Transport phenomena in electrochemical systems:

Charge and mass transport in electrochemical cells

F. Lapicque, CNRS-ENSIC, Nancy, France

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!)
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1- Various physical phenomena in electrolyte solution

H

H
O

Solvatation
O

Metal ions (and also anion

are highly solvated.

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

This atmosphere is distorte

by the motion of Men+
(It is a sphere for nil electr

Electrophoretic effect :
Force on the ionic atmosph
acts as an increase in
solvent viscosity
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1- Transport phenomena: introduction to migration

Electrical force on ions (charge q)

(Stokes law)
Ion: very small particl

Velocity of the charged particle

Absolute mobility of the

ioni'

qi
6 ri

z i e0
6 ri

Specific migration flux

mol m-3

2- Mass transport rates and current density

General equations of transport

Consider a fluid in motion

Species i
Concentration Ci and velocity of ions vi
Defining a barycentric molar velocity
Convection flux
Specific flux of species i

Ci v
Ci vi

Flux for diffusion and migration

Di C i
Theory of irreversible processes
Ji
gra d ie
RT

ie: electrochemical potential

Ion activity

Elec. potential5

2- Mass transport rates : the Nernst-Planck equation

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

Other expressions available from the theory of

irreversible processes
(Stefan maxwell, Onsager )

2- Mass transport rates : expression of the current density

Equations in electrochemical systems

Current density

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

Medium conductivity (low C

NB: The current density can be defined and calculated anywhere in the electr

2- Mass transport rates: some more useful relations

* Relation between diffusivity and ion mobility

For the expression of the migration flux and Nernst-Planck equation:

which leads to the Stokes Einsteins relation

only in dilute
media

For more concentrated media, various laws. D0.7/T = Constant

* Transference number: fraction of the current transported by speci

2- Mass transport rates: the trivial case of binary solutions

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

Replacement of the electrical term, and algebraic rearrangement le

with
Transference numbers

The salt behaves like an

non-dissociated species, with the
overall diffusivity D being
compromise between D+ and D-

Expression for the curren

NB: Although extensively used,

the relation is only valid for binary
so
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3- Flow fields in electrochemical cells (an introduction to)

Fluid in motion along a surface

The stress applied to the fluid has two components
- the normal component, corresponding to a pressure
- the second one, along the plane, corresponds to viscous force

The structure of the flow can be

* Laminar, for which the fluid is divided into thin layers (laminae that
* Turbulent, where the fluid is divided into aggregates. The velocity of the
a random component, in addition to its steady component

NB. For too short systems, with local changes in direction and cross-section,
or non-established

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3- Flow fields in electrochemical cells

Two dimensionless numbers allow the flow to be defined in the considered

Friction factor

Tangent. stress/kinetic e

Reynolds number

Inertia/viscous forces

<u> Average velocity, d charactetistic dimension

A few comments

Laminar/turbulent transition: for Re = 2300? Only in pipes

Very large systems are in turbulent flow e.g. atmosphere, oceans
Minimum length for the flow to be established
Which characteristic length d? Gotta find the length of highest ph

Jf is used for estimation of the pressure drop

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3- Flow fields in electrochemical cells: laminar and turbulent fl

Laminar flow (example of a pipe)

Jf = 8/Re
Parabolic velocity profile

The pressure drop varies with

Turbulent flow (example of a pipe)

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

for 104 < Re < 2 106

(the pressure drop varies w

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4- Analogy between the transports of various variables

Specific flux = - Diffusivity x Gradient of the extensive variable

Heat (J)
Weight (kg)
Example

Dimensionless numbers: ratio of the diffusivities and orders of magnitude

Sc = /D
Gas
1
Liquids 1000

1
10

Pr =
1

Le = /D
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4- Mass transfer to electrode surfaces

Mass balance (transient) in a fluid element near the electrode

C i
DzF
div N i div (C i .u ) Di C i i i div C i .grad s
t
RT

Whow!

The Nernst-film model: a cool shortcut for approximate calculations o

Steady-state conditions
Negligible migration Flux
Vicinity of the electrode (low u
1-D approach

Did2Ci/dx2 = 0

Linear profile of the concentrat

NB: the velocity profile is
Sc1/3 thicker than the
Only the diffusion term
concentration profile. i.e. 10 or so
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4- Mass transfer to electrode surfaces (Ctd)

Expression for the current density

C Ab C As
i ne FD A

Defining the mass transfer coefficient, kL

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

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4- Mass transfer to electrode surfaces Two

(Ctd)
dimensionless numbers:
Re and Sh (Sherwood)

Whats the use of these dimensionless relations??

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Hint: Possible change in velocity, dimensions and physicochemical properties

4- Mass transfer to electrode surfaces (Ctd)

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

0.6 < n < 0.8

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4- Mass transfer to electrode surfaces

How to determine them?

* Measure pressure drops in the system Poorly

and accurate!!
Access to overall data, only
use energy correlations
(bridge between the dissipated energy
and the mass transfer rate)
Reliability of the data?
Is your system so close?

Find the most suitable correlation in

your usual catalogue or in published works

* Measure the limiting current at electrode surfaces

Access to local rates with microelectrodes

Find the right electrochemical system (solution, electroactive
Do measurement with the academic system
Deduce estimate for kL in the real case using dimensionless a

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