Molecular Free Path Statistical Distribution of Multicomponent Systems

2017-6
Molecular Free Path Statistical Distribution of Multicomponent Systems
Hugo Hernandez
ForsChem Research, 050030 Medellin, Colombia
hugo.hernandez@forschem.org
doi: 10.13140/RG.2.2.15605.58088
Abstract
In this work, a method for the calculation of the molecular free path distribution in
multicomponent systems at thermal equilibrium (following Maxwell-Boltzmanns molecular
speed distribution) is presented. The free path is a relevant characteristic of molecular systems,
which determines different important kinetic and transport coefficients. By considering the
complete distribution of molecular speeds, a slightly different result is obtained compared to
the conventional results of Clausius and Maxwell for single-component systems. A Monte Carlo
simulation is used to validate the theoretical results obtained for a single-component (Xenon
gas) and for a binary system (Xenon-Argon mixture in a 2:1 molar ratio), yielding satisfactory
results with a 95% confidence.
Keywords
Kinetic gas theory, Maxwell-Boltzmann distribution, Molecular collision, Molecular free path,
Molecular speed distribution, Monte Carlo Simulation, Multicomponent Systems
1. Introduction
Molecular collision kinetics has been a widely explored topic, especially in gaseous systems.
One of the most important magnitudes for understanding molecular collisions is the distance
that a single molecule travels before colliding with other molecules, which is commonly known
as the free path. Probably the first calculation of the mean free path travelled by ideal gas
molecules was presented by Rudolf Clausius in 1859.[1] He considered that each molecule has
an effective distance of action ( ), such that any two molecules with a distance between
their centers of mass within such distance of action will collide. If ideal gases are considered,
such distance corresponds to the molecular diameter.
08/05/2017 ForsChem Research Reports 2017-6 (1 / 26)

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Molecular Free Path Statistical Distribution
of Multicomponent Systems
Hugo Hernandez
ForsChem Research
Clausius first assumed that all molecules are randomly placed in space and at rest except for
one molecule. The molecules at rest that would collide with the moving molecule can be
obtained by observing the linear path of motion (depicted in Figure 1). By this analysis, he
obtained the following probability distribution function for the distance to collision with
molecules at rest:
( ) (1.1)
Thus, he found that the mean free path considering all other molecules at rest was:
( )
(1.2)
Later, he considers that if all other molecules are in motion at the same speed that the
reference molecule, then the mean distance travelled would be reduced by a factor of .
Thus, the mean free path considering all molecules in motion at the same speed would be:
(1.3)
Figure 1. Linear path followed by a single moving molecule. All molecules with center of mass
within the cylinder are considered potentially colliding molecules.
Clausius himself warns that as a result of the assumptions made, it is possible that the
calculation is not exact, but at least it provides a suitable order of magnitude of the free path.
During the following year, James Clerk Maxwell considered the same problem and arrived to a
slightly different result.[2] Maxwell follows the same line of reasoning of Clausius, but
considering that all molecules are at rest because the motion of the molecule under analysis is
relative to the motion of all other molecules. He then obtained an expression for the mean free
path as a function of the actual ( ) and relative ( ) speeds of the molecule:

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(1.4)
Then, assuming that all molecules have the same average speed of the molecule under
consideration, he finds the following mean free path under motion:

(1.5)
Maxwells result is obtained by considering that all molecules follow the Maxwell-Boltzmanns
speed distribution.
These results obtained by Clausius and Maxwell have been an important contribution to the
kinetic theory of gases.[3-6]
The purpose of this work is to present and explain in detail an alternative derivation of the
molecular free path distribution, considering that all molecules in the system are randomly
placed in space and moving in random directions following the Maxwell-Boltzmann distribution
of speeds (i.e. the system is at thermal equilibrium), and that the molecules in the system may
have different sizes, masses and average speeds with respect to a certain central reference
molecule (i.e. a multicomponent system).
2. Description of the System
Let us consider a certain volume of any arbitrary shape, containing in total molecules, all
assumed to be hard spherical particles. In the system, there are different types of molecules,
with molecules of type , such that:
(2.1)
Molecules of type have a radius and mass , moving in random directions and at speeds
following the Maxwell-Boltzmann distribution. Considering that the system is at thermal
equilibrium, the probability density distribution of relative molecular speeds ( ) in the system
is given by:[7]

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( ) (2.2)
( )
where is Boltzmanns constant and is the equilibrium temperature

of the system.
In Eq. (2.2), the relative molecular speed ( ) corresponds to the magnitude of the velocity of
each molecule ( ) relative to the average molecular velocity of the system. Thus, the
relative molecular speed of any arbitrary molecule is:
(2.3)
Let us now consider that one of the molecules in the system (molecule ) is selected as a
reference molecule. Thus, if the motion of all other molecules is described relative to the
motion of such reference molecule, then the position of any arbitrary molecule relative to
molecule ( ) will be:
(2.4)
and the velocity of molecule relative to molecule ( ) will be:
(2.5)
Eq. (2.5) can be rearranged as:
(2.6)
and therefore, the average velocity of the system can be expressed as:
( ) ( ) ( )

(2.7)
From Eq. (2.3), (2.6) and (2.7) it follows that:
(2.8)
That is, by changing the frame of reference to any arbitrary molecule , even though the values
of the molecular speeds relative to the reference molecule ( ) change by changing the
reference molecule, the value of molecular speed relative to the average velocity of the
system( ) remains unchanged, as well as its probability density distribution (Eq. 2.2).

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Under these conditions, the reference molecule will seem static at the origin of coordinates,
whereas all other molecules move at molecular speeds following the generalized Maxwell-
Boltzmann distribution presented in Eq. (2.2).
All molecules are randomly located in the volume, yielding an overall number density
with a uniform probability distribution. Therefore, a spherical region of radius centered
at the reference molecule will contain on average molecules (including the reference
molecule), where is the radius of action of the reference molecule. A molecule is counted
only if its center lies inside such volume.
A spherical shell of thickness , and radius centered at the reference molecule will contain
on average molecules (with centers inside that shell). Thus, the average number of
molecules lying within that thin shell ( ) of radius will be:
( ) (2.9)
Considering that the reference molecule is at the center of a spherical system with volume ,
the distance between the center of a molecule of type in the system and the center of the
reference molecule can be described by the following probability density function:
( )
( )
)( ( ) ) ( ( ) )
( ) ( )
(
(2.10)
( ) indicates the number of molecules of type discounting molecule . The lower limit for
is given by the distance between their centers at the moment of a collision (the sum of the
radius of action of a molecule of type , , and the radius of action of the reference molecule),
whereas the higher limit is given by the radius of an sphere of volume . This probability is
independent of the type of molecule considered.
Alternative probability density functions can be obtained for other system geometries and
reference molecule positions, although it can be complex in certain cases. However, given that
we are interested in the neighborhood of the reference molecule, the actual shape of the
macroscopic system becomes irrelevant.
The expected distance between the reference molecule and a molecule of type in the system
is:

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( )
( ( ) ) ( ( ) )
( ) (( ) ( ) )
( )
( )
( ( ) ) ( ( ) )
(2.11)
Given that for a macroscopic system, , then the expected distance becomes:
( ) (2.12)
This result, again, is independent of the type of molecule considered (under the macroscopic
assumption), and is clearly related with the factor considered by Clausius.[1]
3. Number of possible collisions
Let us now consider that we want to know if a molecule might collide with the reference
molecule at some time in the future. For that purpose, let us assume that at a certain instant,
another molecule of type is located at a the relative position . Assuming that the
probability of the relative motion of the molecule is the same for any direction, then, the
probability of collision with the reference molecule, given that no other molecule is in the path,
will be given by:
( )
( )
(3.1)
where the numerator corresponds to the area of a spherical cap [8] formed by all possible
relative positions of molecule at an initial intermolecular distance that will
eventually result in a collision with a molecule of type , and the denominator is the area of the
sphere of all possible relative positions of molecule at an initial intermolecular distance
from the molecule of type (see Figure 2). is the half angle of the spherical cone formed
between the center and the cap, and is given by (see Figure 3):
( ) (3.2)

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Figure 2. Geometrical interpretation of the probability of collision between reference molecule

a and a molecule of type j.
Figure 3. Geometrical interpretation of the half angle ( ) of the spherical cone formed
between the center of a molecule of type j and the spherical cap of possible collisions with
molecule a
Now, given that:

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( ) ( ) ( ( )) ( )
(3.3)
Then, from Eq. (3.1) and (3.3):
( ( ) )
( ) ( ) (3.4)
which is the probability that a molecule of type located at a distance with respect to
molecule , will eventually collide with if no other molecule is in the same way.
Given that the total number of molecules of type at a distance around molecule is (from
Eq. 2.9):
( ) (3.5)
Then, the number of molecules of type at a distance that will eventually collide with
molecule is:
( ) ( ) ( ) (3.6)
where , is the distance at which collision between molecules and (of type )
takes place. Eq. (3.6) indicates that the number of potential colliding molecules increases
linearly with the distance , independently of the direction. This result confirms the
assumption initially proposed by Clausius [1] that the probability of a certain molecule hitting
another in a thin layer along its linear path is constant.
4. The Relative and Actual Free Path Distributions
Because the increase in the discrete number of potential colliding molecules of type with
respect to distance is a constant, it is possible to assume that the number of colliding
molecules of type is a random Poisson variable, and consequently, the distance travelled to
collision with molecules of type ( ) behaves as an exponential distribution with spatial rate
, and with the following probability density function:
( )
(4.1)

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corresponds to a relative free path travelled by a molecule of type until it collides with the
reference molecule. It is a relative free path because it has been determined relative to the
central molecule (see Figure 4) and not to the system.
Figure 4. Geometrical interpretation of the relative free path ( ) travelled by a molecule of

type relative to molecule until collision. ( ) is the actual free path travelled by the
molecule of type until collision with molecule , and ( ) is the actual free path travelled by
molecule until collision with the molecule of type .
Thus, the expected value for the relative free path to collision of molecules of type with the
central molecule will be:
( ) ( )
( ) ( )
( | )
( ) ( )
( ) | ( )( )
(4.2)
Please notice that Eq. (4.2) is equivalent to the result obtained by Clausius assuming all other
molecules at rest (Eq. 1.2). That is not a coincidence, but a consequence of the fact that the
relative free path is independent of the molecular motion, that is, independent of the particular
molecular speed distribution.
On the other hand, the variance of the relative free path to collision with molecules of type
can be determined by:

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( ) ( ) ( ( )) (4.3)
where
( ) ( )
( ) ( )
( | )
( )
( )
(4.4)
Therefore:
( ) ( ) ( )
( )
(4.5)
Assuming that the collision between a molecule of type and the central molecule takes
place at a certain time after the initial state, and considering constant velocities during the
paths to collision, then

(4.6)
where is the magnitude of the velocity (speed) of molecules of type relative to

molecule .
Assuming that the velocity of each particle follows the Maxwell-Boltzmann distribution,
then[9]
(4.7)
where is the mean speed of molecule , is the mean speed of molecules of type ,
and are random numbers following a normalized Maxwell-Boltzmann distribution, and
and are random unit direction vectors:
(4.8)

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such that:
(4.9)
Thus,
( ) ( )
( ) ( ) ( )
( )
(4.10)
The expected value of is:
( ) ( ( ) ) (( ) )
[ ( ) ( ) ( ) ( ) ( ) ( )
( ) ( )] [ ] ( )
(4.11)
because for a random number obtained from a normalized Maxwell-Boltzmann distribution:[9]
( ) (4.12)
( ) (4.13)
and for a random unit direction vector in one coordinate axis:
( ) (4.14)
( ) (4.15)
The last result is obtained from the fact that ( ) , and ( ) is the same for each of the
three coordinate axes.
On the other hand, for an arbitrary Maxwell-Boltzmann distribution ,

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( ) ( ) (4.16)
( ) ( ) (4.17)
Therefore, it is possible to conclude that
( ) ( ) (4.18)
Or equivalently,
( ) ( ) (4.19)
Thus,
( ) ( )
(4.20)
The relative molecular speed can then be expressed as a function of the standard
Maxwell-Boltzmann distribution ( ) as follows:

(4.21)
Furthermore, given that for the Maxwell-Boltzmann distribution the average molecular speeds
can be expressed as and , then Eq. (4.21) becomes:
( )
(4.22)
where is the reduced mass of the two molecules involved in the collision.
Returning to the collision time, since it is the same independently of the frame of reference
(and recalling Figure 4), then:
( ) ( )

(4.23)

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where ( ) is the actual free path travelled by molecule before colliding with a molecule of
type , and ( ) is the actual free path travelled by a molecule of type before colliding with
the reference molecule. Please notice that the velocities ( and ) are also relative
velocities, but referred to the system under consideration ( ). Therefore, the
actual free paths are also referred to the system.
From Eq. (4.23):

( ) (4.24)

( ) (4.25)

Eq. (4.24) and (4.25) are consistent with Maxwells equation (Eq. 1.4). Afterwards, Maxwell
( )
assumed in his derivation that ( ) , which is not true for the molecular speed
( )
distribution considered, as will be shown now.
Expressing the actual free paths (Eq. 4.24 and 4.25) in terms of the standard Maxwell-
Boltzmann distribution results in:

( )

(4.26)
( )
(4.27)
The expected value of the actual free path of the reference molecule for the collision with
molecules of type is:
( ( )) ( ) ( ) ( ) ( )
( )
(4.28)

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The expected value of the reciprocal of the standard Maxwell-Boltzmann distribution can be
obtained from its probability density function:[9]
( )
(4.29)
where is any particular realization of . Thus,
( ) ( ) ( ) |
(4.30)
which means that ( ) ( ) ( )

. Replacing Eq. (4.30) in Eq. (4.28):
( ( ))
(4.31)
Similarly,
( ( ))
(4.32)
The variance of the actual free paths would be:
( ( )) ( ) [ (( ) ) ( ( )) ]
[ ( ) (( ) ) ( ) ( ) ]
[ (( ) ) ( ) ]
( )
[ (( ) ) ] [ ( ) ]
( ) ( )
( )
( )
(4.33)

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because:
( ) ( )( )
(4.34)
and the last result is obtained given that: [8]
Similarly, the variance of ( ) is:
( )
( ( ))
( )
(4.35)
Now, the rate of collision (with respect to distance) considering all types of molecules present
in the system will be:
(4.36)
with the following probability density function for the overall relative free path of molecule
( ):

( )
(4.37)
For this distribution, the expected value and variance of the overall free path are:
( )

(4.38)
( ) ( )

(4.39)
For pure (single-component) systems, or systems where the molecular sizes are similar, the
mean overall relative free path and its variance become:

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( )
(4.40)
( ) ( )
(4.41)
where is the overall molecular number density.
On the other hand, given that the overall actual free path of the reference molecule ( ) can
be expressed as:

( )

(4.42)
where the subscript indicates overall system.
Since the overall mass of the multicomponent system is given by:

(4.43)
Then, the mean overall actual free path is:
( ) ( ) ( ) ( )

( ) ( )
( )
( )

( )

( ) ( )

(4.44)

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The variance of the actual free path of the reference molecule is:
( ) ( ) ( ( ))
( ) ( ) ( )
( )

( ) ( ( ) )

( ) ( ( ) )

( ) ( ( ) )

( )
( ) ( ( ) )

(4.45)
For a single-component system:

( ) ( )
(4.46)
( )
( ) ( )( ( )) ( ( ))
( )
(4.47)
With a coefficient of variation:
( )
(4.48)
Even though the results obtained here differ by a constant to the results obtained by Clausius
(Eq. 1.3) and Maxwell (Eq. 1.5), all are in the same of magnitude. The differences can be
explained by the particular assumptions considered, and by the fact that they did not take into
account the effect of the full probability distribution of the molecular speeds.

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5. Monte Carlo Simulation
In order to validate the current approach for the molecular free path calculation, a Monte Carlo
(MC) simulation was set up, considering two examples: A single-component case (Xenon gas),
and a binary mixture (Xenon-Argon gas in a molar ratio 2:1), both at standard conditions (273.15
K, 101.325 kPa).
5.1. Single-component system: Xenon
The algorithm used for the MC simulation is described in the following procedure:
1. Definition of simulation and system parameters:

Number of realizations:
System Temperature:
Mass density:
Molecular weight:
Molecular radius of action (van der Waals radius):
Number of molecules in the simulation:
Avogadros number:
Boltzmanns constant:
2. Initial calculations:
Mass of a molecule:
Gas number density:
System volume:
System radius:
Collision distance:
Average molecular speed:

Relative position of reference molecule ( ):
Relative velocity of reference molecule ( ):
Actual velocity of reference molecule:
( )
where ( ) is a standard Maxwell-Boltzmann
random number,[9] is a random unit direction with Cartesian
components , and are uniform
( ) ( ) ( )
random numbers between 0 and 1.

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3. Molecules setup (for to ):

Relative molecular positions:
(( ) ( ) ( ) )
Relative molecular velocities:
Relative molecular speeds:
4. Determination of potentially colliding molecules (for to ):

Time of closest approach to reference molecule:
Closest distance to reference molecule in the path:
If and then molecule might collide with the reference molecule.

Potential collision time:
5. Free path determination of a single realization

Identify first collision molecule, such that: ( ), s.t. and
Relative free path:

Actual free path:
6. Repeat steps 2 to 5 for all realizations
The histograms of frequencies for the relative and actual free paths for a single component
(Xenon) are presented in Figure 5 and Figure 6, respectively.
The mean relative free path obtained for Xenon at standard conditions, from the Monte Carlo
(MC) simulation is: ( ) , with 95% confidence;
whereas the theoretical value obtained from Eq. (4.40) is: ( ) .
Therefore, both values are statistically the same with a 95% confidence.

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Figure 5. Histogram of relative frequencies for the relative collision free path ( ) of Xenon gas
at standard conditions (273.15 K, 101.325 kPa)
Figure 6. Histogram of relative frequencies for the actual collision free path ( ) of Xenon gas
at standard conditions (273.15 K, 101.325 kPa)
On the other hand, the actual free path of Xenon at standard conditions, obtained by MC
simulation is: ( ) , with 95% confidence; whereas
the theoretical value obtained from Eq. (4.46) is: ( ) .

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For this system, Clausiuss and Maxwells estimates would be: ( ) ,

and ( ) , respectively. Even though all estimates of the actual free
path are within the 95% confidence interval, the calculation made with Eq. (4.46) was closer to
the mean value obtained by simulation.
5.2. Binary system: Xenon-Argon in molar ratio 2:1
In this case, the algorithm used for the MC simulation was modified according to the following
procedure:
1. Definition of simulation and system parameters:

Number of realizations:
System Temperature:
Mass density of component 1:
Mass density of component 2:
Molecular weight of component 1:
Molecular weight of component 2:
Molecular radius of action (van der Waals radius) of component 1:
Molecular radius of action (van der Waals radius) of component 2:
Number of molecules of component 1 in the simulation:
Number of molecules of component 2 in the simulation:
Avogadros number:
Boltzmanns constant:
2. Initial calculations:
Mass of a molecule of component 1:
Mass of a molecule of component 2:

Gas number density of pure component 1:
Gas number density of pure component 2:
System volume:
System radius:
Gas number density of component 1 in mixture:

Gas number density of component 2 in mixture:
Collision distance between two molecules of component 1:

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Collision distance between the reference molecule (component 1) and a molecule

of component 2:
Average molecular speed of component 1:
Average molecular speed of component 2:

Relative position of reference molecule ( ):
Relative velocity of reference molecule ( ):
Actual velocity of reference molecule:
( )
where ( ) is a standard Maxwell-Boltzmann
random number,[9] is a random unit direction with Cartesian
components , and are uniform

( ) ( ) ( )
random numbers between 0 and 1.
3. Molecules setup for component 1 (for to ):

(( ) ( ) ( ) )
4. Molecules setup for component 2 (for to ):

(( ) ( ) ( ) )
5. Determination of potentially colliding molecules (for to ):

Time of closest approach to reference molecule:
Closest distance to reference molecule in the path:

If and then molecule might collide with the reference molecule,
where {

Potential collision time:

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6. Free path determination of a single realization

Identify first collision molecule, such that: ( ), s.t. and
Relative free path:

Actual free path:
7. Repeat steps 2 to 6 for all realizations
Considering a Xenon molecule as the reference molecule, 34.1% of the collisions took place with
an Argon molecule and 65.9% with another Xenon molecule. That indicates a ratio Xenon:Argon
of 1.93:1, consistent with the composition of the system. The histograms of frequencies for the
relative and actual free paths for the collision of a Xenon molecule in a binary mixture of Xenon
and Argon in molar ratio 2:1, are presented in Figure 7 and Figure 8, respectively.
Figure 7. Histogram of relative frequencies for the relative collision free path ( ) of Xenon in a
binary mixture of Xenon and Argon (molar ratio 2:1) at standard conditions (273.15 K, 101.325
kPa)
The mean relative free path obtained for a molecule of Xenon in a binary mixture of Xenon and
Argon (molar ratio 2:1) at standard conditions, from the Monte Carlo (MC) simulation is:
( ) , with 95% confidence; whereas the theoretical
value obtained from Eq. (4.38) is: ( ) . Again, no significant
difference was observed.

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The actual free path obtained for a molecule of Xenon in the binary mixture at standard
conditions, obtained by MC simulation is: ( ) , with
95% confidence; whereas the theoretical value for the actual free path of Xenon obtained from
Eq. (4.44) is: ( ) .
As a conclusion, all results obtained theoretically for both the single-component and the binary
system are within the experimental simulation error with a 95% confidence. Larger scale
simulations are required in order to achieve smaller errors and to test the differences with
higher accuracy.
Figure 8. Histogram of relative frequencies for the actual collision free path ( ) of Xenon in a
binary mixture of Xenon and Argon (molar ratio 2:1) at standard conditions (273.15 K, 101.325
kPa)
It is also interesting noticing that the addition of Argon (a lighter component) to the system
reduced the actual free path of Xenon, as a result of the higher speed of Argon molecules (in
thermal equilibrium with Xenon).
6. Conclusion
Understanding the molecular behavior is a key for predicting several physical and chemical
phenomena of materials. Although the behavior of molecules is, for us, completely random,
average properties can be satisfactorily determined as a result of the large numbers law. In this
report, one of the most important concepts in molecular kinetics was analyzed from an
alternative perspective, considering the mathematical properties of the standard Maxwell-

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Boltzmann distribution. Furthermore, the equations were obtained for the more general case
of multicomponent systems. The results obtained for pure components differed to the
currently accepted calculations only by a constant factor. A Monte Carlo simulation was
performed for testing the validity of the equations obtained for a pure system (Xenon gas) and
a binary mixture (Xenon-Argon in a molar ratio 2:1) under standard conditions. The simulations
confirmed that the results obtained theoretically in this work were valid with a 95% confidence.
Acknowledgments
The author gratefully acknowledges the helpful discussions with Prof. Dr. Silvia Ochoa
(Universidad de Antioquia) and Prof. Jaime Aguirre (Universidad Nacional de Colombia).
This research did not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.
References
[1] Clausius, R. V. (1859). X. On the mean length of the paths described by the separate
molecules of gaseous bodies on the occurrence of molecular motion: together with some other
remarks upon the mechanical theory of heat. The London, Edinburgh, and Dublin Philosophical
Magazine and Journal of Science, 17(112), 81-91.
[2] Maxwell, J. C. (1860). V. 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. (1995). Lectures on gas theory. New York: Dover Publications. Translated by
Stephen G. Brusch from the original works published in German between 1896 and 1898
Vorlesungen ber Gastheorie.
[4] Hinshelwood, C. N. (1929). Kinetics of chemical change in gaseous systems. Oxford:

Clarendon Press.
[5] Kennard, E. H. (1938). Kinetic theory of gases. New York: McGraw-Hill Book Co.
[6] Simon, D. A., & McQuarrie, J. D. (1997). Physical Chemistry: A Molecular Approach.
Sausalito: University Science Book.

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Hugo Hernandez
ForsChem Research
[7] Hernandez, H. (2017). On the generalized validity of the Maxwell-Boltzmann distribution and
the zeroth Law of Thermodynamics. ForsChem Research Reports 2017-4. doi:
10.13140/RG.2.2.26937.16480
[8] Polyanin, A. D., & Manzhirov, A. V. (2007). Handbook of Mathematics for Engineers and
Scientists. Boca Raton: Chapman & Hall/CRC.
[9] Hernandez, H. (2017). Standard Maxwell-Boltzmann distribution: Definition and properties.

ForsChem Research Reports 2017-2. doi: 10.13140/RG.2.2.29888.74244.

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Molecular Free Path Statistical Distribution of Multicomponent Systems

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2. Description of the System

08/05/2017 ForsChem Research Reports 2017-6 (3 / 26)

where is Boltzmanns constant and is the equilibrium temperature

and the velocity of molecule relative to molecule ( ) will be:

Eq. (2.5) can be rearranged as:

From Eq. (2.3), (2.6) and (2.7) it follows that:

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3. Number of possible collisions

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Figure 2. Geometrical interpretation of the probability of collision between reference molecule

Now, given that:

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Then, from Eq. (3.1) and (3.3):

4. The Relative and Actual Free Path Distributions

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Figure 4. Geometrical interpretation of the relative free path ( ) travelled by a molecule of

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where is the magnitude of the velocity (speed) of molecules of type relative to

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The expected value of is:

because for a random number obtained from a normalized Maxwell-Boltzmann distribution:[9]

and for a random unit direction vector in one coordinate axis:

On the other hand, for an arbitrary Maxwell-Boltzmann distribution ,

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Therefore, it is possible to conclude that

can be expressed as and , then Eq. (4.21) becomes:

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From Eq. (4.23):

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where is any particular realization of . Thus,

which means that ( ) ( ) ( )

The variance of the actual free paths would be:

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and the last result is obtained given that: [8]

Similarly, the variance of ( ) is:

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Since the overall mass of the multicomponent system is given by:

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For a single-component system:

With a coefficient of variation:

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5. Monte Carlo Simulation

5.1. Single-component system: Xenon

1. Definition of simulation and system parameters:

Average molecular speed:

random numbers between 0 and 1.

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3. Molecules setup (for to ):

4. Determination of potentially colliding molecules (for to ):

Closest distance to reference molecule in the path:

If and then molecule might collide with the reference molecule.

5. Free path determination of a single realization

Relative free path:

6. Repeat steps 2 to 5 for all realizations

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For this system, Clausiuss and Maxwells estimates would be: ( ) ,

5.2. Binary system: Xenon-Argon in molar ratio 2:1

1. Definition of simulation and system parameters: