Den Broeder and Wagner’s approach

Draw back of the Matano-Boltzmann approach

As seen in the previous lecture, to determine the interdiffusion coefficient, it is

necessary to find first the initial contact plane.

This can be found by equalizing the areas as shown in the figure above.
xo +∞

∫ (C − C )dx = ∫ (C )
− +

Mathematically i i i − Ci dx
−∞ xo

It should be possible to find from any of the composition profiles of A or B.

However, we shall show it in the next lecture that it is impossible to find the exact
location of the initial contact plane, when molar volume deviates from the ideality.

It gives two different values when determined from two different composition
profiles (A or B) and both are actually incorrect values.

So we need a relation, in which we can obviate this problem

Den Broeder followed an easy and graphical approach to develop a relation where
we do not need to find the initial contact plane.

Matano-Boltzmann relation is expressed as

1  ∂x   * * 
*
x
~ *
( )
D C B = −  ( ) ( )
  x C B − C B − ∫ C B − C B dx 
2t  ∂C B C * 
− −

B
−∞ 

We introduce a concentration normalizing variable as
C B − C B−
YC = +
C B − C B−
dC B

So dYC =
C B+ − C B−

Replacing these, the relation of interdiffusion can be written as

1  ∂x   * * 
*
x
~ *
( )
D YC = −    x Yc − ∫ YC dx 
2t  ∂YC Y * 
C
−∞ 

In terms of area as shown in the figure, the
relation can be expressed as

~ 1  ∂x 
( )
D Yc* =   [M + N ]
2t  ∂Yc Y *
c

From the position of the initial contact plane, xo, we

can write (M+N+P) = R

Adding Q in both the sides, we get

M+N+P+Q=R+Q
(R + Q) – N = M + P + Q

( )
M + P + Q = Yc+ x * − x0 = x *
+
since Yc = 1
+∞
R + Q = ∫ (1 − Yc )dx
x*
x*
N = ∫ Yc dx
−∞
 +∞ x*

∫ c ∫c
*
So we get (1 − Y ) dx − Y dx = x
x* −∞

Following, we can write

M = xYc*
+∞ x*
= Yc* ∫ (1 − Yc )dx − Yc* ∫ Yi dx
x* −∞

+∞ x* x*
M + N = Yc* ∫ (1 − Yc )dx − Yc* ∫ Yc d + ∫ Yc dx
x* −∞ −∞
x* +∞
(
= 1− Y * ) ∫ Y dx + +Y ∫ (1 − Y )dx
c c
*
c
−∞ x*

~ 1  ∂x 
since ( )
D Yc* =   [M + N ]
2t  ∂Yc Y *
c

1  ∂x   
x* +∞
~ *
( )
D Yc =   (1 − Yc ) ∫ Yc dx + Yc ∫ (1 − Yc )dx 
2t  ∂Yc Y * 
* *

c
−∞ x* 

So first the composition profile should be
normalized and plotted with respect to

C B − C B−
Yc = +
C B − C B−

Following, interdiffusion coefficient

can be calculated following

1  ∂x   
x* +∞
~ *
( )
D Yc =   (1 − Yc ) ∫ Yc dx + Yc ∫ (1 − Yc )dx 
2t  ∂Yc Y * 
* *

c
−∞ x* 
Slope P Q

Advantage should be noted here that we do not need to find the initial contact plane.
 Wagner’s approach

At that time, rather many scientists were busy to develop the relations for
interdiffusion.

Carl Wagner developed the relation, which is bit different in approach compared
to the Den Broeder’a approach.

In Den Broeder’s approach we first measure the composition profile in atomic

fraction (or mol fraction) and then convert to concentration using the molar volume
data.

Following we normalize the concentration and plot in terms of Yc vs. x to calculate

the interdiffusion coefficient.

Wagner developed the relation in which we normalize the measured composition

first −
NB − NB
Y=
N +B − N −B

Following interdiffusion coefficient is calculated from

~ * Vm  ∂x   
x* +∞
Y * 1−Y
( )
DY =   
2t  ∂Y Y * 
(1 − Y *
) ∫−∞Vm dx + Y ∫x* Vm 
dx
~ * Vm  ∂x   
x* +∞
Y * 1−Y
( )
DY =   (1 − Y ) ∫ dx + Y ∫
2t  ∂Y Y * 
*

V V
dx 
−∞ m x* m 
slope P Q

The calculation steps following Wagner’s relation is shown in the previous slide.

NB vs. x plot shows the measured composition profile

Following, the measured composition is normalized and plotted as Y vs. x. If we

are interested to determine interdiffusion coefficient at x*, then we take slope at
that point.

Further with the help of calculated molar volumes at different compositions, we

plot Y/Vm vs. x and (1-Y)/Vm vs. x.

Areas P and Q give the integral values, as shown.

Finally we determine interdiffusion coefficient at the composition, NB*,

corresponding to x*.