2017-2

Standard Maxwell-Boltzmann distribution: Definition and Properties

Hugo Hernandez
ForsChem Research, 050030 Medellin, Colombia
hugo.hernandez@forschem.org
ORCID : 0000-0002-7634-7161
doi: 10.13140/RG.2.2.29888.74244

Abstract

In this report, a standard Maxwell-Boltzmann distribution () is defined by analogy to the

concept of the standard Gaussian distribution. The most important statistical properties of ,
as well as a simple method for generating random numbers from the standard Maxwell-
Boltzmann distribution are presented. Given that the properties of are already known, it is
advantageous to describe any arbitrary Maxwell-Boltzmann distribution as a function of the
standard Maxwell-Boltzmann distribution . By using this approach, it is possible to
demonstrate that the temperature of a material is a function only of the fluctuating
component of the average molecular kinetic energy, and that it is independent of its
macroscopic kinetic energy.

Keywords
Ideal gases; Maxwell-Boltzmann distribution; Molecular speed; Kinetic energy; Random
numbers; Standard distribution; Temperature

1. Introduction

Atoms and molecules are in permanent motion. Even for solid materials, they move and collide
with their neighbors, although remaining almost at their same positions. The motion of
molecules1 in gases and liquids is perhaps easier to imagine. This motion can be characterized
by their particular velocities. There is no reason to believe that all molecules in a material will
move at exactly the same speed (which is the magnitude of the velocity vector). On the
contrary, it seems more reasonable to think the opposite. In fact, experimental measurements
demonstrate that molecules in a gas do move at different speeds. As an example, Figure 1
shows an experimental distribution of molecular speeds for potassium gas at 544 K.[1] Based

1
The concept of molecule used along this document includes the case of mono-atomic molecules.

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

on this premise, James Clerk Maxwell derived the molecular speed distribution of ideal gases in
1860,[2] almost a century before it could be proved experimentally. Some years later, Ludwig
Boltzmann was able to derive the same distribution using a more rigorous and formal
approach.[3] The distribution they obtained is presently known as the Maxwell-Boltzmann
distribution,[4] and it will be presented and briefly discussed in Section 2. The proposed
standard Maxwell-Boltzmann distribution will be introduced in Section 3, along with their most
important statistical properties. In Section 4, a mathematical procedure for obtaining random
numbers based on the Standard Maxwell-Boltzmann distribution is described. These standard
Maxwell-Boltzmann random numbers can be used to generate random numbers for any
arbitrary Maxwell-Boltzmann distribution. Finally, in Section 5, the Standard Maxwell-
Boltzmann distribution is used for analyzing the data presented in Fig. 1.

0,8
Frequency (a.u.)

0,6

0,4

0,2

0
0 200 400 600 800 1000 1200
Molecular speed (m/s)

Figure 1. Experimental molecular speed distribution for potassium gas at 544 K obtained using a
vacuum oven coupled with a spiral velocity selector and a tungsten surface ionization
detector.[1] The frequency is presented in arbitrary units.

2. The Maxwell-Boltzmann distribution

According to Maxwell [2] and Boltzmann,[3] the (thermal) molecular speeds () of a pure, ideal
gas can be described by the following probability distribution:

2

2 2 22
() = , 0
3

(2.1)

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

where

(2.2)

is a characteristic speed, represents a conversion factor between energy and temperature

(known as the Boltzmann constant) which is equal to 1.3806 1023 /, is the
temperature of the gas, and is the mass of the gas molecules.

Equation (2.1) represents a Gaussian distribution with respect to the kinetic energy of the
molecules, which is proportional to the square molecular speed ( 2 ).

For such speed distribution, the average speed can be calculated as:

2 2
1 2
1 2

() = () = 3 3 22 = 3 2 22
0 0 0
2 2 2
1 2 8 8

= 3 [2 2 22 | + 22 22 ] = [ 22 | ] =
0 0 0

8
=

(2.3)

And the variance of the molecular speed following a Maxwell-Boltzmann distribution is:

2) 2 1 2 4 22 82
() = ( (()) = 3 2
0

1 2 2 2 82

= 3 [2 3 22 | + 32 2 22 ]
0 0

3 2 2 2 82 2 82
= [2 22 | + 2 22 ] = 3 [2 ]
0 0 2
82 8 8
= 32 = 2 (3 ) = (3 )

(2.4)

Consequently, the standard deviation is:

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

8
() = () = (3 )
(2.5)

A particular characteristic of this type of distribution is that the coefficient of variation (CV) is a
constant:

8
() (3 ) 3
() = = = 1
() 8
8

(2.6)

Figure 2 shows the predicted speed distributions of an ideal gas following the Maxwell-
Boltzmann distribution at 3 different temperatures. The points correspond to the experimental
data presented in Figure 1. Even though the fit is not perfect, the similitude is quite remarkable;
this difference is can be explained by the effect of vacuum in the measuring apparatus, which
causes a flow of gas towards the vacuum pump. This effect will be discussed in further detail in
Section 5.

3E-03
T=300 K
2E-03 T=544 K
Relative frequency

T=1000 K
2E-03
T=544 K (Exp)

1E-03

5E-04

0E+00
0 500 1000 1500 2000
Molecular speed (m/s)

Figure 2. Molecular speed distributions for potassium gas obtained from the Maxwell-
Boltzmann distribution at 300 K, 544 K and 1000 K (solid lines), compared to the experimental
speeds measured at 544 K (data points).[1]

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

3. Standard Maxwell-Boltzmann distribution: Definition and Properties

Let us now define a reduced molecular speed () as the ratio between the molecular speed
and the average molecular speed of the distribution:

() ()
= =
(())
8

(3.1)

The variable is a Maxwell-Boltzmann random variable, described by a Maxwell-Boltzmann

distribution where (()) = 1 (in the corresponding units of speed being used), or

equivalently, = 8 , or = 8 . Then, its frequency distribution will be (from Eq. 2.1):

32 2 42
() = , 0
2

(3.2)

The most important characteristic of this dimensionless standard Maxwell-Boltzmann variable

() is that its average value is:

32 3 42 4 8
42
() = () = = 2 ( )
0 2 0 0

4 2 42 8
42

42
= [ | + ( ) ] = | = 1
0
4 0 0

(3.3)

Similarly, it can also be found that the variance, standard deviation and coefficient of variation
of are, respectively:
3
() = 8
1 (3.4)

3
() = 8 1 (3.5)

3
() = 8 1 (3.6)

The reduced molecular speed has been denoted as standard Maxwell-Boltzmann distribution
by analogy with the standard Gaussian distribution.[5]

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

From Eq. (3.1), it is possible to relate any arbitrary Maxwell-Boltzmann distribution of molecular
speeds to the standard Maxwell-Boltzmann variable by:

8
() =

(3.7)

In this way,

8 8 8
[()] = (
) =
() =
(3.8)

and

8 8 8 3 8
[()] = ( ) = () = ( 1) = (3 ) (3.9)
8

which are consistent with Eq. (2.3) and (2.4).

The advantage of defining the dimensionless standard Maxwell-Boltzmann variable , is that it

is now possible to determine all additional properties for , and they can then be used to
describe any Maxwell-Boltzmann distribution by using Eq. (3.7).

For example, the expected values for different powers of are:

2) 2
32 3
42 4 3 8
42
( = () = 2 = ( )
0 0 0

4 42 42 3 8 42
= [ 3 | 3 ] = [ ( ) ]
0 0 2 0

3 42 42 3
= [ | ] =
2 0 0 8

(3.10)

42

This result is obtained given that 0 = 4 .

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

32 4
42 4 8
42
(3 ) = 3 () = = 4 ( )
0 2 0 0

4 42 42 8 42
= [ 4 | 4 2 ] = 2 [ 2 ( ) ]
0 0 0

42
2
42 8
42
= 2 [ | 2 ] = [ ( ) ]
0 0 2 0

42
= [ | ]=
2 0
2

(3.11)

32 5
42 4 8
42
(4 ) = 4 () = = 5 ( )
0 2 0 0

4 5 42 3
42 5 3 8
42
= [ | 5 ] = [ ( ) ]
0 0 2 0

5 42 42 15 8 42
= [ 3 | 3 ] = [ ( ) ]
2 0 0 16 0

15 42 42 15 2
= [ | ] =
16 0 0 64

(3.12)

Generalizing these results, it can be found that:

(1)/2
1 (1)/2
( ) (2 + 2)
2 8
=0
( ) = /2
/2
( ) (2 + 1)
{ 8
=0

(3.13)

On the other hand, the variances of the powers of are:

2 152 92 32
(2 ) = (4 ) ((2 )) = 64
64
= 32
(3.14)

2 1053 2
(3 ) = (6 ) ((3 )) = 512
4
(3.15)

Generalizing these results, it can be found that:

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

(1)/2
1 (1)
( ) (2 + 1) ( ) (2 + 2)2
8 4 8
=0 =0
( ) = /2

( ) [(2 + 1) (2 + 1)2 ]
8
{ =0 =0

(3.16)

Using these results, it is now possible to analyze any nonlinear function () of an arbitrary
Maxwell-Boltzmann distribution (), using a Taylor series expansion approach as follows:[6]

()
(0) 8
() = ( )
!
=0

(3.17)

Then, the expected value of the nonlinear function will be:

() (0) 8
[()] = ( ) ( )
!
=0

(3.18)

which can be readily determined by using Eq. (3.13).

A similar approach can be used to find the variance of the nonlinear function:
2
2
() (0) 8
[()] = ( ) ( ) ( )
!
=1
+

() (0)() (0) 8
+ ( ) ( , )
! !
=1

(3.19)

where

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

( , )
(+)/2 (1)/2 (1)/2
(+)/2
( ) [ (2 + 1) (2 + 2) (2 + 2)] ,
8 2
=0 =0 =0
0 ,
=
0 ,
(+)/2 /2 /2
(+)/2
( ) [ (2 + 1) (2 + 1) (2 + 1)] ,
8
{ =0 =0 =0

(3.20)

Figure 3 shows the probability density function for the standard Maxwell-Boltzmann
distribution , which corresponds to the reduced molecular speed distribution.
1
0,9
f - Probability denisty function

0,8
0,7
0,6
0,5
0,4
0,3
0,2
0,1
0
0 0,5 1 1,5 2 2,5 3
B - Standard Maxwell-Boltzmann random variable

Figure 3. Probability density function for the standard Maxwell-Boltzmann random variable
(reduced molecular speed distribution)

It is also possible to determine the mode of the standard Maxwell-Boltzmann random variable
, by setting the derivative of () with respect to equal to zero, as follows:

() 32 2 42 32
42 8 3 42
= ( ) = 2 (2 )=0
2
(3.21)

The solution of Eq. (3.21) yields the following non-trivial result:

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

() = 4 0.886 (3.22)

and the value of its probability density function is:

8
(()) = 1 0.9368 (3.23)

Table 1 summarizes key descriptive statistics indicators for variable .

Table 1. Descriptive statistics summary of the standard Maxwell-Boltzmann distribution ()

Mean 1.0000
Median 0.9639
Mode 0.8862
First quartile 0.6900
Third quartile 1.2701
Interquartile range 0.5801
Variance 0.1781
Standard deviation 0.4220
Coefficient of variation 0.4220

4. Standard Maxwell-Boltzmann distribution: Random numbers generation

Random numbers belonging to the standard Maxwell-Boltzmann distribution can be obtained

from its cumulative probability function, assuming that the cumulative function behaves as a
uniform random number between 0 and 1. The cumulative probability function of is given by:

32 2 42 4 8
42
() = () = = ( )
0 2 0 0

4 42 4 2 4 42 42
= [ | ] = [ ]
0 0 0

(4.1)

42

Given that the integral 0 does not have an exact analytical solution, it has to be
solved numerically.

In order to reduce the computational load of integrating the distribution during the generation
of random numbers, the cumulative probability distribution of can be approximated by the
following empirical function:
2.5
() (0.9974 + 7.326 3.265 ) 0.005 (4.2)

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Figure 4 shows the numerical solution of () as well as the empirical approximation

presented in Eq. (4.2).

1
F - Cumulative probability function

0,9
0,8
0,7
0,6
0,5
0,4
0,3
0,2 Numerical solution
0,1 Empirical approximation (Eq. 4.2)
0
0 0,5 1 1,5 2 2,5 3
B - Standard Maxwell-Boltzmann random variable

Figure 4. Comparison between the cumulative probability function for the standard Maxwell-
Boltzmann random variable (solid line) and the empirical approximation given in Eq. (4.2)
(dotted line).

Figure 5. Histogram of 10.000 realizations of the standard Maxwell-Boltzmann random variable

using Eq. (4.3), compared to the corresponding probability density function (solid line)

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

From Eq. (4.2) it is now possible to generate random realizations of as:

( + 0.005)0.4 0.9974
() = 0.3063 ( )
7.326

(4.3)

where is a uniform random number between 0 and 1.

Figure 5 shows a histogram of 10.000 random realizations of generated from Eq. (4.3).

5. Application Example: Potassium gas in vacuum oven

As an example of application for the standard Maxwell-Boltzmann variable , let us consider

the data presented in Figure 1 for the distribution of molecular speeds of potassium gas in a
vacuum oven at 544 K.[1] Previously, it was mentioned that the data resembled the shape of
the Maxwell-Boltzmann distribution but the fit was not perfect. In this section, it will be shown
that if the macroscopic flow of gas towards the vacuum pump is considered, the fit of the data
significantly improves. But first, let us determine the average kinetic energy of the
potassium molecules reaching the detector:

= 2
2

(5.1)

where is the molecular mass ( = 6.493 1026 kg for potassium), and is the relative
frequency of molecular speed . For the data presented in Figure 1, the average kinetic
energy of potassium molecules is found to be 1.682 1020 J. If the temperature of the gas is
calculated as:[7]

2
=
3

(5.2)

then, the temperature of the gas reaching the detector would be 812 K, which represents an
increase in temperature of 268 K, almost 50% higher than the temperature of the oven (544 K).

Let us now consider that the molecular velocity of the gas () is composed by a macroscopic
velocity and a fluctuating velocity following a Maxwell-Boltzmann distribution. In that case, the
molecular velocity can be expressed as:

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

8
= +

(5.3)

where is the macroscopic velocity of the gas, and is a random unit direction vector. Given
that the detector only receives gas molecules in a single direction (), then it is possible to
conclude that the molecular speed reaching the detector ( ) is given by:

8
= +

(5.4)

Considering that each result (, ) measured by the detector corresponds to a single realization
( ) of , then:

8
, = +

(5.5)

and rearranging Eq. (5.5):

,
=
8

(5.6)

The value of the probability density function for each particular realization is:

4 2
2 ( )
( ) = (, ) 2 , , 0

(5.7)

There are two unknown variables in this expression: and . A generalized reduced
gradient (GRG) nonlinear optimization algorithm,[8] is used for finding the unknown values by
minimizing the square error between the experimental frequencies (adjusted so that the
8 1
maximum value of the experimental frequency is
, corresponding to the probability

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

density function of the mode of given by Eq. 3.23) and the probability density function
predicted by Eq. (5.7). The results obtained after the optimization are:

= 183.98 / (5.8)

= 568.9 (5.9)

By this route, the temperature obtained from the experimental molecular speeds is only 4.58%
higher than the temperature of the oven, which is within a reasonable experimental error.

Figure 6 shows the experimental distribution of molecular speeds, compared to the results
predicted by Eq. (5.5) using the values obtained in Eq. (5.8) and (5.9).

1,0
0,9 Predicted by Eq. (5.7)
Experimental [1]
Probability density function

0,8
0,7
0,6
0,5
0,4
0,3
0,2
0,1
0,0
0 200 400 600 800 1000 1200
Molecular speed (m/s)

Figure 6. Predicted (solid line) vs. experimental (data points) distributions of molecular speeds
for potassium gas in a vacuum oven at 544 K.

The flaw behind the initial calculations (Eq. 5.2) is the assumption that the temperature is
proportional to the total average kinetic energy of the molecules, whereas only the
contribution of fluctuating velocities to the kinetic energy is related to the temperature of the
system.

Let us consider again the general expression for the molecular velocity presented in Eq. (5.3).
From Eq. (5.3), the total kinetic energy of a molecule becomes2:

2
Neglecting internal motion such as rotation or any type of molecular deformation.

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

2 8 4 2
= = + +
2 2

(5.10)

The expected value of the total molecular kinetic energy will then be:

2 3
() = = +
2 2

(5.11)
3
given that () = and (2 ) = 8
. The first term corresponds to the average macroscopic
kinetic energy of the gas , whereas the second term corresponds to the average
fluctuating kinetic energy which will be denoted as the average thermal kinetic energy .

It is then clear that the temperature is not related to the overall average kinetic energy of the
molecules, but only to their fluctuating component, the thermal component.

6. Conclusion

Based on the idea of the standard Gaussian distribution, a standard Maxwell-Boltzmann

distribution () is defined with the purpose of generalizing the properties of the Maxwell-
Boltzmann distribution, and facilitating the analysis of functions involving Maxwell-Boltzmann
random variables, in particular, the speed of molecules. The most important property of such
dimensionless standard Maxwell-Boltzmann distribution is that its expected value is 1. Random
numbers following a standard Maxwell-Boltzmann distribution can be easily generated simply
by using an empirical algebraic expression as a function of a uniform random number. By
considering the experimental speeds of potassium gas in a vacuum oven, it was possible to
exemplify the use of the standard Maxwell-Boltzmann distribution for describing the results. It
was also possible to show that the temperature of a system is a function only of the fluctuating
component of the average molecular kinetic energy, and that the macroscopic kinetic energy
has no effect on temperature.

Acknowledgments

The author gratefully acknowledges the helpful discussions with Prof. Jaime Aguirre
(Universidad Nacional de Colombia).

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 Standard Maxwell-Boltzmann distribution:
Definition and Properties
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

This research did not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.

References
[1] Miller, R. C., & Kusch, P. (1955). Velocity distributions in potassium and thallium atomic
beams. Physical Review, 99(4), 1314.

[2] Maxwell, J. C. (1860). Illustrations of the dynamical theory of gases. - Part I. On the motions
and collisions of perfectly elastic spheres. The London, Edinburgh, and Dublin Philosophical
Magazine and Journal of Science, 19(124), 19-32.

[3] Boltzmann, L. (1872). Weitere Studien ber das Wrmegleichgewicht unter Gasmoleklen.
K. Acad. Wiss.(Wein) Sitzb., II Abt, 66.

[4] Simon, D. A., & McQuarrie, J. D. (1997). Physical Chemistry: A Molecular Approach.
University Science Books.

[5] Devore, J. L. (2015). Probability and Statistics for Engineering and the Sciences. Cengage
Learning.

[6] H. Hernandez (2016). Modelling the effect of fluctuation in nonlinear systems using variance
algebra - Application to light scattering of ideal gases, ForsChem Research Reports, 2016-1, doi:
10.13140/RG.2.2.36501.52969.

[7] Halliday, D., Walker, J., & Resnick, R. (2010). Fundamentals of Physics, Chapter 21. John Wiley
& Sons.

[8] Lasdon, L. S., Waren, A. D., Jain, A., & Ratner, M. (1978). Design and testing of a generalized
reduced gradient code for nonlinear programming. ACM Transactions on Mathematical
Software (TOMS), 4(1), 34-50.

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