DESALINATION

0011-9164/06/$ See front matter 2006 Elsevier B.V. All rights reserved.
Desalination 201 (2006) 150163
www.elsevier.com/locate/desal
Electrochemical water softening:
principle and application
C. Gabrielli
a
, G. Maurin
a*
, H. Francy-Chausson
b
,
P. Thery
b
, T. T. M. Tran
a,b
, M. Tlili
b,c
,
a
UPR 15 du CNRS Laboratoire Interfaces et Systmes Electrochimiques,
Universit Pierre et Marie Curie, 4 place Jussieu, Paris.
*Tel: +33 (01) 44274168; E-mail: gma@ccr.jussieu.fr
b
Socit SEVA, 43 rue du Pont de Fer, BP 176, Chalon sur Sane
c
Laboratoire de Gochimie et Physico-Chimie de leau, INRST, BP. 95, Hamman-Lif 2050. (Tunisie)
Received 3 October 2005; accepted 17 February 2006
Abstract
The working principle of the electrochemical softening process was studied at the laboratory scale in order to get a bet-
ter understanding and to optimize the construction and the efciency of industrial electrolysers. For this purpose pure calco
carbonic synthetic waters with well defined hardness or distribution water from Paris were used. By using a local pH
sensor, it was shown that the increase of the pH in the very vicinity of the cathode induces the precipitation of the cal-
cium carbonate on the plate, in a first step under the effect of the oxygen reduction, and after that by water reduction
associated with hydrogen evolution. The local pH can reach values greater than 10. The morphology and the crystal form
(calcite, vaterite and/or aragonite) of the deposits were identied by scanning or transmission electron microscopy and
by X ray diffraction. It was shown that, at the beginning of the treatment, vaterite and calcite crystals form a compact layer.
In galvanostatic conditions, the decrease of the active area by deposition of the insulating scale leads to an increase of
the local current density and then, to the transition towards the electrolytic water reduction regime. Adendritic growth of
the calcium carbonate forming a porous layer through which hydrogen diffuses easily is observed.
An investigation carried out on a model scale electrolyser showed the inuence of various operating parameters such as
current intensity, time of treatment etc. on the efciency of the device. This electrochemical process is also able to elim-
inate partially various other species like magnesium.
Keywords: scale, calcium carbonate, softening, electrochemistry, precipitation.
*Corresponding author
doi:10.1016/j.desal.2006.02.012
1. Introduction
The most part of natural, industrial or domes-
tic waters, contain calcium and carbonate ions
which are susceptible to provoke scaling prob-
lems in the installations leading to serious failures
(pipe blocking, membrane clogging, efficiency
decay of heaters or heat exchangers). Various
methods are used to prevent scaling, for example
by acidication of the water, by forcing the cal-
cium carbonate precipitation by some chemical
process, by using exchange resins, or by mem-
brane techniques (reverse osmosis, nanoltration
etc.). An other way consists in blocking the nucle-
ation and crystal growth thanks to chemical
inhibitors [1]. However these chemicals are gen-
erally deleterious for the human health and their
use is forbidden in drinking water.
Recently, appeared on the market softening
devices for industrial or domestic waters based on
electrolysis [2,3]. The water to treat circulates in
an electrolyser where an electrical current passes
between a set of electrodes. A scale layer which
is mainly formed of calcium carbonate is de-
posited on the surface of the cathodic plates. This
layer falls down spontaneously, or in an assisted
manner, and is collected at the bottom of the tank.
This physical process presents the advantage to
avoid any addition of chemicals and to necessi-
tate a light maintenance. In addition, the calcium
carbonate can be recovered and can be valorised.
The electrochemical precipitation of calcium
carbonate has been proposed by Ldion, initially
as a method to evaluate the scaling power of
water [4]. A metallic electrode polarized at the
potential corresponding to the reduction of the
dissolved oxygen, is progressively covered by an
insulating layer and the electrolysis current inten-
sity tends to zero. The time necessary to annul the
current constitutes an empirical criterion of the
scaling power of the water. The shorter this time,
the more the water is susceptible to scale the walls
in contact. The nucleation and growth kinetics of
calcium carbonate by an electrochemical driving
force has been studied on a more quantitative way
by using an electrochemical quartz microbalance,
which allows in situ measurements of the scale
amount with respect to time and to deduce the
nucleation rate and the crystal growth rate [5,6,7].
The crystalline structure and the morphology of
the CaCO
3
crystals have been studied by elec-
tronic microscopy [8], by Infra Red spectroscopy
[9] and by in-situ Raman spectroscopy [10]. The use
of the electrochemical impedance spectroscopy
has lead to a better understanding of the blocking
process of the electrode by the insulating layer [11].
However, these methods were used in potentiostatic
conditions (application of a constant electro-
chemical potential), in such a way that the depo-
sition stops as soon as the electrode is completely
covered by a compact layer. This can last a more
or less long time, depending of the morphology
of the crystals, as well as the crystal structure (cal-
cite, vaterite or aragonite structure). In addition,
the potentiostatic control of an electrolyser needs
a sophisticated electronic power unit, which is too
expensive for industrial applications.
In the various electrochemical softening de-
vices proposed on the market, the electrolysis is
carried out at constant current intensity or at a
constant potential difference between the termi-
nals, in a vessel where water slowly flows. The
scale is deposited without limit, leading to thick
layers up to several millimetres. They can be
spontaneously detached , but it is sometimes nec-
essary to assist the detachment by a mechanical
action. The geometry of the electrolysers are
either cylindrical with coaxial electrodes [2] or
parallelipedic with parallel plates. The electrodes
are currently made of non corrodable materials
(stainless steel, titanium, titanium clad iridium)
For example, on Fig. 1 is presented the scheme of
the ERCA
2
electrolyser, which can treat up to sev-
eral m
3
/h [12,13].
The efciency of the treatment is evaluated by
the abatement H, of the water hardness H. The
hardness H is usually expressed in French degrees
(F). 1 F corresponds to 10
-4
M of a divalent
C. Gabrielli et al. / Desalination 201 (2006) 150163 151
cation such as Ca
++
or Mg
++
. When the water con-
tains only calcium and carbonate ions, 1F cor-
responds to 10 mg. L
1
of dissolved CaCO
3
.
Usually, these electrochemical devices produce
a moderate softening which is largely sufficient
for numerous usual applications as the treated
water is no longer scaling. The efciency of the
process can be expressed in energy cost for a
given flow rate and for a given abatement. It
depends in a complex way on numerous and intri-
cate parameters related to the geometry of the
electrolyser, the current intensity and the applied
potential, the composition, the pH and the tem-
perature of the water, the ow rate, etc. . . . So far,
it is impossible to establish a realistic theoretical
model and a phenomenological approach is still
necessary.
In the present paper are presented some exper-
imental investigations which were carried out
either at the laboratory scale with small electro-
chemical cells to get a better understanding of the
process, or with electrolysers at the pilot scale,
which can be considered as a good simulation of
an industrial device [14].
2. Principle of the electrochemical scaling.
During water electrolysis, dissolved oxygen is
reduced on the cathode in a large potential range
by following the global electrochemical reaction:
O
2
+ 2H
2
O + 4 e

4 OH

(1)
The oxygen diffusion limits the rate of this
reaction and leads to a current plateau on the rep-
resentative polarization curve as seen on Fig. 2,
which was obtained with a PCC synthetic water
(pure calco-carbonic water containing only cal-
cium, CO
2
and related ions). When the applied
potential is more negative than a value which
depends on the substrate, water is directly
reduced according to :
H
2
O + e

1
/2 H
2
+ OH
(2)
The rate of reaction (2) is not limited by mass
transport and the current intensity can be very
high (Fig. 2).
The generation of hydroxyl ions, either by
reaction (1) or by reaction (2), destabilizes the
calco-carbonic equilibrium of the solution [15].
Hydrogenocarbonate ions HCO
3

are converted
into carbonate ions CO
3
2
by following the chem-
ical reaction:
HCO
3

+ OH

CO
3
2
+ H
2
O (3)
In a third step, carbonate ions may react with
calcium ions to initiate the nucleation and growth
152 C. Gabrielli et al. / Desalination 201 (2006) 150163
Fig. 1. Scheme of the ERCA
2
electrolyser.
Fig. 2. Polarization curve: Current density in function of
the electrochemical potential vs. saturated calomel elec-
trode (bare stainless steel electrode. PCC water. H = 30F).
of calcium carbonate crystals if the supersatura-
tion becomes larger than 1:
CO
3
2
+ Ca
2+
CaCO
3
(solid) (4)
The supersaturation is dened by
(Ca
2+
) (CO
3
2
)
= (5)
K
c
where (Ca
2+
) and (CO
3
2
) are the ionic activities
and K
c
is the equilibrium solubility product for a
given calcium carbonate polymorph (for example,
calcite). It is a matter of fact that nucleation occurs
effectively if becomes larger than a critical
value
c
. It was often said, but without serious
proof (1) that
c
is as large as. 40 for the homo-
geneous nucleation. This value is lowered if the
nucleation occurs on a solid wall (heterogeneous
nucleation). The relative importance of the hetero-
geneous nucleation depends on the nature of the
wall and is larger for weak water hardness [16].
When the polarization is restricted to the oxygen
reduction domain, it has been demonstrated that,
in absence of carbonate ions, the interfacial pH
equals 10.6 whatever the hydrodynamic condi-
tions [17]. In the presence of hydrogeno-carbon-
ate ions, the interfacial pH is lowered to c.a. 9, a
value which depends on the experiment, in par-
ticular on hydrodynamic conditions. The super-
saturation proles relatively to the calcite form in
the vicinity of the electrode have been calculated
for pure calco carbonic solution (PCC water)of
various pH [18]. On Fig. 3, it can be seen that
very high supersaturation values are reached in-
side a few micron thick layer, close to the cathode
[18]. An original experimental method, derived
from a technique first proposed by Romankiw
[19], was used to measure the local pH close to
the surface of a metallic electrode. A gold grid,
used as active electrode, was maintained in close
contact with the at extremity of a pH glass elec-
trode. The pH of the small volume of electrolyte
trapped between the meshes of the grid was
directly measured by the pH electrode; it was
practically equal to the pH of the surface of the
metallic grid where the OH

ions were produced.

Experimental local pH values were in full agree-
ment with theoretical expectations. It can be con-
cluded that thanks to the high local super-
saturation, heterogeneous nuclei can be formed in
a very thin liquid layer near the electrode and
deposited on the surface. The high values of
allow the precipitation of various forms of calcium
carbonate, including the metastable hydrated
forms, which have been considered as the precur-
sors of the stable anhydrous polymorphs [20,21,
22]. For example, for a local pH of 9.5 and a
water hardness of 22F at 25C, the supersatu-
ration values with respect to the calcite form and
to the amorphous form reach 200 and 1.7 re-
spectively. According to Ell and Roques [22], if

amorphous
>1, the calcium carbonate nucleation
is instantaneous, homogeneous and independent
of the wall nature.
In the present work, the local pH measurement
technique was used beyond the oxygen reduction
domain in order to explore the hydrogen evolu-
tion domain. Fig. 4 shows the change of the local
pH with respect to the current intensity during
electrolysis of a distribution water. Between 0.2
to 1.2 mA.cm
2
, a pH= 9.5 plateau value is ob-
served which corresponds to the oxygen reduc-
tion domain. For larger intensities, pH values up
C. Gabrielli et al. / Desalination 201 (2006) 150163 153
Fig. 3. Supersaturation prole in the vicinity of the cath-
ode for various values of the bulk water pH (PCC water,
H = 30F).
to 12 were measured., these experimental results
prove that water electrolysis generates local pH
sufciently large to induce nucleation in the oxy-
gen reduction domain and a fortiori in the hydro-
gen evolution domain. It is worth noting that,
thanks to these very high pH, precipitation of
other components can be induced, in particular
strontium carbonate or magnesium hydroxide, for
pH larger than ca. 9.3 [23].
3. System evolution during the scaling process.
The data previously given were valid for a bare
metallic electrode, but as soon as calcium carbon-
ate is deposited, the surface state is continuously
changed. In order to study this phenomenon, ex-
periments were carried out in a 120 cm
3
electro-
chemical cell by using either a stainless steel
cathode (area 1.25 cm
2
) or the gold working elec-
trode (area 0.4 cm
2
) of an electrochemical quartz
microbalance, which allows the in situ measure-
ment of the deposited mass [4]. The working elec-
trode was monitored either at constant electro-
chemical potential with respect to a calomel
reference or at constant current intensity, thanks
to an electronic potentiostat- galvanostat. The sys-
tem evolution was illustrated by scanning electron
microscope observations carried out on the scaled
electrode.
Calcium carbonate scaling in potentiostatic
conditions.
When the electrochemical potential Ewas main-
tained at a constant value which corresponds to
the current limitation by oxygen reduction (E
1.0 0.1 V/SCE), according to Fig. 5, the cur-
rent intensity decreased progressively and reached
154 C. Gabrielli et al. / Desalination 201 (2006) 150163
Fig. 4. Local pH close to a gold grid working electrode
vs. cathodic current density ( Apparent grid area: 1.13 cm
2
.
Distribution water of Paris, pH = 7.8, hardness = 26 F).
(a) E = - 1.0V/ECS (b ) E = 1.4 V/ECS
Fig. 5. Current density vs time during electrolysis in potentiostatic conditions (PCC water, H = 30F, stainless steel elec-
trode, area 1.25 cm
2
).
a value close to zero after a time in the order of
one hour. During this period, a calcium carbonate
layer was formed on the cathode. Detailed SEM
observations show that, in most cases, the calcare-
ous layer was constituted of a mixture of calcite
crystals with a characteristic pseudo-cubic aspect
and vaterite crystals with various morphologies
(Fig. 6). As vaterite is an unstable polymorph, it
often transformed later into aragonite needles [8].
The progressive invasion of the surface by this
dense packed insulating layer was responsible of
the decrease of the intensity down to zero, but,
after that the precipitation process was defini-
tively stopped. The nal thickness of the layer did
not exceed few microns. Therefore, it can be con-
cluded that these operating conditions are not
convenient for the purpose of calcium carbonate
extraction.
When the electrochemical potential of the cath-
ode was maintained at a value sufciently nega-
tive to promote hydrogen evolution according to
reaction (2), the change of current intensity vs.
time was significantly different. After passing
through a sharp peak, I decreased toward a lim-
iting value which differs from zero (Fig. 5b). It
means that the metal surface is never totally
blocked by the scale thanks to the formation of
hydrogen bubbles onto the metal. In addition, ran-
dom uctuations of the current intensity were clearly
related to the spontaneous detachment of flakes
under the effect of the hydrogen pressure. This
phenomenon is illustrated on Fig. 7. Apart of the
scale layer is aking off, whereas another area of
the electrode, which has been previously liberated
by the departure of a ake, is now the seat of the
precipitation of a new generation of calcium carbon-
ate crystals. It has been observed that the average
frequency of detachment was strongly dependent
on the imposed current and also on the micro-
roughness of the metal electrode [14]. So, the
potentiostatic control of the working electrode at
a potential sufciently negative allows the quasi
continuous precipitation of calcium carbonate by
the self regeneration of the surface, but, when the
stationary state is reached, the deposition rate is
too small to be of practical interest.
Calcium carbonate scaling in galvanostatic
conditions.
At constant current intensity the system evolu-
tion is different. The progressive occupancy of the
C. Gabrielli et al. / Desalination 201 (2006) 150163 155
Fig. 6. SEM images of the calcium carbonate layer elec-
trodeposited on a stainless steel cathode in potentiosta-
tic conditions corresponding to oxygen reduction
limitation (E = - 1.0 V/ECS; PCC water, H= 30F). Com-
pact layer made of calcite and vaterite crystals.
Fig. 7. Detachment of a calcium carbonate ake and new
nucleation onto the bare surface (gold electrode, PCC
water H= 30F, potentiostatic polarization corresponding
to hydrogen evolution : E = 1.4 V/ ECS).
surface by the scale induces an increase of the local
current density on the bare areas and, therefore,
an increase of both the cathodic polarization and
the local pH. This phenomenon is illustrated by a
shift to the right of the representative point of the
working conditions on the I=f(E) and pH = f(I)
curves presented on Figs. 2 and 4 respectively. As
a consequence, soon or later the system is shifted
towards the water reduction domain and the for-
mation of hydrogen bubbles impedes the layer to
completely block the electrode surface. For exam-
ple, on Fig. 8 are reported the variation of the
local electrochemical potential of the cathode for
a 10A.m
2
constant current density. At the begin-
ning, the interfacial potential E was 1.05 V/ECS,
thus related to oxygen reduction domain (Fig. 2).
As soon as calcium carbonate started to precipi-
tate, a sharp decrease of E was observed during
about 30 min, to reach a pseudo steady value of
1.45 V/ ECS, a potential which corresponds to
a vigorous hydrogen evolution. In addition, large
potential uctuations are related to bubble depar-
ture or to scale detachment.
In a first step, the calcium carbonate layer is
made of pure calcite crystals (Fig. 9a), but SEM
observations of its lower face, which has been in
direct contact with the metal (Fig. 9b), reveals the
existence of channels between the calcite crystals,
allowing a passage between the metallic surface
and the liquid bulk.
In a second step, the growth of the calcium car-
bonate rapidly carried on under the form of tree-
like dendrites which could reach several millimetres
long (Fig. 10a). It was observed by X ray diffrac-
tion that these dendrites are made of pure calcite
with a preferred crystal orientation. It can be
assumed that the OH

ions generated on the metal

diffuse through the channels and between the
columnar dendrites. The growth front, where
156 C. Gabrielli et al. / Desalination 201 (2006) 150163
Fig. 8. Change of the electrochemical potential of the
cathode during scaling in galvanostatic conditions (Cur-
rent density : 10 A.m
2
; PCC water, H = 30F).
(a) upper face
(b) lower face, showing channels
between the crystal blocks.
Fig. 9. SEM images of the rst calcium carbonate layer
electrodeposited on a stainless steel cathode in galvano-
static conditions.
reactions (3) and (4) occur, is shifted toward the
dendrite tip level according to Fig. 10b. However,
this dendritic structure is very fragile and hydro-
gen bubbles can break the columns, thus con-
tributing to the removal of the scale. In addition
the gaseous overpressure at the metal surface can
also provoke the detachment of the first layer
under the form of large akes.
These results show that in galvanostatic re-
gime, the electrochemical process tends locally to
stabilize on a working point corresponding to
water reduction through the partially clogged
electrode, even if, at the beginning, the oxygen
reduction was the only activated reaction. The
voltage delivered by the power unit and applied
between the terminals slowly increases because
of the increase of both the cathodic overvoltage
and the water resistivity during the decarbonata-
tion process. In fact, when the electrolyser is pow-
ered at a constant DC voltage, the situation is not
very different. Agreat part of the voltage is con-
sumed by the ohmic drop in the bulk water and
inside the porous crust. Therefore the current
intensity varies very little, whereas the electro-
chemical potential becomes progressively more
negative in the open area of the cathode. As for
the galvanostatic regime, the working point tends
to stabilize on the upper branch of the I=f(E)
curve (Fig. 2).
4. Study of a pilot model electrolyser
To study the inuence of the operating param-
eters on the efciency of the electrolytic softening
process, a 1.68 L model electrolyser was built
with planar parallel and vertical electrodes.
The cathode was a 316Lstainless steel plate with
a 5.6 dm
2
area. A grid of titanium cast iridium
oxide was used as anode. In most case the inter-
electrode distance was 30mm. The device was fed
at controlled flow rate thank to a volumetric
pump, with Paris distribution water (mean total
hardness 24F, calcium hardness H
c
= 22.2F,
temperature = 24C) or with a heavy mineral
water. The hardness abatement H of the treated
water was measured through EDTAcomplexom-
etry or, more simply, was deduced from the meas-
urement of the water conductivity by considering
that a conductivity change of 16 S L
1
practi-
cally corresponds to = 1F. The device was
powered at constant current intensity with a DC
generator. The corresponding voltage was in the
C. Gabrielli et al. / Desalination 201 (2006) 150163 157
(a) SEM image (b) scheme
Fig. 10. Dendritic growth of a thick calcium carbonate layer.
6 to 12 V. range. In the present paper the influ-
ences of a few operating parameters are reported.
Effect of the current intensity
Fig. 11 shows the change of the hardness
abatement with respect to time, for various values
of the electrolysis current intensity, when the
experiments were started by using a bare stainless
steel electrode. The ow rate corresponded to a
rather short sojourn time ( =16.8 min) of the
water in the electrolyser. Generally, the hardness
decreased during a 1 to 3 hours stabilization period
before to reach a pseudo stationary value. When
the current intensity was increased, the stabiliza-
tion period was shorter, and the steady-state value of
H was larger. This effect was more pronounced
for low currents. However, above 8 to 10 A.m
2
,
the various curves become practically identical,
which means that a great part of the electrical
energy was consumed to no purpose when the
intensity exceeds this value. It is interesting to
note that this current density corresponds practi-
cally to the plateau current density of the oxygen
reduction on a bare electrode (Fig. 2). From
microscopic observations of the scale structure, it
was shown that the stabilization period corresponds
to the time necessary to recover the full cathode
by the rst scale layer, from the bottom to the top
of the electrolyser (Fig. 9). For longer times,
water reduction with H
2
formation is prevailing
in the OH

generation process. Then, calcium car-

bonate dendrites grew as featured on Fig. 10. For
current densities larger than 10 A dm
2
, the OH

excess does not accelerate the scale formation

probably because the rates of reactions 3 and 4 are
limited by the convective diffusion kinetics of
calcium and hydrogenocarbonate ions towards
the reaction zone. In addition, the acidication of
the anode vicinity by H
+
generation could become
detrimental to the cathodic process. It can be con-
cluded that an optimal efciency of the process is
obtained for a current intensity which corre-
sponds approximately to the current plateau of
oxygen reduction measured on the bare electrode.
On Fig. 12, are reported two H = f(t) curves
obtained either on a bare electrode or on an elec-
trode which has been previously covered by a rst
calcium carbonate layer. It appears that in the sec-
ond case, the abatement reach more rapidly the
same stationary value. It proves that the water
reduction domain is more rapidly reached when
the surface was initially partially scaled.
158 C. Gabrielli et al. / Desalination 201 (2006) 150163
Fig. 11. Abatement H vs. treatment time, for various cur-
rent densities. (Constant sojourn time: 16.8 min., d= 3 cm,
Distribution water of Paris, H = 24F).
Fig. 12. Abatement Hvs time with a bare stainless steel
electrode or a pre-scaled electrode (current density 8
Am
2
, sojourn time 16.8 min., d= 3cm ,distribution water,
H = 24F, Current density 8 A.m
2
).
Effect of the ow rate and the sojourn time
The duration of the presence of the water in
the electrolyser is also a major parameter. It de-
pends on the cell volume and the ow rate. Fig. 13
shows the hardness abatement for various flow
rates, which correspond to sojourn times between
few minutes and one hour. The current density
was set at 8 A.dm
2
, the optimal value deduced
from Fig. 11.
It can be observed that the increase of
increased the time necessary to establish a steady-
state regime (from 40 min for = 8,4 min to 3h
for = 60 min). However, the final steady state
abatement was significantly larger. At low flow
rate, the nal abatement was very important. For
= 1 h, a stationary value H = 16F was ob-
tained, meaning that 66% of the dissolved cal-
cium carbonate was extracted by electrochemical
deposition. It is important to note that in the pres-
ent case, H =16 is close to the maximum value
which can be expected by calcium carbonate pre-
cipitation, knowing that the concentration of
hydrogenocarbonate ions was less than the Ca
2+
concentration. Alonger sojourn time , would not
increase the total amount of scale. However, in
practice, these operating conditions could be too
slow and could necessitate a prohibitive con-
sumption of energy for a given volume of treated
water. With a reasonable treatment time, a H =
8 to 10F can be easily reached, which is rela-
tively important for a 24F hard water and which
is largely sufficient for many applications, the
scaling potentiality of the treated water being
practically suppressed. Ahigher current intensity
would be more expensive and would not improve
signicantly the electrolyser efciency.
Effect of the inter-electrode distance d
The geometry the electrolyser is another im-
portant factor of the process. In particular the
inter-electrode distance d is implied in the defini-
tion of the cell volume and the ow rate. In addi-
tion, the electrical resistance R
e
of the water and
therefore the energy lost due to the ohmic drop
R
e
I are proportional to d. For this reason, the dis-
tance d between the cathode and anode plates of
the pilote scale electrolyser was varied from 10 to
40 mm and the hardness abatement was measured
in a large set of ow rates. The results are sum-
marized on Fig. 14, where the stationary values
of Hmeasured after a sufciently long treatment
C. Gabrielli et al. / Desalination 201 (2006) 150163 159
Fig. 13. Abatement H vs. time, for various sojourn
times in the pilot electrolyser (distribution water of
Paris, H = 24F, d= 3cm, current density = 8 A.m
2
).
Fig. 14. Effect of the inter-electrode distance d on the
variation of hardness abatement in function of the treat-
ment time. (Current density 8 A.m
2
, water hardness 26
F, constant sojourn time: 60 mn).
time, are plotted with respect to the sojourn time
, which itself is a function of d and .
It can be observed that when the gap between
the electrodes was reduced, the efciency of the
precipitation process was increased and the stabi-
lization period was shortened. For example, H
was about 30% larger when the distance was
reduced from 30 to 15 mm. It could be assumed
that when d is decreased the calcium and hydro-
genate carbonate present in the bulk diffuse more
rapidly to the active zone (Fig. 10b), where the
chemical reactions (3) and (4) can occur, and so,
the dissolved calcium carbonate is more com-
pletely exhausted. The mass transport can also be
enhanced by buoyancy forces due to hydrogen
gas evolution on the cathode and oxygen evolu-
tion on the anode. However, for the same volume
of treated water, a decrease of d imposes a larger
electrode area and therefore a higher manufactur-
ing cost. In addition, the maintenance operations
become more difcult. So, it seems that the bet-
ter compromise corresponds to few cm, whereas,
in some commercial cylindrical electrolysers [2],
this distance is in the order of 10 cm.
Treatment of a magnesium rich mineral water
Most results presented above were obtained by
using distribution water of Paris, which is moder-
ately hard (24 to 26F), by containing mainly cal-
cium an carbonate ions and minutes amounts of
other ions such as magnesium, sulphate etc. In
order to verify if the electrochemical device is
efficient for more charged waters, experiments
were carried out with the mineral water of the
Contrexeville source which contents in particular
486 mg.l
1
Ca
2+
, 84 mg.l
1
Mg
2+
, 1187 mg.l
1
SO
4
2
and 400 mg.l
1
HCO
3

That corresponds to
a total hardness of 156.8F with a calcium contri-
bution of 121.5F and a magnesium contribution
of 35F. However, the corresponding value for
hydrogenocarbonate ions is limited to 33F.
Electrochemical precipitation was carried out
in a 120 cm
3
electrochemical cell at constant cur-
rent intensity corresponding to oxygen reduction
limitation. The structure and the composition of
the scale were investigated by SEM, EDX analysis,
micro Raman spectroscopy and X ray diffraction.
After a few minutes of treatment, without circu-
lation, the cathode surface is completely covered
by a thin homogeneous layer, on the top of which
are deposited spherical particles (Fig. 15).
The basal layer is rich in magnesium without
crystalline structure, in agreements with Deslouis
et al [23] who have showed that a porous layer
containing Mg (II) is formed at a pH where crys-
tallized Mg(OH)
2
(brucite) can not be deposited.
Raman micro-analysis was performed on individ-
ual spherulites. On the basis on previous studies
[10,18,24] it was concluded without ambiguity
that they are made of monohydrated calcium car-
bonate CaCO
3
-H
2
O (MCC). This peculiar cal-
cium carbonate variety is very unstable in usual
conditions. It has been observed only at very low
temperature. According to recent works, MCC
nuclei are considered as the precursors of the
anhydrous forms [20,21,22]. It could be assumed
that magnesium ions which are known to inhibit
the calcite polymorph [25,26] could stabilise the
hydrated variety before their transformation into
a stable anhydrous polymorph.
160 C. Gabrielli et al. / Desalination 201 (2006) 150163
Fig. 15. SEM image of a thin scale layer electrodeposited
from Contrexeville mineral water (current density
8A.m
2
, treatment time 15 min, ow rate = 0).
C. Gabrielli et al. / Desalination 201 (2006) 150163 161
Contrexeville mineral water was submitted to
the same electrochemical softening treatment in
the pilot electrolyser. For example, are presented
in Fig. 16 the variation of the hardness abatement
for two relatively short values of sojourn times
and for a large inter-electrode distance. It can be
observed that these results are very similar to the
previous ones obtained with the distribution water
of Paris (Fig. 8). Much higher abatements could
be obtained for longer sojourn times and smaller
inter electrode distance d. After 5 h of treatment,
the morphology of the scale was very irregular
(Fig. 17a). It was not possible to recognize any
characteristic morphology of crystal polymorphs.
According to X ray diffraction the scale is a mix-
ture of calcite and Brucite (crystallised magne-
sium hydroxide) (Fig. 17b). The composition of
the scale, measured by EDX analysis varied sig-
nicantly with the treatment time in relation with
the pH increase. The relative atomic contributions
of Ca and Mg were respectively 98 and 2% after
a treatment time of 15 mn, and they were 87 and
13% after 3 h. It was not possible to detect neither
magnesian calcite Ca
1x
Mg
x
CO
3
nor CaSO
4
by X
ray diffraction, nevertheless, a thin layer of anhy-
drous calcium sulphate was detected by micro
Raman analysis at the surface of the calcium car-
bonate columns. From these results it can be
assumed that, in a rst step, the pH increase in the
vicinity of the cathode induced the formation of a
gel made of amorphous magnesium hydroxide and
dispersed MCC micro crystals. In a further step,
thanks to the shift of the representating point on
the polarization curve towards the water reduction
(a) SEM image (b) X ray diffraction diagram. (Mo K source)
Fig. 17. Scale precipitated on the cathode of the pilot electrolyser from Contrexeville mineral water ( = 30 min., treatment
time = 5 H).
Fig. 16. Hardness abatement during electrochemical
softening of Contrexeville mineral water for two sojourn
times. (current density 8 A.m
2
, 24C, inter-electrode dis-
tance d = 40 mm).
domain, the local pH becomes sufciently large
to promote the precipitation of magnesium as
brucite, whereas the MCC nuclei are transformed
into calcite crystals which growth in columnar
shape. In principle, calcium sulphate does not pre-
cipitate under the effect of a pH increase as it is
the case for calcium carbonate. Nevertheless, cal-
cite crystals induced a small co-precipitation of
CaSO
4
, but it corresponds to the extraction of a
negligible amount of sulphate from the mineral
water. After such an electrochemical treatment a
great part of the carbonate ions was eliminated,
and therefore the water has a weak calcium car-
bonate scaling potentiality for most applications,
but the high releasing concentration of calcium
and sulphate ions could lead to the formation of
a calcium sulphate scale formation by a supersat-
uration effect in the case of water evaporation.
5. Conclusion
This experimental investigation of electrolytic
water softening demonstrated that calcium
carbonate precipitation occurs under the form of
calcite or vaterite through a chemical process fol-
lowing the electrochemical generation of OH

ions in the very vicinity of the electrode surface.

Under potentiostatic control, the scale tends to
block the process. Under galvanostatic control, in
a rst step the formation of a porous scale layer
tends to stabilize the system at a working point
where hydrogen evolves whereas, in a second
step the precipitation process can continue by
the formation of dendritic growth which repels
the reaction zone. The fragile structures are eas-
ily detached and the process is continuously
renewed.
The experimental tests carried out on a pilot
electrolyser allow a better understanding of the
behaviour of an industrial device of water soften-
ing. The information on the specific effects of
operational parameters such as current density,
flow rate, sojourn time and inter electrode dis-
tance will be very precious to improve the soften-
ing efciency for a given energy consumption of
an industrial set-up.
Acknowledgements
This study has been partially supported by the
Saint-Gobain-Seva Company. The authors thank
the referee for his valuable comments.
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