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Topic 2 Non Steady State Diffusion

Non-steady state diffusion occurs when the concentration at a point varies over time until steady-state is reached. Fick's second law describes this transient diffusion process using a partial differential equation. For diffusion in one dimension through a semi-infinite medium, the equation can be solved analytically using the error function. This gives an expression for the fractional concentration as a function of diffusion coefficient, time, and distance into the medium. It can also be used to determine the rate of mass transfer across the surface and total mass transferred over time.

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95 views5 pages

Topic 2 Non Steady State Diffusion

Non-steady state diffusion occurs when the concentration at a point varies over time until steady-state is reached. Fick's second law describes this transient diffusion process using a partial differential equation. For diffusion in one dimension through a semi-infinite medium, the equation can be solved analytically using the error function. This gives an expression for the fractional concentration as a function of diffusion coefficient, time, and distance into the medium. It can also be used to determine the rate of mass transfer across the surface and total mass transferred over time.

Uploaded by

Lorraine
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Topic 2. 8.

Non Steady State Diffusion (FICK’S SECOND LAW)


All mass transfer processes will have an initial period of time with unsteady – state conditions
where the concentration at certain point varies with time until steady – state is reached.

Fig 2.8.1 A Differential Control Volume

( Netintothe
rate of molar flow rate − Net rate of molar flow rate = Rate of accummulation of species A
control volume ) ( out of the control volume ) ( ¿ thecontrol volume )
The molar flow rate of species A by diffusion at the plane Z=Z is given by Fick's law:
∂C A
W Az =−D AB S ( )
∂z z
−−−1
The molar flow rate of species A by diffusion at the plane Z=Z+ΔZ, is:

W Az =−D AB S ( ∂C∂ z )
A

z +∆ z
−−−2

The accumulation of species A in the control volume is:

∂C A
S ∆ z−−−3
∂z

Combining eqns. 1, 2 & 3:

∂ CA ∂ CA ∂ CA
−D AB S ( )
∂z z
+ D AB S
∂z ( ) z +∆ z
=S
∂z
∆ z−−−4

1
Rearranging and simplifying:

( ∂ C A /∂ z )z +∆ z−( ∂C A /∂ z )z ∂ CA
D AB ( ∆z )
=
∂t
−−−5
In the limit, as ΔZ→0

∂C A ∂2 C A
=D AB −−−6 ¿
∂t ∂ z2

The more general form, for three dimensions rectangular coordinates, is:

∂C A ∂2 C A ∂2 C A ∂2 C A
∂t
=D AB
∂x
2
+
∂y
2
+ (
∂z
2
−−−7 )
For one-dimensional diffusion in the redial direction only, for cylindrical and spherical
coordinates, Fick's second law becomes, respectively:
∂C A D AB ∂ ∂ C A
∂t
=
r ∂r
r
∂r (
−−−8 )
And

∂C A D AB ∂ 2 ∂ C A
∂t
= 2
r ∂r
r( ∂r) −−−9

Analytical solutions to these partial differential equations are available for a variety of boundary
conditions.
Only two of the most common useful solutions will be considered.

2.8.1 Semi-infinite Medium

The boundary conditions for this case to solve (eqn.6) are:

2
To solve the above partial differential equation, either the method of combination of variables or
the Laplace method is applicable. The result, in terms of the fractional accomplished
concentration change (θ), is:

C A−C A 0 z
θ=
C A 1−C A 0
=erfc
(2 √ D AB t)−−−10

Equation 10 is used to compute the concentration in the semi-infinite medium, as a function of


time and distance from the surface, assuming no bulk flow.
Thus, it applies most rigorously to diffusion in solids, and also to stagnant liquid and gases when
the medium is dilute in the diffusing solute.
The instantaneous rate of mass transfer across the surface of the medium at Z = 0 can be obtained
by taking the derivative of (eqn. 10) with respect to distance and substituting it into Fick's first
law applied at the surface of the medium:

∂ CA C AS−C A 0 −z 2
n A =−D AB S ( )
∂z z =0 (
=D AB S
√ π D AB t
exp
) (
4 D AB t )z=0
−−11

Thus:
D AB
n A|z =0=
√ πt
S ( C As−C A 0 )−−−12

We can determine the total number of moles of solute, NA, transferred into the semi-infinite
medium by integrating equation 12 with respect to time:
t t
D AB dt D AB t
0 √
N A =∫ n A|z=0 dt =
πt
S ( C As−C A 0 ) ∫ =2 S ( C As−C A 0 )
0 √t π √
−−13

Table 2.8. The Error Function

3
Semi-infinite Medium correlations

4
5

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