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Boltzmann-Matano Diffusion Analysis

The Boltzman-Matano analysis simplifies the diffusion equation, which is complex due to the interdiffusion coefficient being a function of concentration, into a more manageable ordinary differential equation. This method allows for the calculation of interdiffusion and self-diffusion coefficients by transforming variables and integrating the resulting equations. Ultimately, it leads to the definition of the Matano plane, where the concentration profile remains symmetric, facilitating experimental evaluations of diffusion coefficients.

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43 views2 pages

Boltzmann-Matano Diffusion Analysis

The Boltzman-Matano analysis simplifies the diffusion equation, which is complex due to the interdiffusion coefficient being a function of concentration, into a more manageable ordinary differential equation. This method allows for the calculation of interdiffusion and self-diffusion coefficients by transforming variables and integrating the resulting equations. Ultimately, it leads to the definition of the Matano plane, where the concentration profile remains symmetric, facilitating experimental evaluations of diffusion coefficients.

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KartikeySrivastava
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Boltzman-Matano Analysis

Since we have derived in previous section that the interdiffusion coefficient is


the function of concentration, the diffusion equation is not straightforward to
solve as before, and that is where the Boltzman-Matano analysis comes in which
converts the partial differential equation (governing the diffusion process) into an
ordinary one and thus making it tractable as a result. This allows the possibility
of calculation of Interdiffusion coefficient and also self diffusion coefficients of the
involved species. To understand the math we can start with diffusion equation
as,  
∂C ∂ ∂C
= D̃(C)
∂t ∂x ∂x
where C is the concentration of one component ( a function of position x and
time t) and D̃(C) interdiffusion coefficient, which depends on C. To solve this
we redefine C(x, t) as C(η) with the required transformation of variables as,
x
η=√
t
To cast the diffusion equation in terms of η we first evaluate everything in terms
of η using chain rule, which gives,
∂C ∂C ∂η x ∂C
= = − 3/2
∂t ∂η ∂t 2t ∂η
∂C ∂C ∂η 1 ∂C
= =√
∂x ∂η ∂x t ∂η
∂2C 1 ∂2C
2
=
∂x t ∂η 2
Substituting into the diffusion equation:
 
η ∂C ∂ ∂C
− = D̃(C)
2 ∂η ∂η ∂η
integrating wrt to η from 0 to some arbitrary concentration C ′ between 0
and the concentration at infinity ( as we have considered interdiffusion between
bars of infinite length along the diffusion direction) we get,
Z C′ Z C′  
η ∂C ∂ ∂C
− dη = D̃(C) dη
0 2 ∂η 0 ∂η ∂η
Which yields,
Z C′
1 ∂C ∂C
− ηdC = D̃(C) − D̃(C)
2 0 ∂η ∂η
C′ 0
if we analyze this expression at a given time t, for C = 0 and C ′ , we have
∂C
=0
∂η

1
and at a given time, η is effectively a function of x only so above equation
effectively simplifies to,
Z C′
xdC = 0
0
Which basically is the equation defining the Matano plane, and since the mo-
ment across this plane is zero, the number of atoms ( pertaining to concentration
C) that are removed from one side of the Matano plane is exactly equal to the
number of atoms added to it from the other side, which gives rise to the sym-
metric concentration profile for the system under consideration. Now recasting
the equations in x and t by replacing η, we get,
Z C′
1 dx
D̃(C) = − − xdC
2t dC 0
C′

And thus if we can experimentally evaluate the variation of C with x, from


the above expression we can evaluate the interdiffusion coefficient as a func-
tion concentration. And also if marker velocities are know, we can evaluate
the self diffusion coefficients of the involved species as well( based on Darken’s
equations).

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