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Hugo Hernandez
ForsChem Research, 050030 Medellin, Colombia
hugo.hernandez@forschem.org
doi: 10.13140/RG.2.2.32880.00005
Abstract
In this report, the probability distribution of molecular kinetic energy and molecular
temperature for systems with known velocity probability distributions is presented. Also,
conditional probabilities are determined when one or more velocity components of the
molecular are known. Particularly, the mathematical expressions obtained for Maxwell-
Boltzmann systems (zero-mean normal distribution of molecular velocity components) are
included. When all velocity components are random, the thermal kinetic energy distribution
corresponds to a Chi-squared distribution with 3 degrees of freedom.
Keywords
1. Introduction
By definition, kinetic energy (or the energy of motion [1]) is a function of the motion and mass
of a body. Particularly, the translational kinetic energy (or kinetic energy of rigid bodies) is
given by:
(1.1)
where is the mass of the body and is the vector velocity of the body. In a three-dimensional
space, such vector velocity is the result of the different velocity components in each
orthogonal direction ( , , ), as follows:
(1.2)
where represents the velocity component (magnitude) in the -th direction, and is the unit
vector in the -th direction. Since all unit vectors are orthogonal ( , and ),
the product is:
(1.3)
If the mass and all components of the velocity of a body are known, then the kinetic energy of
the body is simply determined from Eq. (1.1) and (1.3).
Now, if the velocity components of the body are unknown, but they can be described as
random variables, then the kinetic energy also becomes as random variable. Furthermore, in a
system of N different moving bodies with random velocities, the individual kinetic energy of the
bodies will be determined by the particular probability distribution of the velocity components
of the bodies. That is the case, for example, of molecular systems.
The purpose of this report is presenting a general procedure for determining the probability
density function and cumulative probability function for the molecular translational kinetic
energy of molecular systems. Furthermore, some expressions will also be obtained for
conditional probabilities, when one or more velocity components of the molecules are known
with certainty. Those expressions are valid considering both absolute and relative velocities.
When only relative molecular velocities are used for the calculation of the kinetic energy, the
concept of thermal kinetic energy emerges.[2] Since the thermal kinetic energy of molecules is
related to their molecular temperature,[3] the distribution of molecular temperatures will also
be discussed.
As a particular illustrative case, a system with a zero-mean normal distribution of all molecular
components, also known as Maxwell-Boltzmann distribution, will be considered. It will then be
possible to determine the distribution of molecular thermal kinetic energies and molecular
temperatures in the system.
2. General Expressions
The kinetic energy of a molecule of mass moving with velocity in a certain system is
given by:
( )
(2.1)
where , and represents the magnitude of the velocity in each Cartesian direction.
If the distribution of velocities in each direction for all molecules in the system is known, then it
is possible to determine the probability distribution of the molecular kinetic energy of the
system. Thus, using the change of variable theorem [4] the probability density function of the
molecular kinetic energy ( ) will be:
( ) ∫ ∫ ( ) ( )
[ ( √ ) ( √ )] | |
( ) ( )
∫ ∫ ( √ )
√
(2.2)
where is any realization of the molecular kinetic energy, and , and represent the
probability density functions of the molecular velocity components. However, Eq. (2.2) is valid
as long as
(2.3)
√ √ ( ) ( )
( ) ∫ ∫ ( √ )
√ √
√
(2.4)
Eq. (2.4) describes the general expression of the probability density function for the molecular
kinetic energy of a system. Such equation does not require any knowledge of the molecular
velocity components, but requires knowledge of their probability distribution.
The cumulative probability distribution of the molecular kinetic energy will then be given by:
( ) ( ) ∫ ( )
√ √ ( ) ( )
∫ ∫ ∫
√ √
√
( √ )
(2.5)
Please notice that the cumulative integral starts at , since negative kinetic energy values
are not possible. ( ) also represents the fraction of molecules whose kinetic energy is lower
or equal than . On the other hand, the fraction of molecules with kinetic energy greater than
is:
( ) ( )
(2.6)
If one of the velocity components of the molecules is known, let us say for example that is
known, then the conditional probability density function of the molecular kinetic energy is:
√ ( )
( | ) ∫ ( √ )
√
√
(2.7)
( | ) ( | )
√ ( )
∫ ∫ ( √ )
√
√
(2.8)
If two velocity components are known, let us say and , then the conditional probability
density function of the molecular kinetic energy becomes:
( | ) ( √ ) ( )
√
(2.9)
In this case, the conditional cumulative probability of the molecular energy is:
( √ )
( | ) ( ( ) | ) ∫
√
(2.10)
( | ) ( ( ))
(2.11)
( | ) ( ( ))
(2.12)
(2.13)
where and are the mass and relative velocity of the particular molecule considered, and
represents Boltzmann’s constant.
If the velocities considered in Eq. (2.1) through (2.12) are relative to the system, then the
molecular kinetic energy term corresponds to the thermal kinetic of each molecule. Thus, Eq.
(2.13) can be expressed as:
(2.14)
It is then possible relating the probability density function of the molecular temperature to the
probability density function of the thermal kinetic energy, using the following general
relationship (from the change of variable theorem [4]):
( ) ( )
(2.15)
Thus, the probability density function of the molecular temperature as a function of the relative
molecular velocity components becomes:
√ √ ( ) ( )
( ) ∫ ∫
√ √
√
( √ )
(2.16)
and the corresponding cumulative probability function is:
√ √ ( ) ( )
( ) ∫ ∫ ∫
√ √
√
( √ )
(2.17)
Equivalent expressions can also be found for the conditional probabilities if any relative
molecular velocity component is known.
(3.1)
where is the temperature of the system, and is the mass of the molecules. Such standard
deviation in the velocity component is assumed identical for all directions, since there is no
preferred direction.
Thus, the probability density function of the relative molecular velocity component in direction
will be:
( ) √
(3.2)
Then, the probability density function of the thermal molecular kinetic energy ( ) will be
(from Eq. 2.4):
√ √
( ) ( ) ∫ ∫
√ √
√
√
( ) ∫ [ ( ) ( )]
√
( ) √ √
( )
(3.3)
and the cumulative probability function of the thermal kinetic energy is (from Eq. 2.5 and 3.3):
( ) ∫ √ (√ ) √
( )
(3.4)
Now, the expected value of the thermal kinetic energy for a Maxwell-Boltzmann system will be:
( ) ∫ √
( )
√ ( ) ( )
√
( ) (√ )
( ) √
[ ]
(3.5)
which is consistent with the definition of the temperature of the system.[3]
On the other hand, the variance of the thermal kinetic energy of the molecules in a Maxwell-
Boltzmann system is:
( ) ( ) ( ) ( ) ( ) ( )
(3.6)
This result is consistent with the properties of the Maxwell-Boltzmann distribution [5].
Thus, the standard deviation of the thermal kinetic energy of the molecules is:
( ) √
(3.7)
The probability density function given in Eq. (3.3) can be transformed into a Type II standard
random probability density function [6] using Eq. (3.5), as follows:
( ) √
(3.8)
where
( )
(3.9)
The behavior of the probability density function described by Eq. (3.8) is presented graphically
in Figure 1. It is possible to observe that the shape of this standard random variable resembles
Figure 1. Probability density function for the Type II standard thermal kinetic energy of a
Maxwell-Boltzmann molecular system (Eq. 3.8)
The cumulative probability function for the standard thermal kinetic energy of the Maxwell-
Boltzmann system will be given by (from Eq. 3.4 and 3.9):
( ) (√ ) √
(3.10)
Eq. (3.10) is illustrated in Figure 2. It can be found that the median of the distribution is
, or .
On the other hand, the conditional probability density functions for the thermal kinetic energy
of Maxwell-Boltzmann molecular systems (when some velocity components are known) are
given by:
( | )
(3.11)
( | ) ( )
√ √ ( )
(3.12)
( | ) ( ( ))
(3.13)
Figure 2. Cumulative probability function for the Type II standard thermal kinetic energy of a
Maxwell-Boltzmann molecular system (Eq. 3.10)
( | )
(3.14)
( )
( | ) (√ ) ( )
(3.15)
( | ) ( ( ))
(3.16)
( | )
(3.17)
( | ) ( ) ( )
(3.18)
( | ) ( )
(3.19)
Finally, the molecular temperature distribution of Maxwell-Boltzmann systems will be given by:
( ) √
(3.20)
( ) (√ ) √
(3.21)
Please notice that ( ) , and therefore the Type II standard molecular temperature defined
as:
(3.22)
also corresponds to the Type II standard thermal kinetic energy random variable (Eq. 3.8 to
3.10).
Acknowledgments
The author gratefully acknowledges Prof. Jaime Aguirre (Universidad Nacional de Colombia)
for helpful discussions on this topic.
This research did not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.
References
[1] Nowikow, I., Heimbecker, B. and Bosomworth, D. (2001). Physics: Concepts and
Connections. Irwin Publishing Limited.
[3] Hernandez, H. (2017). Analysis of Temperature fluctuations in ideal gases - From the
macroscopic to the molecular scale. ForsChem Research Reports 2017-3. doi:
10.13140/RG.2.2.19208.83203.
[7] Walpole, R. E., Myers, R. H., Myers, S. L., & Ye, K. (2012). Probability & Statistics for
Engineers & Scientists. 9th Ed. Prentice Hall.