f (1) =
a3

Distribution function

The MaxwellBoltzmann distribution is the function

f (v) =

0.003

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.[3] The MaxwellBoltzmann distribution applies to the classical ideal gas, which is an idealization of real gases. In real gases, there are various
eects (e.g., van der Waals interactions, vortical ow,
relativistic speed limits, and quantum exchange interactions) that can make their speed distribution dierent
from the MaxwellBoltzmann form. However, rareed
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 simplied explanation of many fundamental gaseous properties, including pressure and diusion.[4]

0.004

2 Typical speeds

(
mv 2
m )3
4v 2 e 2kT ,
2kT

The mean speed, most probable speed (mode), and rootmean-square can be obtained from properties of the
Maxwell distribution.

where m is the particle mass and kT is the product of

Boltzmanns constant and thermodynamic temperature.

The most probable speed, vp, is the speed most

likely to be possessed by any molecule (of the same

This probability density function gives the probability,

1

3 DERIVATION AND RELATED DISTRIBUTIONS

mass m) in the system and corresponds to the maximum value or mode of f(v). To nd it, we calculate
the derivative df/dv, set it to zero and solve for v:
df (v)
=0
dv

vp =

2kT
=
m

Ni is the average number of particles in the singleparticle microstate i,

N is the total number of particles in the system,

which yields:

i and j are indices (or labels) of the single-particle

micro states,

Ei is the energy of microstate i,

2RT
M

T is the equilibrium temperature of the system,

k is the Boltzmann constant.

where R is the gas constant and M = NA m is the The assumptions of this equation are that the particles
molar mass of the substance.
do not interact, and that they are classical; this means
For diatomic nitrogen (N2 , the primary component that each particles state can be considered independently
of air) at room temperature (300 K), this gives vp = from the other particles states. Additionally, the particles
are assumed to be in thermal equilibrium. The denomi422 m/s
nator in Equation (1) is simply a normalizing factor so
The mean speed is the expected value of the speed that the Ni/N add up to 1 in other words it is a kind of
distribution
partition function (for the single-particle system, not the

usual partition function of the entire system).
8kT
8RT
2
v =
v f (v) dv =
=
= vp
Because velocity and speed are related to energy, Equam
M

0
tion (1) can be used to derive relationships between tem The root mean square speed is the second-order perature and the speeds of gas particles. All that is needed
moment of speed:
is to discover the density of microstates in energy, which

isdetermined by dividing up momentum space into equal

(
)1/2

3kT
3RT sized
3 regions.
v 2 =
v 2 f (v) dv
=
=
=
vp
m
M
2
0
The typical speeds are related as follows:

3.1 Distribution for the momentum vector

0.886v = vp < v < v 2 = 1.085v.

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 nonrelativistic particles is

Derivation and related distributions

where p2 is the square of the momentum vector p = [px,

The original derivation in 1860 by James Clerk Maxwell py, pz]. We may therefore rewrite Equation (1) as:
was an argument based on demanding certain symmetries in the speed distribution function.[2] After Maxwell,
Ludwig Boltzmann in 1872 derived the distribution on
more mechanical grounds by using the assumptions of where Z is the partition function, corresponding to the
his Kinetic theory of gases, and showed that gases should denominator in Equation (1). Here m is the molecular
over time tend toward this distribution, due to collisions mass of the gas, T is the thermodynamic temperature and
(see H-theorem). He later (1877) derived the distribution k is the Boltzmann constant. This distribution of N/N
again under the framework of statistical thermodynamics. is proportional to the probability density function f for
The derivations in this section are along the lines of Boltz- nding a molecule with these values of momentum commanns 1877 derivation, starting with result known as ponents, so:
MaxwellBoltzmann statistics (from statistical thermodynamics). MaxwellBoltzmann statistics gives the average number of particles found in a given single-particle
The normalizing constant c, can be determined by recmicrostate, under certain assumptions:[1][5]
ognizing 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.
where:

It can be shown that:

3.3

Distribution for the velocity vector

Substituting Equation (5) into Equation (4) gives:

3
where is the energy per degree of freedom. At equilibrium, this distribution will hold true for any number
of degrees of freedom. For example, if the particles are
rigid mass dipoles of xed dipole moment, they will have
three translational degrees of freedom and two additional
rotational degrees of freedom. The energy in each degree
of freedom will be described according to the above chisquared distribution with one degree of freedom, and the
total energy will be distributed according to a chi-squared
distribution with ve degrees of freedom. This has implications in the theory of the specic heat of a gas.

The distribution is seen to be the product of three independent normally distributed variables px , py , and
pz , with variance mkT . Additionally, it can be seen
that the magnitude of momentum will be distributed
as

a MaxwellBoltzmann distribution, with a = mkT .

The MaxwellBoltzmann distribution can also be obThe MaxwellBoltzmann distribution for the momentum
tained by considering the gas to be a type of quantum
(or equally for the velocities) can be obtained more fungas.
damentally using the H-theorem at equilibrium within the
Kinetic theory of gases framework.

3.3 Distribution for the velocity vector

3.2

Distribution for the energy

The energy distribution is found imposing

Recognizing that the velocity probability density f is

proportional to the momentum probability density function by
(
3

dp
dv

)3

fv d v = fp
d3 v
where d3 p is the innitesimal phase-space volume of momenta corresponding to the energy interval dE . Making
use of the spherical symmetry of the energy-momentum and using p = mv we get
dispersion relation E = |p|2 /2m , this can be expressed
in terms of dE as
which is the MaxwellBoltzmann velocity distribution.
The probability of nding a particle with velocity in the
Using then (8) in (7), and expressing everything in terms innitesimal element [dvx, dvy, dvz] about velocity v =
[vx, vy, vz] is
of the energy E , we get
f (v
(
)3/2
( y dv)z .

1
Ev x ,1vy , vz ) dvx dvE
E/kT
fE (E)dE =
e
4m 2mEdE = 2
exp
dE
kT
(2mkT )3/2
Like
the momentum,kT
this distribution is seen to be the
product of three independent normally distributed variand nally
ables vx , vy , and vz , but with variance kT
m . It can
also be seen that the MaxwellBoltzmann velocity distribution for the vector velocity [vx, vy, vz] is the product
of the distributions for each of the three directions:
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 par- fv (vx , vy , vz ) = fv (vx )fv (vy )fv (vz )
ticular, it is a chi-squared distribution with three degrees
of freedom.
where the distribution for a single direction is
By the equipartition theorem, this energy is evenly distributed among all three degrees of freedom, so that the

[
]
m
mvi2
energy per degree of freedom is distributed as a chi- fv (vi ) =
exp
.
2kT
2kT
squared distribution with one degree of freedom:[6]

f () d =

exp
kT
kT

]
d

Each component of the velocity vector has a normal distribution with mean vx = vy = vz = 0 and standard

deviation vx = vy = vz = kT
m , so the vector has

a 3-dimensional normal distribution, a particular kind of

multivariate normal distribution,
with mean v = 0 and

standard deviation v =

3kT
m

The MaxwellBoltzmann distribution for the speed follows immediately from the distribution of the velocity
vector, above. Note that the speed is

v=

vx2 + vy2 + vz2

EXTERNAL LINKS

[4] Encyclopaedia of Physics (2nd Edition), R.G. Lerner,

G.L. Trigg, VHC publishers, 1991, ISBN (Verlagsgesellschaft) 3-527-26954-1, ISBN (VHC Inc.) 0-89573752-3
[5] McGraw Hill Encyclopaedia of Physics (2nd Edition),
C.B. Parker, 1994, ISBN 0-07-051400-3
[6] Laurendeau, Normand M. (2005). Statistical thermodynamics: fundamentals and applications. Cambridge University Press. p. 434. ISBN 0-521-84635-8., Appendix
N, page 434

and the volume element in spherical coordinates

6 Further reading
dvx dvy dvz = v 2 sin dv d d
where and are the course (azimuth of the velocity
vector) and path angle (elevation angle of the velocity vector). Integration of the normal probability density
function of the velocity, above, over the course (from 0
to 2 ) and path angle (from 0 to ), with substitution of
the speed for the sum of the squares of the vector components, yields the speed distribution.

See also
MaxwellBoltzmann statistics
Maxwell-Jttner distribution
Boltzmann distribution
Boltzmann factor
Rayleigh distribution
Kinetic theory of gases

References

[1] Statistical Physics (2nd Edition), F. Mandl, Manchester Physics, John Wiley & Sons, 2008, ISBN
9780471915331
[2] See:
Maxwell, J.C. (1860) Illustrations of the dynamical theory of gases. Part I. On the motions and
collisions of perfectly elastic spheres, Philosophical Magazine, 4th series, 19 : 19-32.
Maxwell, J.C. (1860) Illustrations of the dynamical theory of gases. Part II. On the process of diffusion of two or more kinds of moving particles
among one another, Philosophical Magazine, 4th
series, 20 : 21-37.
[3] University Physics With Modern Physics (12th Edition),
H.D. Young, R.A. Freedman (Original edition), AddisonWesley (Pearson International), 1st Edition: 1949, 12th
Edition: 2008, ISBN (10-) 0-321-50130-6, ISBN (13-)
978-0-321-50130-1

Physics for Scientists and Engineers - with Modern

Physics (6th Edition), P. A. Tipler, G. Mosca, Freeman, 2008, ISBN 0-7167-8964-7
Thermodynamics, From Concepts to Applications
(2nd Edition), A. Shavit, C. Gutnger, CRC Press
(Taylor and Francis Group, USA), 2009, ISBN (13) 978-1-4200-7368-3
Chemical Thermodynamics, D.J.G. Ives, University Chemistry, Macdonald Technical and Scientic,
1971, ISBN 0-356-03736-3
Elements of Statistical Thermodynamics (2nd Edition), L.K. Nash, Principles of Chemistry, AddisonWesley, 1974, ISBN 0-201-05229-6
Ward, CA & Fang, G 1999, 'Expression for predicting liquid evaporation ux: Statistical rate theory
approach', Physical Review E, vol. 59, no. 1, pp.
429-40.
Rahimi, P & Ward, CA 2005, 'Kinetics of Evaporation: Statistical Rate Theory Approach', Int. J. of
Thermodynamics, vol. 8, no. 9, pp. 1-14.

7 External links
The Maxwell Speed Distribution from The Wolfram Demonstrations Project at Mathworld

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