Electrochimica Acta 51 (2005) 11401156

Modelling and calculation of the current density distribution

evolution at vertical gas-evolving electrodes
Mandin Philippe

, Hamburger J er ome, Bessou Sebastien, Picard G erard

ENSCP-LECA U.M.R. C.N.R.S. 7575 Laboratoire dElectrochimie et de Chimie Analytique 11,
Rue Pierre et Marie Curie, 75005 Paris, France
Received 13 April 2005; received in revised form 1 June 2005; accepted 1 June 2005
Available online 15 July 2005
Abstract
During industrial electrolysis, for hydrogen, dichloride or aluminium production, there is bubbles creation at one or two electrodes which
imply a great hydrodynamic acceleration but also a quite important electrical eld disturbance. This disturbance can lead to the modication
of the local current density and to anode effects for example. There is few works concerning the local modelling of coupled electro active
species transport and electrochemical processes in a biphasic electrolyte. There are also few local experimental measurements in term of
chemical composition, temperature or current density which would allow the numerical calculations validation. Nevertheless, effects like the
anode effect, particularly expensive on the point of the process efciency, should need a better understanding. Nowadays, the respective roles
of the local temperature increases, the electro active specie composition or the transport properties modication due to bubbles are not known.
The goal of the present work is the modelling and the numerical simulation of the vertical electrode conguration for a biphasic electrolysis
process. Bubbles presence is supposed to modify the electrical properties, and then the electro active species diffusive transport and the current
density. Bubbles are also motion sources for the electrolysis cell ow, and then hydrodynamic properties are strongly coupled with species
transport and electrical eld. The present work shows hydrodynamic and electrical properties in a laboratory scale electrolysis cell with a
vertical electrode. The numerical algorithm used was the nite volume used in the computational uid dynamic software Fluent

.
2005 Elsevier Ltd. All rights reserved.
Keywords: Electrochemical; Modelling; Vertical; Biphasic; Electrolysis
1. Introduction
Gas release and induced uid ow over electrodes exist
in many electrochemical processes such as chlorine produc-
tion, water electrolysis, alumina reduction, and many other
chemical processes. The hydrodynamical properties and the
gas-ow motion in electrochemical cells is of great practi-
cal interest in electrochemical engineering science since the
dispersed phase modies the electrical properties of the elec-
trolyte (as well as mass and heat transfers), and therefore
modies the macroscopic cell performances. In most cases,
this phenomenon has to be avoided, but, in some other pro-
cesses, the gas ow rate has only to be controled; this is the

Corresponding author. Tel.: +33 155426380; fax: +33 144276780.

E-mail address: philippe-mandin@enscp.fr (M. Philippe).
case namelyfor gas production(H
2
, O
2
, Cl
2
, . . .) [1] andother
special processes such as, e.g. chemical engraving [2,3]. In all
these different electrochemical processes, a coupling effect is
particularity strong (as shown by Hine [4], e.g. for simple gas
evolvingelectrodes) because bubble-dispersedphase acts like
an electrical shield, the shielding effect depending on the den-
sity of the bubbles, which is namely the gas volume fraction
of the dispersion. Except in some special cases such as alu-
minium extraction (H eroult-Hall process), where high rates
of coalescence occur under the horizontal anode face, the gas
phase is clearly composed of small dispersed bubbles (order
of magnitude 100 m) comparable to little rigid spheres with
a constant radius ([57]). Though many authors [810] men-
tion that the diameter of small bubbles can be considered
constant but dependent with the local current density, it has
been here considered a constant diameter with current density
0013-4686/$ see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2005.06.007
M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156 1141
Fig. 1. Vertical gas-evolving electrode: left is the geometric conguration and right is a current distribution example (y: electrode height; j
x
(y): local current
density).
value. As mentioned by many authors, the absolute velocity
of bubbles (in the cell reference frame) is a key parameter
of the process ([4] and [11,12]) as well as bubble diameter:
the higher the local bubble velocity, the lower the local gas
fraction. Though the hydrodynamical two phase ow prob-
lem is not easy to solve a priori, some coarse assumptions
are usually made to calculate the hydrodynamic ow in elec-
trochemical cells. But some precious information are lost,
especially in region where there are strong velocity gradients
or some void fraction non uniformity. Moreover, experiments
are often very different from one paper to another, and it is
therefore often difcult to extract some general information,
especially for ow structure in cells.
1.1. Problem standing
Fig. 1 is a scheme of a classical electrochemical cell, with
a single vertical gas-evolving electrode conguration.
The purpose of this work is to compute a numerical solu-
tion of the coupled electrical and hydrodynamical properties
in such an electrochemical cell. An accurate tool for coupled
two-phase ow and electrochemical properties seems to be
an important task to develop for industrial applications and
therefore the aim of the present study is also to validate an
original coupled numerical simulation strategy, using compu-
tational uid dynamic (CFD) software to solve the uid ow
resulting from an electrochemically driven bubble-release.
The main purpose of this study is namely to have an estima-
tion of:
(1) the coupling between bubble release and current density
at electrode surface, at the beginning for lowcurrent den-
sity values. This assumption allows the use of Lagrangian
modelling (see biphasic ow modelling part) and also
allows neglecting the shadowing resistance due to grow-
ing bubbles.
(2) Orders of magnitude of induced uid ow in the cell and
its effect on current distribution. This developpement of
numerical simulation using CFD software seems to be
necessary and helpful for a better understanding of the
bubble release effect and help for further modelling. At
last, cell performances could be optimised and enhanced.
According with small current density assumption (mean
current density I/A lower than 4000 Am
2
, according
with Tobias experiments [13]), the electrical resistance
increase due to bubble release is possible to estimate.
The anode effect modelling need to work at larger cur-
rent density values and need to take into account the
bubble shadowing and coalescence (see Vogt et al. and
Wuethrich et al. [10] and [15,16]).
2. Hydrodynamic and electrical coupling
The primary current density distribution j (Am
2
) in an
homogeneous electrolyte cell is, at the macroscopic scale,
uniform along electrode, and is horizontally owing through
the cell fromanode tocathode. But, as a well knowneffect, the
gas dispersion along electrode is not uniform, since bubbles
rise vertically due to Archim ede acceleration. Thus, the void
fractionincreases withincreasingelectrode height (see Fig. 1)
and the conductivity decreases with altitude. Then current
distribution at anode is modied, and also local gas ow rate
due to Faradays law of electrolysis, and so on (Fig. 2).
In the case of an electrochemical reaction with gas
production, gas is produced at the electrode surface with a
local gas mass ow rate q [kg m
2
s
1
]. The local gas mass
ow rate q due to electrochemical reaction is proportional
to the local current density j using the rst law of elec-
trolysis. The distribution q(y) is also, for a homogeneous
electrolyte, uniform, if the electrodes are considered to be
perfectly conducting. Since gas bubbles rise upwards along
electrode, non-uniformity is generated along electrode and
the void fraction of gas, which is a hindering effect for
the electrical current, increases along electrode. The void
fraction distribution depends on local gas production at the
electrode surface, and on the uid ow motion induced by
1142 M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156
Fig. 2. Calculation ow-sheet for the coupling effect in the electrochemical
cell due to the presence of bubble release.
the bubbles. Therefore there is a two way coupling of the
physical problem (see Fig. 2), and the two coupling relations
are:1-The Faraday 1 aw of electrolysis:
q =
Mjn
(nF)
(1)
which determinates the local rate of produced gas by the
electrochemical reaction, in the case of no back reaction
(efciency =100%). q is the gas phase local mass ow
rate, jn the current density normal to boundary, n is the
charge number, F (96485 Cmol
1
) is the Faraday constant,
and M is the molar weight (2 10
3
kg mol
1
for hydrogen
bubbles).2-Bruggeman relation:
=
0
(1 )
3/2
(2)
This is the phenomenological law chosen in the present
work for the local electrical conductivity sensitivity with bub-
bles presence.
0
stands for the electrical conductivity of the
pure electrolyte, and stands for the local void fraction.
The calculations, as shown with algorithm presented
Fig. 2, focused the effort in the coupling programming
between bubble electrode mass owrate and the local current
density j. Surface shadowing leads to the adherence resis-
tance contribution, well described with Wuethrich discrete
modelling works [10], whereas volumetric shadowing leads
to the diffusion resistance effect which will be here taken into
account alone. In the present work, the classical surface cov-
erage function (surface void fraction), often used by authors
like Vogt [11], Tobias [13] or Wuethrich [10], has not been
introduced. The area shadowing effect is negligible for low
current density values studied here. The discrete phase mod-
elling can only be used under this assumption (void fraction
lower than 10%). Due to the reduced active area, the actual
maximum current density is larger (j/) than this calculated
under the present work assumptions.
The adherence resistance has been neglected according
with the low current density assumption.
To take into account the adherence contribution (the sur-
face one), it should be necessary to measure or suppose the
law between and value at surface relation. This will be
done in future work. The Fig. 2 algorithm will be modied
with a stage between void fraction and potential eld cal-
culation with the surface shadowing function calculation.
For simplicity, assumptions are made in both hydrodynamic
and electrical problem solution procedures in order to focus
mainly on the coupling aspect we are interested in, particu-
larity gas evolution on electrodes.
1. Electrical conductivity of the electrodes is supposed very
large (innite). Therefore, the imposed electrical potential
for each electrode is constant.
2. Liquid electrolyte is supposed to be homogenous in term
of dissolved species chemical composition and tempera-
ture.
3. Heat exchanges and therefore energy equation are not con-
sidered here, assuming that the temperature is uniform,
though bubble layer modify heat transfer.
In this two-way coupling (hydrodynamic-electrical), the
uid ow itself also needs a two-way coupling calcula-
tion between continuous and discrete phase. From this, and
reminding that the local gas void fraction calculation is a sine
qua none condition to determine the current distribution in
the electrolytic cell, it is necessary to calculate the two-phase
uid dynamic (gasliquid) properties. It should be possible to
develop a numerical tool; in the present work, the nite vol-
ume numerical method programmed in the Fluent

software
is used.
This coupled problem has been treated by many authors
in the past years, and has had an increasing interest in recent
years for the purpose of optimizing electrochemical pro-
cess through better design of cells, materials and chemicals.
Tobias [13] developed a mathematical model, considering
bubble release in electrochemical cell with a stagnant elec-
trolyte medium (1959). This theoretical approach results in
a differential equation for the void fraction of gas in the
cell, which was considered to be uniform over the width of
the cell. It was a one dimensional modelling with the vertical
coordinate alone to be taken into account. Other mathemati-
cal approaches and experimental works have been done in the
past and are summerized in the paper of Ziegler and Evans
[17].
The most recent works about this subject deal mostly
with numerical simulation but are not numerous, even
though the expansion of computer performance has been
important. Byrne and al [18,19] have nevertheless calculated
numerically primary, secondary and pseudo tertiary current
distribution in chlorate membrane cell with a complicated
geometry, and provided some experimental data on vertical
gas-evolving electrodes under forced convection. Wetind
[20], and Dahlkild [5], solved the coupled hydrodynamic-
electrical problem in the cases of a single vertical electrode
M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156 1143
and in the case of Byrnes experiments ([18,19]), with a
particular attention to diffusion forces acting perpendicular
to the wall (normal dispersion forces). The commercial code
CFX was used. Bech [21] solved the coupled problem in the
case of simplied aluminium reduction cell geometry and
using a discrete phase model in the code FLUENT 4.4.
3. Electrical model
3.1. Voltage components
The electrochemical cell is dened by the applied voltage
U/(V) for given overall electrical current owing through
the cell. The applied voltage decomposes as follows:
U = E
0
+
r,a
+
c,a
+RI +
r,c
+
c,c
+[U
a
+U
c
]
(3)
where E
0
is the reversible thermodynamical potential of
chemical reaction involved in the cell, RI is the ohmic voltage
drop in the biphasic electrolyte,
r
is the reaction overpoten-
tial, respectively for anode and cathode (respective subscripts
(a) and (c)),
c
the concentration over potential, respec-
tively, for anode and cathode (subscripts (a) and (c)), and
U
a
+U
c
ohmic voltage drop in the anode and cathode
material, which are neglected here. R is the overall resistance
of the electrolyte, and I =
_ _
A
j ds is the integral current
owing through the cell. In this work, current density and
bubble mass owrate are locally calculated and not, as usual,
mean values over the electrode area. The reaction over poten-
tial
s
depends on the current density normal to the boundary
through ButlerVolmer Eq. (4):
jn = j
0
_
exp
_

s
F
RT
_
exp
_

(1 )
s
F
RT
__
(4)
where, jn is the local current density normal to electrode sur-
face component (A m
2
), j
0
is the exchange current density,
is the transfer coefcient for anode and cathode (subscripts
(a) and (c)). Further is R=8.314 J mol
1
K
1
the gas con-
stant, F=96487 Cmol
1
the Faraday constant.
Over voltage due to surface reaction is conned in the
double layer, which size is of order magnitude of a molecule
dimension, which is, macroscopically speaking, the surface
itself. Therefore, relations (3) and (4) should be used in the
electrical modelling to dene the electrode boundary con-
dition. The numerical resolution of this equation leads to
the secondary current distribution. Because the concentration
over potential
c
implies the electro active species concentra-
tion at electrode surface, the species mass balance is needed.
The resolution of this coupled mathematical system leads to
the ternary current distribution.
The strategy to solve such non linear problems with
coupled equations and boundary conditions, expressing the
kinetics of the electrochemical reaction at the electrodes, is
difcult and then need patience. To ensure robustness, the
rst stage consists to solve the electrical problem with sim-
plied boundary conditions which allow the calculation of
the primary current density distribution. Under this assump-
tion, reaction and concentration over potentials at electrodes
are neglected. With this electrical modelling, only the ohmic
component of resistance is taken into account. Thus, Eq. (3)
reduces to:
U = E
0
+RI (5)
which is the simplest cell electrolysis modelling. The ohmic
voltage is then simply the applied voltage minus the thermo-
dynamical potential.
3.2. Current distribution
The current distribution is determined by solving the cur-
rent conservation Eq. (6) associated with phenomenological
Ohms law (7):
div j = 0 (6)
j = E = grad (7)
where j (Am
2
) is the current density vector, (V) is the
electrical potential dened in the whole domain of the cell,
the electrical conductivity (Sm
1
) dened in the whole
domain of the cell. Combining Eqs. (6) and (7) leads to
the classical transport equation for the electrical potential
(8):
div( grad ) = 0 (8)
In the particular frame of this study, conductivity is a
functionof the local voidfraction, andtherefore onlya numer-
ical method is likely to be used to compute a solution. The
relation =((x, y, z)) has been dened by many authors and
Bruggemans one is the most commonly used. Void fraction
depends on many factors, and is often strongly non uniform
over cell section since gas evolution is often conned at elec-
trode surface (see next section). There then exists a biphasic
layer in the electrode vicinity.
In this procedure, using a nite volume algorithm for the
numerical solving, the boundary values of the potential are
assumed to be constant at electrodes. Then, under this mod-
elling hypothesis, there is no potential gradient and therefore
no tangential current along electrode.
4. Hydrodynamics
Fluid ow in the cell depends on the gaseous bubbles
release, which depends strongly on the cell design. In some
particular industrial congurations, as e.g. aluminium reduc-
tion cells, the anode surface is not purely vertical (there exists
a non negligible horizontal electro active surface) and there-
fore bubble rise is hindered and lead to special two-phase
owpatterns (coupling between bubbles forming a dispersed
phase and bubbles packet formed under the anode surface).
1144 M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156
However, the simple geometry of a vertical electrode con-
sidered here has already its own complications, and will be
developed here in a rst step.
4.1. Fluid ow
The uid dynamics problem consists in solving the two
phase ow in the electrochemical cell due to the electro-
chemically generated bubble release at electrode surface.
Gasliquid two phase ow modelling is usually encountered
in bubble columns or bubbly pipe ows, in the nuclear eld
particularly or other industrial applications. The two-phase
ow can be treated in two different ways, either consider-
ing the gas phase as discrete particules (lagrangian model)
or as a continuum (eulerian models). When there is a clear
dispersed phase, the ow is called bubble ow. A Lagrange
method is then suited, since bubbles can be considered as
particles. If the gas phase void fraction is too high (the limit
void fraction is said to be 10%), as in slug or churn ow, the
gas phase should better be treated as a continuous phase and
then, a two-continuous phase (EulerEuler) model is then
more suitable.
In the classical vertical gas-evolving electrodes congura-
tion considered here (Fig. 1), if the inter electrode gap is not
too small, with a moderate current distribution, the gas evolu-
tion is clearly a dispersed ow as observed by many authors
(e.g. Hine [4], Boissonneau [7], Schneider [6]). The ow in
these works is composed of tiny bubbles of released H
2
, O
2
,
or Cl
2
. These bubbles are assimilated to rigid spheres with
constant radius. This hypothesis assumes that the electrode
is not too high to neglect the effect of pressure variations and
assumes also a uniformtemperature eld. The bubble diame-
ter will be supposed small compared with the inter electrode
distance. Then diameter d
p
=10
4
and 10
3
m have been
explored in the present study.
4.2. Two phase ow-bubble ow
For vertical electrodes conguration, the bubbles resi-
dence time is small due to the Archim ede acceleration and
void fraction is often sufciently small. Bubbles are then
everywhere not numerous and can be considered as indi-
vidual particles (not as eulerian ow) comparable to rigid
sphere with small radius (d
p
=10
4
m for example). The
model employed here is the lagrangian model. Nevertheless,
this model remains valid if the void fraction near the elec-
trode is smaller than 10%, which is the commonly accepted
limit for lagrangian models. The condition of <10%should
therefore be respected, since void fraction depends on many
factors, especially:
- gas ow rate (or indirectly jn);
- bubble diameter;
- liquid density, liquid ow;
- electrode height.
Therefore, the above condition will have to be checked
after computation, and will be determinating the validity of
the two-phase calculation.
4.3. Equations
Navier-Stokes equations are solved for the liquid
phase (continuum) (9) together with continuity Eq. (10):
Momentum:
(u
i
)
t
+
u
j
(u
i
)
x
j
=
p
x
i
+

x
i
_
u
x
i
_
= g
i
+K
m
(9)
Continuity:

t
+
(u
i
)
x
i
= 0 (10)
where in Eq. (10), the right hand terms are the forces exerced
on the uid volume:
- pressure force;
- continuous viscous force;
- gravity;
- and nally the coupling term K
m
which is in fact the
momentumexchange due to bubbles passing through a unit
volume.
This set of equations constitutes the Navier-Stockes equa-
tions with the coupling exchange term K
m
due to bubble
entrainment force. These equations are solved in the Fluent

[22] software using the Patankar [23] nite volume method

andthe SIMPLEC(Semi Implicit Methodfor pressure Linked
Equations Corrected) algorithm. More details concerning the
ow modelling and the numerical parameters for solving are
given in [24].
4.4. Lagrangian model
Particles are injected from a given surface with a given
mass ow rate q which depend on the local current den-
sity value jn. Therefore, the program computes a number
of bubbles per second (stream) issuing from one injection
point, which is, if the injection surface is a boundary, the
cell center of the face boundary. A more realistic modelling
should use as input data the nucleation sites density and
should deduce the average distance between two sites to
choose the electrode surface partitioning cell dimension. In
the present work, the cell dimension is larger than this aver-
age distance and then the bubble injection frequency is larger
than the actual one. But calculations are done under the steady
state assumption. For each particle, The Newton dynamic
equation (force balance) is solved to calculate each particle
velocity:
d(u
p
)
i
dt
= F
D
(u u
p
)
i
+
g
i
(
p
)

p
+F
x,i
(11)
M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156 1145
Fig. 3. Drag coefcient C
D
vs. Re
p
number (after [25]).
F
D
(u
l
u
p
)
i
: drag
g
i
(
p
)/
p
: buoyancy
_
are the two main forces when gravity is concerned
F
x,i
: other forces; i is the coordinate index (i =l is x and i =2
is y)
The two main forces acting on bubbles in the case of
vertical gas-evolving electrodes are the buoyancy force (or
Achimede force) and the drag force. The former one depends
only on the liquidgas density ratio, and the drag force F
D
is dened by: F
D
=18 C
D
Re
p
/24
p
d
p
2
which depends
on bubble diameter and bubble Reynolds number (based on
relative velocity) and C
D
(drag coefcient). The coefcient
variations C
D
versus Re
p
are well known for rigid spheres
(Fig. 3) and can be dened mathematically by some semi-
empirical relations. In this study, the Morsi and Alexander
[25] (see Appendix A) modelling and values has been used.
C
D
is an important coefcient to determine and its value
depends on Re
p
and on other factors as bubble shape, liq-
uid properties (pure water or contaminated water). A typical
C
D
versus Re
p
evolution scheme is shown in Fig. 3. It can be
seen that drag coefcient C
D
decreases with Re
p
and switches
to a constant value for high Reynolds numbers (which cor-
responds to a transition to turbulence). However, for this
study, bubbles are considered to remain spherical [5] and
the ow over the bubble to remain laminar everywhere in the
electrochemical cell. This hypothesis will be veried after
calculation, using numerical results. The steady-state bubble
rise velocity has been calculated using Eq. (11), neglecting
the F
x,i
forces which are related to special problems (wall
effects, lift forces, vitual mass). A validation of the FLUENT
code is done in Appendix B for the (u
p
, C
D
, Re
p
) triplet in
the case of different bubble radius injections at the bottom
face of the cell.
Additional forces are used in special problems of two
phase ow modelling. For example, the classical virtual
mass force is particularily important near gas injectors and
inuences the bubble motion in bubble columns. Pressure
force (due to pressure gradients) is taken in account for high
pressure variations. . . Close to walls, one should also take
into account the lift force towards the wall and a lubrication
force [26] acting to make the bubbles move away from the
wall. These forces act very close to the wall [27,28]. Another
articial force perpendicular to the wall (close to the wall)
has been implemented by Bech [21] to allowbubbles to move
away from the wall at a distance of approximately one par-
ticle radius. This force was used to avoid mesh dependence,
bubbles being conned in the rst cell column. Under the
Lagrange modelling assumption, each particle is supposed
alone whereas each particle is actually in a cloud of particles,
near the electrode wall and there are non negligible interac-
tion forces. Then, there is an important need of an accurate
description of bubble-wall and bubble-bubbles interactions.
However, since bubbles are growing and departing from
electrode surface all along the surface, there is, in this case, no
needtoensure zerovoidfractions at electrode wall. Moreover,
presence of bubbles is suited since bubble cover the electrode
surface with a given covering factor. For all the reasons above,
it was chosen, in this study, to neglect these forces, and to
introduce a dispersion force perpendicular to gravity as a
parameter of the numerical study.
4.5. Coupling term K
m
The coupling term for motion exchange between contin-
uous and discrete phase in Eq. (9) is therefore:
K
m
=

(F
D
(u
l
u
p
)
i
+F
x,i
)q t (12)
Where q is the mass ow rate of the bubble stream in the
considered computational cell; F
x,i
is an arbitrary dispersion
force, perpendicular to gravity.
5. Results
5.1. Nominal Case
Computations of the coupled problem were performed
on a nominal two-dimensional geometry with height
y
max
=0.45 m and thickness h
g
=0.03 m (Fig. 4). The elec-
trolyte conductivity was set to =60 Sm
1
(which corre-
sponds, for example, to a 10 wt.%KOHsolution at 25

C). In
our model, we have supposed that the electrochemical forma-
tion of a gaseous mole necessitates a number of exchanged
electrons equal to two (this in order to x idea, could corre-
spond for example to the overall heterogeneous reaction for
hydrogen evolution at cathode surface in alkaline solution,
is: 2H
2
O+2e

H
2(g)
+2OH

. Moreover it is supposed
that at the anode surface there is no bubbles creation due to
the oxidation reaction of the electrolyte. At last, bubbles are
assumed to be spherical, with a constant diameter d
p
=10
4
or 10
3
m. This unknown bubble diameter should be small
enough to agree with modelling assumptions.
The electrode materials are supposed to be perfectly
conducting so that the electrical potential over the electrode
height is constant (see electrical modelling) [29]. This
condition can be reached experimentally by using copper
bus bars, e.g. as used by Hine [4]. Thus, in a homogeneous
1146 M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156
Fig. 4. Geometry for computed case (see text for details).
liquid electrolyte (with a constant electrical conductivity,
current is also uniformly distributed over anode height.
Therefore, changes in current distribution are only possible
by a changing of the electrical conductivity over electrode
height in the cell, which is actually the case in vertically
gas-evolving electrodes considered here.
The calculation domain mesh is formed with 10 45 uni-
form cells and has been obtained with the software Gambit

.
The uid mechanics and electrical modelling have been set
in the Fluent

software. Particularly, the electrical poten-

tial
a
and
c
have been xed to an initial value of 2
and 0 V, respectively, which corresponds, without any bub-
bles exhaust, to a uniform current density : I/A=j
av
=
(
a

c
)/h
g
=4.10
+3
Am
2
.
Eq. (8) was solved with software FLUENT

as a user
dened scalar transport equation for the electrical potential
with a diffusivity coefcient being equal to the local electri-
cal conductivity . The local current density and the local gas
ow rate creations along the vertical electrode were coupled
according with the rst law of electrolysis and were com-
puted and set through user dened functions written in C
language, compiled with MS Visual Studio Pro

and hooked
to be taken into account in the FLUENT

calculation proce-
dure. Physical properties for the liquid electrolyte in nominal
case are summarized in Table 1.
Terminal rise velocities for different bubble sizes (com-
puted) are plotted in Fig. 5. The terminal rise velocity is
obtained and is a result of a balance between Archimedes
force and drag force on a bubble (Eq. (11)). This velocity
is reached very rapidly (almost instantaneously for bubbles
<10
3
m) as shown in Appendix B, so that the velocity of a
Fig. 5. Terminal Rise velocity of single bubbles vs. bubble diameter d
p
.
bubble in a stagnant medium can be considered as constant
and equal to this value.
Bubbles are created at the electrode boundary surface, in
the middle of eachface-element of the mesh. Bubbles actually
move up vertically immediately after detachment because
of the Archimedes force and therefore, without any relevant
dispersion force perpendicular to the ow, the bubble trajec-
tory is conned in the rst mesh cells column near the wall
(Fig. 41).
5.2. Dispersed phase
The dispersed phase is rst considered alone (stagnant
liquid assumption) to be a sum of bubbles rising vertically at
their intrinsic terminal rising velocity. This becomes a ctious
case when bubbles are in a sufcient number, and uid owis
entrained, and therefore bubble velocity is changed (absolute
velocity). However, computations were performed in the case
of 10
3
msize bubbles, withthe nominal properties of gas and
liquid electrolyte dened above, and mesh already dened
(cell size 1 cm).
Fig. 6a depicts the local current density distribution along
the electrode length (y
max
=45 cm) in the case of coupled and
non coupled computations. Corresponding values of mass-
ow rate injection of bubbles are shown on Fig. 6b. As a
comparison, Tobias analytical model (coupled) based on the
rising velocity of the bubbles, is added. This model sup-
poses that the void fraction is distributed over the width
of the cell (see Appendix C). A simple manual calculation
made from void fraction prole along electrode divided by
the number of cells shows that the prole t the analytical
Tobias prole (values for the calculation of Tobias proles
are summarized in Table 2). Fig. 6 shows modelling impact
upon current density and local gas owrate distribution along
Table 1
Physical properties for the two phase ow
Nominal case
M
(g)
(kg mol
1
)
p
(kg m
3
) d
p
(m)
1
(kg m
3
)
1
(kg m
1
s
1
)
2.10
3
0.07 1.10
3
1.10
+3
1.10
3
M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156 1147
Fig. 6. Left: comparison of current density distribution along electrode for the case of conned bubbles, distributed bubbles, and with Tobias theoretical model
(Appendix C). Bubble diameter: 10
3
m. Gas ow rate: uniform (no coupling) or non uniform (coupled). Right: gas mass ow rate prole along electrode.
Table 2
Numerical values computed for comparison with Tobiass model [13]
u
s
(ms
1
) C (mA
1
) K- j
av
(A m
2
) y (m) q
(g)
(kg s
1
)
1135.10
1
4.35 10
5
8 10
2
4 10
+3
1 10
2
4.14 10
7
the vertical electrode, under the stagnant liquid (continuous
phase) assumption. The rst step for the rigorous coupled
calculation is called uniform: the gas ow rate is supposed
uniform and independent of the vertical coordinate y, with
the constant value deduced from the average current density
I/A=j
av
=4000 Am
2
. The resulting current density distri-
bution due to this constant gas injection, which could be due
to a non-electrochemical origin injection, is shown in the
Fig. 6 left. In the Tobias work case, the bubble creation is due
to the electrochemical reaction and then to the local current
density. Because this last is not constant, the bubble creation
is not constant and has to be calculated. It has to be done
iteratively, till the convergence and the calculation stabilisa-
tion is reached. This is the so-called coupled calculation.
In this case, because current density decreases with y, the
bubble creation also decreases.
The knowledge of the gas ow rate distribution allows the
void fraction distribution calculation along electrode: this is
plotted in Fig. 7: at left, vertical prole; at right 3 horizontal
proles for y =0, 0.225 and 0.45 m. For the uniforminjection
case, the gas ow rate of bubbles is constant at each injection
cell (since mesh is regular) and therefore void fraction prole
increases linearly. Each injection cell adds its contribution to
the local void fraction (void volume/cell volume) according
with:
=
1

p
q
(g)
y z
_
y
u
p
_
(x y z)
1
=
1

p
q
(g)
_
y
u
p
_
(x)
1
= 1.74 10
2
where q
(g)
is the gas ow rate in one cell adjacent to the
electrode, dened by:
q
(g)
=
j
av
nFM
(g)
y
Fig. 7. Left: void fraction along electrode for the no coupled and coupled calculation. Right: void fraction distribution in the width of the cell at three electrode
heights for the coupled calculation. Bubble diameter: 10
3
m.
1148 M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156
The nal value of (the mass fraction of bubbles) at the
top of the electrode is:
=

= 45 = 0.78
which corresponds to the value computed by the Fluent

software (Fig. 7).

For the coupled calculation and the comparison with
Tobias experimental results, there is a problem: the current
distribution is predicted lower than the Tobias measurements
and correlation. This should be due to the unrealistic bubble
concentration near the electrode which is quite different than
the uniformly distribution at position y assumption used in
Tobias modelling. In the present modelling work, the bub-
bles are conned in the rst column of cell (adjacent to the
electrode), as seen on cross-sectional void fraction proles
(Fig. 7 right), and therefore the void fraction depends actually
on mesh size of the rst cell column. This gure shows well
the mesh dependence of the horizontal void fraction proles:
only one value is calculated at the surface and then, a linear
law is used in the rst cell to access the zero void fraction
bulk value.
Hence, an additional articial dispersion force should
actually exist to ensure the bubble dispersion in the lat-
eral x direction. Numerically, this horizontal force has to
be modelled to avoid the encountered meshing dependence.
Actually there are many forces acting on bubbles transver-
sally, particularly bubbles group force. But these forces are
not yet mathematically formalised, because they are also not
known precisely. Under the discrete phase modelling (DPM)
assumptions, each particle is supposed independent and a
bubble group effect should be programmed as a modelled
force. The Eulerian modelling for bubble group consists in
considering the discrete group as a second continuous phase.
As it can be understood here, it is not easy to choose a realistic
dispersion force. In this work, an arbitrary unknown force is
set in horizontal direction, perpendicular to gravity, to ensure
the bubble layer development in the transversal direction.
5.3. Dispersion force
The simplest modelling of the lateral forces due to wall
interaction or bubble group effect which act upon individual
particles is a constant horizontal force which acceleration
value is called bforce, and then:F
x 1
=bforce (=constant) (x
direction)F
x 2
=0 (y direction)
We can nd in the literature there exists some interesting
tentative of simplied modelling of the dispersion force with
arbitraryaccelerationor withinteractionpotential lawwithan
arbitrary form and identied parameters values. In fact, only
bubble scale works such these of the Lausanne polytechnic
school [2,3], should allowthe determination of realistic inter-
action and forces between bubbles and wall. In this rst work,
only an order of range of the horizontal force value is waited.
For the dispersion study with the applied force, a three time
rened mesh has been used to have a better description of the
prole.
Fig. 8 shows at the left the bubble boundary layer in the
cell under the coupled calculation modelling assumption, for
the three explored bforce values (1500, 3000 and 5000) ms
2
for the bubble diameter d
p
=l0
3
m. At the right is the related
void fraction prole at the exit height cross section (Fig. 8b).
Notice that the void fraction horizontal prole is almost con-
stant. The boundary layer thickness increases with altitude
and also with the transversal force intensity. This is well con-
rmed by visual observations of Fascio et al. [9,10,14]. Fig. 9
left shows that there is an effect of dispersion force on cur-
rent density proles. If bubbles are conned in the rst cell
raw, the electrical resistance is increased, and, inversely, for
bforce =5000 ms
2
, bubbles are distributed enough to obtain
a resistance close to the Tobias results, in which case bubbles
were homogeneously distributed over the whole cell. What
is very important to notice here is that the order of range
of the lateral force seems to be about half the Archim ede
force. It is one of the more important quantitative results:
vertical Archim ede force is famous but the bubble-electrode
or bubble-bubble or bubble-group of bubbles interaction is
Fig. 8. Bubble boundary layer development evolution with transversal force value bforce applied to bubbles: (1) 1500 ms
2
; (2) 3000 ms
2
; (3) 5000 ms
2
:
(a) boundary layer frontier ( =10
2
); (b) void fraction distribution at the exit of the cell. Bubble diameter: 10
3
m.
M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156 1149
Fig. 9. (a) Current density proles along electrode for three different values of bforce (bforce =0 calculated with initial mesh, other cases are calculated with
the three time rened mesh); (b) void fraction evolution along the electrode. Bubble diameter: 10
3
m.
Fig. 10. Typical ow pattern for a Poiseuille forced ow with bubble diameter d
v
=10
3
m (top) and d
p
=10
4
m (bottom) A Poiseuille prole is set at the
bottom entrance with u
y
,
max
=u
y
(x =0.015) =0.3 ms
1
.
1150 M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156
Fig. 11. Void fraction for (a) d
p
=10
3
m; (b) d
p
=10
4
m, in the cross section of the cell at 7 different heights.
much difcult to quantify. It appears that the equivalent effect
of these interactions lead to a normal to the electrode force,
which acceleration value is about half the Archim ede value.
At right, Fig. 9 shows that the existence of a constant transver-
sal acceleration leads to an asymptotic void fraction value
after an establishment length. The asymptotic nal void frac-
tion at electrode decreases with the acceleration value. The
Tobias prole, also given, is very smaller because the bubble
repartition in the x direction is not considered and is averaged
upon the 3 cm width.
Remark:Here, only bubbles of size 10
3
m are consid-
ered, since, for bubbles of size 10
4
m, the velocity of bub-
bles under the stagnant liquid assumption, u
p
=0.0052 ms
1
,
lead to unphysical void fraction values, even if bubbles are
homogenously distributed in the width of the cell.
These previous results have been obtained with the cou-
pled calculation of bubble trajectories and electrical eld.
But the continuous liquid phase motion has not been cal-
culated: it was the stagnant liquid assumption. In fact, cou-
pling between continuous and discrete phase is very strong
and very important in conned electrochemical cells. Actu-
ally, the uid ow entrained, or is entrained, due to bub-
bles motions which are like motion sources or turbulence
providers. The actual modelling and calculation of the two
phases is crucial to obtain a realistic void fraction calculation,
knowing that hydrogen bubbles are effectively of typical size
10
4
m.
In the more rigorous calculation of coupled ow motion,
the drag coupling term is a momentum source for the con-
tinuous phase (electrolyte) close to the wall. Fig. 10 shows a
typical ow pattern for an xed Poiseuille ow (u
y,max
=u
y
(x =0.015) =0.3 ms
1
) at the bottom entrance (y =0). In this
gure, results have been obtained with the bubble diameters
d
p
10
3
and 10
4
m. It is remarkable that, even if lateral
acceleration bforce remains at value 5000 ms
2
, the velocity
of bubbles is enhanced, but the thickness of bubble bound-
ary layer is reduced. The vertical motion source modies the
Poiseuille prole. The continuous phase mass conservation
is obeyed. The maximum velocity is no longer obtained at
centre but near the gas evolving electrode. It is 0.39 ms
1
for d
p
=l0
3
m and 0.48 ms
1
for d
p
=l0
4
m. These val-
ues should be compared with terminal velocities values
obtained under the stagnant liquid assumption: 11.3 cms
1
for d
p
=l0
3
m and 5.2 mms
1
for d
p
=10
4
m. The lower
the bubble size is, the higher is the drag force interacting with
the continuous phase. Finally, liquid velocity reaches almost
the same values for these two different bubble sizes. What is
important is the large decrease of the boundary layer thick-
ness which leads to a large increase of mass or heat transfers.
The void fraction proles are shown in Fig. 11. The void
fraction calculated with rigorous coupling with continuous
phase coupling remains to the value found under the stag-
nant liquid assumption (15%) for diameter d
p
=10
3
m,
which is slightly over acceptable limit for DPM models
Fig. 12. (a) Current density proles along electrode; (b) reduced resistance.
M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156 1151
(which is said to be 10%). For diameter d
p
=l0
4
m, the void
fraction values are larger but becomes realistic which was not
the case under the stagnant liquid assumption.
The major effect of this increased rigor modelling of the
coupled phenomena is the void fraction lowering due to the
velocity enhancing. Then, as shown in Fig. 12 left, the current
density prole is increased when the two primary distribution
for d
p
=l0
3
m are compared. Because the case d
p
=10
4
m
leads, under the stagnant liquid hypothesis, to unrealistic void
fractions, it was not possible to compare. Then, Fig. 12 right
shows the macroscopic result in term of reduced resistivity
which is the ratio between the integral ohmic resistance with
bubble and the same resistance for electrolyte without bub-
bles, for a uniform distribution j =4000 Am
2
. It has to be
noticed that the smaller the bubble is, the larger the resis-
tance increase is: almost 20% for d
p
=l0
4
m and 10% for
d
p
=10
3
m, which is an important value for rigorous elec-
trochemical process modelling.
6. Conclusion
A computational study was performed on selected elec-
trochemical cell geometry with a gas-evolving electrode. A
typical electrochemical reaction with an exchange of two
electrons for generating one gaseous mole and a characteris-
tic electrical conductivity of =10.6 Sm
1
were considered.
The purpose was to compute two-phase ow solution in the
cell by using computational uid dynamic software. Compu-
tations were performed with FLUENT 6.0 version allowing
to customize gas ow injection properties through the use of
custom function compiled with a C compilator. Hence, gas
ow rate depends on the current density satisfying Faradays
law (rst law of electrolysis). A lagrangian model is used at
rst for a dicrete particle modelling of bubbles. In this case,
bubbles are assumed to be spherical and rigid, therefore drag
coefcient is calculated from Morsi and Alexanders empir-
ical functions (Appendix A). This assumption is fairly valid
since electrochemically generated bubbles are usually small
(<10
3
m) and the gas phase is clearly dispersed (coalescence
is rarely observed except in some particular cases of very
small interelectrode gap or high current densities). Numeri-
cal simulations were performed in two steps:
1. With the factious case of a stagnant liquid, where bubbles
dont interact with the electrolyte. In this case, bubbles
move up with their terminal rise velocity. Calculations
were performed with bubbles of size 10
3
m, and the
results were compared to theoretical values of Tobias [13].
A parametric dispersion force was used to approach theo-
retical values of Tobias which consider the bubbles to be
distributed homogeneously over the cell width. This was
done since there is an absence, in this kind of DPM mod-
elling, of any dispersion and diffusion force (specially
related to packing dispersion). The results in term of
current density prole showthat prole over the electrode
length is strongly inuenced by the bubble layer thickness
when bubbles are slumped towards the electrode surface
(see Appendix D). Transversal diffusion and dispersion
modelling is needed because of the sensibility of Laplace
equation to strong variations in space (Appendix E).
2. With an interaction with electrolyte owand the computa-
tion of the uid ow. Bubble drag is a momentum source
in the continuous phase equation of motion when bubbles
cross an electrochemical cell. The coupled computations
with uid ow entrainement by bubbles show a very dif-
ferent trend. The uid motion reaches values which are
several times higher than bubble velocity in a stagnant
uid (up to 100 times for 10
4
m sized bubbles). There-
fore, the liquid velocity becomes the driving velocity,
the void fraction is drastically reduced and the electri-
cal problem is no longer strongly dependent on bubble
size. The DPM model is usable under the small void frac-
tion value assumption (about 10%), according with the
bubble-bubbles neglected interaction assumption. For the
explored average current density value, this criterion has
been obeyed. However, the lack of dispersion force model
due to packing of bubbles remains, and should be imple-
mented in lagrangian models. As a comparison, eulerian
mixture models used by Dahlkild [5] on the based model
of Ishii include the maximum packing of bubbles in the
upwardsupercial velocityformulationbut the problemof
maximum packing formulation remains. Though further
modelling should be developed for the purpose of opti-
mising chemical cells. Fluid ow put in motion by bubble
seems to be an important factor for cell performances and
the development of computational uid dynamic in this
eld should also be strongly promoted.
Acknowledgement
We want to acknowledge reviewers for their helpful and
constructive work.
Appendix A. List of symbols
Variables
Electrical problem
I/A mean current density (Am
2
)
j current density (Am
2
)
electric potential (V)
electrical conductivity (Sm
1
)
over potential (V)
Physical properties
q evolving gas mass ow rate (kg m
2
s
1
)
M molecular weight (kg mol
1
)
viscosity (kg m
1
s
1
)
density (kg m
3
)
1152 M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156
Geometry
A area (m
2
)
h
g
interelectrode gap (m)
y
max
electrode height (m)
x element size (m)
y element size (m)
ds differential area vector (m
2
)
Two phase ow
u velocity (m s
1
)
C
D
drag coefcient (-)
Re Reynolds number (-)
gas-phase volume fraction (-)
d diameter (m)
V volume (m
3
)
Constants
F Faraday (96 485 Cmol
1
)
C Tobias s constant
n electron number
Subscripts:
p bubble particle
g gas
0 free bubble electrolyte
(-)
(1)
liquid phase
(-)
ij
i component
(-)
av
average value
(-)
p,b
relative to particle or bubble
(-)
a
relative to anode
(-)
c
relative to cathode
(-)
s
relative to a surface
Appendix B. Morsi and Alexander [25] coefcient
used for spherical rigid particles
C
D
=a
1
+a
2
/Re
p
+a
3
/Re
p
2
with Re
p
=(u
l
u
p
)/
l
a
1
=0, a
2
=24, a
3
=0 for Re
p
<0.1
a
1
=3.69, a
2
=22.73, a
3
=0.0903 for 0.1 <Re
p
<1.0
a
1
=1.222, a
2
=29.1667, a
3
=3.8889 for 1.0 <Re
p
<10.0
a
1
=0.6167, a
2
=46.5, a
3
=116.67 for 10.0 <Re
p
<100.0
a
1
=0.3644, a
2
=98.33, a
3
=2778 for 100.0 <Re
p
<1000.0
a
1
=0.357, a
2
=148.62, a
3
=4.75 10
4
for 1000.0 <Re
p
<5000.0
a
1
=0.46, a
2
=490.546, a
3
=57.87 10
4
for 5000.0 <Re
p
<10000.0
Appendix C. Terminal velocity and relaxation time
of bubbles obtained with Discrete Phase Modelling.
For three different particle diameters d
p
=10
4
, 10
3
and
10
2
m, terminal rise velocity and relaxation time have been
calculated and are presented in Fig. 13.
In this validation case, bubbles are created and injected
since cell number 20 which has the position: y =20 cm. Bub-
bles relaxation time is small, about 1 ms, for smaller diameter
and terminal velocities are obtained quickly. The discrete
phase modelling programmed in Fluent has been validated
using manual calculation of the bubble velocity evolution.
The terminal velocity using the Morsi and Alexander [25]
analytical calculation is given with the three following equa-
tions:
u
s
2
=
_
1
p

_
(4g d
p
)
(3C
D
)
with:
C
D
=
a
1
+a
2
/Re
p
+a
3
Re
p
2
(drag coefcient)
and:
Re
p
=
(u
1
u
p
)d
p

1
Table 3 shows a good agreement between terminal veloc-
ities calculated with theoretical law of Morsi and Alexander
and numerically calculated values. This is a conrmation that
the virtual mass force negligible assumption is realistic.
Table 4
Appendix D. Analytical solution (Tobias [13])
The analytical expression of the Tobias modelling cou-
pling [13] for the vertical electrodes (see Fig. 14), is given
using Eq. (C.1), (C.2), and (C.3) under the zero polarisation
electrode assumption:
j(y)
j
av
= 8.(K +2)
2
(K +4)
1
_
Ky
y
max
+2
_
3
(C.1)
with
K = 2
_
1
_
1 1
Cy
max
j
av
_
1
_
0.5
2 (C.2)
Table 3
Terminal velocities calculated with the theoretical law of Morsi and Alexander [23] (see Appendix A)
Diameter (m) Theoretical terminal
velocity (ms
1
)
Theoretical Reynolds
number Re
p
Numerical terminal
velocity (ms
1
)
Numerical residence
time (s)
Numerical relaxation
time (s)
10
2
0.5773 5773.5 0.5773 0.5 0.01
10
3
0.1135 113.51 0.1135 2 0.01
10
4
0.005265 0.5265 0.005264 45 0.001
M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156 1153
Fig. 13. Relaxation time and terminal velocity for the three explorer bubble diameters.
Table 4
Calculated resistance according to Eq. (E.1), (E.2), (E.3), with n =10, = 0.7, and x =0.003 m,
0
=60 Sm
1
k =l k =2 k =3 k =4 k =5 k =6 k =7 k =8 k =9
R
k
7.54e-4 5.91e-4 5.73e-4 5.67e-4 5.63e-4 5.61e-4 5.60e-4 5.59e-4 5.58e-4
R
n
5.575e-4
R
k
/R
n
1.35 1.06 1.028 1.017 1.0101 1.006 1.004 1.0027 1.0009
Fig. 14. Electrochemical cell geometry with a vertical electrode studied by
Tobias [13].
and
C =
M
(g)
(u
p

p
nF h
g
)
(C.3)
where Y=y/y
max
is the normalized height of the electrode. In
this expression, the velocity u
p
of the particles is supposed to
be constant in the section, and the void fraction is assumed to
be independent of horizontal component x (bubbles homoge-
nously distributed in the width of the cell).
Appendix E. Resistance evolution with layer
thickness
The local conductivity coefcient is calculated with
Bruggemans formula:
=
0
(1 )
3/2
(2)
The total resistance of the electrochemical cell is:
R
k
=
1

0
_
kx
(1 /k)
3/2
+(n k) x]
_
(D.1)
1154 M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156
Fig. 15. Distributed void fraction in the width of the cell (ID).
where
0
is the conductivity of the electrolyte free of bub-
bles, is the void fraction when the bubbles are conned
in the rst column (k =1), k is the number of computational
cells occupied by bubbles (see Fig. 15) and n is the total
number of cells which cover the cell width h
g
. If the bub-
bles are distributed in the entire width of the cell (Tobias
hypothesis), andnot ina near electrode bubble layer, Eq. (D.1)
becomes:
R
n
=
x

0
_
n
(1 /n)
3/2
_
(D.2)
And the ratio between (D.1) and (D.2) is:
R
k
R
n
=
_
k/(1 /k)
3/2
+(n k)
_
_
n/1 /n)
3/2
_ (D.3)
Results for different values of n and varying parameter k
are plottedinFig. 16. As showFig. 16, it appears anincreasing
resistance when the bubbles are situated in a near electrode
bubble layer. This resistance becomes constant when the
same amounts of bubbles is used and occupy the total width
(Tobias assumption).
Appendix F. Diffusion terms
The consequences on the current density prole computa-
tion due to the unrealistic dispersion force model is illustrated
here, using a mono dimensional problemand considering the
Fig. 16. Resistance evolution with bubble distribution in the electrochemical
width. Calculated according to Eq. (E.1), (E.2), (E.3), with n =10, =0.7,
and x =0.003 m,
0
=60 Sm
1
.
conductivity of the electrolyte to be dened by the following
mathematical function:
=
0
[0.25 tan h((x h
g
/2) +0.75)] (E.1)
where slope is an amplifying coefcient which controls the
sharpness of the conductivity prole. It is then possible to
test numerical robustness for an a priori given bubble layer
thickness.
Fig. 17 shows the analytical prole of the current density
(constant) over the cell width. The Fig. 18 shows the numeri-
cally calculated current density. For a small amplifying coef-
cient ( =10
+2
), the current density prole j calculated with
Eq. (8) exhibits a fairly constant value of j in good accordance
with analytical value (see Fig. 17 right) if the mesh is suf-
ciently rened. For sharper proles ( =10
+3
), an oscillation
appears in current density prole for coarse mesh due to an
abrupt variation of conductivity from 30 to 60. When mesh
is rened, there are more computational points in the transi-
tion gap and therefore accuracy is enhanced and oscillations
are dumped. When the conductance boundary layer thickness
is reduced again ( =10
+4
), abrupt transition remains and the
Fig. 17. Electrical properties evolution with coordinate x; left: electrical conductivity for three different values of (=10
2
, 10
3
or 10
4
); right: constant related
current density j according with electrical conductivity evolution.
M. Philippe et al. / Electrochimica Acta 51 (2005) 11401156 1155
Fig. 18. Numerical robustness with conductivity sharpness: current density prole across the ID cell for three different slope values with four homogenous
successively rened meshes. Top: =10
2
; R=0.000698, centre: =10
3
; R=0.000747 and bottom: =10
4
; R=0.000749.
oscillation in the current density prole remains too with the
explored meshing hypothesis.
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