Journal of Membrane Science 284 (2006) 323–330

Regeneration of hydrochloric acid and sodium hydroxide from

purified sodium chloride by membrane electrolysis using a
hydrogen diffusion anode-membrane assembly
F. Faverjon, G. Durand, M. Rakib ∗
Laboratoire de Génie des Procédés et Matériaux (LGPM), Ecole Centrale Paris, Grande Voie des Vignes, 92295 Châtenay-Malabry Cedex, France
Received 10 April 2006; received in revised form 4 July 2006; accepted 31 July 2006
Available online 12 August 2006

Abstract
Regeneration of hydrochloric acid and sodium hydroxide from sodium chloride solution has been carried out by membrane electrolysis where
the anode was replaced by a membrane-electrode assembly (MEA). Hydrogen diffusion electrode and a Nafion® 117 membrane were assembled
tightly in order to prevent platinum poisoning by chloride ions. The use of this electrode to produce H+ may be compared to the use of metallic
electrodes where H+ is produced by water oxidation with oxygen evolution. The reversible cell voltage is reduced by 1.23 V. The current efficiency
of hydrogen oxidation in the MEA is 100% if, at least, the stoichiometric flow of hydrogen is insured. Acid production is then only limited
by H+ leakage through the anion-exchange membrane. The undesirable flux of H+ through this membrane was found proportional to the acid
concentration in the anolyte. The value of the rate constant of proton leakage is about 0.080 dm3 faraday−1 . The current efficiency decreases when
acid concentration increases. Water transfer was also studied. Transfer towards the base solution is higher than transfer to the acidic solution.
When a current density of 3 kA m−2 is applied the anodic voltage remains below 300 mV for acid concentration lower than 3 mol dm−3 and
increases notably for higher acid concentrations probably due to poisoning of platinum by chloride ions that leak through the membrane owing to
their high concentration in solution.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Hydrochloric acid regeneration; Hydrogen diffusion anode; Membrane-electrode assembly; Membrane electrolysis; Proton leakage; Sodium hydroxide
regeneration

1. Introduction electrodialysis BMED [1] and membrane electrolysis ME [2] are

Chemical industry uses acids and bases as intermediates for
a wide variety of products. These are converted to salts and
must be handled as wastes. In order to achieve a clean process
the salt would be processed to regenerate the original acid and
base. The corresponding reaction is: MX (salt) + H2 O → HX
(acid) + MOH (base). To perform such a reaction, separation of
ionic species is required and also water dissociation or decom-
position. Electrochemical reactions and membranes are used for
these objectives.
Membrane electrochemical processes play an increasingly
key role in the treatment and the recycling of harmful chemicals.
They are clean and environmental friendly. Bipolar membrane
∗ Corresponding author. Tel.: +33 41131556; fax: +33 41131163.
E-mail address: mohammed.rakib@ecp.fr (M. Rakib).
useful for acid and base regeneration and these two processes
can be compared [3]. Due to the ion leakage through the bipolar
membrane which increases with the concentration of acid and
base on both sides of this membrane, the current efficiencies of
both acid and base production are higher for ME than for BMED.
ME leads to products with only traces of salt when BMED leads
to products containing small amounts of salt. Higher concentra-
tions are achieved by ME. For the two operations the salt solution
to be treated must not contain any trace of multivalent cations in
order to prevent hydroxide precipitation within the membranes.
However, the investment cost for ME is higher than for BMED
due to the need of a couple of electrodes per each elementary
cell.
Anion oxidation can be avoided in the case where the
potential is between that of hydrogen oxidation (0 V) and
that of water oxidation with oxygen evolution (1.23 V) by
using ME with a hydrogen diffusion anode. With such a gas

0376-7388/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2006.07.051
324 F. Faverjon et al. / Journal of Membrane Science 284 (2006) 323–330

diffusion electrode (GDE) protons are produced from hydrogen 2. Experimental details
oxidation (H2 → 2H+ + 2e− , E0 = 0.00 V) instead of water
oxidation (H2 O → 21 O2 + 2H+ + 2e− , E0 = 1.23 V). Advan- The cell was fed by the solutions pumped around. The char-
tageously this reaction change leads to 1.23 V decrease of the acteristics of this experimental device are given below.
reversible cell voltage and consequently a decrease of energy
consumption. 2.1. Cell, electrodes and membranes
The wastewater considered in this study, free of multivalent
components, contains sodium chloride as a consequence of the Gas diffusion anode consists of a catalyst deposited on one
use of hydrochloric acid and sodium hydroxide. It is modelled face of porous gas diffusion backing (Elat® 20% Pt on Vulcan
with synthetic solutions of pure sodium chloride. Production of XC 72) purchased from E-TEK (USA). The MEA is obtained by
chlorine and sodium hydroxide from sodium chloride by ME impregnating the active face with Nafion® in solution, heating
is a well-known technique largely used in industrial scale [4]. and pressing the gas-diffusion electrode and Nafion® 117 mem-
BMED is more and more applied to acidify organic salts to brane (Dupont, USA). The procedure is described in a previous
produce acids for industry [5,6]. Electrodialysis of hydrochlo- paper [18]. The current collector of the MEA was a titanium grid
ric acid was studied for extraction and concentration of HCl covered with platinum (30 g/m2 ) (Magneto-anodes, The Nether-
using sulphuric acid in the electrode circuit [7]. Chlorine demand lands).
decreases and new opportunities for sodium chloride electroly- The cell made from PVC-C was a three liquid compart-
sis arise. Production of hydrochloric acid and sodium hydroxide ment cell separated by Nafion® 117 cation-exchange membrane
from sodium chloride is an issue. It was studied using ME [8–10]. (CEM) between salt and base solutions and AW anion-exchange
A four compartment cell was used in order to prevent chloride membrane (AEM), provided by Solvay, between salt and acid
oxidation. The supplementary compartment contains sulphuric solutions as shown in Fig. 1.
acid as anolyte (no chloride in contact with the anode). The The area of the cell was 50 cm2 . The cathode was in nickel.
main problem with strong acid solutions is the permeability of The membranes were heated 1 h at 100 ◦ C in distilled water
the anion-exchange membrane to hydrogen ions [8,10]. Three before the first use. A Luggin capillary was used to measure the
anion-exchange membranes were used in the preceding studies potential near the MEA membrane surface. Each liquid com-
(ARA from Solvay, AAV from Asahi and ACM from Tokuyama partment contains a turbulence promoter.
Corp.). Proton leakage of ARA and AAV membranes is similar
while ACM membrane is less selective. Numerous studies con- 2.2. Procedure
cern other mineral acids. Lorrain et al. [11] studied the proton
leakage from HCl and H2 SO4 solutions through ARA mem- Pure hydrogen was supplied from gas cylinder and intro-
brane. Robbins et al. [12] studied proton leakage through ADP, duced at atmospheric pressure unless otherwise noted. In this
ARA, AW membranes (Solvay) and R5035 (RAI) from nitric case the pressure was obtained by connecting hydrogen outlet to
solutions. They show that proton leakage is linked to water flux a water column. Regeneration has been performed at 3 kA m−2
through the membrane. with humidified hydrogen. The temperature was about 25 ◦ C.
Patents [13,14] describe the confection of a hydrogen diffu- The gas outlet of the cell was connected to a bubble flowmeter
sion anode using platinum as catalyst and a process for producing to measure the flow in order to control that pure hydrogen flow is
H2 SO4 and NaOH from Na2 SO4 by ME using such an anode. higher than the stoichiometric flow (i.e. jA/2F hydrogen moles
The current efficiency is reported but the electrical behaviour
is not described in details. Holze et al. [15] have tested sev-
eral catalysts (Pt, Pd) and current collectors in a ME process
using a hydrogen diffusion anode to regenerate H2 SO4 . The
current–potential curves are reported but not the current effi-
ciency. The lowest anodic overvoltage is obtained with platinum
as catalyst. However, in the HCl regeneration, chloride ions can
be adsorbed on platinum and hinder the hydrogen oxidation
[16,17]. A cation-exchange membrane (CEM) bonded to the
gas diffusion electrode avoids chloride access to the catalyst.
The economy of the process is comparable to BMED concern-
ing operating costs. The investment costs are higher due to the
use of MEA. A membrane-electrode assembly (MEA) was man-
ufactured, used in an electrolytic cell and the current–voltage
curves were recorded and modelled [18].
The aim of this work is to study a ME process using an
MEA to regenerate hydrochloric acid and sodium hydroxide
from sodium chloride. The current efficiency for hydrochloric
acid and sodium hydroxide production is evaluated and the pro- Fig. 1. Three liquid compartment electrolysis cell to produce hydrochloric acid
cess is modelled. and sodium hydroxide from sodium chloride and the main transfers in the system.
 F. Faverjon et al. / Journal of Membrane Science 284 (2006) 323–330 325

per unit time, where j is the current density, A the active area
and F is the faraday constant 96,485 C mol−1 ). The volumetric
flow is V/
t = jART/2PF = 1.9 × 10−6 m3 s−1 for j = 3 kA m−2 ,
A = 50 cm2 . R is the ideal gas constant 8.31 J mol−1 K−1 , T the
absolute temperature (298 K) and P is the atmospheric pres-
sure (P = 101,325 Pa). The hydrogen volume leaving the cell was
measured by the bubble flowmeter during a fixed time
t. V3000
and V0 were the volume obtained, respectively, during opera-
tion at 3 kA m−2 and when no current was applied. V3000 must
be greater than 0 in order to insure at least the stoichiometric
hydrogen flow in the cell. The difference between V0 and V3000
represents the experimental hydrogen consumption during the
time
t.
The cell operated in batch mode with a recirculation of the
electrolytes from a reservoir located in each circuit. Graduations
on these cylindrical reservoirs allowed to measure volume vari-
ations of the circuits. The initial volumes are about 0.5 dm3 for
the three solutions. Solutions circulated through the compart-
ments at about 5–10 cm s−1 . A dc supplier was connected to the
electrodes. The current was applied about 10 min after putting
the solutions in circulation. Acid and base concentrations have
been measured by pH-metric titration.
The MEA voltage, i.e. the sum of the reversible potential
of the anodic reaction, the polarization voltage and the ohmic
losses in membrane and other conductors between the current
collector and the membrane–anolyte interface is noted Uanode . It
is measured as the following: when no current is applied, hydro-
gen is in circulation and an acid electrolyte (concentration about
1 mol dm−3 ) is fed to the anodic compartment, the voltmeter
indicates potential of the reference electrode the sign depending
on the connexion because the platinum electrode is the reversible
hydrogen electrode (0.00 V). The reference electrode is con-
nected to a Luggin capillary. When a current is applied Uanode
is the difference between the value given by the voltmeter and
the value without current.
2.3. Chemicals
Sodium chloride solutions were prepared from pure NaCl.
Hydrochloric acid and sodium hydroxide were of analytical
grade.
3. Results and discussion
The source of hydrogen ions is the gaseous hydrogen
oxidation at the anode catalyst and its migration through the
proton conducting membrane. Logically, the current efficiency
of hydrogen oxidation is firstly determined. Then the proton
leakage through the anion-exchange membrane is studied. A
model is given to predict the hydrochloric acid concentration
evolution during a batch process. This model is based on two
parameters characterising the anion-exchange membrane.
3.1. Current efficiency of hydrogen oxidation on the MEA
The determination of the gaseous hydrogen flow rates at 0
and 3 kA m−2 allows to calculate the mole number of hydrogen
involved in the oxidation reaction at 3 kA m−2 .
V0 − V3000 P
N(H2 )exp = (1)

t RT
The ideal gas equation is applied. As oxidation is
H2 → 2H+ + 2e− , the faraday law allows to calculate the the-
oretical hydrogen consumption:
jA
N(H2 )theo = (2)
2F
The current efficiency of hydrogen oxidation is given by the
following ratio:
N(H2 )exp
rf = (3)
N(H2 )theo
In order to determine the influence of the parameters listed
in Table 1, numbered 1–6, a fractional experimental plan at
26−3 = 8 measures has been used. In order to make only 8 mea-
sures instead of 26 = 64 in a non-fractional experimental plan,
following alias has been made using Box notation [19]: 4 = 123,
5 = 13, 6 = 23. Results of the experimental plan are presented
in Table 2, where a high value is represented by 1 and a low
value by −1. The given values of hydrogen current efficiency
are almost higher than 100% due to uncertainties on P, T, V0 ,
V3000 and
t.
The average current efficiency is 101.7 ± 2.09%. It appears
that the different parameters do not have any influence on the
current efficiency because the contrasts are small and negligi-
ble compared to the average current efficiency (101.7%). No
secondary reactions occur at the anode if the hydrogen flow
is higher than the stoichiometric one. The current efficiency
for hydrogen oxidation on the MEA catalyst is 100% in these
conditions.

Table 1
Parameters of the experimental plan to test the current efficiency
Parameter Parameter number High value Low value

[NaCl] in anolyte 1 4 mol dm−3 1 mol dm−3

[HCl] in anolyte 2 1 mol dm−3 0 mol dm−3
Temperature 3 323 K 298 K
Hydrogen pressure 4 Atmospheric pressure + 0.117 bar Atmospheric pressure
Hydrogen flow 5 Three times stoichiometric flow 1.05 stoichiometric flow
Humidification 6 H2 saturated with water vapour Dry hydrogen
326 F. Faverjon et al. / Journal of Membrane Science 284 (2006) 323–330

Table 2
Results (current efficiency and contrasts) for eight experiments (A–H) of the experimental plan
Experiment Parameter

[NaCl] [HCl] Temperature H2 pressure H2 flow Humidification Average Current efficiency (%)

A −1 −1 −1 −1 1 1 1 103.26
B 1 −1 −1 1 −1 1 1 101.85
C −1 1 −1 1 1 −1 1 102.56
D 1 1 −1 −1 −1 −1 1 103.80
E −1 −1 1 1 −1 −1 1 100.20
F 1 −1 1 −1 1 −1 1 97.39
G −1 1 1 −1 −1 1 1 103.12
H 1 1 1 1 1 1 1 101.42
Contrast (%) −0.59 1.02 −1.17 −0.19 −0.54 0.71 101.70

For each parameter, number 1 represents the high value and number −1 represents the low value.

3.2. Hydrochloric acid and sodium hydroxide current

efficiency

Anodic and cathodic volume variations are reported in Fig. 2.

The volumes of acid and base vary linearly with time. Electro-
osmosis mechanism of water transport is assumed. The salt
volume decreases. The variations of base volume are higher than
those of acidic volume (3.7 × 10−4 and 2.5 × 10−4 dm3 min−1 ,
respectively). Fig. 3 reports the variations of hydrochloric acid
and sodium hydroxide concentrations. The both concentra-
tions increase during electrolysis. These data allow to calculate
the mole numbers of hydrochloric acid and sodium hydroxide
present in their respective solutions versus time. Fig. 4 reports
Fig. 3. Acid and base concentrations vs. time ((
) HCl solution; () NaOH
these results. It appears that the number of moles varies approx- solution), j = 3 kA m−2 .
imately linearly versus the time. However a slight concavity is
observed.
at time t, by the following relation:
It is well known that acid production current efficiency varies
with acid concentration in the anolyte. A pertinent parameter to F dn
quantify this effect is the differential current efficiency of pro- DCE = (4)
jA dt
duction of hydrochloric acid. The differential current efficiency,
DCE, is defined for acid production but also for base production, where dn represents the variations of acid or base mole number
during time dt. To approximate dn/dt from the discrete exper-
imental points (every hour), the slope of the line joining the
point before and the point after the considered point is cho-
sen. The results are given in Fig. 5. This figure shows that the
current efficiency decreases more or less linearly with the acid

Fig. 2. Acid and base volume variations at j = 3 kA m−2 vs. time ((
) HCl solu- Fig. 4. Number of mole variations vs. time ((
) HCl solution; () NaOH solu-
tion; () NaOH solution). tion), j = 3 kA m−2 .
 F. Faverjon et al. / Journal of Membrane Science 284 (2006) 323–330
Fig. 5. Differential current efficiency vs. [HCl] at 3 kA m−2 for HCl and NaOH
regeneration ((
) HCl solution; () NaOH solution).
concentration. This is due to hydrogen ions leakage through the
anion-exchange membrane. The statistical analysis of the exper-
imental results gives the regression line equation and the interval
of variations within 95% confidence:
DCEa = 1.095 ± 0.13 − (0.099 ± 0.036) [HCl]
for acid current efficiency versus [HCl]. This is not in contradic-
tion with the property that DCEa is lower or equal to one. The
linearity assumption will be checked.
The current efficiency for base production is also given in
Fig. 5. It appears that the current efficiency values are rather close
to the acid values but somewhat lower. The statistical analysis
of the experimental points gives:
DCEb = 0.892 ± 0.110 − (0.059 ± 0.032) [HCl]
The decrease of base current efficiency when acid concentra-
tion increases can be explained by proton leakage through the
AEM and hydroxide ion leakage through the CEM. The pro-
tons, coming from the AEM, neutralise hydroxide ions in salt
compartment and also cross the CEM and react with hydroxide
ions. The statistical analysis shows that the difference between
the acid and base current efficiencies is not significant.
The average values of the current efficiency depend on acid
concentration range. In the range 0.5–4.5 mol dm−3 the effi-
ciency is about 73% for hydrochloric acid and about 69% for
base production.
The results obtained in this study are different from the results
of Robbins et al. [12]. The behaviour of DCE versus acid con-
centration depends on the system used: regeneration of an acid
from a salt (when acid concentration tends towards 0 the cur-
rent efficiency tends towards 1 because only chloride ions cross
the anion-exchange membrane) or concentration of acid start-
ing from identical solutions (the current efficiency for an acid
concentration equal to 0 is lower than 1). Lindheimer et al. [7]
confirm the linear variations of acid current efficiency versus
acid concentration in the anolyte.
For regeneration of HCl and NaOH from NaCl by ME,
Mazrou et al. [8] have obtained lower current efficiencies than
our results by using a four liquid compartments cell with ARA
17/10 (Solvay) or ACM (Tokuyama Soda, Japan) as AEM. Their
current efficiencies decrease with increase of current density and
of HCl or NaOH concentration. With the best membrane and
327
with the lowest current density (400 A m−2 ) in order to have the
best results, they obtained current efficiency of 71% for HCl and
45% for NaOH at 1.6 mol dm−3 . The current efficiency of HCl
is the same than in our experiments despite the different cur-
rent density (ARA membrane is similar to AW membrane). But
that of sodium hydroxide is lower because the cation-exchange
membrane is not adapted (CMV from Asahi). Mazrou et al. [8]
have also tested HCl regeneration with a WSI bipolar membrane
with ARA and CMV homopolar membranes and obtained sim-
ilar results than for their membrane electrolysis experiments. It
appears that the process studied in this work is efficient to pro-
duce HCl and NaOH from NaCl with good current efficiencies.
3.3. Modelling of the hydrochloric regeneration by ME
The proportionality of the H+ flow rate through the anion-
exchange membrane and the acid concentration in the anolyte
is assumed:
(5) N = k[HCl] (7)
where N is the H+ mole number per time unit crossing the anion-
exchange membrane, [HCl] the anolyte acid concentration and
k is a constant linearly dependent of current density as stated by
Gineste et al. [20].
The value of k is valid for the actual membrane area A. The
constant k , independent of A and j, is defined as follows:
k = k Aj (8)
(6)
The flux of H+ through the anion-exchange membrane is writ-
ten as:
φ = k j[HCl] (9)
where φ is the flux in mol m−2 s−1 .
During an elemental time dt the net variation of H+ mole
number is the difference between produced H+ mole number
jA dt/F (current efficiency of hydrogen oxidation 100%) and the
H+ mole number leaving the anolyte by leakage through the
anion-exchange membrane. The following relation then gives
the differential current efficiency:
jA dt/F − k [HCl]jA dt
DCEa = = 1 − k F [HCl] (10)
jA dt/F
The trendline in Fig. 5 gives the k value: k F = 0.1 ±
0.04 dm3 mol−1 (statistical analysis).
The acidic volume is noted (Fig. 2):
V = V0 + at (11)
where V0 is the initial volume and a is a parameter which varies
with current density as shown in Ref. [20] and membrane area:
a = a jA (12)
The value of the parameter a is 2.5 × 10−4 dm3 min−1 . The value
of the constant a is 2.9 × 10−10 m3 C−1 = 0.028 dm3 faraday−1 .
328 F. Faverjon et al. / Journal of Membrane Science 284 (2006) 323–330

values of k and V0 . The agreement is excellent. The value

obtained by this procedure is k = 7.6 × 10−4 dm3 min−1 .
The rate constant value is k = 8.3 × 10−10 m3 ,
−1 −5
C = 8.0 × 10 m faraday = 0.080 dm faraday−1 . This
3 −1 3

value is to compare to the value determined by Lorrain et al.

[11] which is 2.2 × 10−4 m3 faraday−1 for HCl through the
ARA membrane at 1000 A m−2 . The ratio of the values for
ARA and AW membranes is 2.75. This means that proton
leakage through ARA membrane is 2.75-fold higher than
through AW membrane for hydrochloric acid.
The current efficiency versus the anolyte acid concentration
should have the following equation derived from Eq. (10) with
k F = 0.080 dm3 mol−1 :

DCEa = 1 − 0.080[HCl] (17)

Fig. 7 reports this line and the experimental results concerning

Fig. 6. Acid concentration vs. time calculated by Eq. (16) and experi-
current efficiency of production of hydrochloric acid. Except one
mental points with the optimised value of k = 7.6 × 10−4 dm3 min−1 and
V0 = 0.587 dm3 . point not well fitted, the accordance between the experimental
results and the predicted values is good.
To model a batch process between time 0 and time t, the H+ The limiting concentration which may be achieved is given
balance is written (between t and t + dt): by the following relation deduced from Eq. (16) where t → ∞:
jA dt jA 1
− k[HCl] dt = d(V [HCl]) = V d[HCl] + [HCl] dV [HCl]l = = (18)
F F (k + a) F (k + a )
(13)
The value is 9.26 mol dm−3 . This value is dependent on the
The first term represents the mole number of hydrogen ion pro- nature of the anion-exchange membrane. Tests of PC 100 acid
duced at the anode (efficiency of production of proton 100%), membrane from PCA Gmbh show that it is less selective than
the second term represents the mole number of H+ that leaks AW membrane for hydrochloric acid.
through the anion-exchange membrane. The difference repre-
sents the net accumulation of H+ moles. 3.4. Water transfer
Eq. (13) may be written using Eq. (11):


jA The ions cross a membrane with water molecules depending
− (k + a)[HCl] dt = (V0 + at) d[HCl] (14) on their nature and on the membrane. When one-electron mole
F
reacts, 1 mol of protons should be produced. But as the current
or:
efficiency CEa is only 73%, CEa Cl− mole crosses AEM and
d[HCl] dt (1 − CEa ) H+ mole crosses the same membrane in the opposite
= (15)
jA/F − (k + a)[HCl] V0 + at direction. The global transfer of α mole of water from the salt
Integration of this differential equation between t = 0 and time t compartment to the acid compartment can be calculated. Dur-
gives: ing the duration of electrolysis:
nHCl = 2.714 mol of HCl are


 produced in anolyte (Fig. 4). Mass variation
m of the anodic
1 jA jA
[HCl] = − − (k + a)[HCl]0
k+a F F


V0 + at
× − (k + a)/a (16)
V0
This relation is similar to that obtained by Jaime Ferrer et al.
[21] in the case where the production of formic acid from its
salt by a three compartment bipolar membrane electrodial-
ysis is lowered by acid diffusion through the membranes. It
may be used to predict the batch process and compared to
experimental results. Eq. (16) may be used to determine k
more precisely by fitting the experimental acid concentration
values and the calculated values by the method of least
squares. Also the acid initial volume V0 is taken as unknown
because the imprecision in its determination. Fig. 6 shows Fig. 7. Calculated current efficiency (line) and experimental acid current effi-
the experimental points and the calculated curve for the best ciencies j = 3 kA m−2 vs. the acid concentration.
 F. Faverjon et al. / Journal of Membrane Science 284 (2006) 323–330 329

solution is then:

nHCl

m = α MH2 O +
nHCl MHCl (19)
CEa
where MHCl and MH2 O are respectively, molar mass of HCl
and H2 O and α is the average water moles per faraday. Initial
and final concentrations (0.478 and 4.702 mol dm−3 ) of anodic
solution allow to determine initial and final densities (1.0086
and 1.0794 kg dm−3 ) of these hydrochloric acid solutions [22].
Then, initial and final volumes (587 and 671 cm3 ) in the anolyte
allow to determine initial and final mass (592 and 724 g) of this
solution. So, the number α is:


CEa
m
α= − MHCl = 0.49 (20)
MH2 O
nHCl
This is in agreement with the accepted assumption that chloride
ion is poorly hydrated. The obtained value may be explained by
the difference between chloride and hydrogen ion transporting Fig. 8. Anodic voltage variations vs. the acid concentration during regeneration
water in the opposite direction. of hydrochloric acid and sodium hydroxide at 3 kA m−2 .
For the base compartment, the cathodic reaction is written:
3.5. Electric behaviour
2H2 O + 2e− → H2 + 2OH− (21)
When one-electron mole reacts, one water mole is consumed; Fig. 8 reports the variations of the anodic voltage versus
one OH− mole and a half mole of hydrogen are produced at the acid concentration when a current density of 3 kA m−2 is
cathode. But as the current efficiency CEb is only 69%, CEb applied. Under an acid concentration below 3 mol dm−3 the volt-
mole of Na+ and (1 − CEb ) mole of H+ cross CEM in the same age is quite low (<300 mV) and varies slowly. This is to compare
direction while β moles of water cross CEM per faraday. During to nearly 1.5 V minimum for a classic anode (the overpotential of
the 420 min of the electrolysis,
nNaOH = 2.688 mol of NaOH oxygen evolution is large). The win is higher than 1 V. When the
are produced at the cathode. Mass variation
m of the cathodic acid concentration exceeds 3 mol dm−3 , the voltage increases
solution is then: notably. This is probably due to chloride anion leakage through
the MEA Nafion® 117 membrane. Chloride may be adsorbed

m =
mNaOH +
mH2 O,electrolysed +
mH2 O,transferred on the catalyst and hinder platinum oxidation sites [9,10]. This
+
mH2 O,synthesised (22) increases the activation potential of the reaction. The MEA volt-
age increases also with the current density as shown in Ref. [18].
where
mNaOH ,
mH2 O,electrolysed ,
mH2 O,transferred , and

mH2 O,synthesised are respectively, mass variation of NaOH,
4. Conclusion
water consumed by electrolysis, water transferred through CEM
and water synthesised by the reaction H+ + OH− → H2 O. This
The MEA used in this study performs oxidation of hydro-
relation can also be written:

gen alone if at least the stoichiometric quantity of this com-
1 β pound is fed to the reactor. It may be used as H+ source in a

m =
nNaOH MNaOH − M H2 O + M H2 O
CEb CEb membrane electrolysis device. Hydrochloric acid and sodium
 hydroxide can be regenerated from sodium chloride solutions
(1 − CEb )
+ M H2 O (23) using a three liquid compartment cell. The undesirable H+
CEb
flux through the anion-exchange membrane is proportional to
(produced hydrogen at the cathode escapes from the solution). acid concentration in the anolyte. The anion-exchange mem-
Initial and final base concentrations (0.501 and 4.453 mol dm−3 ) brane is characterised by the value of the rate constant of H+
in the catholyte allow to determine initial and final densities leakage through the membrane (for HCl and the AW mem-
(1.022 and 1.169 kg dm−3 ) of these sodium hydroxide solutions brane k = 0.080 dm3 faraday−1 ). The differential acid current
[22]. Then, initial and final volumes (539.5 and 665.5 cm3 ) of efficiency varies linearly versus acid concentration. Water trans-
cathodic solution allow to determine initial and final masses fer mechanism through the membranes is by electro-osmosis.
(551.5 and 778.1 g) of this solution. So, the number β is: Anodic voltage remains below 300 mV when chloride con-

 centration is below 3 mol dm−3 and increases for higher concen-
CEb
m
β= − MNaOH + CEb = 2.39 (24) trations. The gas-diffusion electrode allows to decrease anodic
MH2 O
nNaOH
potential compared to a metallic anode while MEA membrane
This value is in agreement with the known results (about 3 mol avoids or reduces chloride migration to GDE which hinder
of water per mole of sodium and 1 mol of water per mole of hydrogen oxidation. In conclusion this process permits to regen-
hydrogen ion) [23]. erate hydrochloric acid and sodium hydroxide from sodium
330 F. Faverjon et al. / Journal of Membrane Science 284 (2006) 323–330
chloride solutions with substantial reduction of cell voltage com-
pared to the four liquid compartment cell.
Acknowledgement
Thanks to Charlotte Sayagh for experimental help.
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