2019-07

On the Relationship between Molecular and Macroscopic Diffusion in

Ideal Gases

Hugo Hernandez
ForsChem Research, 050030 Medellin, Colombia
hugo.hernandez@forschem.org

doi: 10.13140/RG.2.2.30954.98242

Abstract

In this report, two different models of multicomponent diffusion in ideal gases are presented.
The first model, introduced in a previous report, is derived from the probabilistic observation of
individual molecules colliding with a specific molecular neighborhood. The second model is
based on the macroscopic motion of a large number of molecules in one direction (molecular
flux). Since both diffusion models are consistent with Fick’s laws of diffusion, it is proposed
that the macroscopic diffusion coefficient is proportional to the molecular diffusion coefficient.
It is also assumed that during the self-diffusion of a pure ideal gas, the symmetry of the
collisions and the indistinguishability of individual molecules result in the equivalence between
molecular and macroscopic diffusion coefficients. For multicomponent mixtures of ideal gases
with different masses and sizes, the specific composition of the neighborhood influences both
the molecular and macroscopic diffusion coefficients in different ways. It is also shown that
each species has its own diffusion coefficients (macroscopic and molecular), which are a
function of the composition of the mixture and the environmental conditions (e.g. pressure
and temperature). Overall macroscopic diffusion coefficients of multicomponent systems can
be obtained as a molar fraction weighted-average of the macroscopic diffusion coefficients for
each species in the mixture. Significant differences with respect to conventional expressions
used to estimate macroscopic diffusion coefficients of pure ideal gases and mixtures are found.
However, some experimental results seem to be consistent with the proposed model of
diffusion.

Keywords

Diffusion coefficients, Fick’s Laws, Ideal Gases, Molecular Flux, Multicomponent Systems, Self-
diffusion

21/06/2019 ForsChem Research Reports 2019-07 (1 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

1. Introduction

In a previous report,[1] a general framework for describing molecular diffusion of

multicomponent systems was presented. It was found that such molecular diffusion depends
on the mean free path of the molecules present in the system. The molecular diffusion
coefficient (𝔇𝐴 ) of a certain molecular species 𝐴 was defined as the variance of the relative
molecular displacement in one arbitrary dimension (𝑥𝐴,𝑟 ):

𝑉𝑎𝑟(𝑥𝐴,𝑟 (𝑡))
𝔇𝐴 =
2∆𝑡
(1.1)

where 𝑥𝐴,𝑟 (𝑡) = 𝑥𝐴 (𝑡) − 𝑥𝐴 (𝑡0 ), and ∆𝑡 = 𝑡 − 𝑡0 . Please notice that for Brownian motion
2
𝐸(𝑥𝐴,𝑟 ) = 0, and therefore 𝑉𝑎𝑟 (𝑥𝐴,𝑟 (𝑡)) = 𝐸(𝑥𝐴,𝑟 (𝑡)).

By correctly applying the algebra of random vectors,[2] the molecular diffusion coefficient in
three-dimensions can be equivalently defined as:

2
𝐸 (‖𝒙𝐴,𝑟 (𝑡)‖ ) 𝐸(‖𝒙𝐴 (𝑡) − 𝒙𝐴 (𝑡0 )‖2 )
𝔇𝐴 = =
6∆𝑡 6∆𝑡
(1.2)

where 𝒙𝐴,𝑟 represents the relative molecular displacement vector for molecules of species 𝐴,
and ‖𝒙𝐴,𝑟 (𝑡)‖ is its corresponding magnitude (or norm).

Then it is possible to demonstrate [1] that such definition is consistent with the set of
differential equations given by Fick’s laws, resulting in:

𝑱𝐴 ∝ −𝔇𝐴 𝛁𝐶𝐴
(1.3)
𝑑𝐶𝐴 (𝒙1 , 𝑡)
∝ 𝔇𝐴 ∇2 𝐶𝐴 (𝒙1 , 𝑡)
𝑑𝑡
(1.4)

where 𝑱𝐴 = 𝐶𝐴 𝒗𝐴 is the molar flux density vector for species 𝐴 relative to the overall motion of
the system, 𝐶𝐴 is the molar concentration of species 𝐴, 𝒗𝐴 is the average molecular speed of 𝐴
molecules relative to the overall motion of the system, 𝛁 is the gradient operator, and ∇2 is the
Laplacian operator.

Let us now define the exact macroscopic diffusion coefficient of species 𝐴 (𝐷𝐴 ) as:

21/06/2019 ForsChem Research Reports 2019-07 (2 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

𝑑𝐶𝐴
𝑱𝐴
𝐷𝐴 = − = 𝑑𝑡
𝛁𝐶𝐴 ∇2 𝐶𝐴
(1.5)
Then, from Eq. (1.3) to (1.5) it is possible concluding that:

𝐷𝐴 = 𝛼𝐴 𝔇𝐴
(1.6)

where 𝛼𝐴 is a constant factor, which depends on the system composition. Only if 𝛼𝐴 = 1 it

would be possible to state that the molecular diffusion coefficient defined by Eq. (1.1) and (1.2)
and the macroscopic diffusion coefficient defined by Eq. (1.5) are identical.

The purpose of this report is analyzing and relating both definitions of the diffusion coefficient.
In Section 2, a derivation of Fick’s laws from the corresponding molecular fluxes [3,4] of ideal
gas systems is presented. In Section 3, the relationship between the molecular and
macroscopic diffusion coefficients is analyzed for pure systems, binary systems and
multicomponent systems in general.

2. Molecular Nature of Fick’s Laws in Ideal Gases

The goal of this section is demonstrating that both of Fick’s laws of diffusion can be derived
from the expression for calculating molecular flux in ideal gases.[3]

2.1. Fick’s First Law

For an ideal low-density gas system, the molecular flux of species 𝐴 (𝐹𝐴𝑜 ) reaching a certain
permeable boundary per unit time and per unit surface from one particular direction,
considering molecular collisions, can be calculated as:[4]

2
2𝑘𝐵 𝑇 𝜌̃𝐴 −𝜗𝐴⊥ 𝜋 𝜗𝐴⊥
𝐹𝐴𝑜 =√ [𝑒 2 + √ 𝜗𝐴⊥ (1 + erf ( ))]
𝜋𝑚𝐴 2 2 √2
(2.1)

where 𝑘𝐵 = 1.3806 × 10−23 𝐽/𝐾 is Boltzmann’s constant, 𝑇 is the temperature of the

molecular system, 𝑚𝐴 is the molecular mass of species 𝐴, 𝜌̃𝐴 is the number density of species 𝐴,

21/06/2019 ForsChem Research Reports 2019-07 (3 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

𝑚𝐴
and 𝜗𝐴⊥ = √ 〈𝑣 → 〉 is the ratio between the average macroscopic velocity and the standard
𝑘𝐵 𝑇 𝐴,⊥

deviation in the thermal velocity of species 𝐴 perpendicular to the surface.

As a result of molecular crowding, the molecular flux must be corrected considering that the
whole surface is no longer available. In this case,[3]

2
2𝑘𝐵 𝑇 𝜌̃𝐴 𝜗𝐴⊥ 𝜋 𝜗𝐴⊥
𝐹𝐴 = Φ𝐴 𝐹𝐴𝑜 = √ Φ𝐴 [𝑒 − 2 + √ 𝜗𝐴⊥ (1 + erf ( ))]
𝜋𝑚𝐴 2 2 √2
(2.2)

where Φ𝐴 is the free perpendicular surface that molecules of species 𝐴 can effectively cross.

Any macroscopic system can be discretized in different sections along any arbitrary direction as
it is illustrated in Figure 1. Then, it is possible to analyze the net flux of molecules crossing an
arbitrary permeable boundary located at a certain position 𝑥𝑏 , as indicated in Figure 2. Only the
adjacent subsystems are considered.

Figure 1. Partitioning of a molecular system along an arbitrary direction 𝑥. The system

considered has a constant cross surface 𝐴. The thickness of each subsystem is ∆𝑥.

It is assumed that the discretization of the system allows considering each subsystem as
perfectly homogeneous (same molecular density and same temperature), and therefore, the
molecular fluxes at each subsystem can be considered constant. Furthermore, 𝐴 can be
considered small enough in order to neglect changes in concentration in other directions.

21/06/2019 ForsChem Research Reports 2019-07 (4 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Figure 2. Relative molar fluxes of species A (𝐽𝐴 ) reaching the permeable boundary located at
position 𝑥𝑏 .

Molecular fluxes in the same direction of 𝑥 (𝐹𝐴→ ) will be given by Eq. (2.1), whereas molecular
fluxes in the opposite direction (𝐹𝐴← ) will be:[3]

2
2𝑘𝐵 𝑇 𝜌̃𝐴 −𝜗𝐴⊥ 𝜋 𝜗𝐴⊥
𝐹𝐴← = Φ𝐴 √ [𝑒 2 − √ 𝜗𝐴⊥ (1 − erf ( ))]
𝜋𝑚𝐴 2 2 √2
(2.3)
considering the effect of the direction of the macroscopic flow on the molecular fluxes.

Now, the magnitude of the molar fluxes relative to the overall motion of the system at a
certain position 𝑥 will be (by setting 𝜗𝐴⊥ = 0):

𝑘𝐵 𝑇(𝑥) 𝜌̃𝐴 (𝑥) 𝑘𝐵 𝑇(𝑥)

𝐽𝐴→ (𝑥) = 𝐽𝐴← (𝑥) = Φ𝐴 (𝑥)√ = Φ𝐴 (𝑥)√ 𝐶 (𝑥)
2𝜋𝑚𝐴 𝑁𝐴 2𝜋𝑚𝐴 𝐴
(2.4)
23 −1
where 𝑁𝐴 = 6.022 × 10 𝑚𝑜𝑙 represents Avogadro number.

Thus, the net relative molar flux of species 𝐴 in the direction of 𝑥, across the permeable
boundary located at position 𝑥𝑏 will be given by:

21/06/2019 ForsChem Research Reports 2019-07 (5 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

𝐽𝐴,𝑛𝑒𝑡 (𝑥𝑏 ) = 𝐽𝐴→ (𝑥𝑏 − ∆𝑥/2) − 𝐽𝐴← (𝑥𝑏 + ∆𝑥/2)

𝑘𝐵
= Φ𝐴 (𝑥𝑏 )√ (𝐶 (𝑥 − ∆𝑥/2)√𝑇(𝑥𝑏 − ∆𝑥/2)
2𝜋𝑚𝐴 𝐴 𝑏

− 𝐶𝐴 (𝑥𝑏 + ∆𝑥/2)√𝑇(𝑥𝑏 + ∆𝑥/2))

(2.5)
Eq. (2.5) can be equivalently expressed as:

∆𝑥 ∆𝑥 ∆𝑥 ∆𝑥
𝑘𝐵 𝐶𝐴 (𝑥𝑏 + 2 ) √𝑇 (𝑥𝑏 + 2 ) − 𝐶𝐴 (𝑥𝑏 − 2 ) √𝑇 (𝑥𝑏 − 2 )
𝐽𝐴,𝑛𝑒𝑡 (𝑥𝑏 ) = −∆𝑥Φ𝐴 (𝑥𝑏 )√
2𝜋𝑚𝐴 ∆𝑥

𝑘𝐵 𝛿(𝐶𝐴 √𝑇)
= −∆𝑥Φ𝐴 (𝑥𝑏 )√
2𝜋𝑚𝐴 ∆𝑥
(2.6)

where 𝛿( ) represents the central finite difference operator.

Assuming ∆𝑥 to be sufficiently small (compared to the size of the system), Eq. (2.6) can be
represented by the corresponding derivative:

𝑘𝐵 𝑑(𝐶𝐴 √𝑇)
𝐽𝐴,𝑛𝑒𝑡 (𝑥𝑏 ) = −∆𝑥Φ𝐴 (𝑥𝑏 )√
2𝜋𝑚𝐴 𝑑𝑥

𝑘𝐵 𝑇 𝑑𝐶𝐴 ∆𝑥Φ𝐴 (𝑥𝑏 )𝐶𝐴 𝑘𝐵 𝑑𝑇

= −∆𝑥Φ𝐴 (𝑥𝑏 )√ − √
2𝜋𝑚𝐴 𝑑𝑥 2 2𝜋𝑚𝐴 𝑇 𝑑𝑥
(2.7)

Furthermore, assuming a constant temperature along the arbitrary direction 𝑥, results in:

𝑘𝐵 𝑇 𝑑𝐶𝐴 𝑘𝐵 𝑇
𝐽𝐴,𝑛𝑒𝑡 (𝑥𝑏 ) = −∆𝑥Φ𝐴 (𝑥𝑏 )√ = − (∆𝑥Φ𝐴 (𝑥𝑏 )√ ) ∇𝐶𝐴
2𝜋𝑚𝐴 𝑑𝑥 2𝜋𝑚𝐴

(2.8)

which is equivalent to Fick’s first law of diffusion , considering that:

𝑘𝐵 𝑇
𝐷𝐴 = ∆𝑥Φ𝐴 √
2𝜋𝑚𝐴
(2.9)

21/06/2019 ForsChem Research Reports 2019-07 (6 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Please notice the important assumption of constant temperature. If gradients in temperature

are present, a correction to Fick’s law must be considered (Eq. 2.7).

2.2. Fick’s Second Law

In order to derive Fick’s second law, let us consider a molar balance on one of the subsystems
previously defined, as depicted in Figure 3. The subsystem analyzed has its center at position
𝑥𝑠 , in the 𝑥-direction. Only the immediate neighbor subsystems are considered. Please notice
that the volume of all subsystems is the same. The resulting molar balance of species 𝐴 is:

𝑑𝐶𝐴
∆𝑥 = 𝐽𝐴← (𝑥𝑠 + ∆𝑥) − 𝐽𝐴← (𝑥𝑠 ) + 𝐽𝐴→ (𝑥𝑠 − ∆𝑥) − 𝐽𝐴→ (𝑥𝑠 )
𝑑𝑡
𝑘𝐵
= Φ𝐴 √ (√𝑇(𝑥𝑠 + ∆𝑥)𝐶𝐴 (𝑥𝑠 + ∆𝑥) − 2√𝑇(𝑥𝑠 )𝐶𝐴 (𝑥𝑠 ) + √𝑇(𝑥𝑠 − ∆𝑥)𝐶𝐴 (𝑥𝑠 − ∆𝑥))
2𝜋𝑚𝐴
(2.10)

where the term ∆𝑥 corresponds to the ratio of volume to cross section (transfer) area.

Figure 3. Relative molar fluxes of species A (𝐽𝐴 ) entering and leaving the subsystem centered at
position 𝑥𝑠 .

21/06/2019 ForsChem Research Reports 2019-07 (7 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Eq. (2.10) can be equivalently expressed in terms of the second-order central finite difference
(𝛿 2 ) as:
𝑑𝐶𝐴 𝑘𝐵 𝛿 2 (√𝑇𝐶𝐴 )
= ∆𝑥Φ𝐴 √
𝑑𝑡 2𝜋𝑚𝐴 ∆𝑥 2
(2.11)

which can also be expressed in derivative form as:

𝑑𝐶𝐴 𝑘𝐵 𝑑2 (√𝑇𝐶𝐴 ) 𝑘𝐵
= ∆𝑥Φ𝐴 √ 2
= ∆𝑥Φ𝐴 √ ∇2 (√𝑇𝐶𝐴 )
𝑑𝑡 2𝜋𝑚𝐴 𝑑𝑥 2𝜋𝑚𝐴
(2.12)

Assuming constant temperature along the 𝑥-direction, Eq. (2.12) combined with Eq. (2.9)
results in Fick’s second law of diffusion:

𝑑𝐶𝐴 𝑘𝐵 𝑇 2
= ∆𝑥Φ𝐴 √ ∇ 𝐶𝐴 = 𝐷𝐴 ∇2 𝐶𝐴
𝑑𝑡 2𝜋𝑚𝐴
(2.13)

3. Equivalence between Molecular and Macroscopic Diffusion Coefficients

3.1. General Multicomponent Systems

Eq. (2.9) indicates that the macroscopic diffusion coefficient obtained from molecular fluxes
depends on the size of the system partition along the 𝑥-direction (∆𝑥). Thus, the selection of
this thickness is critical for determining macroscopic diffusion coefficients. Since molecular
collisions alter the trajectory of the molecules, the size of ∆𝑥 should be related to the average
actual distance travelled by molecules in the direction 𝑥 between consecutive collisions.§ For
ideal gases such distance (〈𝐿𝐴,⊥ 〉) is:[4]

𝜋/2 𝜋
̅̅̅̅̅̅̅̅̅
𝑚𝑗|𝐴
∫−𝜋/2 ∫0 𝐸(𝐿𝐴 ) sin 𝜃 cos 𝜑 𝑑𝜃𝑑𝜑 ( )
2 4 𝑚𝑗
〈𝐿𝐴,⊥ 〉 = =( )
𝜋/2 𝜋 ̅̅̅̅̅̅̅̅̅̅̅
𝜋 𝜌(𝑑 2
)
∫−𝜋/2 ∫0 𝑑𝜃𝑑𝜑 𝑐𝑜𝑙,𝐴,𝑗

(3.1)

§
Since for this case the determination of molecular fluxes from the constant speed equation of motion
remains valid.

21/06/2019 ForsChem Research Reports 2019-07 (8 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

where 𝜃 and 𝜑 represent the polar and azimuthal angles in an spherical coordinate system,
𝑑𝑐𝑜𝑙,𝐴,𝑗 is the collision diameter (obtained from Clausius’ sphere of action [5]) between a
𝑁 𝑗 𝑌𝑗 𝑚 𝑚
molecule of species 𝐴 and a molecule of species 𝑗, ̅̅̅̅̅
(𝑌) = ∑𝑘𝑗=1
𝑁
= ∑𝑘𝑗=1 𝑋𝑗 𝑌𝑗 , 𝑚𝑗|𝐴 = 𝑚 𝐴+𝑚𝑗 ,
𝐴 𝑗
𝑁𝑗
and 𝑋𝑗 = 𝑁
is the fraction of molecules of species 𝑗 in the system.

In general, let us assume that:

̅̅̅̅̅̅̅̅̅
𝑚𝑗|𝐴
(𝑚 )
𝑗
∆𝑥 = 𝛽
̅̅̅̅̅̅̅̅̅̅̅
𝜌(𝑑 2
)
𝑐𝑜𝑙,𝐴,𝑗
(3.2)

where 𝛽 is a proportionality constant. Such proportionality constant reflects the compromise

of requiring the smallest system partitioning length possible which is also large enough to
guarantee a Maxwellian distribution of molecular speeds.

Furthermore, the fraction of available surface for molecules of species 𝐴 in crowded systems
can be given by:[3]

𝜋 ̅̅̅̅̅̅̅̅̅̅̅
3
Φ𝐴 = 1 − 𝜌(𝑑𝑐𝑜𝑙,𝐴,𝑗 )
4
(3.3)

Thus, Eq. (2.9) can be expressed as:

̅̅̅̅̅̅̅̅̅
𝑚𝑗|𝐴 𝜋 ̅̅̅̅̅̅̅̅̅̅̅
3
( ) (1 − 𝜌(𝑑 𝑐𝑜𝑙,𝐴,𝑗 ))
𝑘𝐵 𝑇 𝑚 𝑗 4
𝐷𝐴 = 𝛽√
2𝜋𝑚𝐴 ̅̅̅̅̅̅̅̅̅̅̅
𝜌(𝑑 2
)
𝑐𝑜𝑙,𝐴,𝑗
(3.4)
Now, recalling that the molecular diffusion coefficient can be expressed as:[1]

𝑚𝑗|𝐴 ̅̅̅̅̅̅̅̅̅̅̅̅
̅̅̅̅̅̅̅̅̅ 2
𝑑𝑐𝑜𝑙,𝐴,𝑗
( )( )
𝑘𝐵 𝑇 𝑚𝑗 √𝑚𝑗|𝐴
𝔇𝐴 ≈ √ 2
2𝜋 ̅̅̅̅̅̅̅̅̅̅̅
2
𝜌 ((𝑑 𝑐𝑜𝑙,𝐴,𝑗 ))
(3.5)
Then,

21/06/2019 ForsChem Research Reports 2019-07 (9 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

̅̅̅̅̅̅̅̅̅̅̅
2 𝜋 ̅̅̅̅̅̅̅̅̅̅̅
3
(𝑑𝑐𝑜𝑙,𝐴,𝑗 ) (1 − 4 𝜌(𝑑 𝑐𝑜𝑙,𝐴,𝑗 ))
𝐷𝐴 ≈ 𝛽 𝔇𝐴
̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
2
𝑑𝑐𝑜𝑙,𝑗
𝑚𝑗
√𝑚 + 𝑚
( 𝑗 𝐴)
(3.6)

and therefore, the ratio between the macroscopic and the molecular diffusion coefficients is:

̅̅̅̅̅̅̅̅̅̅̅
2 𝜋 ̅̅̅̅̅̅̅̅̅̅̅
3
𝐷𝐴 (𝑑𝑐𝑜𝑙,𝐴,𝑗 ) (1 − 4 𝜌(𝑑 𝑐𝑜𝑙,𝐴,𝑗 ))
𝛼𝐴 = ≈𝛽
𝔇𝐴 ̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
2
𝑑𝑐𝑜𝑙,𝑗
𝑚𝑗
√𝑚 + 𝑚
( 𝑗 𝐴)
(3.7)

Please notice that 𝛼𝐴 also includes a geometrical factor since molecular diffusion is considered
in all possible directions, whereas the macroscopic diffusion is considered only in a single
direction. Furthermore, 𝛼𝐴 is independent of the temperature of the system as long as it does
not have a significant effect on the available surface fraction.

Two particular cases will be considered: Self-diffusion in pure systems and diffusion in binary
systems.

3.2. Pure Systems

For pure systems, the macroscopic and molecular self-diffusion coefficients will be (from Eq.
3.4 and 3.5):
𝜋 3
𝛽 𝑘𝐵 𝑇 1 − 4 𝜌𝑑𝑐𝑜𝑙,𝐴
𝐷𝐴 = √ ( 2 )
2 2𝜋𝑚𝐴 𝜌𝑑𝑐𝑜𝑙,𝐴
(3.8)
√2 𝑘𝐵 𝑇 1
𝔇𝐴 ≈ √ ( 2 )
2 2𝜋𝑚𝐴 𝜌𝑑𝑐𝑜𝑙,𝐴
(3.9)
and therefore, the self-diffusion coefficients ratio is:

𝐷𝐴 √2 𝜋 3
𝛼𝐴 = ≈𝛽 (1 − 𝜌𝑑𝑐𝑜𝑙,𝐴 )
𝔇𝑎 2 4
(3.10)

21/06/2019 ForsChem Research Reports 2019-07 (10 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

For low-density systems, Eq. (3.10) becomes:

√2
𝛼𝐴 ≈ 𝛽
2
(3.11)

Now, assuming that for low-density pure systems both diffusion coefficients are identical
(because of the symmetry of all collisions, as well as the indistinguishability of individual
molecules) then:
𝛽 = √2
(3.12)

Table 1. Experimental and calculated self-diffusion coefficient of Argon gas at different

conditions. Experimental data taken from [6]. Diffusion coefficients are calculated using Eq.
(3.8) (𝛽 = √2) for Dcalc and (3.13) for D*. Ideal gas density is assumed.
T (K) P (cm Hg) 𝝆𝑰𝑮 (mol/m3) Dexp (cm2/s) Dcalc (cm2/s) D* (cm2/s)
77.5 12.6 26.1 0.079 0.161 0.215
77.6 12.3 25.4 0.081 0.166 0.221
77.9 16.7 34.4 0.059 0.123 0.164
78.0 16.0 32.9 0.062 0.128 0.171
82.1 8.7 16.9 0.135 0.256 0.342
85.1 11.6 21.9 0.112 0.202 0.269
85.1 8.9 16.7 0.142 0.264 0.353
86.6 9.4 17.4 0.141 0.255 0.341
90.0 43.1 76.8 0.032 0.059 0.079
91.5 39.1 68.5 0.036 0.067 0.089
91.8 28.7 50.1 0.049 0.091 0.122
94.6 44.2 74.9 0.034 0.062 0.083
94.7 49.1 83.1 0.031 0.056 0.075
100.7 49.0 78.0 0.036 0.061 0.082
101.0 53.6 85.1 0.031 0.056 0.075
111.0 28.8 41.6 0.068 0.121 0.161
112.0 12.5 17.9 0.173 0.283 0.377
120.7 52.2 69.4 0.046 0.076 0.101
294.0 40.4 22.0 0.337 0.372 0.496
294.0 56.0 30.5 0.242 0.268 0.358
294.0 49.7 27.1 0.271 0.302 0.403
294.0 28.7 15.7 0.466 0.523 0.698
294.0 46.7 25.5 0.266 0.322 0.429

21/06/2019 ForsChem Research Reports 2019-07 (11 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

As an example, let us consider the self-diffusion of Argon at different temperatures and

pressures, comparing the calculations from Eq. (3.8) and (3.9) to experimental results.[6] The
results are summarized in Table 1 and compared in Figure 4. In addition, a conventional
equation for determining self-diffusion coefficients, described in Eq. (3.13) is also used.[7]

2 𝑘𝐵 𝑇 1
𝐷𝐴∗ = √ ( 2 )
3 𝜋𝑚𝐴 𝜌𝑑𝑐𝑜𝑙,𝐴
(3.13)

Important deviations between the experimental and calculated diffusion coefficients are
evidenced at lower temperatures, probably as a result of non-ideal gas behavior. While not
perfect, Eq. (3.8) provides a fairly good estimation of self-diffusion coefficients, even better
than the estimations obtained with Eq. (3.13).

Thus, the value of 𝛽 = √2 will be considered as a good approximation to reality.

Figure 4. Experimental and calculated self-diffusion coefficient of Argon gas at different

conditions. Experimental data taken from [6]. Green triangles: Diffusion coefficients calculated
using Eq. (3.8) (𝛽 = √2). Purple squares: Diffusion coefficients calculated using Eq. (3.13). Ideal
gas density is assumed in both cases. Black dashed line: Experimental diffusion coefficients.

21/06/2019 ForsChem Research Reports 2019-07 (12 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

3.3. Binary Systems

For a binary system composed of species 𝐴 and 𝐵 (with a molar fraction 𝑋𝐴 of species 𝐴 in the
mixture), the corresponding macroscopic diffusion coefficients will be:

𝑋𝐴 𝑚𝐴 (1 − 𝑋𝐴 ) 𝜋 3 3
𝑘𝐵 𝑇 ( 2 + 𝑚𝐴 + 𝑚𝐵 ) (1 − 4 𝜌(𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴 + (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐴,𝐵 ))
𝐷𝐴 = √ 2 2
𝜋𝑚𝐴 𝜌(𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴 + (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐴,𝐵 )
(3.14)
𝑚𝐵 𝑋𝐴 1 − 𝑋𝐴 𝜋 3 3
𝑘𝐵 𝑇 (𝑚𝐴 + 𝑚𝐵 + 2 ) (1 − 4 𝜌(𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴,𝐵 + (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐵 ))
𝐷𝐵 = √ 2 2
𝜋𝑚𝐵 𝜌(𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴,𝐵 + (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐵 )
(3.15)

Please notice that the diffusion coefficients are a function of the system composition, and in
general, 𝐷𝐴 ≠ 𝐷𝐵 .

On the other hand, the corresponding molecular diffusion coefficients are:

𝑋 𝑚𝐴 (1 − 𝑋𝐴 ) 2 𝑚 +𝑚 2
( 2𝐴 + 𝑚 + 𝑚 ) (√2𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴 + √ 𝐴𝑚 𝐵 (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐴,𝐵 )
𝑘𝐵 𝑇 𝐴 𝐵 𝐵
𝔇𝐴 ≈ √ 2
2𝜋𝑚𝐴 𝜌(𝑋 𝑑2 + (1 − 𝑋 )𝑑2 )
𝐴 𝑐𝑜𝑙,𝐴 𝐴 𝑐𝑜𝑙,𝐴,𝐵
(3.16)

𝑚𝐵 𝑋𝐴 1 − 𝑋𝐴 𝑚 + 𝑚𝐵 2 2
( + ) (√ 𝐴 𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴,𝐵 + √2(1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐵 )
𝑘𝐵 𝑇 𝑚𝐴 + 𝑚𝐵 2 𝑚𝐴
𝔇𝐵 ≈ √ 2
2𝜋𝑚𝐵 𝜌(𝑋 𝑑2 + (1 − 𝑋 )𝑑2 )
𝐴 𝑐𝑜𝑙,𝐴,𝐵 𝐴 𝑐𝑜𝑙,𝐵
(3.17)

And therefore the macroscopic to molecular diffusion coefficient ratios for a binary system are:
2 2 𝜋 3 3
(𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴 + (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐴,𝐵 ) (1 − 4 𝜌(𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴 + (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐴,𝐵 ))
𝛼𝐴 ≈
𝑚 + 𝑚𝐵
2
𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴 +√ 𝐴 2
(1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐴,𝐵
2𝑚𝐵
(3.18)
2 2 𝜋 3 3
(𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴,𝐵 + (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐵 ) (1 − 4 𝜌(𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴,𝐵 + (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐵 ))
𝛼𝐵 ≈
𝑚 +𝑚
√ 𝐴2𝑚 𝐵 𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴,𝐵
2 2
+ (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐵
𝐴
(3.19)
For low-density systems these expressions become:

21/06/2019 ForsChem Research Reports 2019-07 (13 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

2 2
𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴 + (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐴,𝐵
𝛼𝐴 ≈
𝑚 +𝑚
2
𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴 + √ 𝐴2𝑚 𝐵 (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐴,𝐵
2
𝐵
(3.20)
2 2
𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴,𝐵 + (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐵
𝛼𝐵 ≈
𝑚 +𝑚
√ 𝐴2𝑚 𝐵 𝑋𝐴 𝑑𝑐𝑜𝑙,𝐴,𝐵
2 2
+ (1 − 𝑋𝐴 )𝑑𝑐𝑜𝑙,𝐵
𝐴
(3.21)

Please notice that typical model of binary diffusion assumes that for the binary system:

∗ ∗
2 𝑘𝐵 𝑇 1
𝐷𝐴 = 𝐷𝐵 = 𝐷𝐴𝐵 = 𝐷𝐵𝐴 = √ ( 2 )
3 2𝜋𝑚𝐴|𝐵 𝜌𝑑𝑐𝑜𝑙,𝐴,𝐵
(3.22)

In this model, there is no effect of system composition. Thus, it is expected that presence of
just a single molecule of the light species will significantly increase the diffusion coefficient of
the heavy species, which is probably not the case.

If a single diffusion coefficient were to be obtained for the binary mixture, the following mixing
rule is proposed**:
𝐷𝐴𝐵 = 𝑋𝐴 𝐷𝐴 + (1 − 𝑋𝐴 )𝐷𝐵
(3.23)

In general, for a multicomponent system the overall macroscopic diffusion coefficient of the
mixture will be:
𝑘

𝐷𝑀𝑆 = ∑ 𝑋𝑗 𝐷𝑗
𝑗=1
(3.24)

An example of the effect of the composition of the system on the diffusion coefficients is
presented in Figure 5, considering a low-density binary system (Helium (𝐴)-Nitrogen (𝐵) at 300
K, 300 torr)[8] where 𝑚𝐵 ≈ 7𝑚𝐴 = 4.65 × 10−26 𝑘𝑔, and 𝑑𝑐𝑜𝑙,𝐵 ≈ 1.11𝑑𝑐𝑜𝑙,𝐴 = 0.31 𝑛𝑚.

According to the results of the present model of diffusion all diffusion coefficients
(macroscopic and molecular for both species) increase as the molar fraction of the light species
(𝐴) increases. In other words, large and heavy molecules reduce the mobility of all species in

**
Assuming 𝐷𝐴𝐵 to be the number-average diffusion coefficient of the molecules in the system.

21/06/2019 ForsChem Research Reports 2019-07 (14 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

the system. At both limits of pure compounds, the macroscopic and molecular diffusion
coefficients converge to the corresponding self-diffusion coefficient.

Figure 5. Macroscopic and molecular diffusion coefficients in a low-density ideal gas binary
system (Helium (𝐴)-Nitrogen (𝐵)) at constant temperature (300 K) and pressure (300 torr) as a
function of composition. Solid lines indicate macroscopic diffusion coefficients. Dashed lines
indicate molecular diffusion coefficients. Blue lines represent the diffusion coefficients of
species 𝐴. Red lines represent the diffusion coefficients of species 𝐵. Solid green line
represents the overall diffusion coefficient of the binary system (Eq. 3.23). Dotted green line
represents the conventional binary diffusion coefficient (Eq. 3.22). Dotted orange line
corresponds to the experimental diffusion coefficient of Helium highly diluted in Nitrogen.[8]

For this particular case, it is evidenced that the molecular diffusion coefficient of the heavy
molecule is always larger than the molecular diffusion coefficient of the light molecule.
However, the self-diffusion coefficient of the heavy molecule is smaller than the self-diffusion
coefficient of the light molecule, as expected. This apparently contradictory result might be
explained by the fact that the relative mobility of the heavier Nitrogen molecules is significantly
increased by the presence of light Helium atoms. That is, heavy molecules are not easily
constrained by light neighboring molecules. However, this phenomenon is not necessarily
reflected on the macroscopic diffusion coefficient, because other physical and geometrical
factors also play important roles in the process. On the other hand, heavier and larger Nitrogen

21/06/2019 ForsChem Research Reports 2019-07 (15 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

molecules act as an impediment for the displacement of lighter, smaller Helium atoms,
resulting in some type of cage effect. This situation is more evident in the case of macroscopic
diffusion coefficients of Helium at high Nitrogen fractions, where they are even smaller than
the corresponding macroscopic self-diffusion coefficient of Nitrogen. This result seems to be
consistent with the experimental observations for the diffusion of diluted Helium in
Nitrogen.[8] It can also be observed that the conventional estimation of the binary diffusion
coefficient might represent the behavior at high Helium fractions, but overestimates the
diffusivity at high Nitrogen fractions. In fact, the conventional result matches the present
model when the mole fraction of Helium is 0.924.

It is also possible to observe that at a certain composition for this system, both macroscopic
diffusion coefficients (as well as the overall diffusion coefficient of the binary mixture) are
exactly the same. Such composition, for low-density systems, will be given by solving the
following quadratic expression:
2
(𝑚𝐵 − 𝑚𝐴 ) (√𝑚𝐵 (𝑑𝑐𝑜𝑙,𝐴,𝐵 2
− 𝑑𝑐𝑜𝑙,𝐵 2
) − √𝑚𝐴 (𝑑𝑐𝑜𝑙,𝐴 2
− 𝑑𝑐𝑜𝑙,𝐴,𝐵 )) 𝑋𝐴 2
2 2 2 2
+ ((𝑚𝐵 − 𝑚𝐴 )(√𝑚𝐵 𝑑𝑐𝑜𝑙,𝐵 − √𝑚𝐴 𝑑𝑐𝑜𝑙,𝐴,𝐵 ) + 2𝑚𝐴 √𝑚𝐵 (𝑑𝑐𝑜𝑙,𝐴,𝐵 − 𝑑𝑐𝑜𝑙,𝐵 )
2 2
− (𝑚𝐴 + 𝑚𝐵 )√𝑚𝐴 (𝑑𝑐𝑜𝑙,𝐴 − 𝑑𝑐𝑜𝑙,𝐴,𝐵 )) 𝑋𝐴
2 2
+ (2𝑚𝐴 √𝑚𝐵 𝑑𝑐𝑜𝑙,𝐵 − (𝑚𝐴 + 𝑚𝐵 )√𝑚𝐴 𝑑𝑐𝑜𝑙,𝐴,𝐵 )=0
(3.25)

For the Helium-Nitrogen system, such composition corresponds to a mole fraction of Helium of
0.186, and a mole fraction of Nitrogen of 0.814. At this composition, the estimated
macroscopic diffusion coefficient of both Helium and Nitrogen is 1.05 𝑐𝑚2 /𝑠.

If the values of the diffusion coefficient for different compositions span several orders of
magnitude, a significant change in the diffusion coefficients will be observed with time in a
system away from equilibrium, resulting in abnormal “non-Fickian” diffusion.[9] This however,
is not expected to be the case for ideal gases.

Figure 6 shows that the diffusion coefficient ratio of the light species is always larger than the
self-diffusion coefficient ratio, whereas the ratio of the heavy species is always smaller than the
corresponding self-diffusion ratio. Interpreting the diffusion coefficient ratio as a physical
limitation of the molecular diffusion, it could be argued that the increase in mobility of heavy
species due to a higher content of the light species is less likely to be reflected in the
unidirectional macroscopic diffusion compared to molecular diffusion. Similarly, the reduced
molecular mobility of the light species caused by the heavy species is less likely to affect the
macroscopic diffusion, resulting in larger diffusion coefficient ratios.

21/06/2019 ForsChem Research Reports 2019-07 (16 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Such physical limitation of macroscopic diffusion seems to be the result of the difference in
mass for both species. For pure compounds, when motion is transferred by collision from one
molecule to another, the colliding molecules are indistinguishable, causing the effect of such
collision to be irrelevant from the macroscopic point of view. However, for binary and
multicomponent systems, the transfer of motion between two different molecular species is
influenced by their differences in mass. Macroscopic diffusion is then influenced by such
motion transfer, resulting in deviations from the ideal molecular diffusive behavior. Since light
molecules will on average gain speed from collisions with heavy molecules, they will get a
boost in their mobility. Heavy molecules on the other hand, will experience a hindrance.

Figure 6. Ratio between macroscopic and molecular diffusion coefficients for a low-density
ideal gas binary system (Helium (𝐴)-Nitrogen (𝐵)) at constant temperature (300 K) and
pressure (300 torr) as a function of composition. Blue line: Diffusion coefficient ratio of Helium.
Red line: Diffusion coefficient ratio of Nitrogen. The dashed line indicates the self-diffusion
coefficient ratio.

4. Concluding Remarks

It was possible to show that Fick’s laws of diffusion are consistent with the macroscopic
description of molecular fluxes, and that both molecular and macroscopic diffusion coefficients
are related by proportionality constants. The particular proportionality values are the result of
the physical and geometrical interaction of the different species in a multicomponent system.

21/06/2019 ForsChem Research Reports 2019-07 (17 / 18)

www.forschem.org
 On the Relationship between Molecular
and Macroscopic Diffusion in Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

While the models of macroscopic and molecular diffusion presented in this report are not
expected to perfectly describe real systems (because of all the assumptions involved), a fairly
good approximation is expected. Furthermore, some insights about the diffusion phenomenon
obtained from these models might be valuable. Improved models of diffusion should take into
account the effect of intermolecular forces, simultaneous diffusion in all three directions,
anisotropy, and dense systems.

Acknowledgments

The author gratefully acknowledges the helpful discussions with Prof. Jaime Aguirre
(Universidad Nacional de Colombia), as well as his contribution by reviewing the whole
manuscript.

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

References

[1] Hernandez, H. (2017). Multicomponent Molecular Diffusion: A Mathematical Framework.

ForsChem Research Reports 2017-9. doi: 10.13140/RG.2.2.14828.46724.

[2] Hernandez, H. (2019). Algebra of Random Arrays. ForsChem Research Reports 2019-06. doi:
10.13140/RG.2.2.28607.15520.

[3] Hernandez, H. (2019). Calculation of Molecular Fluxes and Equivalent Pressure in Ideal
Gases. ForsChem Research Reports 2019-03. doi: 10.13140/RG.2.2.35898.44483.

[4] Hernandez, H. (2019). Molecular Fluxes of Ideal Gases: Some Additional Remarks. ForsChem
Research Reports 2019-05. doi: 10.13140/RG.2.2.11249.12646.

[5] Hernandez, H. (2017). Clausius’ sphere of action for different intermolecular potentials.
ForsChem Research Reports 2017-10. doi: 10.13140/RG.2.2.25246.23363.

[6] De Paz, M., Turi, B., & Klein, M. L. (1967). New self diffusion measurements in argon gas.
Physica, 36(1), 127-135.

[7] Bird, R. B., Stewart, W. E., & Lightfoot, E. N. (2007). Transport phenomena. John Wiley &
Sons.

[8] Trengove, R. D., & Dunlop, P. J. (1982). Diffusion coefficients and thermal diffusion factors
for five binary systems of nitrogen and a noble gas. Physica A: Statistical Mechanics and its
Applications, 115(3), 339-352.

[9] Crank, J. (1975). The mathematics of diffusion. 2nd ed. Oxford University Press.

21/06/2019 ForsChem Research Reports 2019-07 (18 / 18)

www.forschem.org