Desalination 296 (2012) 16–23

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Desalination
journal homepage: www.elsevier.com/locate/desal

Statistical optimization of active chlorine production from a synthetic saline effluent

by electrolysis
François Zaviska a, 1, Patrick Drogui a,⁎, Gortáres Pablo b, 2
a
Institut national de la recherche scientifique (INRS-Eau Terre et Environnement), Université du Quebec, 490 rue de la Couronne, Quebec, QC, Canada, G1K 9A9
b
Instituto Tecnologico de Sonora (ITSON), Departamento de Biotecnologia y Ciencias Alimentarias, 5 de Febrero 818 Sur C.P. 85000 Cuidad Obregon, Sonora, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: This study examines the possibility to optimally produce active chlorine from a synthetic concentrate of seawater
Received 30 January 2012 by electrolysis using an experimental design methodology. Different operating parameters were investigated
Received in revised form 28 March 2012 such as current density, reaction time, hydrochloric acid concentration and chloride ion concentration. Using a
Accepted 29 March 2012
24 factorial matrix, the best performance for active chlorine production (46 mg/l of HClO) was obtained at a cur-
Available online 28 April 2012
rent intensity of 1.6 A during 35 min of treatment time in the presence of 0.11 M of H3O+ and 0.8 M of NaCl. The
Keywords:
current intensity and treatment time were the main parameters influencing the active chlorine production. Sub-
Saline effluent sequently, a central composite design methodology has been investigated to determine the optimal experimen-
Seawater tal parameters for chlorine production. The electrolytic cell applied under optimal conditions (at a current
Electro-oxidation intensity of 1.6 A during 27 min in the presence of 0.11 M of NaCl and 0.8 M of H3O+) is able to produce
Active chlorine 31 mg/l of chlorine for an energy consumption of 0.54 kWh/m3.
Experimental design © 2012 Elsevier B.V. All rights reserved.

1. Introduction common methods to treat concentrates include : (i) disposal to evap-

Chlorine is a chemical commonly used as an oxidizing agent for
drinking-water disinfection and wastewater treatment. This oxidizing
agent can be used in different forms: gaseous (e.g. Cl2, ClO2, etc.), liquid
(e.g. NaClO, HClO, NH2Cl, etc.) and solid (e.g. Ca (OCl)2). Chlorine is cur-
rently produced commercially by electrolysis of sodium chloride (NaCl)
solution [1,2]. It can be generated from electrolysis of seawater or from
electrolysis of saline effluent from desalination plants. Seawater desali-
nation is becoming more and more popular for production of fresh pota-
ble water and many coastal municipalities are looking for this technique
of water supply [3]. For instance, during desalination of seawater for
drinking water production, salts can be totally or partially removed
from the filtrate or permeate, while at the same time the retentate is
enriched with salts. Desalination processes generate discharge of elevat-
ed salinity which is usually 1.5 to 2 times higher than the concentration
of total dissolved solids (TDS or salinity) of the ambient seawater [3].
The high-salinity side-stream generated is commonly referred to as con-
centrate or brine waste that must be dispose safely.
Due to the lack of suitable methods for the disposal of waste brine
produced during desalination processes (such as reverse osmosis and
nanofiltration), the use of desalination system is limited [4]. The most
⁎ Corresponding author. Tel.: + 1 418 654 3119; fax: + 1 418 654 2600.
E-mail addresses: francois.zaviska@ete.inrs.ca (F. Zaviska),
patrick.drogui@ete.inrs.ca (P. Drogui), pgortare@itson.edu.mx (G. Pablo).
1
Tel.: + 1 418 654 2530; fax: + 1 418 654 2600.
2
Tel.: + 52 644 410 0900x2110/2911.
oration ponds [5–7], (ii) discharge in deep disused gold mines or
wells [8] and (iii) coastal discharge [9,10]. The typical range of pH of
reverse osmosis brine varies from 4.0 to 7.0 [19,20]. Usually, the concen-
trate is returned to the sea (pollution transfer). When returned to the
sea without dilution, the concentrate may have a negative impact on
the aquatic environment in the area of the discharge [3]. However,
such a saline effluent can be considered as a saline resource. Alternative
approaches can be developed to either extract available salts, to recover
purified water or can be advantageously used to produce chlorine via
brine electrolysis [16–18]. The use of seawater as electrolyte should
contribute to reduce chemical cost for chlorine production that can be
used for water treatment.
The aim of the present study is to optimally evaluate the efficiency
of an electrolytic cell using Ti/IrO2 anode material for active chlorine
production from a synthetic saline effluent (SSE). The SSE was a sim-
ulated brine waste resulting from the reverse osmosis filtration of
seawater. To this end, an experimental design methodology [11]
was put in place to firstly investigate the influence of the principal ex-
perimental parameters (current intensity, treatment time, chloride
concentration and hydrochlorid acid concentration) on the efficiency
of the experimental unit for active chlorine production. A second ob-
jective of this study was to use a statistical methodology for a rational
analysis of the combination of operational factors that led to the best
treatment process. Factorial design (FD) and Central composite de-
sign (CCD) methodologies have been successively applied in order
to point out the main and interaction effects of the factors and to op-
timize active chlorine production.

0011-9164/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2012.03.023
 F. Zaviska et al. / Desalination 296 (2012) 16–23 17

2.3. Analytical details

Nomenclature

The hypochlorous acid production was estimated using the Wessler

CCD Central composite design
reaction, which consists to oxidize iodide ions (I −) into iodine (I2)
COD Chemical oxygen demand
using active chlorine [12]. Then, I2 reacts with the excess of I − to
DSA Dimensionally stable anodes
form tri-iodide (I3−) according to Eq. (1).
FD Factorial design
SSE Saline synthetic effluent − −
TMP Transmembrane pressure I2 þ I ⇔I3 ð1Þ
RO Reverse osmosis
The tri-iodide ion is then analyzed by absorbance measurements
(εI3 − = 26,303 L mol − 1 cm − 1) [31] using a spectrophotometer Carry
2. Materials and methods UV 50 (Varian, Canada) at 353 nm [13]. pH and conductivity have
been measured during the experiments using a pH/conductimeter
2.1. Saline effluent preparation (Oakton, model 510). Intensity (I) and voltage (V) was recorded
using a power supply (Enduro 250 V, Labnet international, Inc., New
The synthetic saline effluent (SSE) was prepared with distilled Jersey, USA).
water using sodium chloride (NaCl, Fisher Scientific, ACS reagent)
added at a concentration varying between 0.05 M and 0.105 M. The 2.4. Experimental design
initial pH of SSE was respectively set at 0.9 and 1.3 using HCl
(0.02 M to 0.14 M.). Initial pH values varying from 0.9 to 1.3 were Experimental design of the electrochlorination process was car-
chosen in order to avoid to exceed the limit value of pH (pH = 2.0) ried out using successively factorial design (FD) and central compos-
from which chlorine gas can be decomposed into hypochlorite ion ite design (CCD) methodology. Both FD and CCD are widely used for
(ClO −) and hypochlorous acid (HClO) [22,23]. the response surface methodology (RSM). RSM is a collection of
mathematical and statistical methods for modeling and analysis of a
process in which a response of interest can be influenced by several
2.2. Experimental unit variables. Indeed, it is used to determine the optimum operating con-
ditions or to determine a region for the factors in which certain spe-
The assays were carried out in a batch system depicted schematically ciation are met. In our study, the FD was employed to firstly
in Fig. 1. The electrolytic cell (1), a power supply (2), a peristaltic pump investigate the main and interaction effects of the factors on the gas
(3), an air diffuser (5) and a 4 liters glass tank (4). The electrolytic reactor chlorine production. Subsequently, the CCD was used to describe
unit used had 400 ml of capacity, and was made in PVC material with a the process in the experimental domain and also for the optimization
dimension of 135 mm (L)× 35 mm (l)× 140 mm (h). The electrolytic of this process to have the best gas chlorine production at the lowest
cell was comprised of a rectangular anode of Ti/IrO2 in the form of energy cost. This design is formed by uniformly distributed points
expanded metal and a rectangular stainless steel (SS) plate using as within the space of the coded variable (Xi). One of the advantages
cathode electrode. of CCD is the possibility to explore the whole of the experimental

H2 Cl 2

Power Supply

1
4

Stirring system Stirring system

Fig. 1. Schematic diagram of the experimental unit for chlorine gas production: (1) electrolytic cell; (2) power supply; (3) peristaltic pump; (4) glass tank; (5) air diffuser.
18 F. Zaviska et al. / Desalination 296 (2012) 16–23

region and the usefulness of interpolating the response. The CCD ma-
trix allows the description of a region around an optimal response. It
is comprised of factorial matrix (described above) and 14 additional
experiments. The fourteen additional assays consisted of six runs re-
quired at the center of the experimental region investigated, plus
eight other axial runs. For the axial runs matrix, α has been chosen
in order to have iso-variance property by using rotation, with
α = (Nf) 1/4 = 2, Nf being the number of points required for the factorial
matrix. The experimental response associated to a CCD matrix is repre-
sented by a quadratic polynomial model:
X
k
k 2 k
Y ¼ b0 þ bi :Xi þ ∑i¼1 bii :X i þ ∑j ∑i¼2 bij :Xi Xj
i¼1
Where
Y Experimental response
b0 Average of the experimental response
bi Estimation of the principal effect of the factor j for the
response Y
bii Estimation of the second effect of the factor i for the
response Y
bij Estimation of the interaction effect between factors i and j
for the response Y.
The coefficients of this model are calculated in the experimental
region (see Table 4) using the least square method [11]:
 −1
T T
B¼ X X X Y
with B, vector of estimates of the coefficients; X, the model matrix; Y,
the vector of the experiment results. A four-factorial and a two-level
central composite design, with six replicate at the center point led
to a total number of thirty experiments employed for response surface
modeling. The independent process variables used in this study were:
the application time (X1), the applied current intensity (X2), the pH in
term of H3O+ concentration (X3), and NaCl (electrolyte) concentration
(X4). The experimental values of Ui can be calculated from the coded
variables Xi using the following equation:
Ui Ui;0
Xi ¼
ΔUi
Where Ui,0=(Ui,max+ Ui,min)/2, represents the value of Ui at the
center of the experimental field; ΔUi=(Ui,max - Ui,min)/2, represents
the step of the variation, with Ui,max and Ui,min which are the maximum
and minimum values of the effective variable Ui, respectively.
Gas chlorine production (Y1) and energy cost (Y2) was considered
as dependents factors (response). The values of process variables and
their variation limits were selected based on the preliminary experi-
ments. Experimental data were analyzed using Design-Expert 7.1
program software including ANOVA in order to obtain the interac-
tions between the process variables.
þ 
Cl2 þ H2 O→HClO þ H þ Cl ð6Þ
HCl→ClO þ Hþ pKa ¼ 7:3 ð7Þ
Generally, on classical electrodes, the oxidation of chloride ions
takes place at a potential very close to that of the oxidation of water
(Eq. (8)), so that there is a competitive reaction between hypochlorous
acid formation and oxygen formation.
þ
2H2 O→2O2 þ 4H þ 4e− ð8Þ
ð2Þ
To limit the oxygen formation, it is possible to use some electrodes
having high over potential of oxygen and/or having a catalytic effect
toward chloride ion oxidation (such as Ti/IrO2). In this way, chloride
ions oxidation is carried out before water oxidation [23,24].
3.1. Preliminary experiments and determination of the experimental
domain
During the preliminary experiments, the experimental domain
has been determined. The experiment region investigated for gas
chlorine production, and the coded values are shown in Table 1. It is
worth noting that chloride concentration has been fixed in function
of the objective of the study (electrochlorination of the concentrate
of seawater obtained from a reverse osmosis process). The chloride
ion concentrations (0.3–0.8 M) of RO brine depends on the operating
conditions imposed during filtration. Several parameters such as the
type of membrane (rated pore of the membrane), the permeability
ð3Þ of the membrane, the transmembrane pressure (TMP) and the initial
characteristics of influent affect the residual chloride concentration of
RO brine [19,20]. Generally, the chloride concentration in seawater is
~0.45 M, whereas a concentration around 0.8 M is most often
recorded in the concentrate obtained from reverse osmosis filtration
of sea water [3]. Based on Pourbaix diagram (potential versus pH)
for chlorine, there is a minimal value of pH for chlorine gas produc-
tion (Fig. 2). Indeed, up to pH 2, it's not possible to produce chlorine
gas, only hypochlorous acid and hypochlorite ions are formed
[21,22]. During the preliminary experiments, a minimum pH value
of 1.8 was required to have a significant production of hypochlorous
acid (HClO). A correlation between conductivity and hypochlorous
acid production has been established. The results are presented in
ð4Þ
Fig. 3. It can be seen that the conductivity increases with active chlo-
rine concentration in solution. After 15 min of electrolysis, the pro-
duction of active chlorine is almost proportional to the conductivity
with a ratio [conductivity]/[HClO] close to 4.77. During the process,
chlorine gas from the anodic compartment is transferred and dis-
solved in the 4.0 l tank of distilled water. If we admit that the com-
partment of gas is perfectly hermetic, only chlorine gas and oxygen
could be injected into the 4 l tank. During the experiments, pH of
the 4 l of distilled water decreases due to the dissociation of chlorine
gas into H +, hypochlorous acid (HClO) and chloride ions (Cl −) (see
Eq. (2)). Thus, the increase of conductivity was attributed to the pres-
ence of chloride (Cl −), H + and hypochlorous acid (HClO) in solution.

3. Results and discussion

Table 1
Data for optimization operation: experimental range and levels of independent process
During electrolysis of SSE containing chloride ions, chlorine was
variables.
produced at the anode (Eq. (5)) and hydrogen gas was produced at
the cathode. Due to the dissociation of the generated chlorine in Coded Factor (Ui) Experimental field Ui,0 ΔUi
variables
water, hypochlorous acid and chloride were produced as illustrated Max. value Min. value
(Xi)
by Eq. (6). The chlorine gas (Cl2) was transferred from the electrolytic (− 1) (+1)
cell into a storage tank by mean of a peristaltic pump as described in X1 U1 : Electrolysis time (min) 15 35 25 10
Fig. 1. X2 U2 : Current intensity (A) 0.8 1.6 1.2 0.4
X3 U3 : [H3O+] (M) 0.05 0.11 0.08 0.03
−
2Cl →Cl2 þ 2e− ð5Þ X4 U4 : NaCl conc. (M) 0.3 0.8 0.55 0.25
 F. Zaviska et al. / Desalination 296 (2012) 16–23 19

120

100 l=0.8A; pH=1.3

l=1.6A; pH=1.3

80 l=0.8A; pH=0.9

[HCIO] (mg/I)
l=1.6A; pH=0.9
60

40

20

0
0 5 10 15 20 25 30 35 40 45 50 55 60 65
time (min)
Fig. 2. Pourbaix diagram (potential versus pH) for chlorine.
Fig. 4. Production of hypochlorous acid in function of time for different intensities and
pHs while imposing chloride ion concentration of 0.3 M (1srt part of the factorial
+ −
H and Cl are directly proportional to chlorine gas dissociation in design).
water. However, from a pH 5.5 a part of HClO is dissociated into hypo-
chlorite ions (ClO −) and H +. At pH 10, all HClO was dissociated into electrolysis, as the current intensity increases the kinetic of hydroxide
ClO − and the conductivity depend on ClO −, H + and Cl −.. ion production increases.
To clearly define the experimental region for the factorial design
−
methodology, additional experiments were carried by imposing two 2H2 O þ 2e−→2OH þ H2 ð9Þ
current intensities (0.8 A and 1.6 A) and two initial pHs (0.9 and 1.3)
for a period of treatment of 60 min. Samples were withdrawn every In order to avoid to exceed the limit value of pH for chlorine gas
5 min of electrolysis for HClO analysis. The results are summarized in production, the range of electrolysis time was fixed between 15 min
Fig. 4. From this figure, it can be seen that, HClO concentrations increase (low level (−1)) to 35 min (high level (+1)).
with the current intensity and electrolyse time. By comparing the
curves (I= 0.8 A, pH0 = 1.3) and (I= 0.8 A, pH0 = 0.9), it can also be 3.2. Factorial design
seen that, the decrease of pH has a negative effect on chlorine produc-
tion. Indeed, after 1 h of electrolysis, it was possible to produce 33 mg/l The influence of four main factors has been investigated: electrol-
of hypochlorous acid at pH0 = 1.3 compared to 20 mg l− 1 recorded at ysis time (U1), current intensity (U2), pH in term of H3O + concentra-
pH =0.9. However, for a current intensity two times higher (i.e. 1.6 A), tion (U3) and NaCl concentration (U4) on the efficiency of chlorine
the influence of pH is totally different (comparison of curves (I = 1.6 A, production using the experimental design methodology by means of
pH0 =1.3) and (I = 1.6 A, pH0 = 0.9)). Relatively high concentrations of factorial matrix (2 k, k being the number of factors ; k = 4). In this
HClO were recorded at low initial pH imposed (pH0 = 0.9) and more type of design, variables (k) are set at two levels (minimum) and
than 100 mg HClO/l was measured after 60 min of electrolysis. By com- (maximum) normalized as (− 1) and (+1). With such a design, it is
parison, a residual HClO concentration around 44 mg/l was recorded possible to determine the average and the principle effects of each
after 60 min of electrolysis for pH0 =1.3. Likewise, the HClO concentra- factors and their interaction 2 to 2, 3 to 3, until k factors [11]. The ex-
tion reached a steady state after 40 min of electrolysis because the pH perimental response associated to a 2 4 factorial design (four vari-
of the electrolysed-solution increased up to 1.8. In fact, during electrolysis, ables) is represented by a linear polynomial model with interaction:
pH of the electrolysed-solution increases due to the production of hydrox-
ide ions at the cathode electrode (Eq. (8)). It is well-known that during Yi ¼ b0 þ b1 X 1 þ b2 X 2 þ b3 X 3 þ b4 X 4 þ b12 X 1 X 2 þ b13 X 1 X 3
ð10Þ
þ b14 X 1 X 4 þ b23 X 2 X 3 þ b24 X 2 X 4 þ b34 X 3 X 4

35 160 Where Yi represents the experimental responses, Xi the coded vari-

able (−1 or +1), bi represents the estimation of the principal effect of
30 140 the factor i on the response. The responses Y1 investigated is the chlo-
rine production and Y2 the energy consumption for this process. The co-
120
25 efficients of the mathematical model were calculated using the half-
conductivity mS
[HClO] mgL-1

100 difference between the arithmetic average of the values of the response
20 when the associated coded variable is at level (+1) and the arithmetic
80 average of the values of the response while the associated coded vari-
15 able is at level (−1). The experimental design and results are repre-
60
sented in Table 2. The coefficients of the polynomial model were
10 [HClO] calculated by means of Design-Expert Program Software (Design Expert
40
conductivity 7, 2007, Stat-Ease Inc., Minneapolis):
5 20
Y1 ¼14:16 þ10:19X1 þ8:4X2 þ0:08X3 þ0:7X4 þ5:8X1 X2 þ1:53X2 X4 ð11Þ
0 0
0 10 20 30 40 50 60 70
It is worth noting that the responses recorded are well fitted to the
time (min)
polynomial model with a regression coefficient R2 of 0.982. Besides,
Fig. 3. Evolution of hypochlorous acid concentration and conductivity during electrolysis the low relative deviation values recorded (between the actual and pre-
of synthetic saline effluent; I = 0.8 A ; pH= 1.3 ; [Cl−]= 0.8 M. dicted values) indicated that the linear polynomial model described by
20 F. Zaviska et al. / Desalination 296 (2012) 16–23

Eq. (11) is satisfactory (see Table 2). The coefficient b0 = 14.16 repre- 50
sents the average value of the response of the 16 assays. From 45
Eq. (11), it can be seen that the electrolysis time (b1 = +10.2) greatly 40

contribution (%)
influenced the active chlorine production. The active chlorine concen- 35
tration increases on average of 20.4% (2× 10.2) when the treatment 30
time goes from 15 to 35 min. The second most important factor on the 25
chlorine production is the current intensity with a positive effect 20
(b2 = +8.40). The increase of current intensity contributes to increase 15
the rate of chlorine production. The chlorine concentration increases 10
on average of 16.8% (2× 8.40) when the current intensity goes from 5
0.8 to 1.6 A. However, the effects of H3O + concentration (b3 = +0.08) 0

X1 (time)

X2 (Intensity)

X1X2 (time-intensity)

X1X4 (time-Cl-conc.)

X4 (Cl-conc.)

X3 (H3O+ conc.)
and NaCl concentration (b4 = +0.7) are relatively weak. Among the in-
teraction terms, (X1X2) and (X2X4) have the most important coefficient
(b12 = +5.8 and b24 = +1.53, respectively). Pareto analysis can be used
to give more significant information to interpret these results [11,14].
Indeed, this analysis calculates the percentage effect of each factor on
the response, according to the following relation:

!
b2i Fig. 5. Graphical Pareto analysis of the effect of current intensity, treatment time,
Pi ¼  100 ði≠0Þ ð12Þ chloride ion concentration and acid concentration on active chlorine production.
∑b2i

is fixed at the lowest level (0.8 A), the production rate passed from
bi represents the estimation of the principal effect of the factor i. Fig. 5
1.36 mg/l to 10.2 mg/l (a production gain of 8.8 units). Consequently,
represents the Pareto graphic analysis. It can be seen that the treatment
it can be noticed that the effect of treatment time is not constant; it
time (X1) and current intensity (X2) are the most determining factors
depends on another factor, here the current intensity. Finally, using
on the chlorine production, their effect is 82.8% (the sum of the two ef-
a 24 factorial matrix, the best performance for active chlorine production
fects) on the investigated response. However, the H3O + concentration,
(46 mg/l of HClO) was obtained at a current intensity of 1.6 A during
NaCl concentration and the other interaction effects represent 17.2% on
35 min of treatment time in the presence of 0.11 M of H3O+ and 0.8 M
the investigated response (chlorine production).
of NaCl.
With the exception of the interaction X1X2, the other interactions
have a negligible or very low effect. The interpretation of the interac-
3.3. Optimisation of the hypochlorous acid production
tions X1X2 (electrolysis time and current intensity) can be facilitated
by seeing the Fig. 6. This figure is obtained as follows: each summit
In this section, the optimal values of four factors: electrolysis time
of the square represents a combination of the levels of the two fac-
(X1), current intensity (X2), H3O + concentration (X3) and chloride
tors: electrolysis time and current intensity. For instance, the corner
concentration (X4) for gas chlorine production were studied using
at the top (at the right) of this figure corresponds to 35 min of elec-
Central Composite Design (CCD) (Table 3). The regression model in
trolysis time and current intensity of 1.6 A imposed. The value of
terms of coded variables has been expressed by the following
38.5 mg/l of chlorine concentration represented in the rounded-
second-order polynomial equation:
cartridge is obtained by calculating the average of the experimental
results from the assays carried out with a current intensity of 1.6 A
Y1 ¼ 10:7 þ 9:75X1 þ 9:39X2 þ 1:13X3 þ 0:54X4 þ 5:74X1 X2
imposed during 35 min of electrolysis (assays 4, 8, 12 and 16). 2 2 ð13Þ
þ1:13X2 X3 þ 1:59X2 X4 þ 1:42X1 þ 2:94X2
When the current intensity (X2) is fixed at the highest level (1.6 A),
the treatment time has a significant influence on the chlorine produc-
tion rate. The chlorine production rate passed from 6.56 mg/l to With Xi varying from − 2 and +2 and Y1 represents the chlorine
38.5 mg/l (a production gain of 32 units). When the current intensity production. In terms of actual factors, an empirical relation between

Table 2
Experimental factorial matrix in the 24 design for calculation of effects and experimental results.

Exp. Experiment design Experiment plan Y1a : Actual Y1b : predicted Relative Y2
number HClO HClO deviation energy
X1 X2 X3 X4 U1 (min) U2 (A) U3 (M) U4 (M)
production production (Y1a–Y1b) (kWh/m3)
(mg/l) (mg/l)

1 −1 −1 −1 −1 15 0.8 0.05 0.3 1.60 2.12 − 0.52 0.12

2 +1 −1 −1 −1 35 0.8 0.05 0.3 13.5 10.9 2.60 0.33
3 −1 +1 −1 −1 15 1.6 0.05 0.3 5.04 4.26 0.78 0.25
4 +1 +1 −1 −1 35 1.6 0.05 0.3 34.4 36.2 − 1.80 0.82
5 −1 −1 +1 −1 15 0.8 0.11 0.3 1.74 − 0.78 2.52 0.12
6 +1 −1 +1 −1 35 0.8 0.11 0.3 9.52 8.62 0.90 0.31
7 −1 +1 +1 −1 15 1.6 0.11 0.3 5.32 7.48 − 2.16 0.30
8 +1 +1 +1 −1 35 1.6 0.11 0.3 36.5 39.5 − 3.0 0.77
9 −1 −1 −1 +1 15 0.8 0.05 0.8 1.54 3.52 − 1.98 0.12
10 +1 −1 −1 +1 35 0.8 0.05 0.8 10.3 12.3 − 2.0 0.31
11 −1 +1 −1 +1 15 1.6 0.05 0.8 8.96 5.66 3.3 0.30
12 +1 +1 −1 +1 35 1.6 0.05 0.8 37.2 37.6 − 0.4 0.78
13 −1 −1 +1 +1 15 0.8 0.11 0.8 0.56 0.62 − 0.06 0.12
14 +1 −1 +1 +1 35 0.8 0.11 0.8 7.26 5.82 1.44 0.30
15 −1 +1 +1 +1 15 1.6 0.11 0.8 6.94 8.88 − 1.94 0.28
16 +1 +1 +1 +1 35 1.6 0.11 0.8 46.0 40.9 5.10 0.76
 F. Zaviska et al. / Desalination 296 (2012) 16–23 21

Table 4
ANOVA results for the response surface quadratic model for hypochlorous acid produc-
tion and energy consumption.

Source Analysis of variance

d.f.a Sum of square Mean square F-value Pr > F

Chlorine production
Model 9 5299.24 588.8 59.83 b0.0001
Residual 20 196.83 9.84
Lack of fit 15 174.13 11.61 2.56 b0.1527
Pure error 5 22.69 4.54

Energy consumption
Model 7 1.34 0.19 297.09 b0.0001
Residual 22 0.014 0.00064
Lack of fit 17 0.014 0.00082 14.33 0.004
Pure error 5 0.00029 0.000057
a
Degree of freedom.
R2 =0.9642 for chlorine production.
R2 =0.990 for energy consumption.

chloride concentrations were kept constant at 0.08 M and 0.55 M re-

Fig. 6. Interaction X12 between current intensity and treatment time.
hypochlorous acid production and the variables has been expressed
by the following second-order polynomial equation:
Y1 ¼ 51:85−1:46U1 −72:8U2 −74:9U3 −16:9U4 þ 1:43U1 U2
ð14Þ
þ93:9U2 U3 þ 15:9U2 U4 þ 0:01U21 þ 18:4U22
Where 5 min ≤U1 ≤45 min ; 0.4 A ≤ U2 ≤ 2 A ; 0.02 M ≤U3≤0.14 M
and 0.05 M≤ U4 ≤ 0.105 M. The coefficients of the polynomial model
(quadratic model) were calculated using the Design-Expert ® Program
Software.
Table 4 shows the analysis of variance (ANOVA) of regression
parameters of the predicted response surface quadratic model for
active chlorine production. As it can be seen from this table, the model
F-value of 59.83 and a low probability value (Pr > F = 0.0001) indicate
that the model is very significant. The value of the correlation coefficient
(R2 = 0.964) means that only 3.6% of the total variation could not be
explained by the empirical model and indicates that the regression
model explained the electrochloration process well. According to
Joglekar and May [15], R 2 should be at least 0.80 for a good fit of a
model. Furthermore, the lack of fit F-value of 2.56 and the probability
value (Pr > F = 0.1527) indicate that the lack of fit of the model is not
significant. The effect of treatment time and current intensity on the
active chlorine production is illustrated in Fig. 7. When the acid and
spectively (at the center of the experimental region investigated),
chlorine concentration increased with increasing treatment time
for all current intensity studied. As seen from the contour plot,
more than 33 mg l − 1 of chlorine production could be recorded at at
0.08 M of H3O + and 0.55 M of chloride while the treatment times
were higher than 30 min and the current intensities higher than
1.4 A.
Considering now the energy consumption (Y2), the regression
model in terms of coded variables can be also expressed by the fol-
lowing second-order polynomial equation:
Y2 ¼ 0:33 þ 0:16X1 þ 0:16X2 þ 0:009X3 þ 0:0071X4
2 2
þ 0:076X1 X2 þ 0:022X1 þ 0:019X2 ð15Þ
The energy consumption is calculated from the followed equation:
IUt
E¼ ð16Þ
V
Where “E” is the energy consumption in kWh.m − 3, “I” the current
intensity (A), “U” the electrical potential (V), “t” the treatment time
(h) and “V” the volume of treated water (L). During electrolysis, the
voltage varied from 0.20 to 0.50 V. The analysis of variance
(ANOVA) of regression parameters of the predicted response surface
quadratic model for energy consumption shows that that the model
is significant (F-value of 297 and a low probability value Pr > F =
0.0001). The value of the correlation coefficient (R 2 = 0.990) indicate

Table 3
Central composite matrix and experimental results.

Experiment Experimental design Experimental plan HClO Energy

number production consumption
X1 X2 X3 X4 U1 (min) U2 (A) U3 (M) U4 (M)
(mg/l) (kWh/m3)
(Y1) (Y2)

17 −2 0 0 0 5 1.2 0.08 0.55 0.10 0.125

18 +2 0 0 0 45 1.2 0.08 0.55 36.0 0.688
19 0 −2 0 0 25 0.4 0.08 0.55 1.68 0.083
20 0 +2 0 0 25 2.0 0.08 0.55 46.6 0.708
21 0 0 −2 0 25 1.2 0.02 0.55 4.0 0.375
22 0 0 +2 0 25 1.2 0.14 0.55 16.4 0.3
23 0 0 0 −2 25 1.2 0.08 0.05 13.0 0.375
24 0 0 0 +2 25 1.2 0.08 1.05 13.4 0.308
25 0 0 0 0 25 1.2 0.08 0.55 9.4 0.318
26 0 0 0 0 25 1.2 0.08 0.55 10.7 0.312
27 0 0 0 0 25 1.2 0.08 0.55 13.76 0.323
28 0 0 0 0 25 1.2 0.08 0.55 9.0 0.31
29 0 0 0 0 25 1.2 0.08 0.55 13.8 0.33
30 0 0 0 0 25 1.2 0.08 0.55 10.2 0.314
22 F. Zaviska et al. / Desalination 296 (2012) 16–23

Fig. 7. Effect of the electrolysis time and current intensity on active chlorine production. ([H3O+] and [Cl−] kept constant at 0.08 M and 0.55 M respectively, at the center of the
experimental region investigated).

that only 1.00% of the total variation could not be explained by the
empirical model.
To rigorously determine the optimal condition for active chlorine
production in terms of cost/effectiveness, the energy consumption dur-
ing electrolysis has to be taken into account. The criteria selected for the
optimization condition for this electrochloration process are the follow-
ing: production of active chlorine has to be maximized with the highest
importance (5/5 weighting factor) and the energy consumption has to
be minimized with lesser importance (3/5 weighting factor) in order
to reduce the treatment cost related to energy consumption. Based on
these criteria imposed, the Design-Expert® Program Software proposed
different solution classified per order of desirability. The best solution is
presented in Table 5. The desirability is a value varying from zero to one
and it gives information about the adequacy between the solution and
the criteria imposed. If the value is closer to one, it's mean that the solu-
tion is very close from what we want and the software have done only
few compromise to satisfy the imposed criteria. On the other hand, if
the desirability is closer from zero, it means that it's very difficult
to satisfy the criteria without making a lot of compromise. The best
solution for active chlorine production in terms of energy consumption/
effectiveness has been found after 27 min of treatment using a concentra-
tion of 0.11 M of chloride sodium and 0.8 M of hydrochloric acid under
the maximum of current intensity 1.6 A. In this condition, the production
of active chlorine should be nearly 31 mg/l with an energy consumption
of 0.54 kWh/m3.
gas production. The effect of these two main factors is around 82.8%
on the investigated response, whereas the chloride ion concentration,
the acid concentration and the other interaction effects represent
17.2% on the investigated response. Subsequently, a central composite
design was employed to define the optimal operating conditions for ac-
tive chlorine production. Current intensity and treatment time were
found to be very meaningful for chlorine production. They are positive
effects on the response. The electrolytic cell operated at a current inten-
sity of 1.6 A during 27 min of treatment time using a concentration of
0.11 M of chloride sodium and 0.8 M of hydrochloric acid were found
to be the optimal conditions in terms of cost/energy consumption.
Under these conditions, 31 mg/l of chlorine can be produced for an en-
ergy consumption of 0.54 kWh/m3. This process appears to be a very
good alternative to reuse concentrates of seawater from reverse osmo-
sis in order to produce an oxidant agent that can be used in drinking
water treatment. Likewise, it could form the basis of a process that
can be used either as a pretreatment to protect membrane against bio-
film formation or as tertiary treatment for disinfection.
Acknowledgments
Sincere thanks are extended to the Ministry of International Rela-
tion (MRI) of the government of Québec and CONACYT of Mexican
government for their financial contributions to this study.

References
4. Conclusions
[1] F.H. Oliveira, M.E. Osugi, F.M.M. Paschoal, D. Profeti, P. Olivi, M. Valnice, B. Zanoni,
This study investigated active chlorine production by saline water Electrochemical oxidation of an acid dye by active chlorine generated using
Ti/Sn (1-x) IrxO2 electrodes, J. Appl. Electrochem. 35 (2007) 583–592.
electrolysis using Ti/IrO2 as anode material. An experimental design
[2] Y.F. Xie, Disinfection byproducts in drinking water, formation, analysis and control,
methodology has been applied to determine the optimal experimental CRC Press LLC, Boca Raton, Florida, 2004.
conditions. The factorial design demonstrated that the current intensity [3] N. Voutchkov, Overview of seawater concentrate disposal alternatives, Desalination
and treatment time are the most influent parameters on the chlorine 273 (2011) 205–219.
[4] D.H. Kim, A review of desalting process techniques and economic analysis of the
recovery of salts from retentates, Desalination 270 (2011) 1–8.
[5] M. Ahmed, W.H. Shayya, D. Hoey, A. Mahendran, R. Morris, J. Al-Handaly, Use of
evaporation ponds for brine disposal in desalination plants, Desalination 130
Table 5
(2) (2000) 155–168.
Determination of optimal condition in terms of cost/effectiveness proposed by [6] M. Ahmed, W.H. Shayya, D. Hoey, J. Al-Handaly, Brine disposal from reverse osmosis
Design-Expert ® Program Software. desalination plants in Oman and the United Arab Emirates, Desalination 133 (2)
(2001) 135–147.
Treatment Current [H3O+] Chloride Active Energy Desirability
[7] A.M.O. Mohamed, M. Maraqa, J.A. Handhaly, Impact of land disposal of reject
time intensity (M) conc. chlorine consumption brine from desalination plants on soil and groundwater, Desalination 182 (1–3)
(min) (A) (M) production (kWh/m3) (2005) 411–433.
(mg/l) [8] J.L. Hunt, K. Frazier, B.P. Pendergraft, M.Y. Soliman, Evaluation and completion
procedure for produced brine and waste water disposal wells, J. Petrol. Sci. Eng.
27 1.6 0.11 0.8 30.6 0.539 0.534
11 (1) (1994) 51–60.
 F. Zaviska et al. / Desalination 296 (2012) 16–23
[9] J.V. Del Bene, G. Jirka, J. Largier, Ocean brine disposal, Desalination 97 (1–3)
(1994) 365–372.
[10] D. Orhon, Scientific basis for wastewater treatment and disposal in Istanbul,
Water Sci. Technol. 32 (2) (1995) 199–208.
[11] R.H. Myers, D.C. Montgomery, Response surface methodology: process and product
optimization using designed experiments, 2nd edition John Wiley and Sons, New
York, NY, USA, 2002.
[12] M.H. Entezari, P. Kruus, Effect of frequency on sonochemical reactions I. Oxidation
of iodide, Ultrason. Sonochem. 1 (2) (1994) S75–S79.
[13] S. Koda, T. Kimura, T. Kondo, H. Mitome, A standard method to calibrate
sonochemical efficiency of an individual reaction system, Ultrason. Sonochem. 10
(3) (2003) 149–156.
[14] D.P. Haaland, Experimental design in biotechnology, Marcel Dekker Inc., N.Y.,
1989.
[15] A.M. Joglekar, A.T. May, Product excellence through design of experiments, Cereal
Foods World 32 (1987) 857–868.
[16] H. Nath, X.J. Wang, R. Torrent, A. Langdong, A novel perforated electrode flow
through cell design for chlorine generation, J. Appl. Electrochem. 41 (4) (2011)
389–395.
23
[17] K.C. Pillai, T.O. Kwon, B.B. Park, I.S. Moon, Using RuO2 anode for chlorine dioxide
production in an un-divided electrochemical cell, Water Sci. Technol. 61 (8)
(2010) 2151–2160.
[18] K.C. Pillai, T.O. Kwon, B.B. Park, I.S. Moon, Studies on process parameters for chlorine
dioxide production using IrO2 anode in an un-divided electrochemical cell, J. Hazard.
Mater. 164 (2–3) (2009) 812–819.
[19] A. Perez-Gonzalez, A.M. Urtiaga, R. Ibanez, I. Ortiz, State of the art and review on
the treatment technologies of water reverse osmosis concentrates, Water Res. 46
(2012) 267–283.
[20] D. Squire, J. Murrerl, P. Holden, C. Fitzpatrick, Disposal of reverse osmosis membrane
concentrate, Desalination 108 (1996) 143–147.
[21] M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, Pergamon,
New York, 1966.
[22] M. Doré, Chimie des oxydants et traitement des eaux, Tec. Doc. Lav., Paris, 1989.
[23] F. Persin, M. Rumeau, Le traitement électrochimique des eaux et des effluents,
Tribune l'Eau 42 (1989) 45–56.
[24] F. Zaviska, P. Drogui, J.F. Blais, G. Mercier, In situ hypochlorous generation for the
treatment of dye-containing effluents, J. Appl. Electrochem. 39 (2009)
2397–2408.