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Outline
1- Various phenomena in electrolyte solutions
2- Mass transport rates and current density
3- Flow fields in electrochemical cells (a brief introduction
4- Mass transfer rates to electrode surfaces
Dr Bradley P Ladewig,
presenting instead of Francois
Lapicque
PhD in Chemical Engineering
(Nafion Nanocomposite
membranes for the Direct
Methanol Fuel Cells)
Currently working as a
Postdoc for Francois Lapicque
at CNRS ENSIC, Nancy
France
Originally from Australia (which
is a long, long way from
Serbia!)
2
H
O
Solvatation
O
Men+
O
Relaxation:
caused by interactions
Existing forces and hindrance to motion
between the cation and the
Ionic atmosphere
ionic atmosphere
(negative charge)
Electric field
Me
n+
Fionic atm.
Fion
NB: these effects are rarely accounted for in models
Electrophoretic effect :
Force on the ionic atmosph
acts as an increase in
solvent viscosity
3
(Stokes law)
Ion: very small particl
ioni'
qi
6 ri
z i e0
6 ri
Ci v
Ci vi
Di C i
Theory of irreversible processes
Ji
gra d ie
RT
Elec. potential5
From the expression for Ji and the relation between Ni and Ji:
Assuming ideal solutions (ai = Ci) leads to the Nernst Planck equatio
Di C i
N i C i u D.gradC i
z i F .grad s
RT
Convection :
Overall motion
Diffusion
of particles with
barycentric velocity term
(Fick)
Migration :
Motion of ions (zi) under
the electric field
NB: This equation is not rigorous in most cases, however, it is often used bec
i zi F N i
i
zi Ci 0
Electroneutrality equation
i F z i Di .gradC i .grad s
Without C gradients:
i grad s
z
i
2
i
Di C
RT
NB: The current density can be defined and calculated anywhere in the electr
only in dilute
media
Binary solutions: one salt dissolved (one cation and one anion)
Assuming total dissociation of the salt leads to (general transient ex
same for the anion
with
Transference numbers
NB. For too short systems, with local changes in direction and cross-section,
or non-established
10
Tangent. stress/kinetic e
Reynolds number
Inertia/viscous forces
A few comments
11
More complex expression for the velocity, but the profiles are much fla
One example for the expression of the friction factor: Blasius relation
Jf = 0.023 Re-0.2
12
Heat (J)
Weight (kg)
Example
Sc = /D
Gas
1
Liquids 1000
1
10
Pr =
1
Le = /D
13
C i
DzF
div N i div (C i .u ) Di C i i i div C i .grad s
t
RT
Whow!
Steady-state conditions
Negligible migration Flux
Vicinity of the electrode (low u
1-D approach
Did2Ci/dx2 = 0
C Ab C As
i ne FD A
i nneeFD
FkAL C Ab C As
i L tone0Fk L C Ab
Limiting current density: when CAS tends
Miximum value for the current density iL : e can be equal to 1
maximum production rate
15
Examples
L=1m
dp=0.005 m
=10-6 m2/s
D=10-9 m2/s
kL = A <u>n
Laminar flow 1/3 < n < 0.5
Turbulent flow
17
18