Mass transfer by migration and

diffusion

28/10/2014

Mass transfer equation

Mass transfer in solution occurs by diffusion,
migration, and convection

Diffusion and migration result from a gradient

in electrochemical potential, .
Convection results from an imbalance of forces
on the solution

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Mass transfer cont.

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Mass transfer cont.

For linear mass transfer

(4)
Consider, aj ~ Cj, the Nernst-Planck equ is;
(5)
(6)
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Migration
In the bulk solution (away from the electrode),
concentration gradients are generally small, and the
total current is carried mainly by migration.
All charged species contribute.
For species j in the bulk region of a linear masstransfer system having a cross-sectional area ,
ij = im,j or,
(7)
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Migration
Resistance,

tj, the transference number of j

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Mixed migration and diffusion

i = im + id
Note that im and id may be in the same or opposite
directions, depending on the direction of the
electric field and the charge on the electroactive
species

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Mixed migration and diffusion

The migrational component is always in the same

direction as id for cationic species reacting at
cathodes and for anionic species reacting at anodes

It opposes id when anionic species are reduced at

cathodes and when cations are oxidized at anodes.
When neutral species are reduced at cathode only
id is present.
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Mixed migration and diffusion

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Mixed migration and diffusion

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Diffusion
It is possible to restrict mass transfer of an
electroactive species near the electrode to the
diffusive mode by using a supporting electrolyte and
operating in a quiescent solution.
Most electrochemical methods are built on the
assumption that such conditions prevail
Diffusion is a process of central importance
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Diffusion: A macroscopic view

Diffusion, which normally leads to the
homogenization of a mixture, occurs by a
"random walk" process
moving in steps of length, l, with one step
being made per unit time,
Where will the molecule be after a time, t?
Answer: will be found at different locations
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Diffusion

Equivalently, we can envision a large number of

molecules concentrated in a line at t = 0 and ask what
the distribution of molecules will be at time t.
This is sometimes called the "drunken sailor problem"

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Diffusion
Where, we envision a very drunk sailor emerging
from a bar and staggering randomly left and right
What is the probability that the sailor will get
down the street a certain distance after a certain
time t?

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Diffusion
At time , it is equally likely that the molecule is at
+l and -l; and
at time 2, the relative probabilities of being at +2l,
0, and -2l, are 1, 2, and 1, respectively.

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Diffusion
The probability, P(m, r), that the molecule is at a
given location after m time units (m = t/) is given
by the binomial coefficient

Where, x = (-m + 2r)l, with r = 0, 1 , . . . m.

Mean square displacement,
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Diffusion

Diffusion coefficient, D, identified as

is a
constant related to the step size and step frequency

This equation provides a handy rule of thumb for

estimating the thickness of a diffusion layer (e.g., how
far product molecules have moved, on the average,
from an electrode in a certain time)
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Conclusions

Mass transfer equation, migration, and Diffusion

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Next class

Fick's Laws of Diffusion

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